CN114388772A - Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN114388772A CN114388772A CN202111499320.2A CN202111499320A CN114388772A CN 114388772 A CN114388772 A CN 114388772A CN 202111499320 A CN202111499320 A CN 202111499320A CN 114388772 A CN114388772 A CN 114388772A
- Authority
- CN
- China
- Prior art keywords
- titanium
- source
- niobium
- molybdenum
- vanadium
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- ZESXRMPHQZAUAI-UHFFFAOYSA-N [V].[Ti].[Nb].[Mo] Chemical compound [V].[Ti].[Nb].[Mo] ZESXRMPHQZAUAI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims description 25
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000001354 calcination Methods 0.000 claims abstract description 41
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010406 cathode material Substances 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 32
- 239000011733 molybdenum Substances 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010955 niobium Substances 0.000 claims abstract description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- -1 molybdenum ions Chemical class 0.000 abstract description 11
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 238000007599 discharging Methods 0.000 description 10
- 238000007600 charging Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000006257 cathode slurry Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- H01M4/36—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a molybdenum-vanadium-titanium-niobium composite oxide cathode material, a preparation method thereof and a lithium ion battery. The preparation method comprises the step S1 of mixing and crushing a first solvent, a niobium source and a titanium source to form a first mixed material, and calcining the first mixed material for the first time to obtain the titanium niobium oxide; step S2, mixing and crushing a second solvent, a vanadium source, a molybdenum source and a titanium niobium oxide to form a second mixed material; and carrying out secondary calcination on the second mixed material to obtain the molybdenum vanadium titanium niobium composite oxide cathode material. By applying the technical scheme of the invention, the vanadium ions and the molybdenum ions can be doped in the titanium niobium oxide, the electronic mixed arrangement is improved, the lattice parameter and the unit cell volume are increased, so that the conductivity of the material is improved, the molybdenum vanadium titanium niobium composite oxide cathode material can be directly prepared through two-step calcination, the preparation process is simple, and the rate capability and the cycle performance of the battery prepared by using the cathode material are also obviously improved.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a molybdenum-vanadium-titanium-niobium composite oxide cathode material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, high working voltage, small environmental pollution and the like, and is widely applied to energy storage systems and electric automobiles. As one of the most critical links in the lithium ion battery industry, the production cost of the lithium ion battery cathode material can account for 25-28% of the whole battery cost. At present, negative electrode materials of lithium ion batteries which are commercially applied mainly comprise carbon materials and lithium titanate materials, wherein the lithium intercalation potential of the carbon materials is low, lithium dendrites are likely to be formed by rapid charging and discharging, certain potential safety hazards exist, and the dynamic performance is poor under high power; the lithium titanate material has a stable spinel structure, the lithium titanate structure hardly changes along with the insertion and the release of lithium ions in the charging and discharging processes, the material is called a zero-strain material, and the material also has a high lithium intercalation potential (1.55V), so that the safety problems caused by the formation of an SEI film and lithium dendrites can be effectively avoided. However, the theoretical specific capacity of the lithium titanate material is relatively low, and is only 175mAh/g, which greatly limits the application of the lithium titanate.
The titanium niobium oxide TiNb is firstly prepared by Goodenough in 20112O7As a negative electrode material of a lithium ion battery, the material has the theoretical specific capacity up to 385mAh/g, higher discharge potential and highly reversible cycle process, and a high voltage platform can effectively avoid the formation of an SEI film. However, the absence of unpaired electrons in the titanium niobium oxide results in a titanium niobium oxide material that is extremely poor in conductivity and nearly insulating. The low electronic conductivity and ionic conductivity results in great loss of capacity performance and poorer rate capability and cycle performance when the titanium niobium oxide material is actually applied to batteries. In addition, in the prior art, a sol-gel method is adopted for preparation, which is to mix and centrifuge a niobium source, a titanium source and a carbon source solution and then calcine the mixture to obtain the titanium-niobium oxide, and the method can reduce the calcinationAnd (4) obtaining the titanium niobium oxide with fine particles at the sintering temperature. However, the sol-gel method has complex process, is not easy to control, and has poor cycle characteristics, and the carbon coating modification can not achieve ideal effects.
Disclosure of Invention
The invention mainly aims to provide a molybdenum-vanadium-titanium-niobium composite oxide cathode material, a preparation method thereof and a lithium ion battery, and aims to solve the problems that a titanium-niobium oxide cathode material used for a lithium battery in the prior art is complex in preparation process, low in conductivity and poor in rate performance and cycle performance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a molybdenum vanadium titanium niobium composite oxide anode material, comprising the steps of: step S1, mixing and crushing the first solvent, the niobium source and the titanium source to form a first mixed material; calcining the first mixed material for the first time to obtain a titanium niobium oxide; step S2, mixing and crushing a second solvent, a vanadium source, a molybdenum source and a titanium niobium oxide to form a second mixed material; and carrying out secondary calcination on the second mixed material to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
Further, the niobium source is one or more of niobium pentoxide, niobium ethoxide, niobium pentachloride and niobium hydroxide; preferably, the niobium source is niobium pentoxide or niobium hydroxide; preferably, the titanium source is one or more of titanium dioxide, metatitanic acid, titanium ethoxide, tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate; more preferably, the titanium source is titanium dioxide or tetrabutyl titanate.
Further, the vanadium source is one or more of ammonium metavanadate, vanadium pentoxide, sodium metavanadate and potassium metavanadate; preferably, the vanadium source is ammonium metavanadate or vanadium pentoxide; preferably, the molybdenum source is one or more of molybdenum disulfide, molybdenum dioxide, ammonium molybdate; more preferably, the molybdenum source is molybdenum disulfide or ammonium molybdate; preferably, the first solvent and the second solvent are each independently selected from one or more of ethanol, acetone, isopropanol, deionized water; more preferably, the first solvent and the second solvent are both ethanol.
Further, the sum of the mole numbers of the niobium element in the niobium source, the vanadium element in the vanadium source and the molybdenum element in the molybdenum source is represented as m, the mole number of the titanium element in the titanium source is represented as n, and m: n is (2-2.1): 1; preferably, m is n ═ (2-2.05): 1; preferably, the mole ratio of the vanadium element in the vanadium source to the titanium element in the titanium source is (0.2-0.6): 1, more preferably (0.2-0.5): 1; preferably, the molar ratio of the molybdenum element in the molybdenum source to the titanium element in the titanium source is (0.01-0.05): 1, more preferably (0.01-0.03): 1.
Further, the first calcination process comprises: heating the first mixed material to 1300-1500 ℃ at a heating rate of 5-7 ℃/min, and calcining for 12-15 h to obtain the titanium niobium oxide; preferably, the second calcination process comprises: and heating the second mixed material to 750-800 ℃ at the heating rate of 8-10 ℃/min, and calcining for 8-10 h to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
Further, in step S1, performing first ball milling on the first solvent, the niobium source, and the titanium source in a high-energy planetary ball mill to obtain a first mixed material; preferably, in step S2, performing secondary ball milling on the second solvent, the vanadium source, the molybdenum source, and the titanium niobium oxide in a high-energy planetary ball mill to obtain a second mixed material; more preferably, the revolution speed of the high-energy planetary ball mill is set to be 100-150 rpm, the rotation speed is set to be 550-600 rpm, and the ball milling and crushing time is 10-12 h in the first ball milling and crushing process; further preferably, the revolution speed of the high-energy planetary ball mill is set to 180-200 rpm, the rotation speed is set to 750-800 rpm, and the ball milling and grinding time is 9-10 h in the second ball milling and grinding process.
Further, step S2 includes, before the second calcination process, sequentially filtering and drying the second mixture.
According to another aspect of the invention, a molybdenum-vanadium-titanium-niobium composite oxide cathode material is provided, which is prepared by the preparation method of the invention.
Further, the general structural formula of the molybdenum vanadium titanium niobium composite oxide cathode material is TiNb2-x-yVxMoyO7Wherein x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.05; preferably, the first and second electrodes are formed of a metal,0.2≤x≤0.5，0.01≤y≤0.03。
according to another aspect of the invention, a lithium ion battery is provided, which comprises a negative electrode material, and is prepared by the preparation method of the invention, or is the molybdenum-vanadium-titanium-niobium composite oxide negative electrode material of the invention.
By applying the technical scheme of the invention, the molybdenum vanadium titanium niobium composite oxide cathode material can be directly prepared by doping vanadium ions and molybdenum ions in the titanium niobium oxide and calcining the titanium niobium oxide in two steps, and the preparation process is simple and convenient. According to the invention, vanadium ions and molybdenum ions are doped in the titanium niobium oxide simultaneously, so that the electron mixed emission can be improved, the lattice parameter and the unit cell volume are increased, the prepared cathode material has small and uniform particle size, the better structural stability is kept, and the conductivity is obviously improved. The cathode slurry is prepared from the material, and the lithium titanate battery cathode sheet prepared by coating the cathode slurry on a current collector is applied to a lithium ion battery, so that the cathode slurry has high safety and high capacity when the titanium niobium oxide is used as the cathode material, and the rate capability and the cycle performance of the battery are also obviously improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows 10C discharge curves for inventive example 1 and comparative example;
FIG. 2 shows the normal temperature 2C/2C cycle curves of inventive example 1 and comparative example.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background of the present application, the problems of complex preparation process, low conductivity, and poor rate performance and cycle performance of the titanium niobium oxide negative electrode material used in the lithium battery exist in the prior art. In order to solve the problems, the application provides a molybdenum-vanadium-titanium-niobium composite oxide negative electrode material, a preparation method thereof and a lithium ion battery.
In an exemplary embodiment of the present application, a method for preparing a molybdenum-vanadium-titanium-niobium composite oxide negative electrode material is provided, which includes step S1, mixing and crushing a first solvent, a niobium source and a titanium source to form a first mixed material; calcining the first mixed material for the first time to obtain a titanium niobium oxide; step S2, mixing and crushing a second solvent, a vanadium source, a molybdenum source and a titanium niobium oxide to form a second mixed material; and carrying out secondary calcination on the second mixed material to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
By doping vanadium ions and molybdenum ions in the titanium niobium oxide, the electron mixed arrangement in the titanium niobium oxide can be improved, the lattice parameter and the unit cell volume are increased, more defect vacancies appear in the material, and the desorption of lithium ions in the negative electrode material is facilitated. The twice procedure calcination can ensure that all niobium and titanium elements can react at an atomic level, and vanadium ions and molybdenum ions can be uniformly doped, so that the synthesized molybdenum-vanadium-titanium-niobium composite oxide cathode material has a complete crystal structure, the electronic conductivity and the ion diffusion rate of the material are effectively improved, and the rate capability and the cycle performance of a battery are improved. The solid phase method used in the invention has simple preparation process, and only a small amount of solvent is used in the mixing and crushing stage, thus being more environment-friendly. In addition, the reaction is easy to control, the cost is low, the industrialization is easy, and the prepared cathode material and the lithium battery have good crystallization performance, high conductivity, high rate performance and high cycle performance.
In a preferred embodiment, the niobium source is one or more of niobium pentoxide, niobium ethoxide, niobium pentachloride and niobium hydroxide, and the niobium source has small steric hindrance in the process of lithium intercalation in bulk, has the capability of realizing rapid lithium deintercalation, and shows good lithium deintercalation performance and good cycle stability. Preferably, the niobium source is niobium pentoxide or niobium hydroxide, and particularly, the niobium pentoxide has a three-dimensional porous structure and a quasi-two-dimensional lithium ion storage and migration channel, the shear plane structure of the niobium pentoxide can keep good structural stability during lithium ion intercalation and deintercalation, and the lithium ion channel formed by the structure is also beneficial to lithium ion deintercalation and diffusion.
Preferably, the titanium source is one or more of titanium dioxide, metatitanic acid, titanium ethoxide, tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate; more preferably, the titanium source is titanium dioxide or tetrabutyl titanate. These titanium sources can reduce the resistance to charge transfer and shorten the ion diffusion path. Particularly, the titanium dioxide has the advantages of no toxicity, low price, large reserve and stable chemical structure, and the lithium ion battery prepared by the cathode material has higher rate performance and cycle performance and greatly reduces the cost.
The selection of the doping material is important for improving the conductivity of the titanium niobium oxide, and as mentioned above, the beneficial effects are achieved by selecting vanadium ions and molybdenum ions to carry out co-doping on the titanium niobium oxide. In the actual selection process, it is sufficient to use raw materials capable of forming vanadium oxide and molybdenum oxide during calcination. Of course, in view of raw material cost, environmental protection during calcination, and the like, in a preferred embodiment, the vanadium source is one or more of ammonium metavanadate, vanadium pentoxide, sodium metavanadate, and potassium metavanadate. In addition to the above advantages, the above materials can improve electron mixing, increase lattice parameter and unit cell volume. Preferably, the vanadium source is ammonium metavanadate or vanadium pentoxide, the materials can enable the negative electrode material to keep better structural stability, the conductivity is also remarkably improved, and meanwhile, the material structure can be optimized, so that the rate capability and the cycling stability of the battery are further improved.
Preferably, the molybdenum source is one or more of molybdenum disulfide, molybdenum dioxide or ammonium molybdate; more preferably, the molybdenum source is molybdenum disulfide or ammonium molybdate; the molybdenum sources can achieve the purpose of improving the electronic conductivity and the structural stability of the cathode material through a small amount of doping in the cathode material. Particularly, the molybdenum disulfide is doped together with a vanadium source, so that more two-dimensional channels for lithium ion transmission can be provided, the charge transfer resistance is reduced, the ion diffusion path is shortened, more active sites are provided for lithium storage, the conductivity is better improved, a more stable lattice structure is formed, the conductivity of the doped titanium niobium oxide is further improved, and the multiplying power performance and the cycle performance of the battery are further improved.
In the two ball milling and crushing processes, the first solvent and the second solvent are respectively and independently selected from one or more of ethanol, acetone, isopropanol and deionized water; more preferably, the first solvent and the second solvent are both ethanol. The solvents have good infiltration or dispersibility on all raw materials, are beneficial to constructing a stable mixed system and obtain materials with smaller and uniform particle size. Meanwhile, the boiling point of the raw materials is low, the raw materials are easy to volatilize, the residue is little, and the influence on a subsequent reaction system is small.
In a preferred embodiment, the sum of the number of moles of niobium in the niobium source, vanadium in the vanadium source, and molybdenum in the molybdenum source is represented as m, the number of moles of titanium in the titanium source is represented as n, where m: n ═ 1 (2 to 2.1), more preferably m: n ═ 1 (2 to 2.05); preferably, the mole ratio of the vanadium element in the vanadium source to the titanium element in the titanium source is (0.2-0.6): 1, more preferably (0.2-0.5): 1; preferably, the molar ratio of the molybdenum element in the molybdenum source to the titanium element in the titanium source is (0.01-0.05): 1, more preferably (0.01-0.03): 1. The proportion is beneficial to more uniformly doping vanadium ions and molybdenum ions into the titanium niobium oxide, so that the conductivity of the titanium niobium oxide is better improved, the problem that the conductivity is not obviously improved, or impurities are generated to destroy the original crystal structure of the titanium niobium oxide and hinder the transmission of lithium ions and electrons to cause the performance reduction of a battery is avoided, the electrochemical capacity of the prepared cathode material is better, and better balanced cycle performance and rate capability can be obtained when the cathode material is applied to a lithium ion battery.
To make the doping process more stable to further improve the uniformity of doping, in a preferred embodiment, the first calcination process comprises: heating the first mixed material to 1300-1500 ℃ at a heating rate of 5-7 ℃/min, and calcining for 12-15 h to obtain the titanium niobium oxide; preferably, the second calcination process comprises: and heating the second mixed material to 750-800 ℃ at the heating rate of 8-10 ℃/min, and calcining for 8-10 h to obtain the molybdenum vanadium titanium niobium composite oxide cathode material. The reaction temperature and time are controlled within the range, so that the doping uniformity is better facilitated, the generation of a mixed phase possibly caused by overhigh temperature is avoided, the doping effect is better improved, the performance of the titanium niobium oxide is better improved, the conductivity of the molybdenum vanadium titanium niobium composite oxide cathode material after doping is further improved, and the multiplying power performance and the cycle performance of the battery are better improved.
In a preferred embodiment, in step S1, performing a first ball milling process on the first solvent, the niobium source and the titanium source in a high-energy planetary ball mill to obtain a first mixed material; preferably, in step S2, the second solvent, the vanadium source, the molybdenum source, and the titanium niobium oxide are subjected to second ball milling and pulverization in a high-energy planetary ball mill to obtain a second mixed material. The material before calcination is subjected to ball milling and crushing, so that the material can be crushed to a target particle size, the time is short, and the efficiency is high. Meanwhile, the wet ball milling can utilize a solvent to aid the grinding, so that the impact force on a grinding ball is reduced, and the impact collision loss on the ball mill is small.
Preferably, the revolution speed of the high-energy planetary ball mill is set to be 100-150 rpm, the rotation speed is set to be 550-600 rpm, and the ball milling and crushing time is 10-12 h in the first ball milling and crushing process; preferably, the revolution speed of the high-energy planetary ball mill is set to be 180-200 rpm, the rotation speed is set to be 750-800 rpm, and the ball milling and grinding time is 9-10 h in the second ball milling and grinding process. The degree of pulverization of the material under the ball milling condition is higher, the improvement of the molding density is facilitated, the corresponding sintering density is also higher, and the uniform mixing of different materials in the subsequent calcining process is facilitated.
In addition, in a preferred embodiment, before the second calcination process, step S2 further includes a process of sequentially filtering and drying the second mixture, so that the second solvent can be removed, the burden of subsequent calcination is reduced, and the preparation process is more environment-friendly and energy-saving.
According to another aspect of the invention, the molybdenum-vanadium-titanium-niobium composite oxide cathode material is prepared by the preparation method, under the co-doping action of vanadium ions and molybdenum ions, more defect vacancies appear in the material, and the de-intercalation of lithium ions in the cathode material is facilitated.
Preferably, the general structural formula is TiNb2-x-yVxMoyO7Wherein x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.05; more preferably, 0.2. ltoreq. x.ltoreq.0.5, 0.01. ltoreq. y.ltoreq.0.03. The proportion is beneficial to more uniform doping of vanadium ions and molybdenum ions in the titanium niobium oxide, so that the conductivity of the titanium niobium oxide is better improved, the prepared cathode material can also obtain better high conductivity, and the cathode material can also obtain high rate capability and high cycle performance when applied to a lithium ion battery. Compared with a sol-gel method, the preparation method provided by the invention has the advantages of simpler preparation process, mild reaction conditions and lower cost, and is suitable for large-scale industrial application.
According to another aspect of the invention, a lithium ion battery is provided, which comprises a negative electrode material, wherein the negative electrode material is prepared by the preparation method of the invention, or is the molybdenum-vanadium-titanium-niobium composite oxide negative electrode material in the invention. The used negative electrode material has good lithium intercalation and deintercalation performance, good circulation stability and structural stability, the conductivity is further improved, the material is made into negative electrode slurry, and the negative electrode slurry is coated on a current collector to form a negative electrode plate, the prepared lithium ion battery has higher rate performance and circulation performance, the electrochemical capacity is also better, the defect of lower battery conductivity when the traditional titanium-niobium composite oxide is used as the negative electrode material is overcome, and the lithium ion battery with better rate performance and circulation performance is integrally obtained while the conductivity is obviously improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Comparative example 1
500g of absolute ethyl alcohol and 200g of niobium pentoxide are added into a high-energy planetary ball mill74.3g of titanium dioxide, setting the revolution speed of a ball mill to be 150rpm and the rotation speed to be 600rpm, carrying out ball milling in the ball mill for 12h, heating to 1500 ℃ at the speed of 7 ℃/min, calcining in the air for 12h, grinding and crushing the calcined material to obtain the TiNb oxide2O7And (3) a negative electrode material.
Example 1
Step 1, preparation of titanium niobium oxide: adding 500g of absolute ethyl alcohol into a high-energy planetary ball mill, adding 200g of niobium pentoxide and 74.3g of titanium dioxide, setting the revolution speed of the ball mill to be 150rpm and the rotation speed to be 600rpm, after ball milling for 12 hours in the ball mill, heating to 1500 ℃ at the speed of 7 ℃/min, calcining for 12 hours in the air, grinding and crushing the calcined materials to obtain the TiNb oxide2O7A material.
Step 2, preparation of the molybdenum vanadium titanium niobium composite oxide negative electrode material: weighing TiNb prepared in step 12O7200g of the material (containing 0.58mol of Ti and 1.16mol of Nb), 20.358g of ammonium metavanadate (containing 0.174mol of V) and 1.856g of molybdenum disulfide (containing Mo0.0116mol) are added into a high-energy planetary ball mill, 500g of absolute ethyl alcohol is added, the revolution speed of the ball mill is set to be 200rpm, the rotation speed is set to be 800rpm, and the ball milling is carried out in the ball mill for 10 hours. Filtering the ball-milled mixture to remove the solvent after the completion, drying the ball-milled mixture in an environment of 100 ℃, transferring the ball-milled mixture into a crucible, then placing the crucible into a muffle furnace for calcination, and calcining the crucible for 10 hours at a rate of 8 ℃/min to 800 ℃ to obtain TiNb1.68V0.3Mo0.02O7And (3) further mechanically crushing the product to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
Example 2
Example 2 differs from example 1 only in that 27.144g of ammonium metavanadate (containing 0.232mol of V), 0.928g of molybdenum disulfide (containing 0.0058mol of Mo) and a muffle furnace calcination temperature of 850 ℃ are weighed in step 2, and a composite oxide anode material TiNb is finally prepared1.59V0.4Mo0.01O7。
Example 3
Example 3 differs from example 1 only in that metavanadate is weighed in step 213.572g of ammonium (containing V0.116mol), 2.784g of molybdenum disulfide (containing Mo 0.0174mol), and the muffle furnace calcination temperature is 850 ℃, and finally the TiNb composite oxide negative electrode material is prepared1.77V0.2Mo0.03O7。
Example 4
Example 4 differs from example 1 only in that 33.930g of ammonium metavanadate (containing 0.290mol of V), 0.928g of molybdenum dioxide (containing 0.0058mol of Mo) and a muffle furnace calcination temperature of 900 ℃ are weighed in step 2, and a composite oxide anode material TiNb is finally prepared1.49V0.5Mo0.01O7。
Example 5
Example 5 differs from example 1 only in that 40.716g of ammonium metavanadate (containing 0.348mol of V), 4.640g of molybdenum dioxide (containing 0.0290mol of Mo) are weighed in step 2, the muffle furnace calcination temperature is 800 ℃, and the composite oxide anode material TiNb is finally prepared1.35V0.6Mo0.05O7。
Example 6
Example 6 is different from example 1 only in that 6.786g of ammonium metavanadate (containing 0.058mol of V), 0.464g of molybdenum dioxide (containing 0.0029mol of Mo) are weighed in the step 2, the muffle furnace calcination temperature is 850 ℃, and the composite oxide anode material TiNb is finally prepared1.895V0.1Mo0.005O7。
Example 7
The difference between the embodiment 7 and the embodiment 1 is only that 54.288g of ammonium metavanadate (containing 0.464mol of V) and 6.496g of molybdenum dioxide (containing 0.0406mol of Mo) are weighed in the step 2, the muffle furnace calcination temperature is 850 ℃, and the composite oxide anode material TiNb is finally prepared1.13V0.8Mo0.07O7。
The resistance of each of the materials prepared in comparative example and examples 1 to 7 was measured using a resistance tester, and the results are shown in table 1.
And (3) performance testing:
the materials prepared in comparative example 1 and examples 1 to 7, the conductive agent and the binder were uniformly mixed in a mass ratio of 92:4.5:3.5, wherein the conductive agent was a mixture of SP: the carbon nano tube is 3:1, PVDF (900: 5130: 2:1) is used as a binder, a solvent N-methyl pyrrolidone is added and uniformly stirred to prepare negative electrode slurry with the solid content of 54.5%, the slurry is uniformly coated on a current collector carbon coating aluminum foil, and then drying, rolling and cutting are carried out to prepare the negative electrode plate. The NCM 111: conductive agent: the adhesive is uniformly mixed according to the mass ratio of 94:3:3, wherein the conductive agent is acetylene black: and SP (SP) ═ 1:2, PVDF (900:5130 ═ 2:1) is used as a binder, N-methyl pyrrolidone serving as a solvent is added and uniformly stirred to prepare positive electrode slurry with the solid content of 65%, the positive electrode slurry is uniformly coated on a current collector carbon coating aluminum foil, and then drying, rolling and cutting are carried out to prepare the positive electrode piece. The positive pole piece, the negative pole piece and the polypropylene isolating membrane are assembled into a 2Ah small soft package battery by adopting a lamination process, the battery is subjected to liquid injection and standing, constant-current and constant-voltage charging and discharging are carried out by using a 1C current, then the battery is aged at a high temperature for 24-48 h, and then the electrochemical performance of the battery is tested, wherein the charging and discharging cut-off voltage is 1.5-2.9V.
1) Discharge test
After the soft package battery is assembled, 1C discharging is carried out: discharging: 2A, constant current is released to 1.5V; charging: 2A is charged to 2.9V by constant current; the specific discharge capacity was designated as Q1.
10C discharging: discharging: 20A is discharged to 1.5V at constant current; charging: charging to 2.9V at a constant current of 20A; the specific discharge capacity was designated as Q10.
2) Cycle performance test
Discharging: 4A, constant current is released to 1.5V, and the interval is 10 min; charging: charging 4A at constant current to 2.9V at an interval of 10 min; thirdly, repeating the first and second circles for 2000 circles to calculate the capacity conservation rate.
3) Rate capability test
Discharging to 1.5V at constant current of 6A at intervals of 10min, and then charging to 2.9V at constant current of 6A; ② repeating the first 10 circles; thirdly, the current density in the ' first and ' second ' is improved to 12 and 20A, and the capacity retention rate is calculated.
The results of the performance tests of the comparative example and examples 1 to 7 are shown in Table 1. The 10C discharge curve of the comparative example and the 10C discharge curve of the example 1 are shown in FIG. 1, and the normal temperature 2C/2C cycle curve is shown in FIG. 2.
TABLE 1
As shown in Table 1, the comparative example directly uses the titanium niobium oxide as the cathode material, so that the resistivity is high, the conductivity is low, and the rate capability and the cycle performance of the prepared lithium ion battery are poor. Compared with the negative electrode material prepared by the preparation method in the embodiments 1 to 7, especially the negative electrode material doped with vanadium ions and molybdenum ions according to the preferred proportion, the resistivity is obviously reduced, the conductivity is higher, the rate capability and the cycle performance of the prepared lithium ion battery are obviously improved, and the conductivity, the rate capability and the cycle performance can be better considered.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the molybdenum vanadium titanium niobium composite oxide cathode material is characterized by comprising the following steps of:
step S1, mixing and crushing the first solvent, the niobium source and the titanium source to form a first mixed material; calcining the first mixed material for the first time to obtain a titanium niobium oxide;
step S2, mixing and crushing a second solvent, a vanadium source, a molybdenum source and the titanium niobium oxide to form a second mixed material; and carrying out secondary calcination on the second mixed material to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
2. The production method according to claim 1,
the niobium source is one or more of niobium pentoxide, niobium ethoxide, niobium pentachloride and niobium hydroxide; preferably, the niobium source is niobium pentoxide or niobium hydroxide;
preferably, the titanium source is one or more of titanium dioxide, metatitanic acid, titanium ethoxide, tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate; preferably, the titanium source is titanium dioxide or tetrabutyl titanate.
3. The production method according to claim 1 or 2,
the vanadium source is one or more of ammonium metavanadate, vanadium pentoxide, sodium metavanadate and potassium metavanadate; preferably, the vanadium source is ammonium metavanadate or vanadium pentoxide;
preferably, the molybdenum source is one or more of molybdenum disulfide, molybdenum dioxide and ammonium molybdate; preferably, the molybdenum source is molybdenum disulfide or ammonium molybdate;
preferably, the first solvent and the second solvent are each independently selected from one or more of ethanol, acetone, isopropanol, deionized water; preferably, the first solvent and the second solvent are both ethanol.
4. The production method according to any one of claims 1 to 3,
the sum of the mole numbers of niobium in the niobium source, vanadium in the vanadium source and molybdenum in the molybdenum source is recorded as m, the mole number of titanium in the titanium source is recorded as n, and m: n is (2-2.1): 1; preferably, m is n ═ (2-2.05): 1;
preferably, the molar ratio of the vanadium element in the vanadium source to the titanium element in the titanium source is (0.2-0.6): 1, more preferably (0.2-0.5): 1;
preferably, the molar ratio of the molybdenum element in the molybdenum source to the titanium element in the titanium source is (0.01-0.05): 1, more preferably (0.01-0.03): 1.
5. The production method according to any one of claims 1 to 4,
the first calcination process comprises: heating the first mixed material to 1300-1500 ℃ at a heating rate of 5-7 ℃/min, and calcining for 12-15 h to obtain the titanium niobium oxide;
preferably, the second calcination process comprises: and heating the second mixed material to 750-800 ℃ at a heating rate of 8-10 ℃/min, and calcining for 8-10 h to obtain the molybdenum vanadium titanium niobium composite oxide cathode material.
6. The preparation method according to any one of claims 1 to 5, wherein in step S1, the first solvent, the niobium source and the titanium source are subjected to first ball milling pulverization in a high-energy planetary ball mill to obtain the first mixed material; preferably, in step S2, performing secondary ball milling on the second solvent, the vanadium source, the molybdenum source, and the titanium niobium oxide in a high-energy planetary ball mill to obtain a second mixed material;
preferably, the revolution speed of the high-energy planetary ball mill is set to be 100-150 rpm, the rotation speed is set to be 550-600 rpm, and the ball milling and crushing time is 10-12 hours in the first ball milling and crushing process; preferably, the revolution speed of the high-energy planetary ball mill in the second ball milling and crushing process is set to be 180-200 rpm, the rotation speed is set to be 750-800 rpm, and the ball milling and crushing time is 9-10 h.
7. The preparation method according to any one of claims 1 to 6, wherein the step S2 further comprises sequentially filtering and drying the second mixed material before the second calcination process.
8. A molybdenum vanadium titanium niobium composite oxide negative electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The molybdenum vanadium titanium niobium composite oxide anode material as claimed in claim 8, wherein the general structural formula of the molybdenum vanadium titanium niobium composite oxide anode material is TiNb2-x-yVxMoyO7Wherein x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.05; preferably, the first and second electrodes are formed of a metal,0.2≤x≤0.5，0.01≤y≤0.03。
10. a lithium ion battery comprising a negative electrode material, wherein the negative electrode material is prepared by the preparation method of any one of claims 1 to 7 or the molybdenum vanadium titanium niobium composite oxide negative electrode material of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111499320.2A CN114388772B (en) | 2021-12-09 | 2021-12-09 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111499320.2A CN114388772B (en) | 2021-12-09 | 2021-12-09 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114388772A true CN114388772A (en) | 2022-04-22 |
| CN114388772B CN114388772B (en) | 2024-10-01 |
Family
ID=81195167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111499320.2A Active CN114388772B (en) | 2021-12-09 | 2021-12-09 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388772B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083792A (en) * | 2022-06-28 | 2022-09-20 | 上海瑞浦青创新能源有限公司 | Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof |
| CN115744986A (en) * | 2022-11-30 | 2023-03-07 | 哈尔滨理工大学 | Preparation of titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping |
| CN116040686A (en) * | 2023-02-14 | 2023-05-02 | 上海理工大学 | Preparation method of ferrotitanium niobium oxide electrode |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800315A (en) * | 2010-04-09 | 2010-08-11 | 曲阜毅威能源股份有限公司 | Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof |
| JP2010287496A (en) * | 2009-06-12 | 2010-12-24 | Mitsubishi Chemicals Corp | Negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using it |
| CN103000881A (en) * | 2012-12-18 | 2013-03-27 | 江苏菲思特新能源有限公司 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
| KR20150131800A (en) * | 2014-05-16 | 2015-11-25 | 부산대학교 산학협력단 | Active material for anode, method of fabricating the same and battery having the same |
| US20150364757A1 (en) * | 2013-02-06 | 2015-12-17 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Mixed Oxide of Titanium and Niobium Comprising a Trivalent Metal |
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
| WO2016038716A1 (en) * | 2014-09-11 | 2016-03-17 | 株式会社東芝 | Nonaqueous electrolyte secondary battery and battery pack provided with same |
| CN105990571A (en) * | 2015-03-19 | 2016-10-05 | 株式会社东芝 | Active material, non-aqueous electrolyte battery, battery pack and battery module |
| JP6030708B1 (en) * | 2015-05-26 | 2016-11-24 | 太平洋セメント株式会社 | Method for producing titanium niobium oxide negative electrode active material |
| CN109616628A (en) * | 2018-11-26 | 2019-04-12 | 天津普兰能源科技有限公司 | A kind of titanium niobium zirconium composite oxide electrode material, preparation method and application |
| CN110380054A (en) * | 2019-08-02 | 2019-10-25 | 北方奥钛纳米技术有限公司 | A kind of titanium niobium oxide electrode material and preparation method thereof, lithium ion button shape cell |
| CN111137919A (en) * | 2018-11-06 | 2020-05-12 | 财团法人工业技术研究院 | Doped titanium niobate and battery |
| CN111170364A (en) * | 2019-12-30 | 2020-05-19 | 北方奥钛纳米技术有限公司 | Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery |
| CN111354923A (en) * | 2018-12-24 | 2020-06-30 | 北方奥钛纳米技术有限公司 | Negative electrode material and preparation method thereof, negative plate and lithium ion battery |
| CN111874947A (en) * | 2020-07-09 | 2020-11-03 | 江苏理工学院 | Tin-carbon co-doped titanium niobate material and preparation method and application thereof |
-
2021
- 2021-12-09 CN CN202111499320.2A patent/CN114388772B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010287496A (en) * | 2009-06-12 | 2010-12-24 | Mitsubishi Chemicals Corp | Negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using it |
| CN101800315A (en) * | 2010-04-09 | 2010-08-11 | 曲阜毅威能源股份有限公司 | Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof |
| CN103000881A (en) * | 2012-12-18 | 2013-03-27 | 江苏菲思特新能源有限公司 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
| US20150364757A1 (en) * | 2013-02-06 | 2015-12-17 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Mixed Oxide of Titanium and Niobium Comprising a Trivalent Metal |
| KR20150131800A (en) * | 2014-05-16 | 2015-11-25 | 부산대학교 산학협력단 | Active material for anode, method of fabricating the same and battery having the same |
| WO2016038716A1 (en) * | 2014-09-11 | 2016-03-17 | 株式会社東芝 | Nonaqueous electrolyte secondary battery and battery pack provided with same |
| CN105990571A (en) * | 2015-03-19 | 2016-10-05 | 株式会社东芝 | Active material, non-aqueous electrolyte battery, battery pack and battery module |
| JP6030708B1 (en) * | 2015-05-26 | 2016-11-24 | 太平洋セメント株式会社 | Method for producing titanium niobium oxide negative electrode active material |
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
| CN111137919A (en) * | 2018-11-06 | 2020-05-12 | 财团法人工业技术研究院 | Doped titanium niobate and battery |
| CN109616628A (en) * | 2018-11-26 | 2019-04-12 | 天津普兰能源科技有限公司 | A kind of titanium niobium zirconium composite oxide electrode material, preparation method and application |
| CN111354923A (en) * | 2018-12-24 | 2020-06-30 | 北方奥钛纳米技术有限公司 | Negative electrode material and preparation method thereof, negative plate and lithium ion battery |
| CN110380054A (en) * | 2019-08-02 | 2019-10-25 | 北方奥钛纳米技术有限公司 | A kind of titanium niobium oxide electrode material and preparation method thereof, lithium ion button shape cell |
| CN111170364A (en) * | 2019-12-30 | 2020-05-19 | 北方奥钛纳米技术有限公司 | Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery |
| CN111874947A (en) * | 2020-07-09 | 2020-11-03 | 江苏理工学院 | Tin-carbon co-doped titanium niobate material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 娄帅锋;程新群;马玉林;杜春雨;高云智;尹鸽平;: "锂离子电池铌基氧化物负极材料", 化学进展, no. 1 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083792A (en) * | 2022-06-28 | 2022-09-20 | 上海瑞浦青创新能源有限公司 | Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof |
| CN115083792B (en) * | 2022-06-28 | 2024-02-09 | 上海瑞浦青创新能源有限公司 | Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof |
| CN115744986A (en) * | 2022-11-30 | 2023-03-07 | 哈尔滨理工大学 | Preparation of titanium niobium oxide lithium ion battery cathode material based on high oxidation state ion doping |
| CN116040686A (en) * | 2023-02-14 | 2023-05-02 | 上海理工大学 | Preparation method of ferrotitanium niobium oxide electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114388772B (en) | 2024-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3021386B1 (en) | Layered oxide material containing copper, and preparation method and use thereof | |
| CN114388772B (en) | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery | |
| CN102760876B (en) | Niobate and niobate composite material and application of niobate composite material to secondary lithium battery | |
| CN107732205B (en) | Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material | |
| CN103456936A (en) | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance | |
| CN105161688B (en) | A kind of phosphoric acid ferrisodium vanadium phosphate sodium composite of carbon coating and preparation method thereof | |
| CN105845974A (en) | Preparation method for positive electrode material NaFePO4/C of sodium ion battery | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| WO2016176928A1 (en) | Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN113562714A (en) | High-compaction-density lithium iron phosphate and preparation method thereof | |
| CN114744287A (en) | Preparation method and application of sulfide solid electrolyte | |
| Zhu et al. | A novel electrochemical supercapacitor based on Li4Ti5O12 and LiNi1/3Co1/3Mn1/3O2 | |
| CN110611091A (en) | Method for improving electrochemical performance of lithium-rich manganese-based positive electrode material | |
| CN104425810A (en) | Modified lithium nickel manganese oxygen material, preparation method of modified lithium nickel manganese oxygen material, and lithium ion battery | |
| CN105810901A (en) | Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material | |
| CN106159216B (en) | Lithium-rich oxide material and preparation method and application thereof | |
| CN110289399A (en) | Negative electrode material and preparation method thereof, lithium ion battery | |
| CN110336026A (en) | The preparation method and water system sodium-ion battery of water system sodium-ion battery positive material | |
| CN104779393A (en) | Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction | |
| CN112768664A (en) | Preparation method of ruthenium-doped lithium iron phosphate composite positive electrode material | |
| CN116826008A (en) | 4d transition metal doped modified vanadium manganese sodium phosphate positive electrode material and preparation method thereof | |
| CN114804210A (en) | Layered manganese oxide and preparation method and application thereof | |
| CN114864894A (en) | High-pressure-resistant coating-layer-modified lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN112038595A (en) | Preparation method and application of strontium-doped lithium titanate composite electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |