CN106299267A - 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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- CN106299267A CN106299267A CN201510666912.7A CN201510666912A CN106299267A CN 106299267 A CN106299267 A CN 106299267A CN 201510666912 A CN201510666912 A CN 201510666912A CN 106299267 A CN106299267 A CN 106299267A
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- carbon source
- cathode material
- titanium phosphate
- source
- titanium
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 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 42
- 239000010406 cathode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 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
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 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
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- 239000001116 FEMA 4028 Substances 0.000 claims description 5
- 229920002774 Maltodextrin Polymers 0.000 claims description 5
- 239000005913 Maltodextrin Substances 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 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 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 5
- 229960004853 betadex Drugs 0.000 claims description 5
- 229940035034 maltodextrin Drugs 0.000 claims description 5
- 239000005720 sucrose Substances 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
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000006229 carbon black 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
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 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 3
- 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
- 239000008103 glucose Substances 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
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 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
- 150000001336 alkenes Chemical class 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000005253 cladding 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
- 239000008187 granular material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000001694 spray drying Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 235000001727 glucose Nutrition 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 150000002304 glucoses Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 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
- 239000002228 NASICON Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000002242 deionisation method 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003292 glue 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene pyrrole Pyrrolidone Polymers 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
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to green energy resource field of material technology, the preparation method of a kind of titanium phosphate lithium titanate cathode material for the lithium ion battery with aqueous solution as electrolyte.The present invention, by adding the carbon source that glass transition temperature is higher in the slurry, can thoroughly solve the wall sticking phenomenon caused in spray-drying process owing to organic carbon source adds.Carbon source is divided into two batches add in materials, is formed and just add the secondary carbon source of the second batch and make secondary carbon source and first presoma mixed at high speed after precursor, compounded carbons with the use of can act to obtain very well carbon covered effect on titanium phosphate lithium surface.Cladding through secondary carbon source can increase LiTi2(PO4)3Electric conductivity between granule, makes LiTi2(PO4)3Electrical conductivity be significantly improved, carbon cladding LiTi2(PO4)3There is in aqueous electrolyte good cyclical stability.The present invention has that production process is continuous, product property is uniform, stay-in-grade feature, and simple for process, production suitable for industrialized.
Description
Technical field
The present invention relates to green energy resource field of material technology, particularly relate to a kind of for aqueous solution as electricity
Solve the preparation method of the titanium phosphate lithium titanate cathode material of the lithium ion battery of liquid.
Background technology
The negative material of lithium ion battery uses various embedding lithium material with carbon element mostly at present.But the electricity of carbon electrode
Position and the current potential of lithium metal very close to, when the battery is overcharged, carbon electrodes easy precipitating metal lithium, meeting
Form dendrite and cause short circuit；Thermal runaway etc. is easily caused when temperature is too high.Meanwhile, lithium ion is repeatedly
Insert and during deintercalation, material with carbon element structure can be made to be destroyed, thus cause the decay of capacity.Therefore,
Searching can embed lithium, cheap and easy to get, safe and reliable and Fabrication of High Specific Capacitance under the current potential more positive than Carbon anode current potential
The new negative material of amount is necessary.
For negative material, there is the LiTi of NASICON structure2(PO4)3Lithium ion battery negative material
Material has high ionic conductivity, and theoretical discharge specific capacity is 138.3mAh/g, and intercalation potential is left at 2.5V
The right side, and charge and discharge process has smooth electrochemical reaction platform, is provided that stable running voltage.
It is-0.5V to standard hydrogen electrode, just (1.5V in the range of the electrochemical stability window of water under neutral environment
-0.5V), comply fully with the negative electrode active material requirement of aquo-lithium ion battery.
There are some researches show, by LiTi2(PO4)3With LiMn2O4Prepare aquo-lithium ion battery, battery defeated
Going out voltage is 1.5V, and higher than ni-mh, nickel-cadmium cell (1.2V), electric discharge specific energy density reaches 60Wh/kg,
Substantially exceed lead-acid battery.
But LiTi2(PO4)3As during negative material due to its low conductivity, cause material discharge and recharge
Polarization in journey is relatively big, and the chemical property of material is poor.Synthesis LiTi2(PO4)3Time need carry out repeatedly heat
Processing and grind, complex process, cost is the highest.It is thus desirable to it is simple to explore a set of technique, cost is relatively
Low, can guarantee that simultaneously and obtain high-purity LiTi2(PO4)3Preparation method.
Summary of the invention
The present invention is directed to existing LiTi2(PO4)3Under negative material conductivity, chemical property difference and life
Produce the problem that cost is high, it is provided that a kind of good conductivity, excellent electrochemical performance and applicable industrialized production
The preparation method of titanium phosphate lithium titanate cathode material.
For achieving the above object, the present invention is by the following technical solutions.
The preparation method of a kind of titanium phosphate lithium titanate cathode material, comprises the following steps:
S1 disperses: lithium source, titanium source, phosphorus source, a carbon source and dispersant is uniform, and
The granularity controlling 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, obtains dispersed mixture；The most again dispersed mixture is placed in sand mill, sand milling
1-6h is 500-800nm to the granularity of material, obtains slurry.
The solid content of described slurry is 10-50%；In described slurry, the mol ratio of lithium, titanium and phosphorus
For 1-1.05:2:3.
Described lithium source is at least one in lithium carbonate, lithium dihydrogen phosphate and Lithium hydrate；Described titanium
Source is titanium dioxide and/or titanium phosphate；Phosphorus source is ammonium dihydrogen phosphate, phosphoric acid and biphosphate
At least one in lithium；A described carbon source be maltodextrin, betacyclodextrin, phenolic resin,
At least one in polyvinylpyrrolidone, Polyethylene Glycol and carbon black；Described dispersant is deionization
Water.
S2 is spray-dried: slurry is placed in drying-granulating in spray dryer, obtains just presoma.
The inlet temperature of described spray dryer is 200-400 DEG C, and outlet temperature is 90-150 DEG C；
Bis-mixing of S3: first presoma is placed in mixer with secondary carbon source and mixes 2-4h,
Mixing presoma.
A described carbon source forms carbon source with secondary carbon source, and the quality of described carbon source is titanium phosphate lithium reason
The 1-10% of opinion growing amount；A described carbon source is 0.1-10 with the mass ratio of secondary carbon source.
Described secondary carbon source is at least one in glucose, sucrose, succinic acid and stearic acid.
S4 sinters: is placed in by mixing presoma in having the kiln of protective atmosphere and is sintered,
Making material be cooled to room temperature after terminating, comminuting matter obtains titanium phosphate lithium titanate cathode material.
Preferably, during sintering, heat up with the speed of 2-10 DEG C/min, burn at 800-1000 DEG C
Knot 8-20h, then naturally cools to room temperature.
Preferably, described protective atmosphere is nitrogen or argon.
Compared with prior art, the invention has the beneficial effects as follows:
(1) present invention is by adding the carbon source that glass transition temperature is higher in the slurry, permissible
Thoroughly solve the wall sticking phenomenon caused in spray-drying process owing to organic carbon source adds.
(2) present invention adds in material by carbon source is divided into two batches, adds after forming first precursor again
Enter the secondary carbon source of the second batch and make secondary carbon source and first presoma mixed at high speed, the cooperation of compounded carbons
Use and can act to obtain very well carbon covered effect on titanium phosphate lithium surface.Cladding through secondary carbon source can
Increase LiTi2(PO4)3Electric conductivity between granule, makes LiTi2(PO4)3Electrical conductivity obtained significantly carrying
High；Additionally, the carbon-coating that titanium phosphate lithium titanate cathode material is coated with due to it, lithium ion not only can be made to pass through, and
And can also effectively stop the side reaction caused because of water and electrode material contacts.Therefore, carbon is coated with
LiTi2(PO4)3There is in aqueous electrolyte good cyclical stability.
(3) preparation method of the titanium phosphate lithium titanate cathode material of the present invention have production process continuously, product
Uniform properties, stay-in-grade feature, and simple for process, production suitable for industrialized.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the titanium phosphate lithium titanate cathode material of embodiment 1 preparation；
Fig. 2 is the charging and discharging curve figure of the titanium phosphate lithium titanate cathode material of embodiment 1 preparation；
Fig. 3 is the charging and discharging curve figure of the titanium phosphate lithium titanate cathode material of embodiment 2 preparation.
Detailed description of the invention
In order to understand the technology contents of the present invention more fully, below in conjunction with specific embodiment to the present invention's
Technical scheme is described further and illustrates.
Embodiment 1
By lithium dihydrogen phosphate 24.6 kilograms (236.7mol), ammonium dihydrogen phosphate 51.5 kilograms (445mol),
Titanium dioxide 36.8 kilograms (453.8mol), betacyclodextrin 7.12 kilograms are placed in ball mill, then add
Entering deionized water 180 kilograms and carry out ball milling, Ball-milling Time is 4 hours, makes dispersed mixture (admittedly contain
Amount is 40%)；With membrane pump dispersed mixture squeezed into the most again a mixing bowl of sand mill is carried out ultra-fine
Mill, high speed sand milling 4h, make the Task-size Controlling of material between 500-800nm, prepare slurry.(according to
The consumption of lithium source, titanium source and phosphorus source calculates, and the theoretical growing amount of titanium phosphate lithium is 227.25mol,
88.14Kg。)
Being placed in spray dryer by gained slurry and carry out mist projection granulating, holding inlet temperature is
200-250 DEG C, outlet temperature is 100 DEG C, obtains presoma at the beginning of 108 kilograms.Again by before at the beginning of 108 kilograms
Drive in body is placed in VCH type high-speed mixer together with 10 kilograms of glucoses and carry out mix homogeneously, during mixing
Between be 2.5h, obtain mixing presoma.
Then, then by mixing presoma it is placed in the kiln of nitrogen atmosphere sintering, with 2-10 DEG C/min
Programming rate heat up, at 800 DEG C sinter 12h, then make material naturally cool to room temperature.Finally
Pulverize gained material after sintering, obtain titanium phosphate lithium titanate cathode material.
The XRD figure of titanium phosphate lithium titanate cathode material prepared by the present embodiment sees Fig. 1.
Meanwhile, the titanium phosphate lithium titanate cathode material preparing the present embodiment carries out charge-discharge test, and half-cell is surveyed
Strip part is as follows: the test of battery is carried out under room temperature (25 DEG C), with metal lithium sheet as negative pole, and positive pole
Sheet by the titanium phosphate lithium material of 80% (mass ratio), the super P (super conductive black) of 10%, 10% glue
Connect agent (Kynoar, PVDF), with NMP (N-2 methyl pyrrolidone) as solvent with dispersant,
Making slurry, the solid content of slurry is 45%, and then slurry is coated on 20 microns of thick aluminium foils system
Become thin film, then thin film is washed into after 120 DEG C of vacuum dryings 10mm thin slice makes.Electrolyte is 1mol/l
LiPF6/(EC+DME).Barrier film uses Celgard 2400 film (barrier film bought from market).Battery
Make in the glove box being filled with high-purity argon gas.0.2C charging and discharging curve is as shown in Figure 2.
In titanium phosphate lithium titanate cathode material prepared by this example, carbon content is 5.29%, half-cell capacity 0.2C
It is 123mAh/g for 127.8mAh/g, 1C.
Embodiment 2
By Lithium hydrate 9.90 kilograms (233.7mol), the phosphoric acid that mass percentage concentration is 85% of phosphoric acid
Liquid 8.72 kilograms (75.6mol, first with 20 kilograms of deionized water dilutions before mixing), ammonium dihydrogen phosphate
70.04 kilograms (605.12mol), titanium dioxide 36.8 kilograms (453.8mol), maltodextrin 8 kilograms
Being placed in ball mill, be subsequently adding deionized water 175 kilograms and carry out ball milling, Ball-milling Time is 4 hours,
Make dispersed mixture (solid content is 40%).With membrane pump, dispersed mixture is squeezed into sand milling the most again
The sand milling a mixing bowl of machine carries out Ultrafine Grinding, at a high speed mill 4h, make the granularity of material 500-800nm it
Between, prepare slurry.
Being placed in spray dryer by gained slurry and carry out mist projection granulating, holding inlet temperature is
200-250 DEG C, outlet temperature is 100 DEG C, obtains presoma at the beginning of 108 kilograms.Again by before at the beginning of 108 kilograms
Drive in body is placed in VCH type high-speed mixer together with 10 kilograms of glucoses and carry out mix homogeneously, during mixing
Between be 2.5h, obtain mix presoma.
Then, mixing presoma is placed in the kiln of nitrogen atmosphere sintering, with the liter of 2-10 DEG C/min
Temperature speed heats up, and sinters 12h, then make material naturally cool to room temperature at 800 DEG C.Finally pulverize
Gained material after sintering, obtains titanium phosphate lithium titanate cathode material.
The titanium phosphate lithium titanate cathode material preparing the present embodiment carries out charge-discharge test, half-cell test condition
Identical with the half-cell test condition in embodiment 1.0.2C charging and discharging curve is as shown in Figure 3.
In titanium phosphate lithium titanate cathode material prepared by the present embodiment, carbon content is 6.08%, half-cell capacity 0.2C
It is 114.6mAh/g for 118mAh/g, 1C.
Embodiment 3
By lithium dihydrogen phosphate 24.8 kilograms (238.3mol), ammonium dihydrogen phosphate 51.2 kilograms (442.5mol),
Titanium dioxide 36.8 kilograms of (453.8mol), betacyclodextrin 3Kg, phenolic resin 1Kg and carbon black
0.587Kg is placed in ball mill, is subsequently adding deionized water 121.5 kilograms and carries out ball milling, Ball-milling Time
It is 10 hours, makes dispersed mixture (solid content is 50%)；The most again with membrane pump by dispersion mixing
Thing is squeezed in a mixing bowl of sand mill and is carried out Ultrafine Grinding, high speed sand milling 1h, makes the Task-size Controlling of material exist
Between 500-800nm, prepare slurry.(calculate according to the consumption of lithium source, titanium source and phosphorus source, titanium phosphate
The theoretical growing amount of lithium is 226.9mol, 88.0Kg.)
Being placed in spray dryer by gained slurry and carry out mist projection granulating, holding inlet temperature is
370-400 DEG C, outlet temperature is 150 DEG C, obtains presoma at the beginning of 108 kilograms.Again by before at the beginning of 108 kilograms
Drive in body is placed in VCH type high-speed mixer together with 2.587 kilograms of glucoses, 2Kg sucrose and mix
Closing uniformly, incorporation time is 4h, obtains mixing presoma.
Then, then by mixing presoma it is placed in the kiln of argon gas atmosphere sintering, with 2-10 DEG C/min
Programming rate heat up, at 100 DEG C sinter 8h, then make material naturally cool to room temperature.Final powder
Gained material after broken sintering, obtains titanium phosphate lithium titanate cathode material.
The titanium phosphate lithium titanate cathode material preparing the present embodiment carries out charge-discharge test, half-cell test condition
Identical with the half-cell test condition in embodiment 1.
In titanium phosphate lithium titanate cathode material prepared by the present embodiment, carbon content is 3.38%, half-cell capacity 0.2C
It is 110.2mAh/g for 116mAh/g, 1C.
Embodiment 4
By lithium dihydrogen phosphate 24.8 kilograms (238.3mol), ammonium dihydrogen phosphate 51.2 kilograms (442.5mol),
Titanium dioxide 36.8 kilograms of (453.8mol), maltodextrin 2Kg, Polyethylene Glycol 1.5Kg and polyethylene pyrrole
Pyrrolidone 1.087Kg is placed in ball mill, is subsequently adding deionized water 1093 kilograms and carries out ball milling, ball
Time consuming is 3 hours, makes dispersed mixture (solid content is 10%)；To divide with membrane pump the most again
Scattered mixture is squeezed in a mixing bowl of sand mill and is carried out Ultrafine Grinding, high speed sand milling 6h, makes the granularity control of material
System, between 500-800nm, prepares slurry.(calculate according to the consumption of lithium source, titanium source and phosphorus source, phosphorus
The theoretical growing amount of acid titanium lithium is 226.9mol, 88.0Kg.)
Being placed in spray dryer by gained slurry and carry out mist projection granulating, holding inlet temperature is
350-400 DEG C, outlet temperature is 90 DEG C, obtains presoma at the beginning of 108 kilograms.Again by before at the beginning of 108 kilograms
Drive body and be placed in VCH type high-speed mixer together with 3 kilograms of succinic acid, 2Kg stearic acid, 2Kg sucrose
Inside carrying out mix homogeneously, incorporation time is 2h, obtains mixing presoma.
Then, then by mixing presoma it is placed in the kiln of nitrogen atmosphere sintering, with 2-10 DEG C/min
Programming rate heat up, at 800 DEG C sinter 20h, then make material naturally cool to room temperature.Finally
Pulverize gained material after sintering, obtain titanium phosphate lithium titanate cathode material.
The titanium phosphate lithium titanate cathode material preparing the present embodiment carries out charge-discharge test, half-cell test condition
Identical with the half-cell test condition in embodiment 1.
In titanium phosphate lithium titanate cathode material prepared by the present embodiment, carbon content is 4.91%, half-cell capacity 0.2C
It is 116.2mAh/g for 121.5mAh/g, 1C.
In other embodiments, lithium source used can also is that lithium carbonate, lithium dihydrogen phosphate and hydrogen-oxygen
Change one or more in lithium；Titanium source used can also be titanium phosphate or titanium dioxide and titanium phosphate
Mixture；Phosphorus source used can also is that the one in ammonium dihydrogen phosphate, phosphoric acid and lithium dihydrogen phosphate
Or it is several；A used carbon source can also is that maltodextrin, betacyclodextrin, phenolic resin,
One or more in polyvinylpyrrolidone, Polyethylene Glycol and carbon black；Secondary carbon source used is also
Can be at least one in glucose, sucrose, succinic acid and stearic acid or several.
The above only further illustrates the technology contents of the present invention with embodiment, in order to reader more holds
Readily understood, but do not represent embodiments of the present invention and be only limitted to this, any technology done according to the present invention is prolonged
Stretch or recreate, all being protected by the present invention.
Claims (10)
1. the preparation method of a titanium phosphate lithium titanate cathode material, it is characterised in that comprise the following steps:
S1 disperses: lithium source, titanium source, phosphorus source, a carbon source and dispersant is uniform, and
The granularity controlling material is 500-800nm, obtains slurry；The solid content of described slurry is 10-50%；
In described slurry, the mol ratio of lithium, titanium and phosphorus is 1-1.05:2:3；
S2 is spray-dried: slurry is placed in drying-granulating in spray dryer, obtains just presoma；
The inlet temperature of described spray dryer is 200-400 DEG C, and outlet temperature is 90-150 DEG C；
Bis-mixing of S3: first presoma is placed in mixer with secondary carbon source and mixes 2-4h,
Mixing presoma；
A described carbon source forms carbon source with secondary carbon source, and the quality of described carbon source is titanium phosphate lithium reason
The 1-10% of opinion growing amount；A described carbon source is 0.1-10 with the mass ratio of secondary carbon source；
S4 sinters: is placed in by mixing presoma in having the kiln of protective atmosphere and is sintered,
Making material be cooled to room temperature after terminating, comminuting matter obtains titanium phosphate lithium titanate cathode material.
The preparation method of a kind of titanium phosphate lithium titanate cathode material, its feature exists
In, in step S1, lithium source, titanium source, phosphorus source, a carbon source and dispersant are placed in ball mill
In, ball milling 3-10h, obtain dispersed mixture；The most again dispersed mixture is placed in sand mill,
Sand milling 1-6h is 500-800nm to the granularity of material, obtains slurry.
The preparation method of a kind of titanium phosphate lithium titanate cathode material, its feature exists
In, in step S4, during sintering, heat up, at 800-1000 DEG C with the speed of 2-10 DEG C/min
Lower sintering 8-20h, then naturally cools to room temperature.
The preparation method of a kind of titanium phosphate lithium titanate cathode material, its feature exists
In, in step S4, described protective atmosphere is nitrogen or argon.
5. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It is characterized in that, described lithium source is at least one in lithium carbonate, lithium dihydrogen phosphate and Lithium hydrate.
6. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It is characterized in that, described titanium source is titanium dioxide and/or titanium phosphate.
7. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It is characterized in that, phosphorus source is at least one in ammonium dihydrogen phosphate, phosphoric acid and lithium dihydrogen phosphate.
8. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It is characterized in that, a described carbon source is maltodextrin, betacyclodextrin, phenolic resin, poly-second
At least one in alkene pyrrolidone, Polyethylene Glycol and carbon black.
9. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It is characterized in that, described secondary carbon source be in glucose, sucrose, succinic acid and stearic acid at least
A kind of.
10. according to the preparation method of titanium phosphate lithium titanate cathode material a kind of described in any one of claim 1-4,
It 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 |
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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 |
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| CN111477863A (en) * | 2020-05-15 | 2020-07-31 | 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 |
| 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 |
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| 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 |
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| 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 |
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Effective date of registration: 20190522 Address after: 338000 Saiwei Avenue, Xinyu High-tech Development Zone, Jiangxi Province Patentee after: Jiangxi Jin Li Polytron Technologies Inc Address before: 518000 Six 602 Champs Elysees Garden, Futian District, Shenzhen City, Guangdong Province Patentee before: Xiao Shuilong |