CN106299267B - A kind of preparation method of titanium phosphate lithium titanate cathode material - Google Patents
A kind of preparation method of titanium phosphate lithium titanate cathode material Download PDFInfo
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- CN106299267B CN106299267B CN201510666912.7A CN201510666912A CN106299267B CN 106299267 B CN106299267 B CN 106299267B CN 201510666912 A CN201510666912 A CN 201510666912A CN 106299267 B CN106299267 B CN 106299267B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000010406 cathode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 229920002774 Maltodextrin Polymers 0.000 claims description 5
- 239000005913 Maltodextrin Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229940035034 maltodextrin Drugs 0.000 claims description 5
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 4
- 229960004853 betadex Drugs 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000001694 spray drying Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It is specially a kind of for using aqueous solution as the preparation method of the titanium phosphate lithium titanate cathode material of the lithium ion battery of electrolyte the present invention relates to green energy resource field of material technology.The present invention can thoroughly solve wall sticking phenomenon caused by being added due to organic carbon source in spray-drying process by the way that the higher carbon source of glass transition temperature is added in the slurry.Carbon source is divided into two batch admixture material, is formed and is just added the secondary carbon source of second lot after precursor and make secondary carbon source and first presoma mixed at high speed, being used cooperatively for compounded carbons can act to obtain very well carbon coating effect on titanium phosphate lithium surface.Cladding by secondary carbon source can increase LiTi2(PO4)3Electric conductivity between particle, makes LiTi2(PO4)3Conductivity be significantly improved, carbon-coated LiTi2(PO4)3There is good cyclical stability in aqueous electrolyte.The present invention has the characteristics that production process is continuous, product property is uniform, stable quality, and simple for process, suitable for industrialized production.
Description
Technical field
The present invention relates to green energy resource field of material technology more particularly to it is a kind of for using aqueous solution as the lithium of electrolyte from
The preparation method of the titanium phosphate lithium titanate cathode material of sub- battery.
Background technology
The negative material of lithium ion battery mostly uses greatly various embedding lithium carbon materials at present.But the current potential of carbon electrode and metal
The current potential of lithium is very close to when the battery is overcharged, the easy precipitating metal lithium of carbon electrodes can form dendrite and cause short circuit；Temperature
It spends Gao Shiyi and causes thermal runaway etc..Meanwhile lithium ion is being repeatedly inserted into and during deintercalation, can make carbon material structure by
It destroys, so as to cause the decaying of capacity.Therefore, lithium can be embedded under the current potential slightly more positive than Carbon anode current potential by finding, cheap and easy to get,
Safe and reliable and height ratio capacity new negative material is necessary.
For negative material, the LiTi with NASICON structures2(PO4)3Lithium ion battery negative material has height
Ionic conductivity, theoretical discharge specific capacity be 138.3mAh/g, intercalation potential is in 2.5V or so, and charge and discharge process has
Flat electrochemical reaction platform can provide stable operating voltage.It is -0.5V to standard hydrogen electrode, just in neutral environment
Within the scope of the electrochemical stability window of lower water (1.5V--0.5V), the negative electrode active material of aquo-lithium ion battery is complied fully with
It is required that.
Some researches show that by LiTi2(PO4)3With LiMn2O4Aquo-lithium ion battery is prepared, the output voltage of battery is
1.5V, is higher than ni-mh, nickel-cadmium cell (1.2V), and electric discharge specific energy density reaches 60Wh/kg, substantially exceeded lead-acid battery.
But LiTi2(PO4)3Due to its low conductivity when as negative material, lead to the pole in material charge and discharge process
Change larger, the chemical property of material is poor.Synthesize LiTi2(PO4)3When need carry out repeatedly be heat-treated and grind, complex process,
Cost is quite high.Therefore need to explore a set of simple for process, cost is relatively low, while can guarantee to obtain high-purity LiTi2(PO4)3's
Preparation method.
Invention content
The present invention is directed to existing LiTi2(PO4)3Under negative material conductivity, chemical property difference and production cost are high
The problem of, the system of a kind of good conductivity, excellent electrochemical performance and the titanium phosphate lithium titanate cathode material of suitable industrialized production is provided
Preparation Method.
To achieve the above object, the present invention uses following technical scheme.
A kind of preparation method of titanium phosphate lithium titanate cathode material, includes the following steps：
S1 disperses：Lithium source, titanium source, phosphorus source, a carbon source and dispersant is uniform, and the granularity of control material is
500-800nm obtains slurry.
Preferably, lithium source, titanium source, phosphorus source, a carbon source and dispersant are placed in ball mill, ball milling 3-10h must disperse
Mixture；Then dispersed mixture is placed in sand mill again, the granularity that 1-6h is sanded to material is 500-800nm, is starched
Material.
The solid content of the slurry is 10-50%；In the slurry, the molar ratio of lithium, titanium and phosphorus is 1-1.05:2:3.
The lithium source is at least one of lithium carbonate, lithium dihydrogen phosphate and lithium hydroxide；The titanium source is titanium dioxide
And/or titanium phosphate；Phosphorus source is at least one of ammonium dihydrogen phosphate, phosphoric acid and lithium dihydrogen phosphate；Carbon source is
At least one of maltodextrin, betadex, phenolic resin, polyvinylpyrrolidone, polyethylene glycol and carbon black；Described point
Powder is deionized water.
S2 is spray-dried：Slurry is placed in drying-granulating in spray dryer, obtains just presoma.
The inlet temperature of the spray dryer is 200-400 DEG C, and outlet temperature is 90-150 DEG C；
Bis- mixing of S3：First presoma is placed in secondary carbon source in mixing machine and mixes 2-4h, obtains mixing presoma.
Carbon source forms carbon source with secondary carbon source, and the quality of the carbon source is the 1- of titanium phosphate lithium theory production quantity
10%；The mass ratio of carbon source and secondary carbon source is 0.1-10.
The secondary carbon source is at least one of glucose, sucrose, succinic acid and stearic acid.
S4 is sintered：Mixing presoma is placed in the kiln with protective atmosphere and is sintered, object is made after sintering
Material is cooled to room temperature, and comminuting matter obtains titanium phosphate lithium titanate cathode material.
Preferably, it when sintering, is heated up with the speed of 2-10 DEG C/min, 8-20h is sintered at 800-1000 DEG C, it is then natural
It is cooled to room temperature.
Preferably, the protective atmosphere is nitrogen or argon gas.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention can be solved thoroughly by the way that the higher carbon source of glass transition temperature is added in the slurry
Wall sticking phenomenon caused by being added due to organic carbon source in spray-drying process.
(2) present invention adds second lot by the way that carbon source to be divided into two batch admixture material after forming just precursor
Secondary carbon source and make secondary carbon source and first presoma mixed at high speed, compounded carbons with the use of can be on titanium phosphate lithium surface
Act to obtain very well carbon coating effect.Cladding by secondary carbon source can increase LiTi2(PO4)3Electric conductivity between particle, makes
LiTi2(PO4)3Conductivity be significantly improved；In addition, carbon-coating of the titanium phosphate lithium titanate cathode material due to its cladding, not only
Lithium ion can be made to pass through, but also can effectively prevent the side reaction because of caused by water and electrode material contacts.Therefore, carbon-coated
LiTi2(PO4)3There is good cyclical stability in aqueous electrolyte.
(3) preparation method of titanium phosphate lithium titanate cathode material of the invention is continuous with production process, product property is uniform, matter
Stable feature is measured, and simple for process, suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD diagram of titanium phosphate lithium titanate cathode material prepared by embodiment 1；
Fig. 2 is the charging and discharging curve figure of titanium phosphate lithium titanate cathode material prepared by embodiment 1；
Fig. 3 is the charging and discharging curve figure of titanium phosphate lithium titanate cathode material prepared by embodiment 2.
Specific implementation mode
In order to more fully understand the technology contents of the present invention, with reference to specific embodiment to technical scheme of the present invention
It is described further and illustrates.
Embodiment 1
By lithium dihydrogen phosphate 24.6 kilograms (236.7mol), ammonium dihydrogen phosphate 51.5 kilograms of (445mol), titanium dioxide
36.8 kilograms (453.8mol), 7.12 kilograms of betadex are placed in ball mill, and 180 kilograms of progress of deionized water are then added
Ball milling, Ball-milling Time are 4 hours, and dispersed mixture (solid content 40%) is made；Then again with diaphragm pump by dispersed mixture
It squeezes into and carries out Ultrafine Grinding in a mixing bowl of sand mill, 4h is sanded in high speed, so that the granularity of material is controlled between 500-800nm, system
Obtain slurry.(it being calculated according to the dosage of lithium source, titanium source and phosphorus source, the theoretical production quantity of titanium phosphate lithium is 227.25mol,
88.14Kg。)
Gained slurry is placed in spray dryer and carries out mist projection granulating, it is 200-250 DEG C to keep inlet temperature, outlet temperature
Degree is 100 DEG C, presoma at the beginning of obtaining 108 kilograms.Presoma at the beginning of 108 kilograms is placed in VCH types together with 10 kilograms of glucose again
It is uniformly mixed in high-speed mixer, incorporation time 2.5h obtains mixing presoma.
Then it, then by mixing presoma is placed in the kiln of nitrogen atmosphere into sintering, with the heating rate of 2-10 DEG C/min
Heating, 12h is sintered at 800 DEG C, then makes material cooled to room temperature.Resulting material after being sintered finally is crushed, phosphorus is obtained
Sour titanium lithium titanate cathode material.
The XRD diagram of titanium phosphate lithium titanate cathode material manufactured in the present embodiment is referring to Fig. 1.
Meanwhile charge-discharge test is carried out to titanium phosphate lithium titanate cathode material manufactured in the present embodiment, half-cell test condition is such as
Under：The test of battery carries out under room temperature (25 DEG C), using metal lithium sheet as cathode, positive plate by 80% (mass ratio) titanium phosphate
Lithium material, 10% super P (super conductive black), 10% bonding agent (Kynoar, PVDF), with NMP (N-2 methyl
Pyrrolidones) it is solvent and dispersant, slurry is made, the solid content of slurry is 45%, and slurry is then coated in 20 microns of thickness
Aluminium foil on film is made, then film is made through 120 DEG C of vacuum drying backlash at 10mm thin slices.Electrolyte is 1mol/l's
LiPF6/(EC+DME).Diaphragm is using 2400 films of Celgard (diaphragm bought from market).Battery is filled with high-purity argon gas
It is made in glove box.0.2C charging and discharging curves are as shown in Figure 2.
In titanium phosphate lithium titanate cathode material prepared by this example, carbon content 5.29%, half-cell capacity 0.2C is
127.8mAh/g, 1C 123mAh/g.
Embodiment 2
The phosphoric acid liquid 8.72 thousand for being 85% by the mass percentage concentration of lithium hydroxide 9.90 kilograms (233.7mol), phosphoric acid
Gram (75.6mol, first with the dilutions of 20 kilograms of deionized waters before mixing), ammonium dihydrogen phosphate 70.04 kilograms of (605.12mol), dioxies
Change titanium 36.8 kilograms (453.8mol), 8 kilograms of maltodextrin is placed in ball mill, then 175 kilograms of progress of addition deionized water
Ball milling, Ball-milling Time are 4 hours, and dispersed mixture (solid content 40%) is made.Then again with diaphragm pump by dispersed mixture
It squeezes into the sand milling a mixing bowl of sand mill and carries out Ultrafine Grinding, high speed grinds 4h, makes the granularity of material between 500-800nm, is made
Slurry.
Gained slurry is placed in spray dryer and carries out mist projection granulating, it is 200-250 DEG C to keep inlet temperature, outlet temperature
Degree is 100 DEG C, presoma at the beginning of obtaining 108 kilograms.Presoma at the beginning of 108 kilograms is placed in VCH types together with 10 kilograms of glucose again
It is uniformly mixed in high-speed mixer, incorporation time 2.5h, obtains mixing presoma.
Then, mixing presoma is placed in the kiln of nitrogen atmosphere into sintering, with the heating rate liter of 2-10 DEG C/min
Temperature, is sintered 12h at 800 DEG C, then makes material cooled to room temperature.Resulting material after being sintered finally is crushed, phosphoric acid is obtained
Titanium lithium titanate cathode material.
Charge-discharge test, half-cell test condition and embodiment are carried out to titanium phosphate lithium titanate cathode material manufactured in the present embodiment
Half-cell test condition in 1 is identical.0.2C charging and discharging curves are as shown in Figure 3.
In titanium phosphate lithium titanate cathode material manufactured in the present embodiment, carbon content 6.08%, half-cell capacity 0.2C is
118mAh/g, 1C 114.6mAh/g.
Embodiment 3
By lithium dihydrogen phosphate 24.8 kilograms (238.3mol), ammonium dihydrogen phosphate 51.2 kilograms of (442.5mol), titanium dioxide
36.8 kilograms (453.8mol), betadex 3Kg, phenolic resin 1Kg and carbon black 0.587Kg are placed in ball mill, are then added
Enter 121.5 kilograms of progress ball millings of deionized water, Ball-milling Time is 10 hours, and dispersed mixture (solid content 50%) is made；So
Dispersed mixture is squeezed into diaphragm pump again afterwards in a mixing bowl of sand mill and carry out Ultrafine Grinding, 1h is sanded in high speed, makes the grain of material
Slurry is made between 500-800nm in degree control.It (is calculated according to the dosage of lithium source, titanium source and phosphorus source, the theory of titanium phosphate lithium
Production quantity is 226.9mol, 88.0Kg.)
Gained slurry is placed in spray dryer and carries out mist projection granulating, it is 370-400 DEG C to keep inlet temperature, outlet temperature
Degree is 150 DEG C, presoma at the beginning of obtaining 108 kilograms.Again by presoma at the beginning of 108 kilograms and 2.587 kilograms of glucose, 2Kg sucrose one
It rises to be placed in VCH type high-speed mixers and be uniformly mixed, incorporation time 4h obtains mixing presoma.
Then it, then by mixing presoma is placed in the kiln of argon gas atmosphere into sintering, with the heating rate of 2-10 DEG C/min
Heating, 8h is sintered at 100 DEG C, then makes material cooled to room temperature.Resulting material after being sintered finally is crushed, phosphoric acid is obtained
Titanium lithium titanate cathode material.
Charge-discharge test, half-cell test condition and embodiment are carried out to titanium phosphate lithium titanate cathode material manufactured in the present embodiment
Half-cell test condition in 1 is identical.
In titanium phosphate lithium titanate cathode material manufactured in the present embodiment, carbon content 3.38%, half-cell capacity 0.2C is
116mAh/g, 1C 110.2mAh/g.
Embodiment 4
By lithium dihydrogen phosphate 24.8 kilograms (238.3mol), ammonium dihydrogen phosphate 51.2 kilograms of (442.5mol), titanium dioxide
36.8 kilograms (453.8mol), maltodextrin 2Kg, polyethylene glycol 1.5Kg and polyvinylpyrrolidone 1.087Kg are placed in ball mill
In, 1093 kilograms of deionized water progress ball millings are then added, Ball-milling Time is 3 hours, and dispersed mixture is made, and (solid content is
10%)；Then dispersed mixture is squeezed into diaphragm pump again in a mixing bowl of sand mill and carries out Ultrafine Grinding, 6h is sanded in high speed, makes
The granularity of material controls between 500-800nm, and slurry is made.It (is calculated according to the dosage of lithium source, titanium source and phosphorus source, titanium phosphate
The theoretical production quantity of lithium is 226.9mol, 88.0Kg.)
Gained slurry is placed in spray dryer and carries out mist projection granulating, it is 350-400 DEG C to keep inlet temperature, outlet temperature
Degree is 90 DEG C, presoma at the beginning of obtaining 108 kilograms.Again by presoma at the beginning of 108 kilograms and 3 kilograms of succinic acid, 2Kg stearic acid, 2Kg sugarcanes
Sugar, which is placed in together in VCH type high-speed mixers, to be uniformly mixed, and incorporation time 2h obtains mixing presoma.
Then it, then by mixing presoma is placed in the kiln of nitrogen atmosphere into sintering, with the heating rate of 2-10 DEG C/min
Heating, 20h is sintered at 800 DEG C, then makes material cooled to room temperature.Resulting material after being sintered finally is crushed, phosphorus is obtained
Sour titanium lithium titanate cathode material.
Charge-discharge test, half-cell test condition and embodiment are carried out to titanium phosphate lithium titanate cathode material manufactured in the present embodiment
Half-cell test condition in 1 is identical.
In titanium phosphate lithium titanate cathode material manufactured in the present embodiment, carbon content 4.91%, half-cell capacity 0.2C is
121.5mAh/g, 1C 116.2mAh/g.
In other embodiments, lithium source used can also be one in lithium carbonate, lithium dihydrogen phosphate and lithium hydroxide
Kind is several；Titanium source used can also be the mixture of titanium phosphate or titanium dioxide and titanium phosphate；Phosphorus source used can also be
One or more of ammonium dihydrogen phosphate, phosphoric acid and lithium dihydrogen phosphate；A carbon source used can also be maltodextrin, again he
One or more of cyclodextrin, phenolic resin, polyvinylpyrrolidone, polyethylene glycol and carbon black；Secondary carbon source used is also
Can be at least one of glucose, sucrose, succinic acid and stearic acid or several.
It is described above only with embodiment come the technology contents that further illustrate the present invention, in order to which reader is easier to understand,
But embodiments of the present invention are not represented and are only limitted to this, any technology done according to the present invention extends or recreation, is sent out by this
Bright protection.
Claims (9)
1. a kind of preparation method of titanium phosphate lithium titanate cathode material, which is characterized in that include the following steps：
S1 disperses：Lithium source, titanium source, phosphorus source, a carbon source and dispersant is uniform, and the granularity of control material is 500-
800nm obtains slurry；The solid content of the slurry is 10-50%；In the slurry, the molar ratio of lithium, titanium and phosphorus is 1-
1.05：2：3；
The wherein described primary carbon source be maltodextrin, betadex, phenolic resin, polyvinylpyrrolidone, polyethylene glycol and
At least one of carbon black；
S2 is spray-dried：Slurry is placed in drying-granulating in spray dryer, obtains just presoma；The spray dryer into
Mouth temperature is 200-400 DEG C, and outlet temperature is 90-150 DEG C；
Bis- mixing of S3：First presoma is placed in secondary carbon source in mixing machine and mixes 2-4h, obtains mixing presoma；
Carbon source forms carbon source with secondary carbon source, and the quality of the carbon source is the 1- of titanium phosphate lithium theory production quantity
10%；The mass ratio of carbon source and secondary carbon source is 0.1-10；
S4 is sintered：Mixing presoma is placed in the kiln with protective atmosphere and is sintered, makes material cold after sintering
But to room temperature, comminuting matter obtains titanium phosphate lithium titanate cathode material.
2. a kind of preparation method of titanium phosphate lithium titanate cathode material according to claim 1, which is characterized in that, will in step S1
Lithium source, titanium source, phosphorus source, a carbon source and dispersant are placed in ball mill, and ball milling 3-10h obtains dispersed mixture；Then will divide again
Scattered mixture is placed in sand mill, and the granularity that 1-6h is sanded to material is 500-800nm, obtains slurry.
3. a kind of preparation method of titanium phosphate lithium titanate cathode material according to claim 1, which is characterized in that in step S4, burn
When knot, is heated up with the speed of 2-10 DEG C/min, 8-20h is sintered at 800-1000 DEG C, then cooled to room temperature.
4. a kind of preparation method of titanium phosphate lithium titanate cathode material according to claim 1, which is characterized in that in step S4, institute
It is nitrogen or argon gas to state protective atmosphere.
5. according to a kind of any one of claim 1-4 preparation methods of titanium phosphate lithium titanate cathode material, which is characterized in that described
Lithium source is at least one of lithium carbonate, lithium dihydrogen phosphate and lithium hydroxide.
6. according to a kind of any one of claim 1-4 preparation methods of titanium phosphate lithium titanate cathode material, which is characterized in that described
Titanium source is titanium dioxide and/or titanium phosphate.
7. according to a kind of any one of claim 1-4 preparation methods of titanium phosphate lithium titanate cathode material, which is characterized in that described
Phosphorus source is at least one of ammonium dihydrogen phosphate, phosphoric acid and lithium dihydrogen phosphate.
8. according to a kind of any one of claim 1-4 preparation methods of titanium phosphate lithium titanate cathode material, which is characterized in that described
Secondary carbon source is at least one of glucose, sucrose, succinic acid and stearic acid.
9. according to a kind of any one of claim 1-4 preparation methods of titanium phosphate lithium titanate cathode material, which is characterized in that described
Dispersant is deionized water.
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| CN107658458A (en) * | 2017-10-10 | 2018-02-02 | 合肥国轩高科动力能源有限公司 | Preparation method of polypyrrole-coated lithium titanium phosphate negative electrode material |
| CN107910514A (en) * | 2017-11-06 | 2018-04-13 | 中国人民解放军63971部队 | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium |
| CN110137482B (en) * | 2019-06-17 | 2021-02-19 | 桑顿新能源科技(长沙)有限公司 | Carbon-coated negative electrode material, preparation method thereof and battery |
| CN111477863B (en) * | 2020-05-15 | 2021-09-03 | 宁波锋成纳米科技有限公司 | Graphene/lithium titanium phosphate composite material, preparation method thereof and lithium ion battery |
| CN111755694B (en) * | 2020-06-15 | 2022-04-01 | 宁波锋成先进能源材料研究院 | Titanium phosphate composite material and preparation method and application thereof |
| CN111816873A (en) * | 2020-06-23 | 2020-10-23 | 江苏理工学院 | Carbon-coated lithium manganese titanium phosphate composite material, preparation method thereof and application thereof in lithium ion battery |
| CN113086960A (en) * | 2021-03-26 | 2021-07-09 | 深圳市鹏冠新材料科技有限公司 | Preparation method of lithium titanium phosphate cathode material |
| CN113697789A (en) * | 2021-08-27 | 2021-11-26 | 江苏理工学院 | Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate |
| CN118529707A (en) * | 2024-07-22 | 2024-08-23 | 超威电源集团有限公司 | Negative electrode material, preparation method thereof, negative electrode dry electrode plate and water-based battery |
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| CN104779392A (en) * | 2015-04-14 | 2015-07-15 | 淄博蓝印化工有限公司 | Titanium phosphate lithium doped lithium titanate electrode material and manufacturing method thereof |
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| CN104779392A (en) * | 2015-04-14 | 2015-07-15 | 淄博蓝印化工有限公司 | Titanium phosphate lithium doped lithium titanate electrode material and manufacturing method thereof |
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