EP4114797A1 - Process for thermally treating a battery material in a thermal reactor - Google Patents
Process for thermally treating a battery material in a thermal reactorInfo
- Publication number
- EP4114797A1 EP4114797A1 EP21710210.2A EP21710210A EP4114797A1 EP 4114797 A1 EP4114797 A1 EP 4114797A1 EP 21710210 A EP21710210 A EP 21710210A EP 4114797 A1 EP4114797 A1 EP 4114797A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- battery
- reactor
- battery material
- hot gas
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 188
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007858 starting material Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 51
- 229910052744 lithium Inorganic materials 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- 238000007669 thermal treatment Methods 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000004220 aggregation Methods 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 4
- 239000000443 aerosol Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 101100495769 Caenorhabditis elegans che-1 gene Proteins 0.000 claims 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229940116007 ferrous phosphate Drugs 0.000 claims 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 25
- 239000011572 manganese Substances 0.000 description 22
- 230000010349 pulsation Effects 0.000 description 21
- 239000010941 cobalt Substances 0.000 description 18
- 229910017052 cobalt Inorganic materials 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 16
- 229910052748 manganese Inorganic materials 0.000 description 16
- 239000000446 fuel Substances 0.000 description 14
- 239000000567 combustion gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 229910013733 LiCo Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910006025 NiCoMn Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 1
- CROQDZTZYUXPHE-UHFFFAOYSA-N [O-2].[Mn+2].[Fe+2].[Na+] Chemical compound [O-2].[Mn+2].[Fe+2].[Na+] CROQDZTZYUXPHE-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
- B01J6/004—Calcining using hot gas streams in which the material is moved
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention relates to a method for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material.
- Devices for the thermal treatment of a raw material are, for example, pulsation reactors, as they are described in WO 02/072471 A1 or DE 102004044266 A1 and WO 2019/197147 A1.
- Pulsation reactors are used, for example, for a thermal synthesis of a raw material for the production of fine particles, in particular fine materials.
- the invention is based on the object of specifying a particularly environmentally friendly method for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material.
- the object is achieved according to the invention by a method for thermal treatment, in particular by synthesis and / or drying and calcination, of a nano- and / or microscale or nano- and / or microcrystalline battery material in a reaction chamber of a thermal reactor, comprising the steps: Introducing a starting compound into the reaction space, with a battery material and / or a battery precursor material, in particular a sodium- or lithium-containing battery material and / or battery precursor material, being introduced as the starting compound, and the starting compound in the form of a solution, slurry, suspension or in a solid state of aggregation is introduced into the reaction chamber,
- Another aspect provides a method for thermal treatment, in particular by synthesis and / or drying and calcination, of a nano- and / or microscale or nano- and / or microcrystalline battery material and / or battery precursor material in a thermal reactor with an application space and a reaction space which includes the following steps:
- the thermal treatment is in particular a method in which the battery material and / or the battery precursor material is synthesized, dried and / or calcined by means of the hot gas flow.
- a sufficiently high energy input takes place within a short dwell time of less than 2 s due to the finely distributed direct treatment in the hot gas flow.
- Drying and calcining are understood to mean, in particular, drying and calcining of the liquid substance, in particular the solution, slurry, suspension or a solid but moist starting material.
- the thermal treatment takes place in a flowing hot gas, which converts the starting compound, in particular a battery precursor material, to the battery material by synthesis and / or drying and calcination.
- a single step is understood to mean, in particular, the continuous thermal treatment of the starting compound and its conversion to the battery material in the hot gas stream of the thermal reactor, namely from the introduction of the starting compound, in particular through extremely fine distribution, into the hot gas stream of the thermal reactor and thermal treatment of this starting compound by synthesis and / or drying and calcining in a hot gas stream with short dwell times of 0.1 s to 2 s in combination with low to high temperatures of 150 ° C to 1,000 ° C until the dried and calcined battery material is removed from the thermal reactor.
- a starting compound introduced as a battery precursor material can be converted to the battery material by synthesis and drying and calcination in a single step in the hot gas flow in the thermal reactor.
- the starting compound is converted into the battery material only by drying and calcining in a single step in the hot gas flow in the thermal reactor.
- the process according to the invention differs considerably from the process known from the prior art in the energy transfer and the conversion process through synthesis and / or drying and calcination through extremely fine distribution of the starting compound in the hot gas and its thermal treatment in the hot gas stream with a very short residence time of approx. 0.1 s to 2 s, as a result of which, surprisingly, very fine particles can be produced.
- the advantages achieved with the invention are in particular that the battery material is cleaned and / or thermally treated, in particular dried and calcined, quickly, easily and in just one step in an environmentally friendly manner, compared to conventional methods.
- a higher yield and special properties (such as setting the crystallite size, in particular homogeneous particle and / or crystallite size distribution, crystal annealing) are achieved for the thermally treated battery material.
- an escape of substance into an environment is preferably avoided.
- Complex pre-drying, intermediate steps, purification, and thermal pre- and / or post-treatments, such as long-lasting calcinations, are avoided.
- a combustion gas and a fuel are fed into the reactor, in particular into the application space, and ignited there.
- a hot gas stream is generated in which the starting compound is in the flow direction of the hot gas stream in the reactor seen at a front loading point into the reactor, for example into the application space and / or in the flow inlet-side area into the reaction space, and is carried and transported by the hot gas stream.
- the hot gas flow is formed by the hot gases produced during combustion.
- the combustion of fuel and combustion gases can take place flamelessly or with a flame.
- a pulsating, in particular a regularly or irregularly pulsing, or a uniformly turbulent hot gas flow can be generated as the hot gas flow.
- the battery material and / or battery precursor material obtained is separated from the hot gas flow at only one separation point.
- all solid substances are separated from the hot gas flow at the separation point.
- the thermal treatment of the battery material and / or battery precursor material, in particular containing sodium or lithium is carried out with a residence time of 0.1 s to 2 s in the reaction chamber.
- the dwell time defines the duration of treatment and the desired thermal treatment of the battery material, for example whether it should only be dried or only calcined or both dried and calcined.
- Another aspect of the invention provides that the battery material and / or battery precursor material is dried and calcined in the treatment zone in a single step.
- the thermal treatment of the battery material and / or battery precursor material as the starting compound and its conversion in the thermal reactor by synthesis and / or drying and calcination takes place in a self-contained system.
- Such a synthesis and / or drying and calcination process which is reduced to a single step, is particularly environmentally friendly and saves resources.
- the synthesis and / or drying and calcination takes place in direct contact with the hot gas stream in a single operation within the thermal reactor.
- the result of the direct heat exchange per unit of material can for example be caused by the combustion, in particular by the supplied amount of combustion gas and / or fuel, and / or the material flow, in particular of the battery material and / or battery precursor material, in the reaction space of the thermal reactor can be regulated.
- the thermal reactor when the thermal reactor is designed as a pulsation reactor, the thermal treatment is particularly homogeneous and uniform.
- the thermal reactor can, however, also be designed as an entrained flow reactor.
- the starting compound is introduced into the reaction space by means of a carrier fluid and / or as an aerosol.
- the carrier fluid is a gas, in particular ambient air or oxygen or an inert gas, such as. B. nitrogen.
- the starting compound can be fed into the reactor in the area of the reaction space and / or in the area of a combustion chamber in the case of a directly fired reactor.
- the choice of the place of application in the reactor depends on which thermal treatment is to be achieved. The choice of the place of application changes the duration of treatment and the effect of temperature in particular.
- the reactor For example, for drying and calcining the battery material, it is introduced into the reactor at a front loading point, in particular into the combustion chamber and / or the reaction space, viewed in the direction of flow of the hot gas flow in the reactor. In order to dry the battery material, it is introduced into the reactor at a rear loading point, viewed in the direction of flow of the hot gas flow in the reactor, in particular only into the reaction space.
- the hot gas flow in the reaction chamber preferably pulsates or oscillates regularly or irregularly, in particular at a frequency between 5 Hz and 350 Hz.
- the battery material is transferred to a cooling zone of the reaction space and then discharged from the reaction space and deposited in powder form.
- the battery material can in particular be a battery material containing sodium or lithium.
- the lithium-containing battery material is in particular a nickel, manganese and / or cobalt-containing lithium material, for example LiMn 2 0, LiCo x Mn 2.x 0 4 or Li (NiCoMn) 0 2 (also called NCM for short), a lithium material containing iron phosphate, for Example LiFePCL (also called LFP for short), a lithium material containing nickel and manganese, for example LiNi x Mn 2.x 0 4 (also called LNMO for short), a lithium material containing iron phosphate and manganese phosphate, for example LiFei.
- LiCo0 2 also briefly called LCO
- Li 2 Ti 5 0i also called a titanium and oxygen-containing lithium material, shortly LTO
- manganese, iron lithium phosphate-containing material a lithium material containing nickel, cobalt and / or aluminum, for example LiA10 2 or LiNiCoA10 2 (also called NCA for short)
- a lithium material containing cobalt and oxygen for example LiCo0 2 (also briefly called LCO) or, for example, Li 2 Ti 5 0i (also called a titanium and oxygen-containing lithium material, shortly LTO)
- the sodium-containing battery material is in particular a nickel, manganese, titanium and iron-containing sodium material or an iron-phosphate-containing sodium material, permanganate-containing sodium material or a chromium-containing sodium material.
- the lithium material containing nickel, manganese and cobalt is in particular a lithium starting compound with proportions of nickel, cobalt and manganese.
- the lithium material containing nickel, cobalt and manganese can contain stoichiometric proportions of nickel, cobalt and manganese (1: 1: 1) or non-stoichiometric proportions (5: 3: 1, 6: 2: 2, 8: 1: 1 (nickel-rich) ) exhibit.
- stoichiometric proportions of nickel, cobalt and manganese (1: 1: 1) or non-stoichiometric proportions (5: 3: 1, 6: 2: 2, 8: 1: 1 (nickel-rich) ) exhibit.
- a lithium-containing battery material with a lower proportion of lithium than the proportions of other components of this battery material has advantages in terms of necessary resources and environmental protection.
- the proportion of lithium is lower in the nickel, cobalt and manganese-containing lithium material compared to the proportions of nickel, cobalt and manganese. Also in the case of the other lithium materials with other proportions, such as iron phosphate, aluminum, oxygen, the lithium proportion is lower compared to these other proportions, such as iron phosphate, aluminum, oxygen.
- the nano- and / or microscale or nano- and / or microcrystalline battery material obtained and deposited has, in particular, an average particle size in the range from 10 nm to a few micrometers, in particular up to 50 ⁇ m.
- nano- and / or microscale or nano- and / or microcrystalline battery materials and / or battery precursor materials can be thermally treated, in particular dried and / or calcined.
- a thermally treated nano- and / or microscale or nano- and / or microcrystalline battery material is particularly suitable for use as a cathode or anode material.
- the invention also provides the use of a thermal reactor with at least one reaction chamber and at least one heating arrangement and / or an arrangement for generating a hot gas flow, in particular a pulsation arrangement for generating a pulsating hot gas flow, in the reaction chamber for thermal treatment by synthesis and / or drying and Calcination of a nano- and / or microscale or nano- and / or microcrystalline battery material in the reaction space of the thermal reactor.
- the thermal reactor is set up to carry out the method described above.
- Figure is a block diagram of an apparatus for producing
- the single FIGURE shows a block diagram of a device V for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material BM in a reaction space 1.1 of a thermal reactor 1.
- the battery material BM in the end product has an average particle or grain size in the range from 10 nm to a few micrometers.
- a battery material BM is or are understood to mean, in particular, one or more battery materials, a battery material mixture or a preprocessed battery material or a preprocessed battery material mixture or a battery precursor material BM.
- the battery material BM is a nano- and / or microscale or nano- and / or microcrystalline, in particular a sodium- or lithium-containing, battery material BM.
- the device V is designed as a thermal reactor 1.
- the thermal reactor 1 comprises at least one reaction space 1.1 and at least one loading location 1.2 for loading the battery material BM for thermal treatment of the battery material RM in the reaction space 1.1 and a separation point 1.3 for outputting and depositing the thermally treated battery material BM in powder form.
- the battery material BM or a battery precursor material is introduced in the form of an output connection AV at the task location (s) 1.2.
- the output compound AV of the battery material BM or of the battery precursor material is abandoned and in the form of a solution, slurry, suspension or in a solid aggregate state of a battery material or battery material mixture or a battery precursor material BM introduced into the reaction chamber 1.1.
- the thermal reactor 1 can be, for example, an entrained flow reactor, a pulsation reactor, a dryer, a calciner or another suitable system or container for the thermal treatment of the battery material BM and / or the battery precursor material BM in a hot gas flow HGS or in a pulsating hot gas flow HGS.
- the thermal reactor 1 as an entrained flow reactor or as a pulsation reactor is characterized by a thermal treatment of the droplets or particles down to the powder in a hot, flowing gas or a hot, flowing and pulsating gas, which carries the particles simultaneously and thus through the thermal reactor 1, in particular depending on the task location 1.2 through an application space 2.1 and / or through the reaction space 1.1.
- this thermal reactor 1 can be an entrained flow reactor, a pulsation reactor, a dryer, a calciner or another suitable system or container for the thermal treatment of the battery material BM in a hot gas flow HGS, in particular a pulsating or oscillating hot gas flow HGS.
- the battery material BM and / or the battery precursor material BM is carried by a hot gas flow HGS and guided through the reaction space 1.1 and thermally treated in it.
- the battery material BM and / or battery precursor material BM carried in the hot gas stream HGS is at a temperature of 150 ° C to 1,000 ° C with a Dwell time from 0.1 s to 2 s thermally treated.
- the starting compound, in particular a battery precursor material is converted to the battery material BM by synthesis and / or drying and calcination in a single step in the hot gas stream HGS in the thermal reactor 1.
- the battery material BM obtained in this way in powder form is then discharged from the thermal reactor 1.
- Such a synthesis and / or drying and calcination process for the thermal treatment of the battery material BM, which is reduced to a single step, is particularly environmentally friendly and saves resources.
- the synthesis and / or drying and calcination takes place in direct contact with the hot gas stream HGS in a single operation within the thermal reactor 1.
- the hot gas flow HGS is generated by feeding and igniting a fuel BS and a combustion gas VG in the thermal reactor 1.
- the hot gas flow HGS is formed by the hot gases produced during the combustion of the fuel BS and the combustion gases VG.
- the combustion can be carried out without a flame, for example. Combustion with a flame is also possible.
- the hot gas flow HGS generated can flow regularly or irregularly in pulsing fashion in reactor 1 or flow uniformly in turbulence in reactor 1.
- the thermal reactor 1 is described below with reference to a pulsation reactor and is therefore referred to below as a pulsation reactor 1.
- the battery material BM is thermally treated in a pulsating, oscillating stream of hot gas HGS.
- the pulsation reactor 1 comprises a generator 2 for generating the pulsating hot gas flow HGS.
- a generator 2 for generating the pulsating hot gas flow HGS.
- B a combustion chamber, and / or another technical implementation for heating the hot gas flow HGS in combination with the application space 2.1.
- the pulsation reactor 1 can comprise at least one pulsator (not shown) which is attached to the reaction space 1.1, which the application room 2.1 is connected downstream, is arranged.
- the pulsator can for example be coupled from the outside to the reaction space 1.1 and impresses at least one pressure oscillation to generate or amplify the pulsating hot gas flow HGS in the reaction space 1.1.
- the hot gas flow HGS can be heated instead of the fired generation and heating or in addition to the fired generation and heating by means of a heat exchanger or electrically and generated by means of the pulsator.
- the pulsating hot gas stream HGS flows from the application space 2.1 into the downstream reaction space 1.1 or through the reaction space 1.1.
- combustion gases VG and at least one fuel BS are introduced jointly or separately into the burner via a feed line 3 and via this into the combustion chamber.
- a combustible gas such as natural gas and / or hydrogen
- a suitable gas can also be supplied as fuel gas.
- the supplied combustion gases VG and fuels BS are ignited, for example, in the application space 2.1, in particular in the combustion chamber.
- the resulting flame pulsates due to a self-excited periodic-unsteady combustion in the application space 2.1 and generates the pulsating hot gas flow HGS in the application space 2.1.
- the pulsating hot gas flow HGS flows from the application space 2.1 on the flow outlet side into the reaction space 1.1.
- the reaction space 1.1 is designed, for example, as a resonance tube.
- the reaction space 1.1 can optionally be followed by a further reaction space (not shown).
- the reaction space 1.1 indicates a region of the pulsation reactor 1, which extends from the feed 3 to at least the end of the reaction space 1.1 designed as a resonance tube and in which the battery material BM is thermally treated.
- the fuel BS and the necessary combustion gas VG are fed jointly (for example, premixed in an upstream mixing chamber) or separately via the generator 2, in particular the burner, to the application space 2.1, in particular the combustion chamber, and ignited there.
- the fuel BS and the combustion gas VG burn very quickly and generate a pressure wave in the direction of the reaction chamber 1.1, for example in the direction of the resonance tube. Due to the lower flow resistance in the direction of the reaction chamber 1.1, a pressure wave propagates.
- the pressure in the application space 2.1, in particular in the combustion chamber is reduced so that new fuel gas mixture or new fuel BS and combustion gas VG can or can flow in. This process of post-flow due to pressure fluctuations takes place periodically in a self-regulating manner.
- a reaction gas such as, for example, air and / or nitrogen and / or forming gas
- a heat exchanger This heats the reaction gas to the desired temperature and then feeds it to the application space 2.1.
- pulsators in the reaction space 1.1 also creates a pulsating hot gas flow.
- the composition of the hot gas flow HGS is not tied to a combustion exhaust gas, but can be selected almost freely. If a reaction is therefore required in reaction space 1.1 under inert conditions, nitrogen, for example, can be used as the reaction gas.
- the pulsating hot gas flow HGS therefore only consists of nitrogen.
- the pulsating hot gas flow HGS is characterized by a high degree of turbulence.
- the high flow turbulence and the constantly changing flow speed prevent the build-up of an insulating gas envelope (Boundary layer) around the solid particles of the battery material BM, as a result of which a higher heat transfer and mass transfer (between battery material BM and hot gas), i.e. a faster reaction at comparatively lower temperatures, is possible.
- the dwell time is less than a second to a few milliseconds.
- a suitable separation device 4 adjoins the reaction space 1.1. After the thermal treatment, the battery material BM is transferred to a cooling zone in the reaction space 1.1 in a treatment zone in the reaction space 1.1 and then discharged from the reaction space 1.1 and deposited in powder form in the separating device 4.
- the frequency of the pulsating hot gas flow HGS is in the Hertz range, in particular in a range of a few Hertz, for example greater than 5 Hz, in particular greater than 50 Hz, for example in a range from 5 Hz to 350 Hz, in particular from 10 Hz to 150 Hz
- Parameters of the hot gas flow HGS such as the amplitude and / or frequency of the oscillation, can be set particularly easily by means of the generator 2 and / or the pulsator.
- combustion parameters such as the amount of fuel, amount of air, air temperature, fuel temperature and / or flame temperature, location of the fuel / air feed and / or via proportions and / or changes to these from application space 2.1, in particular combustion chamber, generator 2, in particular burner and / or or reaction chamber 1.1.
- the reaction space 1.1 is designed, for example, as a resonance tube. If a flame is burning in the application space 2.1, this is a combustion chamber.
- the combustion chamber is then designed as a combustion chamber whose dimensions, in particular its diameter, are greater than the dimensions, in particular the diameter of the reaction chamber 1.1.
- the application room 2.1 (without Flame) is larger in its dimensions, in particular its diameter, than the reaction space 1.1.
- At least one feed location 1.2 is arranged, at which the battery material BM is fed.
- the choice of the task location 1.2 in the pulsation reactor 1 depends on which thermal treatment is to be achieved. By choosing the task location 1.2, the treatment duration and the temperature effect are changed in particular.
- the battery material BM it is introduced into the reactor 1, in particular into the combustion chamber and / or the application space 2.1, at a front loading location 1.2, viewed in the direction of flow of the hot gas flow HGS in the reactor 1.
- a rear loading point viewed in the flow direction of the hot gas flow HGS in the reactor 1, in particular only into the reaction space 1.1.
- the starting compound AV of the battery material BM is introduced into the reactor 1, for example, by means of a carrier fluid and / or as an aerosol, for example in atomized form.
- the carrier fluid is a gas, in particular ambient air, oxygen or nitrogen.
- a battery material BM in the form of a solution, slurry, suspension or in a solid state of aggregation is introduced into the reactor 1 as the starting compound AV and is thermally treated there in a treatment zone by means of the pulsating hot gas flow HGS at a temperature of 150 ° C to 1,000 ° C, in particular dried and / or calcined.
- the battery material BM obtained is then deposited in powder form from the reactor 1.
- the battery material BM obtained is separated from the hot gas flow HGS at only one separation point 1.3.
- all solid substances are separated from the hot gas stream HGS at separation point 1.3. From the separation point 1.3 can be designed, for example, as a filter or centrifugal separator.
- One embodiment provides that the thermal treatment of the battery material BM is carried out in the reactor 1 with a residence time of 0.1 s to 2 s.
- the dwell time determines the duration of treatment and the desired thermal treatment of the battery material BM, whether it is only to be dried or only calcined or both dried and calcined, for example.
- the battery material BM can be dried and calcined in the treatment zone of the reactor 1 in a single step.
- Such a drying and calcination process which is reduced to a single step, is particularly environmentally friendly and saves resources.
- the battery material BM is in particular a lithium material containing nickel, manganese and / or cobalt, for example LiMn 2 0 4 , LiCo x Mn 2.x 0 4 or Li (NiCoMn) 0 2 (also called NCM for short), a lithium material containing iron phosphate, for example LiFePCE (also called LFP for short), a lithium material containing nickel and manganese, for example LiNi x Mn 2.x 04 (also called LNMO for short), a lithium material containing iron and manganese, for example LiFei.
- a lithium material containing nickel, cobalt and / or aluminum for example LiA10 2 or LiNiCoA10 2 (also called NCA for short)
- a lithium material containing cobalt and oxygen for example LiCo0 2 (also briefly called LCO) or, for example, Li 2 Ti 5 0i (also called a titanium and oxygen-containing lithium material, shortly LTO)
- a nickel, manganese, titanium and iron-containing material or a sodium manganese, egg senphosphat termes lithium material.
- the lithium material containing nickel, manganese and cobalt is in particular a lithium starting compound with proportions of nickel, cobalt and manganese.
- the lithium material containing nickel, manganese and cobalt can contain stoichiometric proportions of nickel, cobalt and manganese (1: 1: 1) or non-stoichiometric proportions (5: 3: 1, 6: 2: 2, 8: 1: 1 (nickel-rich) ) exhibit.
- the proportion of lithium is lower in the nickel, manganese and cobalt-containing lithium material compared to the proportions of nickel, cobalt and manganese.
- the obtained and deposited nano- and / or microscale or nano- and / or microcrystalline battery material BM has in particular an average particle size in the range from 10 nm to a few micrometers, in particular up to 50 ⁇ m.
- Example 1 thermal treatment and production of a compound LiFePCL (LFP) as an example of a lithium-containing battery material
- a metal phosphate powder with the composition LiFePCL was produced as the lithium-containing battery material BM.
- an aqueous solution of iron (III) nitrate nonahydrate, lithium hydroxide monohydrate and phosphoric acid in the appropriate stoichiometric ratio and a total product concentration of 15% by weight (calculated as LiFeP0) in the hot gas stream HGS in the pulsation reactor 1 was converted into lithium iron phosphate implemented.
- the aqueous solution (starting compound AV) was introduced into the combustion chamber (application space 2.1) by means of a two-substance nozzle at 3 kg / h and thermally treated at a temperature of 650 ° C in the pulsation reactor 1, in particular reacted in a single step and thus in one single step in the thermal reactor 1 synthesized, dried and calcined.
- the product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
- the brown powder formed had a specific surface area (BET) of 2 m 2 / g and a loss on ignition of 0.6% by weight.
- BET specific surface area
- the X-ray diffraction analysis showed an amorphous background with reflections of a lithium iron phosphate phase.
- the chemical analysis (ICP-OES) showed 34% by weight of iron (theoretical 35.4% by weight), 4.3% by weight of lithium (4.4% by weight of theoretical) and 18.9% by weight of phosphorus (theoretical 19.63% by weight).
- the product stoichiometry corresponds to the composition set in the educt solution.
- Example 2 thermal treatment and production of a compound LiMno .5 Feo .5 PO 4 (LMFP) as an example of a lithium-containing battery material
- LMFP LiMno .5 Feo .5 PO 4
- a metal phosphate powder with the composition LiMno .5 Feo .5 PO 4 was produced as the lithium-containing battery material BM.
- an aqueous solution of iron (III) nitrate nonahydrate, lithium hydroxide monohydrate, manganese (II) acetate tetrahydrate and phosphoric acid in the corresponding stoichiometric ratio and a total product concentration of 15% by weight (calculated as LiMno .5 Feo .5 PO 4 ) implemented in the hot gas stream HGS in the pulsation reactor 1.
- the aqueous solution (starting compound AV) was introduced into the combustion chamber (application room 2.1) by means of a two-substance nozzle at 3 kg / h and reacted at a temperature of 500 ° C in the hot gas stream HGS in the pulsation reactor 1 in a single step and thus in a single step synthesized in the thermal reactor 1, dried and calcined.
- the product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
- the brown powder formed had a specific surface area (BET) of 14 m 2 / g and a loss on ignition of 2.2% by weight.
- BET specific surface area
- the X-ray diffraction analysis showed an amorphous background with reflections of a lithium iron phosphate as well Lithium manganese iron phosphate phase.
- Chemical analysis (ICP-OES) showed 19.9% by weight of iron (theoretical 17.75% by weight), 4.3% by weight of lithium (theoretical 4.41% by weight), 15.3% by weight of manganese (theoretical 17.46% by weight) and 19.3% by weight phosphorus (theoretical 19.69% by weight).
- the product stoichiometry corresponds approximately to the composition established in the educt solution.
- Example 3 thermal treatment and production of a joint
- a metal oxide powder with the composition Nao ⁇ Mno ⁇ Feo ⁇ CE was produced as the sodium-containing battery material BM.
- an aqueous solution of iron (III) nitrate nonahydrate, sodium carbonate and manganese (II) acetate tetrahydrate in the appropriate stoichiometric ratio and a total product concentration of 15% by weight (calculated as Nao. 7Mno 5Feo. 5O2) in the hot gas stream HGS in the Pulsation reactor 1 implemented.
- the aqueous solution (starting compound AV) was introduced into the combustion chamber (application space 2.1) by means of a two-substance nozzle at 3 kg / h and thermally treated at a temperature of 800 ° C in the pulsation reactor 1, in particular reacted in a single step and thus in one single step in the thermal reactor 1 synthesized, dried and calcined.
- the product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
- the gray-black powder formed had a specific surface area (BET) of 9 m 2 / g and a loss on ignition of 6.2% by weight.
- BET specific surface area
- the X-ray diffraction analysis showed an amorphous background with reflections of a sodium-manganese-iron oxide and sodium-manganese oxide phase.
- Chemical analysis (ICP-OES) showed 25.8% by weight of iron (theoretical 27.16% by weight), 14.1% by weight of sodium (theoretical 14.98% by weight) and 25.8% by weight of manganese (theoretical 26.72% by weight).
- the product stoichiometry corresponds to the composition set in the educt solution.
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Abstract
The invention relates to a process for thermally treating, in particular synthesizing and/or drying and calcinating, a nano- and/or micro-scale or nano- and/or micro-crystalline battery material (BM) and/or battery material precursor (BM) in a thermal reactor (1), comprising the steps of: introducing a starting compound (AV) into the reactor (1), the starting material (AV) being a battery material (BM) and/or battery material precursor (BM) and the starting material (AV) being introduced into the reactor (1) in the form of a solution, slurry, suspension or in a solid state of matter, thermally treating the battery material (BM) and/or battery material precursor (BM) carried in a hot gas flow (HGS) in a treatment zone in the reactor (1) at a temperature of 150°C to 1000°C, and discharging the battery material (BM) obtained from the reactor (1) in the form of a powder.
Description
Verfahren zur thermischen Behandlung eines Batteriematerials in einem thermischen Reaktor Process for the thermal treatment of a battery material in a thermal reactor
B E S C H R E I B U N G DESCRIPTION
Die Erfindung betrifft ein Verfahren zur thermischen Behandlung eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials. The invention relates to a method for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material.
Vorrichtungen zur thermischen Behandlung eines Rohstoffs sind beispielsweise Pulsationsreaktoren, wie sie in der WO 02/072471 Al oder der DE 102004044266 Al sowie WO 2019/197147 Al beschrieben sind. Devices for the thermal treatment of a raw material are, for example, pulsation reactors, as they are described in WO 02/072471 A1 or DE 102004044266 A1 and WO 2019/197147 A1.
Pulsationsreaktoren dienen beispielsweise einer thermischen Synthese eines Rohstoffs zur Herstellung von feinteiligen Partikeln, insbesondere feinteiligen Materialien. Pulsation reactors are used, for example, for a thermal synthesis of a raw material for the production of fine particles, in particular fine materials.
Der Erfindung liegt die Aufgabe zu Grunde, ein besonders umweltfreundliches Verfahren zur thermischen Behandlung eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials anzugeben. The invention is based on the object of specifying a particularly environmentally friendly method for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material.
Die Aufgabe wird erfmdungsgemäß durch die Merkmale des Patentanspruchs 1 gelöst. The object is achieved according to the invention by the features of claim 1.
Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche. Advantageous refinements of the invention are the subject matter of the subclaims.
Die Aufgabe wird erfmdungsgemäß gelöst durch ein Verfahren zur thermischen Behandlung, insbesondere durch Synthese und/oder Trocknung und Kalzinierung, eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials in einem Reaktionsraum eines thermischen Reaktors, umfassend die Schritte:
- Einbringen einer Ausgangsverbindung in den Reaktionsraum, wobei als Ausgangsverbindung ein Batteriematerial und/oder ein Batterievorläufermaterial, insbesondere ein natrium- oder lithiumhaltiges Batteriematerial und/oder Batterievorläufermaterial, eingebracht wird und wobei die Ausgangsverbindung in Form einer Lösung, Aufschlämmung, Suspension oder in einem festen Aggregatszustand in den Reaktionsraum eingebracht wird, The object is achieved according to the invention by a method for thermal treatment, in particular by synthesis and / or drying and calcination, of a nano- and / or microscale or nano- and / or microcrystalline battery material in a reaction chamber of a thermal reactor, comprising the steps: Introducing a starting compound into the reaction space, with a battery material and / or a battery precursor material, in particular a sodium- or lithium-containing battery material and / or battery precursor material, being introduced as the starting compound, and the starting compound in the form of a solution, slurry, suspension or in a solid state of aggregation is introduced into the reaction chamber,
- thermische Behandlung des in einem Heißgasstrom (HGS) getragenen Batteriematerials und/oder Batterievorläufermaterials in einer Behandlungszone im Reaktionsraum bei einer Temperatur von 150°C bis 1.000°C, und thermal treatment of the battery material and / or battery precursor material carried in a hot gas flow (HGS) in a treatment zone in the reaction space at a temperature of 150 ° C. to 1,000 ° C., and
- Ausbringen des erhaltenen Batteriematerials in Pulverform aus dem Reaktor. - Discharge of the battery material obtained in powder form from the reactor.
Ein weiterer Aspekt sieht ein Verfahren zur thermischen Behandlung, insbesondere durch Synthese und/oder Trocknung und Kalzinierung, eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials und/oder Batterievorläufermaterials in einem thermischen Reaktor mit einem Applikationsraum und einem Reaktionsraum vor, welches folgende Schritte umfasst: Another aspect provides a method for thermal treatment, in particular by synthesis and / or drying and calcination, of a nano- and / or microscale or nano- and / or microcrystalline battery material and / or battery precursor material in a thermal reactor with an application space and a reaction space which includes the following steps:
- Einbringen einer Ausgangsverbindung in Strömungsrichtung eines Heißgasstromes im thermischen Reaktor gesehen an einem vorderen Aufgabeort in den thermischen Reaktor, wobei als Ausgangsverbindung ein Batteriematerial und/oder ein Batterievorläufermaterial in Form einer Lösung, Aufschlämmung, Suspension oder in einem festen Aggregatszustand in den Reaktor eingebracht wird, - Introducing an output compound in the flow direction of a hot gas stream in the thermal reactor at a front loading point into the thermal reactor, with a battery material and / or a battery precursor material being introduced into the reactor as a starting compound in the form of a solution, slurry, suspension or in a solid state of aggregation,
- thermische Behandlung des in dem Heißgasstrom getragenen Batteriematerials und/oder Batterievorläufermaterials in einer Behandlungszone im thermischen Reaktor bei einer Temperatur von 150°C bis 1.000°C mit einer Verweilzeit von 0,1 s bis 2 s, wobei eine Elmsetzung der Ausgangsverbindung zu dem Batteriematerial durch Synthese und/oder Trocknung und Kalzinierung in einem einzigen Schritt in dem Heißgasstrom im thermischen Reaktor erfolgt, - Thermal treatment of the battery material and / or battery precursor material carried in the hot gas flow in a treatment zone in the thermal reactor at a temperature of 150 ° C. to 1,000 ° C. with a residence time of 0.1 s to 2 s, with the starting compound becoming the battery material takes place by synthesis and / or drying and calcination in a single step in the hot gas stream in the thermal reactor,
- Ausbringen des erhaltenen Batteriematerials in Pulverform aus dem Reaktor.
Die thermische Behandlung ist insbesondere ein Verfahren, bei welchem mittels des Heißgasstromes das Batteriematerial und/oder das Batterievorläufermaterial synthetisiert, getrocknet und/oder kalziniert werden bzw. wird. Dabei erfolgt innerhalb kurzer Verweilzeit von weniger als 2 s aufgrund der fein verteilten direkten Behandlung im Heißgasstrom ein hinreichend hoher Energieeintrag. Durch die Reduzierung der Flüssigkeitsmenge in dem Batteriematerial und/oder Batterievorläufermaterial innerhalb der kurzen Verweilzeit und bei entsprechenden Temperaturen, insbesondere im niedrigen Bereich, kann das Sintern verhindert werden. - Discharge of the battery material obtained in powder form from the reactor. The thermal treatment is in particular a method in which the battery material and / or the battery precursor material is synthesized, dried and / or calcined by means of the hot gas flow. A sufficiently high energy input takes place within a short dwell time of less than 2 s due to the finely distributed direct treatment in the hot gas flow. By reducing the amount of liquid in the battery material and / or battery precursor material within the short dwell time and at corresponding temperatures, in particular in the low range, sintering can be prevented.
Unter Trocknen und Kalzinieren wird insbesondere ein Eintrocknen und Kalzinie ren der flüssigen Substanz, insbesondere der Lösung, Aufschlämmung, Suspension, oder eines festen, aber feuchten Ausgangsstoffes verstanden. Dabei erfolgt die thermische Behandlung in einem strömenden Heißgas, welches eine Umsetzung der Ausgangsverbindung, insbesondere eines Batterievorläufermaterials, zu dem Batteriematerial, durch Synthese und/oder Eintrocknen und Kalzinieren bewirkt. Überraschend wurde festgestellt, dass aufgrund der geringen Verweilzeit und damit geringen Reaktionszeit infolge der erzielten Umsetzung durch Synthese und/oder des erzielten (Ein)Trocknens und Kalzinierens in dem thermischen Reaktor in einem einzigen Schritt sehr feinteilige Partikel mit der korrekten Stöchiometrie für das erhaltene Batteriematerial in Pulverform erzielt werden. Drying and calcining are understood to mean, in particular, drying and calcining of the liquid substance, in particular the solution, slurry, suspension or a solid but moist starting material. The thermal treatment takes place in a flowing hot gas, which converts the starting compound, in particular a battery precursor material, to the battery material by synthesis and / or drying and calcination. Surprisingly, it was found that, due to the short residence time and thus short reaction time as a result of the conversion achieved through synthesis and / or the drying and calcination achieved in the thermal reactor in a single step, very finely divided particles with the correct stoichiometry for the battery material obtained in Powder form can be achieved.
Unter einem einzigen Schritt wird insbesondere die durchgehende thermische Behandlung der Ausgangsverbindung und deren Umsetzung zu dem Batteriematerial im Heißgasstrom des thermischen Reaktors verstanden und zwar vom Einbringen der Ausgangsverbindung, insbesondere durch extrem feine Verteilung, in den Heißgasstrom des thermischen Reaktors und thermische Behandlung dieser Ausgangsverbindung durch Synthese und/oder Trocknen und Kalzinieren im Heißgasstrom mit kurzen Verweilzeiten von 0,1 s bis 2 s in Kombination mit niedrigen bis hohen Temperaturen von 150°C bis 1.000°C bis zum Ausscheiden des getrockneten und kalzinierten Batteriematerials aus dem thermischen Reaktor verstanden.
Dabei kann in einem ersten möglichen Ausführungsbeispiel bei einer als Batterievorläufermaterial eingebrachten Ausgangsverbindung die Umsetzung zu dem Batteriematerial durch Synthese und Trocknen und Kalzinieren in einem einzigen Schritt im Heißgasstrom im thermischen Reaktor erfolgen. In einem zweiten Ausführungsbeispiel bei einer als feuchtes Batteriematerial eingebrachten Ausgangsverbindung erfolgt die Umsetzung der Ausgangsverbindung zu dem Batteriematerial nur durch Trocknen und Kalzinieren in einem einzigen Schritt im Heißgasstrom im thermischen Reaktor. A single step is understood to mean, in particular, the continuous thermal treatment of the starting compound and its conversion to the battery material in the hot gas stream of the thermal reactor, namely from the introduction of the starting compound, in particular through extremely fine distribution, into the hot gas stream of the thermal reactor and thermal treatment of this starting compound by synthesis and / or drying and calcining in a hot gas stream with short dwell times of 0.1 s to 2 s in combination with low to high temperatures of 150 ° C to 1,000 ° C until the dried and calcined battery material is removed from the thermal reactor. In a first possible embodiment, a starting compound introduced as a battery precursor material can be converted to the battery material by synthesis and drying and calcination in a single step in the hot gas flow in the thermal reactor. In a second exemplary embodiment, in the case of a starting compound introduced as a moist battery material, the starting compound is converted into the battery material only by drying and calcining in a single step in the hot gas flow in the thermal reactor.
Das erfindungsgemäße Verfahren unterscheidet sich erheblich von dem aus dem Stand der Technik bekannten Verfahren durch den Energieübertrag und den Umsetzungsablauf durch Synthese und/oder Trocknung und Kalzinierung durch extrem feine Verteilung der Ausgangsverbindung im Heißgas und deren thermische Behandlung im Heißgasstrom mit sehr kurzer Verweilzeit von ca. 0,1 s bis 2 s, wodurch überraschend sehr feinteilige Partikel hergestellt werden können. The process according to the invention differs considerably from the process known from the prior art in the energy transfer and the conversion process through synthesis and / or drying and calcination through extremely fine distribution of the starting compound in the hot gas and its thermal treatment in the hot gas stream with a very short residence time of approx. 0.1 s to 2 s, as a result of which, surprisingly, very fine particles can be produced.
Die mit der Erfindung erzielten Vorteile bestehen insbesondere darin, dass das Batteriematerial gegenüber herkömmlichen Verfahren schnell, einfach und in nur einer Stufe umweltfreundlich gereinigt und/oder thermisch behandelt, insbesondere getrocknet und kalziniert wird. Darüber hinaus werden eine höhere Ausbeute sowie besondere Eigenschaften (wie Einstellung der Kristallitgröße, insbesondere homogene Partikel- und/oder Kristallitgrößenverteilung, Kristallausheilung) für das thermisch behandelte Batteriematerial erzielt. Dabei wird bevorzugt ein Stoffaustritt in eine Umgebung vermieden. Aufwendige Vortrocknungen, Zwischenschritte, Aufreinigen, und thermische Vor- und/oder Nachbehandlungen, wie zum Beispiel langandauemde Kalzinierungen, sind vermieden. The advantages achieved with the invention are in particular that the battery material is cleaned and / or thermally treated, in particular dried and calcined, quickly, easily and in just one step in an environmentally friendly manner, compared to conventional methods. In addition, a higher yield and special properties (such as setting the crystallite size, in particular homogeneous particle and / or crystallite size distribution, crystal annealing) are achieved for the thermally treated battery material. In this case, an escape of substance into an environment is preferably avoided. Complex pre-drying, intermediate steps, purification, and thermal pre- and / or post-treatments, such as long-lasting calcinations, are avoided.
In einer möglichen Ausführungsform werden ein Verbrennungsgas und ein Brennstoff in den Reaktor, insbesondere in den Applikationsraum, zugeführt und dort gezündet. Daraus resultierend wird ein Heißgasstrom erzeugt, in welchem die Ausgangsverbindung in Strömungsrichtung des Heißgasstromes im Reaktor
gesehen an einem vorderen Aufgabeort in den Reaktor, zum Beispiel in den Applikationsraum und/oder im strömungseingangsseitigen Bereich in den Reaktionsraum, aufgegeben wird und vom Heißgasstrom getragen und transportiert wird. Der Heißgasstrom wird durch bei der Verbrennung entstehende heiße Gase gebildet. Dabei kann die Verbrennung von Brennstoff und Verbrennungsgasen flammenlos oder mit einer Flamme erfolgen. Als Heißgasstrom kann ein pulsierender, insbesondere ein regelmäßig oder unregelmäßig pulsierender, oder ein gleichmäßig turbulenter Heißgasstrom erzeugt werden. In one possible embodiment, a combustion gas and a fuel are fed into the reactor, in particular into the application space, and ignited there. As a result, a hot gas stream is generated in which the starting compound is in the flow direction of the hot gas stream in the reactor seen at a front loading point into the reactor, for example into the application space and / or in the flow inlet-side area into the reaction space, and is carried and transported by the hot gas stream. The hot gas flow is formed by the hot gases produced during combustion. The combustion of fuel and combustion gases can take place flamelessly or with a flame. A pulsating, in particular a regularly or irregularly pulsing, or a uniformly turbulent hot gas flow can be generated as the hot gas flow.
In einer bevorzugten Ausführungsform wird das erhaltene Batteriematerial und/oder Batterievorläufermaterial an nur einem Ab scheidepunkt vom Heißgasstrom abgetrennt. Insbesondere werden alle festen Stoffe am Abscheidepunkt vom Heißgasstrom abgetrennt. In a preferred embodiment, the battery material and / or battery precursor material obtained is separated from the hot gas flow at only one separation point. In particular, all solid substances are separated from the hot gas flow at the separation point.
Erfindungsgemäß wird die thermische Behandlung desinsbesondere natrium- oder lithiumhaltigen Batteriematerials und/oder Batterievorläufermaterials mit einer Verweilzeit von 0,1 s bis 2 s im Reaktionsraum durchgeführt. Die Verweilzeit legt dabei die Behandlungsdauer und die gewünschte thermische Behandlung des Batteriematerials fest, ob dieses beispielsweise nur getrocknet oder nur kalziniert oder sowohl getrocknet als auch kalziniert werden soll. According to the invention, the thermal treatment of the battery material and / or battery precursor material, in particular containing sodium or lithium, is carried out with a residence time of 0.1 s to 2 s in the reaction chamber. The dwell time defines the duration of treatment and the desired thermal treatment of the battery material, for example whether it should only be dried or only calcined or both dried and calcined.
Ein weiterer Aspekt der Erfindung sieht vor, dass das Batteriematerial und/oder Batterievorläufermaterial in der Behandlungszone in einem einzigen Schritt getrocknet und kalziniert wird. Mit anderen Worten: Die thermische Behandlung des Batteriematerials und/oder Batterievorläufermaterials als Ausgangsverbindung und deren Umsetzung in dem thermischen Reaktor durch Synthese und/oder Trocknung und Kalzinierung erfolgt in einem in sich geschlossenen System. Ein solches auf einen einzigen Schritt reduziertes Synthese- und/oder Trocknungs- und Kalzinierungsverfahren ist besonders umweltschonend und ressourcensparend. Dabei erfolgt die Synthese und/oder Trocknung und Kalzinierung im direkten Kontakt mit dem Heißgasstrom in einem einzigen Arbeitsgang innerhalb des thermischen Reaktors. Die durch den direkten Wärmeaustausch pro Materialeinheit
übertragene Wärmemenge und somit auch die Länge der Synthesedauer und/oder Trocknungsdauer und Kalzinierungsdauer kann dabei beispielsweise durch die Verbrennung, insbesondere durch die zugeführte Menge von Verbrennungsgas und/oder Brennstoff, und/oder den Materialstrom, insbesondere des Batteriematerials und/oder Batterievorläufermaterials, im Reaktionsraum des thermischen Reaktors geregelt werden. Another aspect of the invention provides that the battery material and / or battery precursor material is dried and calcined in the treatment zone in a single step. In other words: the thermal treatment of the battery material and / or battery precursor material as the starting compound and its conversion in the thermal reactor by synthesis and / or drying and calcination takes place in a self-contained system. Such a synthesis and / or drying and calcination process, which is reduced to a single step, is particularly environmentally friendly and saves resources. The synthesis and / or drying and calcination takes place in direct contact with the hot gas stream in a single operation within the thermal reactor. The result of the direct heat exchange per unit of material The amount of heat transferred and thus also the length of the synthesis time and / or drying time and calcination time can for example be caused by the combustion, in particular by the supplied amount of combustion gas and / or fuel, and / or the material flow, in particular of the battery material and / or battery precursor material, in the reaction space of the thermal reactor can be regulated.
Bei der Ausbildung des thermischen Reaktors als ein Pulsationsreaktor ist darüber hinaus die thermische Behandlung besonders homogen und einheitlich. Der thermische Reaktor kann aber auch als ein Flugstromreaktor ausgebildet sein. In addition, when the thermal reactor is designed as a pulsation reactor, the thermal treatment is particularly homogeneous and uniform. The thermal reactor can, however, also be designed as an entrained flow reactor.
In einer weiteren Ausführungsform wird die Ausgangsverbindung in den Reaktionsraum mittels eines Trägerfluides und/oder als Aerosol eingebracht. Beispielsweise ist das Trägerfluid ein Gas, insbesondere Umgebungsluft oder Sauerstoff oder auch ein inertes Gas, wie z. B. Stickstoff. Eine Aufgabe der Ausgangsverbindung in den Reaktor kann dabei im Bereich des Reaktionsraums und/oder im Bereich einer Brennkammer bei einem direkt gefeuerten Reaktor erfolgen. Die Wahl des Aufgabeortes in den Reaktor richtet sich danach, welche thermische Behandlung erzielt werden soll. Durch die Wahl des Aufgabeortes wird insbesondere die Behandlungsdauer und die Temperatureinwirkung verändert. So wird beispielsweise für eine Trocknung und Kalzinierung des Batteriematerials dieses in Strömungsrichtung des Heißgasstromes im Reaktor gesehen an einem vorderen Aufgabeort in den Reaktor, insbesondere in die Brennkammer und/oder den Reaktionsraum, eingebracht. Für eine Trocknung des Batteriematerials wird dieses in Strömungsrichtung des Heißgasstromes im Reaktor gesehen an einem hinteren Aufgabeort in den Reaktor, insbesondere nur in den Reaktionsraum, eingebracht. In a further embodiment, the starting compound is introduced into the reaction space by means of a carrier fluid and / or as an aerosol. For example, the carrier fluid is a gas, in particular ambient air or oxygen or an inert gas, such as. B. nitrogen. The starting compound can be fed into the reactor in the area of the reaction space and / or in the area of a combustion chamber in the case of a directly fired reactor. The choice of the place of application in the reactor depends on which thermal treatment is to be achieved. The choice of the place of application changes the duration of treatment and the effect of temperature in particular. For example, for drying and calcining the battery material, it is introduced into the reactor at a front loading point, in particular into the combustion chamber and / or the reaction space, viewed in the direction of flow of the hot gas flow in the reactor. In order to dry the battery material, it is introduced into the reactor at a rear loading point, viewed in the direction of flow of the hot gas flow in the reactor, in particular only into the reaction space.
Bevorzugt pulsiert oder schwingt die Heißgasströmung im Reaktionsraum regelmäßig oder unregelmäßig, insbesondere mit einer Frequenz zwischen 5 Hz bis 350 Hz.
Darüber hinaus kann vorgesehen sein, dass das, Batteriematerial nach der thermischen Behandlung in der Behandlungszone in eine Kühlzone des Reaktionsraums überführt und anschließend aus dem Reaktionsraum ausgebracht und in Pulverform abgeschieden wird. The hot gas flow in the reaction chamber preferably pulsates or oscillates regularly or irregularly, in particular at a frequency between 5 Hz and 350 Hz. In addition, it can be provided that, after the thermal treatment in the treatment zone, the battery material is transferred to a cooling zone of the reaction space and then discharged from the reaction space and deposited in powder form.
Das Batteriematerial kann insbesondere ein natrium- oder lithiumhaltiges Batteriematerial sein. The battery material can in particular be a battery material containing sodium or lithium.
Das lithiumhaltige Batteriematerial ist insbesondere ein nickel-, mangan- und/oder cobalthaltiges Lithiummaterial, zum Beispiel LiMn20 , LiCoxMn2.x04 oder Li(NiCoMn)02 (auch kurz NCM genannt), ein eisenphosphathaltiges Lithiummaterial, zum Beispiel LiFePCL (auch kurz LFP genannt), ein nickel- und manganhaltiges Lithiummaterial, zum Beispiel LiNixMn2.x04 (auch kurz LNMO genannt), ein eisenphosphat- und manganphosphathaltiges Lithiummaterial, zum Beispiel LiFei.xMnxP04 (auch kurz LMP genannt), ein nickel-, cobalt- und/oder aluminiumhaltiges Lithiummaterial, zum Beispiel LiA102 oderLiNiCoA102 (auch kurz NCA genannt), ein cobalt- und sauerstoffhaltiges Lithiummaterial, zum Beispiel LiCo02 (auch kurz LCO genannt) oder ein titan- und sauerstoffhaltiges Lithiummaterial, zum Beispiel Li Ti50i2 (auch kurz LTO genannt) oder ein mangan-, eisenphosphathaltiges Lithiummaterial. The lithium-containing battery material is in particular a nickel, manganese and / or cobalt-containing lithium material, for example LiMn 2 0, LiCo x Mn 2.x 0 4 or Li (NiCoMn) 0 2 (also called NCM for short), a lithium material containing iron phosphate, for Example LiFePCL (also called LFP for short), a lithium material containing nickel and manganese, for example LiNi x Mn 2.x 0 4 (also called LNMO for short), a lithium material containing iron phosphate and manganese phosphate, for example LiFei. x Mn x P0 4 (also called LMP for short), a lithium material containing nickel, cobalt and / or aluminum, for example LiA10 2 or LiNiCoA10 2 (also called NCA for short), a lithium material containing cobalt and oxygen, for example LiCo0 2 (also briefly called LCO) or, for example, Li 2 Ti 5 0i (also called a titanium and oxygen-containing lithium material, shortly LTO), or a manganese, iron lithium phosphate-containing material.
Das natriumhaltige Batteriematerial ist insbesondere ein nickel-, mangan-, titan- und eisenhaltiges Natriummaterial oder ein eisenphosphathaltiges Natriummaterial, permanganathaltiges Natriummaterial oder ein chromhaltiges Natriummaterial. The sodium-containing battery material is in particular a nickel, manganese, titanium and iron-containing sodium material or an iron-phosphate-containing sodium material, permanganate-containing sodium material or a chromium-containing sodium material.
Das nickel-, mangan- und cobalthaltige Lithiummaterial ist insbesondere eine Lithiumausgangsverbindung mit Anteilen von Nickel, Cobalt und Mangan. Dabei kann das nickel-, cobalt- und manganhaltige Lithiummaterial stöchiometrische Anteile von Nickel, Cobalt und Mangan (1:1:1) oder nichtstöchiometrische Anteile (5:3:1, 6:2:2, 8:1:1 (nickelreich)) aufweisen. Überraschenderweise hat sich gezeigt, dass ein lithiumhaltiges Batteriematerial mit einem geringeren Lithiumanteil als die Anteile anderer Bestandteile dieses Batteriematerials Vorteile hinsichtlich
notwendiger Ressourcen und Umweltschonung hat. Der Lithiumanteil ist im Vergleich zu den Anteilen von Nickel, Cobalt und Mangan geringer im nickel-, cobalt- und manganhaltigen Lithiummaterial. Auch bei den anderen Lithiummaterialien mit anderen Anteilen, wie zum Beispiel Eisenphosphat, Aluminium, Sauerstoff, ist der Lithiumanteil im Vergleich zu diesen anderen Anteilen, wie zum Beispiel Eisenphosphat, Aluminium, Sauerstoff, geringer. The lithium material containing nickel, manganese and cobalt is in particular a lithium starting compound with proportions of nickel, cobalt and manganese. The lithium material containing nickel, cobalt and manganese can contain stoichiometric proportions of nickel, cobalt and manganese (1: 1: 1) or non-stoichiometric proportions (5: 3: 1, 6: 2: 2, 8: 1: 1 (nickel-rich) ) exhibit. Surprisingly, it has been shown that a lithium-containing battery material with a lower proportion of lithium than the proportions of other components of this battery material has advantages in terms of necessary resources and environmental protection. The proportion of lithium is lower in the nickel, cobalt and manganese-containing lithium material compared to the proportions of nickel, cobalt and manganese. Also in the case of the other lithium materials with other proportions, such as iron phosphate, aluminum, oxygen, the lithium proportion is lower compared to these other proportions, such as iron phosphate, aluminum, oxygen.
Das erhaltene und abgeschiedene nano- und/oder mikroskalige oder nano- und/oder mikrokristalline Batteriematerial weist insbesondere eine mittlere Partikelgröße im Bereich von 10 nm bis wenige Mikrometer, insbesondere bis 50 pm, auf. The nano- and / or microscale or nano- and / or microcrystalline battery material obtained and deposited has, in particular, an average particle size in the range from 10 nm to a few micrometers, in particular up to 50 μm.
Mit dem erfindungsgemäßen Verfahren können insbesondere nano- und/oder mikroskalige oder nano- und/oder mikrokristalline Batteriematerialien und/oder Batterievorläufermaterialien thermisch behandelt, insbesondere getrocknet und/oder kalziniert werden. Ein solches thermisch behandeltes nano- und/oder mikroskaliges oder nano- und/oder mikrokristallines Batteriematerial eignet sich insbesondere zur Verwendung als Kathoden- oder Anodenmaterial. With the method according to the invention, in particular nano- and / or microscale or nano- and / or microcrystalline battery materials and / or battery precursor materials can be thermally treated, in particular dried and / or calcined. Such a thermally treated nano- and / or microscale or nano- and / or microcrystalline battery material is particularly suitable for use as a cathode or anode material.
Die Erfindung sieht darüber hinaus die Verwendung eines thermischen Reaktors mit mindestens einem Reaktionsraum und mindestens einer Heizanordnung und/oder einer Anordnung zur Erzeugung einer Heißgasströmung, insbesondere einer Pulsationsanordnung zur Erzeugung einer pulsierenden Heißgasströmung, in dem Reaktionsraum zur thermischen Behandlung durch Synthese und/oder Trocknung und Kalzinierung, eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials in dem Reaktionsraum des thermischen Reaktors. Dabei ist der thermische Reaktor eingerichtet, das zuvor beschriebene Verfahren durchzuführen. The invention also provides the use of a thermal reactor with at least one reaction chamber and at least one heating arrangement and / or an arrangement for generating a hot gas flow, in particular a pulsation arrangement for generating a pulsating hot gas flow, in the reaction chamber for thermal treatment by synthesis and / or drying and Calcination of a nano- and / or microscale or nano- and / or microcrystalline battery material in the reaction space of the thermal reactor. The thermal reactor is set up to carry out the method described above.
Ausführungsbeispiele der Erfindung werden im Folgenden anhand einer Zeichnung näher erläutert. Embodiments of the invention are explained in more detail below with reference to a drawing.
Darin zeigt die einzige:
Figur ein Blockschaltbild einer Vorrichtung zur Herstellung vonIn it the only one shows: Figure is a block diagram of an apparatus for producing
Partikeln mit einem Reaktor. Particles with a reactor.
Die einzige Figur zeigt ein Blockschaltbild einer Vorrichtung V zur thermischen Behandlung eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials BM in einem Reaktionsraum 1.1 eines thermischen Reaktors 1. The single FIGURE shows a block diagram of a device V for the thermal treatment of a nano- and / or microscale or nano- and / or microcrystalline battery material BM in a reaction space 1.1 of a thermal reactor 1.
Beispielsweise weist das Batteriematerial BM im Endprodukt eine mittlere Partikel oder Korngröße im Bereich von 10 nm bis wenige Mikrometer auf. Unter einem Batteriematerial BM wird bzw. werden insbesondere ein oder mehrere Batteriestoffe, ein Batteriestoffgemisch oder ein vorverarbeiteter Batteriestoff oder ein vorverarbeitetes Batteriestoffgemisch oder ein Batterievorläufermaterial BM verstanden. Das Batteriematerial BM ist ein nano- und/oder mikroskaliges oder nano- und/oder mikrokristallines, insbesondere ein natrium- oder lithiumhaltiges, Batteriematerial BM. For example, the battery material BM in the end product has an average particle or grain size in the range from 10 nm to a few micrometers. A battery material BM is or are understood to mean, in particular, one or more battery materials, a battery material mixture or a preprocessed battery material or a preprocessed battery material mixture or a battery precursor material BM. The battery material BM is a nano- and / or microscale or nano- and / or microcrystalline, in particular a sodium- or lithium-containing, battery material BM.
Die Vorrichtung V ist als ein thermischer Reaktor 1 ausgebildet. Der thermische Reaktor 1 umfasst zumindest einen Reaktionsraum 1.1 und mindestens einen Aufgabeort 1.2 zur Aufgabe des Batteriematerials BM zur thermischen Behandlung des Batteriematerials RM in dem Reaktionsraum 1.1 und einen Abscheidepunkt 1.3 zur Ausgabe und Abscheidung des thermisch behandelten Batteriematerials BM in Pulverform. The device V is designed as a thermal reactor 1. The thermal reactor 1 comprises at least one reaction space 1.1 and at least one loading location 1.2 for loading the battery material BM for thermal treatment of the battery material RM in the reaction space 1.1 and a separation point 1.3 for outputting and depositing the thermally treated battery material BM in powder form.
An dem oder den Aufgabeort/en 1.2 wird das Batteriematerial BM oder ein Batterievorläufermaterial in Form einer Ausgangsverbindung AV eingebracht. Insbesondere wird die Ausgangsverbindung AV des Batteriematerials BM oder des Batterievorläufermaterials in Form einer Lösung, Aufschlämmung, Suspension oder in einem festen Aggregatszustand eines Batteriestoffes oder Batteriestoffgemisches oder eines Batterievorläufermaterials BM aufgegeben und
in den Reaktionsraum 1.1 eingebracht. The battery material BM or a battery precursor material is introduced in the form of an output connection AV at the task location (s) 1.2. In particular, the output compound AV of the battery material BM or of the battery precursor material is abandoned and in the form of a solution, slurry, suspension or in a solid aggregate state of a battery material or battery material mixture or a battery precursor material BM introduced into the reaction chamber 1.1.
Der thermische Reaktor 1 kann beispielsweise ein Flugstromreaktor, ein Pulsationsreaktor, ein Trockner, ein Kalzinierer oder eine andere geeignete Anlage oder Behältnis zur thermischen Behandlung des Batteriematerials BM und/oder des Batterievorläufermaterials BM in einer Heißgasströmung HGS oder in einer pulsierenden Heißgasströmung HGS sein. The thermal reactor 1 can be, for example, an entrained flow reactor, a pulsation reactor, a dryer, a calciner or another suitable system or container for the thermal treatment of the battery material BM and / or the battery precursor material BM in a hot gas flow HGS or in a pulsating hot gas flow HGS.
Der thermische Reaktor 1 als Flugstromreaktor oder als Pulsationsreaktor zeichnet sich durch eine thermische Behandlung der Tropfen oder Partikel bis zum Pulver in einem heißen, strömenden Gas bzw. einem heißen, strömenden und pulsierenden Gas aus, welches die Partikel gleichzeitig trägt und somit durch den thermischen Reaktor 1, insbesondere je nach Aufgabeort 1.2 durch einen Applikationsraum 2.1 und/oder durch den Reaktionsraum 1.1, befördert. Im speziellen kann dieser thermische Reaktor 1 ein Flugstromreaktor, ein Pulsationsreaktor, ein Trockner, ein Kalzinierer oder eine andere geeignete Anlage oder Behältnis zur thermischen Behandlung des Batteriematerials BM in einer Heißgasströmung HGS, insbesondere einer pulsierenden oder schwingenden Heißgasströmung HGS, sein. The thermal reactor 1 as an entrained flow reactor or as a pulsation reactor is characterized by a thermal treatment of the droplets or particles down to the powder in a hot, flowing gas or a hot, flowing and pulsating gas, which carries the particles simultaneously and thus through the thermal reactor 1, in particular depending on the task location 1.2 through an application space 2.1 and / or through the reaction space 1.1. In particular, this thermal reactor 1 can be an entrained flow reactor, a pulsation reactor, a dryer, a calciner or another suitable system or container for the thermal treatment of the battery material BM in a hot gas flow HGS, in particular a pulsating or oscillating hot gas flow HGS.
In einem Flugstromreaktor wird das Batteriematerial BM und/oder das Batterievorläufermaterial BM von einem Heißgasstrom HGS getragen und durch den Reaktionsraum 1.1 geführt und in diesem thermisch behandelt. In an entrained flow reactor, the battery material BM and / or the battery precursor material BM is carried by a hot gas flow HGS and guided through the reaction space 1.1 and thermally treated in it.
Im thermischen Reaktor 1, insbesondere in einer Behandlungszone, zum Beispiel im Applikationsraum 2.1 und/oder im Reaktionsraum 1.1, wird das in dem Heißgasstrom HGS getragene Batteriematerial BM und/oder Batterievorläufer material BM bei einer Temperatur von 150°C bis 1.000°C mit einer Verweilzeit von 0,1 s bis 2 s thermisch behandelt. Dabei erfolgt eine Umsetzung der Ausgangsverbindung, insbesondere eines Batterievorläufermaterials, zu dem Batteriematerial BM durch Synthese und/oder Trocknung und Kalzinierung in einem einzigen Schritt in dem Heißgasstrom HGS im thermischen Reaktor 1. Das
dabei erhaltene Batteriematerial BM in Pulverform wird anschließend aus dem thermischen Reaktor 1 ausgebracht. In the thermal reactor 1, in particular in a treatment zone, for example in the application space 2.1 and / or in the reaction space 1.1, the battery material BM and / or battery precursor material BM carried in the hot gas stream HGS is at a temperature of 150 ° C to 1,000 ° C with a Dwell time from 0.1 s to 2 s thermally treated. The starting compound, in particular a battery precursor material, is converted to the battery material BM by synthesis and / or drying and calcination in a single step in the hot gas stream HGS in the thermal reactor 1. The The battery material BM obtained in this way in powder form is then discharged from the thermal reactor 1.
Ein solches auf einen einzigen Schritt reduziertes Synthese- und/oder Trocknungs und Kalzinierungsverfahren zur thermischen Behandlung des Batteriematerials BM ist besonders umweltschonend und ressourcensparend. Dabei erfolgt die Synthese und/oder Trocknung und Kalzinierung im direkten Kontakt mit dem Heißgas strom HGS in einem einzigen Arbeitsgang innerhalb des thermischen Reaktors 1. Such a synthesis and / or drying and calcination process for the thermal treatment of the battery material BM, which is reduced to a single step, is particularly environmentally friendly and saves resources. The synthesis and / or drying and calcination takes place in direct contact with the hot gas stream HGS in a single operation within the thermal reactor 1.
Der Heißgasstrom HGS wird durch Zuführen und Zündung eines Brennstoffs BS und eines Verbrennungsgases VG im thermischen Reaktor 1 erzeugt. Der Heißgasstrom HGS wird durch bei der Verbrennung des Brennstoffs BS und der Verbrennungsgase VG entstehende heiße Gase gebildet. Die Verbrennung kann dabei beispielsweise flammenlos erfolgen. Auch ist eine Verbrennung mit einer Flamme möglich. Der erzeugte Heißgasstrom HGS kann regelmäßig oder unregelmäßig pulsierend im Reaktor 1 strömen oder gleichmäßig turbulent im Reaktor 1 strömen. The hot gas flow HGS is generated by feeding and igniting a fuel BS and a combustion gas VG in the thermal reactor 1. The hot gas flow HGS is formed by the hot gases produced during the combustion of the fuel BS and the combustion gases VG. The combustion can be carried out without a flame, for example. Combustion with a flame is also possible. The hot gas flow HGS generated can flow regularly or irregularly in pulsing fashion in reactor 1 or flow uniformly in turbulence in reactor 1.
Der thermische Reaktor 1 wird nachfolgend anhand eines Pulsationsreaktors beschrieben und daher nachfolgend als Pulsationsreaktor 1 bezeichnet. The thermal reactor 1 is described below with reference to a pulsation reactor and is therefore referred to below as a pulsation reactor 1.
In dem Pulsationsreaktor 1 wird das Batteriematerial BM in einem pulsierenden, schwingenden Heißgasstrom HGS thermisch behandelt. In the pulsation reactor 1, the battery material BM is thermally treated in a pulsating, oscillating stream of hot gas HGS.
Hierzu umfasst der Pulsationsreaktor 1 einen Erzeuger 2 zur Erzeugung des pulsierenden Heißgasstroms HGS. Der Erzeuger 2 ist beispielsweise ein Brenner mit einem sich dem Brenner anschließenden Applikationsraum 2.1, z. B. eine Brennkammer, und/oder eine andere technische Umsetzung zur Erwärmung des Heißgasstroms HGS in Kombination mit dem Applikationsraum 2.1. For this purpose, the pulsation reactor 1 comprises a generator 2 for generating the pulsating hot gas flow HGS. B. a combustion chamber, and / or another technical implementation for heating the hot gas flow HGS in combination with the application space 2.1.
Alternativ oder zusätzlich kann der Pulsationsreaktor 1 zumindest einen Pulsator (nicht dargestellt) umfassen, welcher an dem Reaktionsraum 1.1, welcher
dem Applikationsraum 2.1 nachgeschaltet ist, angeordnet ist. Der Pulsator kann beispielsweise von außen an den Reaktionsraum 1.1 gekoppelt sein und prägt mindestens eine Druckschwingung zur Erzeugung oder Verstärkung des pulsierenden Heißgasstrom HGS in den Reaktionsraum 1.1 ein. Alternatively or additionally, the pulsation reactor 1 can comprise at least one pulsator (not shown) which is attached to the reaction space 1.1, which the application room 2.1 is connected downstream, is arranged. The pulsator can for example be coupled from the outside to the reaction space 1.1 and impresses at least one pressure oscillation to generate or amplify the pulsating hot gas flow HGS in the reaction space 1.1.
In einer alternativen oder zusätzlichen Ausführung kann der Heißgasstrom HGS anstelle der gefeuerten Erzeugung und Erwärmung oder zusätzlich zur gefeuerten Erzeugung und Erwärmung mittels eines Wärmeübertragers oder elektrisch erwärmt und mittels des Pulsators erzeugt werden. In an alternative or additional embodiment, the hot gas flow HGS can be heated instead of the fired generation and heating or in addition to the fired generation and heating by means of a heat exchanger or electrically and generated by means of the pulsator.
Der pulsierende Heißgasstrom HGS strömt dabei vom Applikationsraum 2.1 in den nachgeschalteten Reaktionsraum 1.1 oder durch den Reaktionsraum 1.1. The pulsating hot gas stream HGS flows from the application space 2.1 into the downstream reaction space 1.1 or through the reaction space 1.1.
Bei der Verwendung eines Brenners als Erzeuger 2 werden im Detail Verbrennungsgase VG und zumindest ein Brennstoff BS über eine Zuführung 3 gemeinsam oder separat in den Brenner und über diesen in die Brennkammer eingebracht. When a burner is used as a generator 2, combustion gases VG and at least one fuel BS are introduced jointly or separately into the burner via a feed line 3 and via this into the combustion chamber.
Als Brennstoff BS wird insbesondere ein brennbares Gas, wie zum Beispiel Erdgas und/oder Wasserstoff, zugeführt. Auch kann ein anderes geeignetes Gas als Brenngas zugeführt werden. In particular, a combustible gas, such as natural gas and / or hydrogen, is supplied as the fuel BS. Another suitable gas can also be supplied as fuel gas.
Als Verbrennungsgas VG wird zum Beispiel Umgebungsluft, Sauerstoff, etc. verwendet. Die zugeführten Verbrennungsgase VG und Brennstoffe BS werden beispielsweise im Applikationsraum 2.1, insbesondere in der Brennkammer gezündet. Die daraus resultierende Flamme pulsiert aufgrund einer selbsterregten periodisch-instationären Verbrennung im Applikationsraum 2.1 und erzeugt den pulsierenden Heißgasstrom HGS im Applikationsraum 2.1. Der pulsierende Heiß gasstrom HGS strömt vom Applikationsraum 2.1 strömungsausgangsseitig in den Reaktionsraum 1.1. Der Reaktionsraum 1.1 ist beispielsweise als ein Resonanzrohr ausgebildet. Dem Reaktionsraum 1.1 kann optional ein weiterer Reaktionsraum (nicht dargestellt) nachgeschaltet sein. Der Reaktionsraum 1.1 kennzeichnet dabei
einen Bereich des Pulsationsreaktors 1, welcher sich von der Zuführung 3 bis zumindest zum Ende des als Resonanzrohr ausgebildeten Reaktionsraums 1.1 erstreckt und in welchem das Batteriematerial BM thermisch behandelt wird. For example, ambient air, oxygen, etc. are used as combustion gas VG. The supplied combustion gases VG and fuels BS are ignited, for example, in the application space 2.1, in particular in the combustion chamber. The resulting flame pulsates due to a self-excited periodic-unsteady combustion in the application space 2.1 and generates the pulsating hot gas flow HGS in the application space 2.1. The pulsating hot gas flow HGS flows from the application space 2.1 on the flow outlet side into the reaction space 1.1. The reaction space 1.1 is designed, for example, as a resonance tube. The reaction space 1.1 can optionally be followed by a further reaction space (not shown). The reaction space 1.1 indicates a region of the pulsation reactor 1, which extends from the feed 3 to at least the end of the reaction space 1.1 designed as a resonance tube and in which the battery material BM is thermally treated.
Im Detail werden der Brennstoff BS sowie das notwendige Verbrennungsgas VG gemeinsam (beispielsweise vorgemischt in einer vorgeschalteten Mischkammer) oder getrennt über den Erzeuger 2, insbesondere dem Brenner, dem Applikations raum 2.1, insbesondere der Brennkammer, zugeführt und dort gezündet. Dabei verbrennen der Brennstoff BS und das Verbrennungsgas VG sehr schnell und erzeugen eine Druckwelle in Richtung des Reaktionsraums 1.1, beispielsweise in Richtung des Resonanzrohrs. Durch den geringeren Strömungswiderstand in Richtung des Reaktionsraums 1.1 erfolgt die Ausbreitung einer Druckwelle. Während des akustischen Schwingungsverlaufes wird der Druck im Applikations raum 2.1, insbesondere in der Brennkammer reduziert, so dass neues Brenngas gemisch oder neuer Brennstoff BS und Verbrennungsgas VG nachströmen kann bzw. können. Dieser Vorgang des Nachströmens durch Druckschwankungen erfolgt selbstregelnd periodisch. In detail, the fuel BS and the necessary combustion gas VG are fed jointly (for example, premixed in an upstream mixing chamber) or separately via the generator 2, in particular the burner, to the application space 2.1, in particular the combustion chamber, and ignited there. The fuel BS and the combustion gas VG burn very quickly and generate a pressure wave in the direction of the reaction chamber 1.1, for example in the direction of the resonance tube. Due to the lower flow resistance in the direction of the reaction chamber 1.1, a pressure wave propagates. During the acoustic oscillation, the pressure in the application space 2.1, in particular in the combustion chamber, is reduced so that new fuel gas mixture or new fuel BS and combustion gas VG can or can flow in. This process of post-flow due to pressure fluctuations takes place periodically in a self-regulating manner.
In einer weiteren möglichen Ausführung wird ein Reaktionsgas, wie zum Beispiel Luft und/oder Stickstoff und/oder Formiergas, einem Wärmeübertrager zugeführt. Dieser erwärmt das Reaktionsgas auf die gewünschte Temperatur und führt es dann dem Applikationsraum 2.1 zu. Durch eine Verwendung von einem oder mehreren Pulsatoren am Reaktionsraum 1.1 entsteht so ebenfalls ein pulsierender Heißgasstrom . Hierbei ist die Zusammensetzung des Heißgasstroms HGS nicht an ein Verbrennungsabgas gebunden, sondern kann nahezu frei gewählt werden. Ist somit eine Reaktion im Reaktionsraum 1.1 unter inerten Bedingungen erforderlich, so kann als Reaktionsgas beispielsweise Stickstoff verwendet werden. Der pulsierende Heißgasstrom HGS besteht somit auch nur aus Stickstoff. In a further possible embodiment, a reaction gas, such as, for example, air and / or nitrogen and / or forming gas, is fed to a heat exchanger. This heats the reaction gas to the desired temperature and then feeds it to the application space 2.1. Using one or more pulsators in the reaction space 1.1 also creates a pulsating hot gas flow. Here, the composition of the hot gas flow HGS is not tied to a combustion exhaust gas, but can be selected almost freely. If a reaction is therefore required in reaction space 1.1 under inert conditions, nitrogen, for example, can be used as the reaction gas. The pulsating hot gas flow HGS therefore only consists of nitrogen.
Die pulsierende Heißgasströmung HGS ist durch einen hohen Turbulenzgrad gekennzeichnet. Die hohe Strömungsturbulenz und die sich stetig wechselnde Strömungsgeschwindigkeit verhindern den Aufbau einer isolierenden Gashülle
(Grenzschicht) um die festen Partikel des Batteriematerials BM, wodurch ein höherer Wärmeübertrag und Stofftransport (zwischen Batteriematerial BM und Heißgas), das heißt eine schnellere Reaktion bei vergleichsweise niedrigeren Temperaturen, möglich ist. Typischerweise liegt die Verweilzeit bei weniger als einer Sekunde bis wenige Millisekunden. The pulsating hot gas flow HGS is characterized by a high degree of turbulence. The high flow turbulence and the constantly changing flow speed prevent the build-up of an insulating gas envelope (Boundary layer) around the solid particles of the battery material BM, as a result of which a higher heat transfer and mass transfer (between battery material BM and hot gas), i.e. a faster reaction at comparatively lower temperatures, is possible. Typically, the dwell time is less than a second to a few milliseconds.
Zur Abscheidung des thermisch behandelten Batteriematerials BM als Endprodukt in Pulverform aus dem Heißgasstrom HGS schließt sich an den Reaktionsraum 1.1 eine geeignete Abscheidevorrichtung 4 an. Dabei wird das Batteriematerial BM nach der thermischen Behandlung in einer Behandlungszone im Reaktionsraum 1.1 in eine Kühlzone des Reaktionsraums 1.1 überführt und anschließend aus dem Reaktionsraum 1.1 ausgebracht und in Pulverform in der Ab Scheidevorrichtung 4 abgeschieden. In order to separate the thermally treated battery material BM as an end product in powder form from the hot gas flow HGS, a suitable separation device 4 adjoins the reaction space 1.1. After the thermal treatment, the battery material BM is transferred to a cooling zone in the reaction space 1.1 in a treatment zone in the reaction space 1.1 and then discharged from the reaction space 1.1 and deposited in powder form in the separating device 4.
Die Frequenz des pulsierenden Heißgasstroms HGS liegt dabei im Hertz-Bereich, insbesondere in einem Bereich von wenigen Hertz, beispielsweise von größer 5 Hz, insbesondere größer 50 Hz, beispielsweise in einem Bereich von 5 Hz bis 350 Hz, insbesondere von 10 Hz bis 150 Hz. Parameter des Heißgasstroms HGS, wie Amplitude und/oder Frequenz der Schwingung, sind mittels des Erzeugers 2 und/oder Pulsators besonders einfach einstellbar. Zudem kann dies über die Verbrennungsparameter, wie Brennstoffmenge, Luftmenge, Lufttemperatur, Brennstofftemperatur und/oder Flammentemperatur, Ort der Brennstoff-/Luftaufgabe und/oder über Proportionen und/oder Änderungen dieser vom Applikationsraum 2.1, insbesondere Brennkammer, Erzeuger 2, insbesondere Brenner und/oder Reaktionsraum 1.1 erfolgen. The frequency of the pulsating hot gas flow HGS is in the Hertz range, in particular in a range of a few Hertz, for example greater than 5 Hz, in particular greater than 50 Hz, for example in a range from 5 Hz to 350 Hz, in particular from 10 Hz to 150 Hz Parameters of the hot gas flow HGS, such as the amplitude and / or frequency of the oscillation, can be set particularly easily by means of the generator 2 and / or the pulsator. In addition, this can be done via the combustion parameters, such as the amount of fuel, amount of air, air temperature, fuel temperature and / or flame temperature, location of the fuel / air feed and / or via proportions and / or changes to these from application space 2.1, in particular combustion chamber, generator 2, in particular burner and / or or reaction chamber 1.1.
Der Reaktionsraum 1.1 ist zum Beispiel als ein Resonanzrohr ausgebildet. Brennt im Applikationsraum 2.1 eine Flamme, so ist dieser eine Brennkammer. Die Brennkammer ist dann als ein Brennraum ausgebildet, dessen Abmessungen, insbesondere dessen Durchmesser, größer ist als die Abmessungen, insbesondere der Durchmesser des Reaktionsraums 1.1. Auch der Applikationsraum 2.1 (ohne
Flamme) ist in seinen Abmessungen, insbesondere mit dessen Durchmesser, größer als der Reaktionsraum 1.1. The reaction space 1.1 is designed, for example, as a resonance tube. If a flame is burning in the application space 2.1, this is a combustion chamber. The combustion chamber is then designed as a combustion chamber whose dimensions, in particular its diameter, are greater than the dimensions, in particular the diameter of the reaction chamber 1.1. The application room 2.1 (without Flame) is larger in its dimensions, in particular its diameter, than the reaction space 1.1.
In einem Bereich zwischen einem Strömungsausgang des Applikationsraums 2.1, insbesondere der Brennkammer, und einem Strömungseingang des Reaktions raums 1.1 ist mindestens ein Aufgabeort 1.2 angeordnet, an welchem eine Aufgabe des Batteriematerials BM erfolgt. In an area between a flow outlet of the application space 2.1, in particular the combustion chamber, and a flow inlet of the reaction space 1.1, at least one feed location 1.2 is arranged, at which the battery material BM is fed.
Die Wahl des Aufgabeortes 1.2 in den Pulsationsreaktor 1 richtet sich danach, welche thermische Behandlung erzielt werden soll. Durch die Wahl des Aufgabe ortes 1.2 wird insbesondere die Behandlungsdauer und die Temperatureinwirkung verändert. So wird beispielsweise für eine Trocknung und Kalzinierung des Batteriematerials BM dieses in Strömungsrichtung des Heißgasstromes HGS im Reaktor 1 gesehen an einem vorderen Aufgabeort 1.2 in den Reaktor 1, insbesondere in die Brennkammer und/oder den Applikationsraum 2.1, eingebracht. Für eine Trocknung des Batteriematerials BM wird dieses in Strömungsrichtung des Heißgasstromes HGS im Reaktor 1 gesehen an einem hinteren Aufgabeort in den Reaktor 1, insbesondere nur in den Reaktionsraum 1.1, eingebracht. The choice of the task location 1.2 in the pulsation reactor 1 depends on which thermal treatment is to be achieved. By choosing the task location 1.2, the treatment duration and the temperature effect are changed in particular. For example, for drying and calcining the battery material BM, it is introduced into the reactor 1, in particular into the combustion chamber and / or the application space 2.1, at a front loading location 1.2, viewed in the direction of flow of the hot gas flow HGS in the reactor 1. In order to dry the battery material BM, it is introduced into the reactor 1 at a rear loading point, viewed in the flow direction of the hot gas flow HGS in the reactor 1, in particular only into the reaction space 1.1.
Die Ausgangsverbindung AV des Batteriematerials BM wird beispielsweise in den Reaktor 1 mittels eines Trägerfluides und/oder als Aerosol, zum Beispiel in verdüster Form, eingebracht. Beispielsweise ist das Trägerfluid ein Gas, insbesondere Umgebungsluft, Sauerstoff oder Stickstoff. The starting compound AV of the battery material BM is introduced into the reactor 1, for example, by means of a carrier fluid and / or as an aerosol, for example in atomized form. For example, the carrier fluid is a gas, in particular ambient air, oxygen or nitrogen.
Als Ausgangsverbindung AV wird insbesondere ein Batteriematerial BM in Form einer Lösung, Aufschlämmung, Suspension oder in einem festen Aggregatszustand in den Reaktor 1 eingebracht und dort in einer Behandlungszone mittels der pulsierenden Heißgasströmung HGS bei einer Temperatur von 150°C bis 1.000°C thermisch behandelt, insbesondere getrocknet und/oder kalziniert. Anschließend wird das erhaltene Batteriematerial BM in Pulverform aus dem Reaktor 1 abgeschieden.
In einer bevorzugten Ausführungsform wird das erhaltene Batteriematerial BM an nur einem Abscheidepunkt 1.3 vom Heißgasstrom HGS abgetrennt. Insbesondere werden alle festen Stoffe am Ab scheidepunkt 1.3 vom Heißgasstrom HGS abgetrennt. Der Ab scheidepunkt 1.3 kann beispielsweise als Filter oder Fliehkraftabscheider ausgeführt sein. In particular, a battery material BM in the form of a solution, slurry, suspension or in a solid state of aggregation is introduced into the reactor 1 as the starting compound AV and is thermally treated there in a treatment zone by means of the pulsating hot gas flow HGS at a temperature of 150 ° C to 1,000 ° C, in particular dried and / or calcined. The battery material BM obtained is then deposited in powder form from the reactor 1. In a preferred embodiment, the battery material BM obtained is separated from the hot gas flow HGS at only one separation point 1.3. In particular, all solid substances are separated from the hot gas stream HGS at separation point 1.3. From the separation point 1.3 can be designed, for example, as a filter or centrifugal separator.
Eine Ausführungsform sieht vor, dass die thermische Behandlung des Batterie materials BM mit einer Verweilzeit von 0,1 s bis 2 s im Reaktor 1 durchgeführt wird. Die Verweilzeit legt dabei die Behandlungsdauer und die gewünschte thermische Behandlung des Batteriematerials BM fest, ob dieses beispielsweise nur getrocknet oder nur kalziniert oder sowohl getrocknet als auch kalziniert werden soll. One embodiment provides that the thermal treatment of the battery material BM is carried out in the reactor 1 with a residence time of 0.1 s to 2 s. The dwell time determines the duration of treatment and the desired thermal treatment of the battery material BM, whether it is only to be dried or only calcined or both dried and calcined, for example.
Dabei hat sich überraschenderweise ergeben, dass das Batteriematerial BM in der Behandlungszone des Reaktors 1 in einem einzigen Schritt getrocknet und kalziniert werden kann. Ein solches auf einen einzigen Schritt reduziertes Trocknungs- und Kalzinierungsverfahren ist besonders umweltschonend und ressourcensparend. It has surprisingly been found that the battery material BM can be dried and calcined in the treatment zone of the reactor 1 in a single step. Such a drying and calcination process, which is reduced to a single step, is particularly environmentally friendly and saves resources.
Das Batteriematerial BM ist insbesondere ein nickel-, mangan- und/oder cobalthaltiges Lithiummaterial, zum Beispiel LiMn204, LiCoxMn2.x04 oder Li(NiCoMn)02 (auch kurz NCM genannt), ein eisenphosphathaltiges Lithiummaterial, zum Beispiel LiFePCE (auch kurz LFP genannt), ein nickel- und manganhaltiges Lithium-material, zum Beispiel LiNixMn2.x04 (auch kurz LNMO genannt), ein eisen- und manganhaltiges Lithiummaterial, zum Beispiel LiFei. xMnxP04 (auch kurz LMP genannt), ein nickel-, cobalt- und/oder aluminiumhaltiges Lithiummaterial, zum Beispiel LiA102 oderLiNiCoA102 (auch kurz NCA genannt), ein cobalt- und sauerstoffhaltiges Lithiummaterial, zum Beispiel LiCo02 (auch kurz LCO genannt) oder ein titan- und sauerstoffhaltiges Lithiummaterial, zum Beispiel Li Ti50i2 (auch kurz LTO genannt) oder ein nickel-, mangan-, titan- und eisenhaltiges Natriummaterial oder ein mangan-, ei senphosphathaltiges Lithiummaterial .
Das nickel-, mangan- und cobalthaltige Lithiummaterial ist insbesondere eine Lithiumausgangsverbindung mit Anteilen von Nickel, Cobalt und Mangan. Dabei kann das nickel-, mangan- und cobalthaltige Lithiummaterial stöchiometrische Anteile von Nickel, Cobalt und Mangan (1:1:1) oder nichtstöchiometrische Anteile (5:3:1, 6:2:2, 8:1:1 (nickelreich)) aufweisen. Der Lithiumanteil ist im Vergleich zu den Anteilen von Nickel, Cobalt und Mangan geringer im nickel-, mangan- und cobalthaltigen Lithiummaterial. The battery material BM is in particular a lithium material containing nickel, manganese and / or cobalt, for example LiMn 2 0 4 , LiCo x Mn 2.x 0 4 or Li (NiCoMn) 0 2 (also called NCM for short), a lithium material containing iron phosphate, for example LiFePCE (also called LFP for short), a lithium material containing nickel and manganese, for example LiNi x Mn 2.x 04 (also called LNMO for short), a lithium material containing iron and manganese, for example LiFei. x Mn x P0 4 (also called LMP for short), a lithium material containing nickel, cobalt and / or aluminum, for example LiA10 2 or LiNiCoA10 2 (also called NCA for short), a lithium material containing cobalt and oxygen, for example LiCo0 2 (also briefly called LCO) or, for example, Li 2 Ti 5 0i (also called a titanium and oxygen-containing lithium material, shortly LTO), or a nickel, manganese, titanium and iron-containing material or a sodium manganese, egg senphosphathaltiges lithium material. The lithium material containing nickel, manganese and cobalt is in particular a lithium starting compound with proportions of nickel, cobalt and manganese. The lithium material containing nickel, manganese and cobalt can contain stoichiometric proportions of nickel, cobalt and manganese (1: 1: 1) or non-stoichiometric proportions (5: 3: 1, 6: 2: 2, 8: 1: 1 (nickel-rich) ) exhibit. The proportion of lithium is lower in the nickel, manganese and cobalt-containing lithium material compared to the proportions of nickel, cobalt and manganese.
Das erhaltene und abgeschiedene nano- und/oder mikroskalige oder nano- und/oder mikrokristalline Batteriematerial BM weist insbesondere eine mittlere Partikelgröße im Bereich von 10 nm bis wenige Mikrometer, insbesondere bis 50 gm, auf. The obtained and deposited nano- and / or microscale or nano- and / or microcrystalline battery material BM has in particular an average particle size in the range from 10 nm to a few micrometers, in particular up to 50 μm.
An Beispielen von Pulvern auf Basis von natrium- oder lithiumhaltigem Batteriematerial BM kann gezeigt werden, dass mittels der Kombination der erfinderischen Maßnahmen besonders feinteilige Pulver in einem einzigen Schritt im Heißgasstrom HGS im thermischen Reaktor 1 thermisch behandelt und hergestellt werden können. Using examples of powders based on sodium or lithium-containing battery material BM, it can be shown that by means of the combination of the inventive measures, particularly finely divided powders can be thermally treated and produced in a single step in the hot gas flow HGS in the thermal reactor 1.
Beispiel 1 - thermische Behandlung und Herstellung einer Verbindung LiFePCL (LFP) als Beispiel für ein lithiumhaltiges Batteriematerial Example 1 - thermal treatment and production of a compound LiFePCL (LFP) as an example of a lithium-containing battery material
Es wurde ein Metallphosphatpulver mit der Zusammensetzung LiFePCL als lithiumhaltiges Batteriematerial BM hergestellt. Zu diesem Zwecke wurde eine wässriger Lösung aus Eisen(III)nitrat Nonahydrat, Lithiumhydroxid Monohydrat und Phosphorsäure im entsprechenden stöchiometrischen Verhältnis und einer Gesamtproduktkonzentration von 15 Gew.% (berechnet als LiFeP0 ) im Heißgasstrom HGS in dem Pulsationsreaktor 1 zu Lithium -Ei sen-Phosphat umgesetzt. Die wässerige Lösung (Ausgangsverbindung AV) wurde mittels einer Zweistoffdüse mit 3 kg/h in die Brennkammer (Applikationsraum 2.1) eingebracht und bei einer Temperatur von 650°C im Pulsationsreaktor 1 thermisch behandelt, insbesondere in einem in einem einzigen Schritt umgesetzt und somit in einem
einzigen Schritt im thermischen Reaktor 1 synthetisiert, getrocknet und kalziniert. Das Produkt (Batteriematerial BM in Pulverform) wurde aus dem abgekühlten Gasstrom durch einen Filter (Abscheidevorrichtung 4) abgetrennt. A metal phosphate powder with the composition LiFePCL was produced as the lithium-containing battery material BM. For this purpose, an aqueous solution of iron (III) nitrate nonahydrate, lithium hydroxide monohydrate and phosphoric acid in the appropriate stoichiometric ratio and a total product concentration of 15% by weight (calculated as LiFeP0) in the hot gas stream HGS in the pulsation reactor 1 was converted into lithium iron phosphate implemented. The aqueous solution (starting compound AV) was introduced into the combustion chamber (application space 2.1) by means of a two-substance nozzle at 3 kg / h and thermally treated at a temperature of 650 ° C in the pulsation reactor 1, in particular reacted in a single step and thus in one single step in the thermal reactor 1 synthesized, dried and calcined. The product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
Das entstandene braune Pulver hatte eine spezifische Oberfläche (BET) von 2 m2/g und einen Glühverlust von 0,6 Gew.%. Die Röntgenbeugungsanalyse zeigte einen amorphen Untergrund mit Reflexen einer Lithium-Eisenphosphat Phase. Die chemische Analyse (ICP-OES) lieferte 34 Gew.% Eisen (theoretisch 35,4 Gew.%), 4,3 Gew.% Lithium (theoretisch 4,4 Gew.%) und 18,9 Gew.% Phosphor (theoretisch 19,63 Gew.%). Die Produktstöchiometrie entspricht der in der Eduktlösung eingestellten Zusammensetzung. The brown powder formed had a specific surface area (BET) of 2 m 2 / g and a loss on ignition of 0.6% by weight. The X-ray diffraction analysis showed an amorphous background with reflections of a lithium iron phosphate phase. The chemical analysis (ICP-OES) showed 34% by weight of iron (theoretical 35.4% by weight), 4.3% by weight of lithium (4.4% by weight of theoretical) and 18.9% by weight of phosphorus (theoretical 19.63% by weight). The product stoichiometry corresponds to the composition set in the educt solution.
Beispiel 2 - thermische Behandlung und Herstellung einer Verbindung LiMno.5Feo.5PO4 (LMFP) als Beispiel für ein lithiumhaltiges Batteriematerial Example 2 - thermal treatment and production of a compound LiMno .5 Feo .5 PO 4 (LMFP) as an example of a lithium-containing battery material
Es wurde ein Metallphosphatpulver mit der Zusammensetzung LiMno.5Feo.5PO4 als lithiumhaltiges Batteriematerial BM hergestellt. Zu diesem Zwecke wurde eine wässriger Lösung aus Eisen(III)nitrat Nonahydrat, Lithiumhydroxid Monohydrat, Mangan(II)acetat Tetrahydrat und Phosphorsäure im entsprechenden stöchiome trischen Verhältnis und einer Gesamtproduktkonzentration von 15 Gew.% (berechnet als LiMno.5Feo.5PO4) im Heißgasstrom HGS in dem Pulsationsreaktor 1 umgesetzt. Die wässerige Lösung (Ausgangsverbindung AV) wurde mittels einer Zweistoffdüse mit 3 kg/h in die Brennkammer (Applikationsraum 2.1) eingebracht und bei einer Temperatur von 500°C im Heißgasstrom HGS in dem Pulsationsreaktor 1 in einem einzigen Schritt umgesetzt und somit in einem einzigen Schritt im thermischen Reaktor 1 synthetisiert, getrocknet und kalziniert. Das Produkt (Batteriematerial BM in Pulverform) wurde aus dem abgekühlten Gasstrom durch einen Filter (Abscheidevorrichtung 4) abgetrennt. A metal phosphate powder with the composition LiMno .5 Feo .5 PO 4 was produced as the lithium-containing battery material BM. For this purpose, an aqueous solution of iron (III) nitrate nonahydrate, lithium hydroxide monohydrate, manganese (II) acetate tetrahydrate and phosphoric acid in the corresponding stoichiometric ratio and a total product concentration of 15% by weight (calculated as LiMno .5 Feo .5 PO 4 ) implemented in the hot gas stream HGS in the pulsation reactor 1. The aqueous solution (starting compound AV) was introduced into the combustion chamber (application room 2.1) by means of a two-substance nozzle at 3 kg / h and reacted at a temperature of 500 ° C in the hot gas stream HGS in the pulsation reactor 1 in a single step and thus in a single step synthesized in the thermal reactor 1, dried and calcined. The product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
Das entstandene braune Pulver hatte eine spezifische Oberfläche (BET) von 14 m2/g und einen Glühverlust von 2,2 Gew.%. Die Röntgenbeugungsanalyse zeigte einen amorphen Untergrund mit Reflexen einer Lithium -Eisenphosphat sowie
Lithium-Mangan-Eisenphosphat Phase. Die chemische Analyse (ICP-OES) lieferte 19,9 Gew.% Eisen (theoretisch 17,75 Gew.%), 4,3 Gew.% Lithium (theoretisch 4,41 Gew.%), 15,3 Gew.% Mangan (theoretisch 17,46 Gew.%) und 19,3 Gew.% Phosphor (theoretisch 19,69 Gew.%). Die Produktstöchiometrie entspricht annähernd der in der Eduktlösung eingestellten Zusammensetzung. The brown powder formed had a specific surface area (BET) of 14 m 2 / g and a loss on ignition of 2.2% by weight. The X-ray diffraction analysis showed an amorphous background with reflections of a lithium iron phosphate as well Lithium manganese iron phosphate phase. Chemical analysis (ICP-OES) showed 19.9% by weight of iron (theoretical 17.75% by weight), 4.3% by weight of lithium (theoretical 4.41% by weight), 15.3% by weight of manganese (theoretical 17.46% by weight) and 19.3% by weight phosphorus (theoretical 19.69% by weight). The product stoichiometry corresponds approximately to the composition established in the educt solution.
Beispiel 3 - thermische Behandlung und Herstellung einer VerbindungExample 3 - thermal treatment and production of a joint
Nao,67Mn0,5Feo,502_als Beispiel für ein natriumhaltiges Batteriematerial Nao , 67Mn 0, 5Feo , 502_as an example of a sodium-containing battery material
Es wurde ein Metalloxidpulver mit der Zusammensetzung Nao^Mno^Feo^CE als natriumhaltiges Batteriematerial BM hergestellt. Zu diesem Zwecke wurde eine wässriger Lösung aus Eisen(III)nitrat Nonahydrat, Natriumcarbonat und Mangan(II)acetat Tetrahydrat im entsprechenden stöchiometrischen Verhältnis und einer Gesamtproduktkonzentration von 15 Gew.% (berechnet als Nao. 7Mno 5Feo.5O2) im Heißgasstrom HGS in dem Pulsationsreaktor 1 umgesetzt. Die wässerige Lösung (Ausgangsverbindung AV) wurde mittels einer Zweistoffdüse mit 3 kg/h in die Brennkammer (Applikationsraum 2.1) eingebracht und bei einer Temperatur von 800°C im Pulsationsreaktor 1 thermisch behandelt, insbesondere in einem in einem einzigen Schritt umgesetzt und somit in einem einzigen Schritt im thermischen Reaktor 1 synthetisiert, getrocknet und kalziniert. Das Produkt (Batteriematerial BM in Pulverform) wurde aus dem abgekühlten Gasstrom durch einen Filter (Abscheidevorrichtung 4) abgetrennt. A metal oxide powder with the composition Nao ^ Mno ^ Feo ^ CE was produced as the sodium-containing battery material BM. For this purpose, an aqueous solution of iron (III) nitrate nonahydrate, sodium carbonate and manganese (II) acetate tetrahydrate in the appropriate stoichiometric ratio and a total product concentration of 15% by weight (calculated as Nao. 7Mno 5Feo. 5O2) in the hot gas stream HGS in the Pulsation reactor 1 implemented. The aqueous solution (starting compound AV) was introduced into the combustion chamber (application space 2.1) by means of a two-substance nozzle at 3 kg / h and thermally treated at a temperature of 800 ° C in the pulsation reactor 1, in particular reacted in a single step and thus in one single step in the thermal reactor 1 synthesized, dried and calcined. The product (battery material BM in powder form) was separated from the cooled gas stream by a filter (separator 4).
Das entstandene grau-schwarze Pulver hatte eine spezifische Oberfläche (BET) von 9 m2/g und einen Glühverlust von 6,2 Gew.%. Die Röntgenbeugungsanalyse zeigte einen amorphen Untergrund mit Reflexen einer Natrium-Mangan-Eisenoxid sowie Natrium-Manganoxid Phase. Die chemische Analyse (ICP-OES) lieferte 25,8 Gew.% Eisen (theoretisch 27,16 Gew.%), 14,1 Gew.% Natrium (theoretisch 14,98 Gew.%) und 25,8 Gew.% Mangan (theoretisch 26,72 Gew.%). Die Produkt stöchiometrie entspricht der in der Eduktlösung eingestellten Zusammensetzung.
BEZUGSZEICHENLISTE The gray-black powder formed had a specific surface area (BET) of 9 m 2 / g and a loss on ignition of 6.2% by weight. The X-ray diffraction analysis showed an amorphous background with reflections of a sodium-manganese-iron oxide and sodium-manganese oxide phase. Chemical analysis (ICP-OES) showed 25.8% by weight of iron (theoretical 27.16% by weight), 14.1% by weight of sodium (theoretical 14.98% by weight) and 25.8% by weight of manganese (theoretical 26.72% by weight). The product stoichiometry corresponds to the composition set in the educt solution. REFERENCE LIST
1 Reaktor, Pulsationsreaktor 1 reactor, pulsation reactor
1.1 Reaktionsraum 1.1 reaction space
1.2 Aufgabeort 1.2 Place of posting
1.3 Abscheidepunkt 1.3 separation point
2 Erzeuger 2 producers
2.1 Applikationsraum 2.1 Application area
3 Zuführung 3 feed
4 Abscheidevorrichtung 4 separation device
AV Ausgangsverbindung AV output connection
BM Batteriematerial / Batterievorläufermaterial BS Brennstoff BM battery material / battery precursor material BS fuel
HGS Heißgasströmung HGS hot gas flow
VG Verbrennungsgas
VG combustion gas
Claims
1. Verfahren zur thermischen Behandlung, insbesondere durch Synthese und/oder Trocknung und/oder Kalzinierung, eines nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials (BM) und/oder Batterievorläufermaterials (BM) in einem thermischen Reaktor (1) mit einem Applikationsraum (2.1) und einem Reaktionsraum (1.1), umfassend die Schritte: 1. A method for thermal treatment, in particular by synthesis and / or drying and / or calcination, of a nano- and / or microscale or nano- and / or microcrystalline battery material (BM) and / or battery precursor material (BM) in a thermal reactor (1 ) with an application space (2.1) and a reaction space (1.1), comprising the steps:
- Einbringen einer Ausgangsverbindung (AV) in Strömungsrichtung eines Heißgasstromes (HGS) im thermischen Reaktor (1) gesehen an einem vorderen Aufgabeort (1.2) in den thermischen Reaktor (1), wobei als Ausgangsverbindung (AV) ein Batteriematerial (BM) oder ein Batterievorläufermaterial (BM) in Form einer Lösung, Aufschlämmung, Suspension oder in einem festen Aggregatszustand in den Reaktor (1) eingebracht wird, - Introduction of an output connection (AV) in the direction of flow of a hot gas stream (HGS) in the thermal reactor (1) seen at a front loading point (1.2) in the thermal reactor (1), the output connection (AV) being a battery material (BM) or a battery precursor material (BM) is introduced into the reactor (1) in the form of a solution, slurry, suspension or in a solid state of aggregation,
- thermische Behandlung des in dem Heißgasstrom (HGS) getragenen Batteriematerials (BM) und/oder Batterievorläufermaterials (BM) in einer Behandlungszone im thermischen Reaktor (1) bei einer Temperatur von 150°C bis 1.000°C mit einer Verweilzeit von 0,1 s bis 2 s, wobei eine Umsetzung der Ausgangsverbindung (AV) zu dem Batteriematerial (BM) durch Synthese und/oder Trocknung und Kalzinierung in einem einzigen Schritt in dem Heißgasstrom im thermischen Reaktor (1) erfolgt, und - Thermal treatment of the battery material (BM) and / or battery precursor material (BM) carried in the hot gas flow (HGS) in a treatment zone in the thermal reactor (1) at a temperature of 150 ° C to 1,000 ° C with a residence time of 0.1 s up to 2 s, the starting compound (AV) being converted to the battery material (BM) by synthesis and / or drying and calcination in a single step in the hot gas flow in the thermal reactor (1), and
- Ausbringen des erhaltenen Batteriematerials (BM) in Pulverform aus dem Reaktor (1). - Discharge of the battery material (BM) obtained in powder form from the reactor (1).
2. Verfahren nach Anspruch 1, wobei, wenn die Ausgangsverbindung (AV) ein Batterievorläufermaterial ist, die Umsetzung zu dem Batteriematerial (BM) durch Synthese, Trocknung und Kalzinierung in einem einzigen Schritt im Heißgasstrom (HGS) des thermischen Reaktors (1) erfolgt.
2. The method according to claim 1, wherein, if the starting compound (AV) is a battery precursor material, the conversion to the battery material (BM) by synthesis, drying and calcination takes place in a single step in the hot gas flow (HGS) of the thermal reactor (1).
3. Verfahren nach Anspruch 1, wobei, wenn die Ausgangsverbindung (AV) ein feuchtes Batteriematerial ist, die Umsetzung zu dem Batteriematerial (BM) durch Trocknung und Kalzinierung in einem einzigen Schritt im Heißgasstrom (HGS) des thermischen Reaktors (1) erfolgt. 3. The method according to claim 1, wherein, if the starting compound (AV) is a moist battery material, the conversion to the battery material (BM) takes place by drying and calcination in a single step in the hot gas stream (HGS) of the thermal reactor (1).
4. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Ausgangsverbindung (AV) in den Reaktor (1) mittels eines Trägerfluides und/oder als Aerosol eingebracht wird. 4. The method according to any one of the preceding claims, wherein the starting compound (AV) is introduced into the reactor (1) by means of a carrier fluid and / or as an aerosol.
5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Heißgasströmung (HGS) regelmäßig oder unregelmäßig pulsiert, insbesondere mit einer Frequenz zwischen 5 Hz bis 350 Hz. 5. The method according to any one of the preceding claims, wherein the hot gas flow (HGS) pulsates regularly or irregularly, in particular with a frequency between 5 Hz to 350 Hz.
6. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Batterie material (BM) nach der thermischen Behandlung in der Behandlungszone in eine Kühlzone des Reaktors (1) überführt und anschließend aus dem Reaktor (1) ausgebracht und in Pulverform abgeschieden wird. 6. The method according to any one of the preceding claims, wherein the battery material (BM) after the thermal treatment in the treatment zone is transferred to a cooling zone of the reactor (1) and then discharged from the reactor (1) and deposited in powder form.
7. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Batterie material ein lithiumhaltiges oder natriumhaltiges Batteriematerial (BM) ist. 7. The method according to any one of the preceding claims, wherein the battery material is a lithium-containing or sodium-containing battery material (BM).
8. Verfahren nach Anspruch 7, wobei das lithiumhaltiges Batteriematerial ein nickel-, mangan- und cobalthaltiges Lithiummaterial, ein eisenphosphathaltiges Lithiummaterial, ein nickel- und manganhaltiges Lithiummaterial, ein eisen- und manganhaltiges Lithiummaterial, ein nickel-, cobalt- und aluminiumhaltiges Lithiummaterial, ein cobalt- und sauerstoffhaltiges Lithiummaterial oder ein titan- und sauerstoffhaltiges Lithiummaterial oder ein mangan-, eisenphosphathaltiges Lithiummaterial ist. 8. The method according to claim 7, wherein the lithium-containing battery material is a nickel-, manganese- and cobalt-containing lithium material, an iron-phosphate-containing lithium material, a nickel- and manganese-containing lithium material, an iron- and manganese-containing lithium material, a nickel-, cobalt- and aluminum-containing lithium material cobalt- and oxygen-containing lithium material or a titanium and oxygen-containing lithium material or a manganese, iron-phosphate-containing lithium material.
9. Verfahren nach Anspruch 7, wobei das natriumhaltiges Batteriematerial ein nickel-, mangan-, titan- und eisenhaltiges Natriummaterial oder ein
eisenphosphathaltiges Natriummaterial, permanganathaltiges Natriummaterial oder ein chromhaltiges Natriummaterial ist. 9. The method according to claim 7, wherein the sodium-containing battery material is a nickel, manganese, titanium and iron-containing sodium material or a ferrous phosphate-containing sodium material, permanganate-containing sodium material, or a chromium-containing sodium material.
10. Nano- und/oder mikroskaliges oder nano- und/oder mikrokristallines Batteriematerial (BM) erhältlich durch ein Verfahren nach einem der vorhergehenden Ansprüche. 10. Nano- and / or microscale or nano- and / or microcrystalline battery material (BM) obtainable by a method according to one of the preceding claims.
11. Nano- und/oder mikroskaliges oder nano- und/oder mikrokristallines Batteriematerial (BM) nach Anspruch 10, aufweisend eine durchschnittliche Partikelgröße im Bereich von 10 nm bis wenige Mikrometer, insbesondere bis 50 pm. 11. Nano- and / or microscale or nano- and / or microcrystalline battery material (BM) according to claim 10, having an average particle size in the range from 10 nm to a few micrometers, in particular up to 50 μm.
12. Verwendung des nano- und/oder mikroskaligen oder nano- und/oder mikrokristallinen Batteriematerials (BM) nach Anspruch 10 oder 11 als Batterie-, insbesondere Kathoden- oder Anodenmaterial. 12. Use of the nano- and / or microscale or nano- and / or microcrystalline battery material (BM) according to claim 10 or 11 as a battery, in particular cathode or anode material.
13. Verwendung eines thermischen Reaktors (1) mit mindestens einem Reaktionsraum (1.1) und mindestens einem Erzeuger (2) zur Erzeugung einer Heißgasströmung (HGS) zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 7.
13. Use of a thermal reactor (1) with at least one reaction space (1.1) and at least one generator (2) for generating a hot gas flow (HGS) for carrying out the method according to one of claims 1 to 7.
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| PCT/EP2021/055177 WO2021175849A1 (en) | 2020-03-02 | 2021-03-02 | Process for thermally treating a battery material in a thermal reactor |
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| DE10111938A1 (en) | 2001-03-13 | 2002-09-26 | Merck Patent Gmbh | Production of high-temperature superconductor powders in a pulsation reactor |
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