CN116565180A - High tap density lithium iron phosphate positive electrode material, and preparation method and application thereof - Google Patents
High tap density lithium iron phosphate positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN116565180A CN116565180A CN202310770970.9A CN202310770970A CN116565180A CN 116565180 A CN116565180 A CN 116565180A CN 202310770970 A CN202310770970 A CN 202310770970A CN 116565180 A CN116565180 A CN 116565180A
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- China
- Prior art keywords
- iron phosphate
- positive electrode
- tap density
- lithium iron
- electrode material
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 138
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000011247 coating layer Substances 0.000 claims abstract description 36
- 150000001768 cations Chemical class 0.000 claims abstract description 31
- 150000001450 anions Chemical class 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 titanium ions Chemical class 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 239000002019 doping agent Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 18
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- 239000011163 secondary particle Substances 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 238000004321 preservation Methods 0.000 claims description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000021552 granulated sugar Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 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 description 2
- 229940063013 borate ion Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a high tap density lithium iron phosphate positive electrode material, a preparation method and application thereof. The high tap density lithium iron phosphate anode material comprises a carbon coating layer, and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material; the cations include at least one of titanium ions, zinc ions, manganese ions, aluminum ions, and vanadium ions; the anions include at least one of fluoride ions and borate ions. The lithium iron phosphate positive electrode material with high tap density combines the tap density and the electrochemical performance of the lithium iron phosphate positive electrode material with high tap density by carrying out anion-cation doping and arranging a carbon coating layer.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high tap density lithium iron phosphate anode material, a preparation method and application thereof; more particularly, relates to a high tap density lithium iron phosphate positive electrode material, a preparation method thereof, a positive electrode plate and a lithium ion battery.
Background
Lithium ion batteries are considered as the most prominent representative of new energy storage devices due to their high energy density, long cycle life and environmental friendliness. Olivine lithium iron phosphate has become the first choice for power and energy storage batteries due to its high theoretical capacity and flat operating voltage, stable structure, and low cost, pollution-free characteristics. With the rapid development of new energy industry and the support of new energy industry policy, the market ratio and market demand of lithium iron phosphate are also increasing.
Along with the gradual development of new energy industry, the requirements on the endurance mileage of the power battery are higher and higher, and the continuous improvement of the energy density of the material becomes a common target of the industry. Generally, under the same process conditions, the higher the tap density of the material, the higher the energy density of the battery. The tap density of lithium iron phosphate in the industry is currently generally 0.8g/cm 3 ～1.2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The lower tap density limits the energy density of lithium iron phosphate batteries.
Therefore, the lithium iron phosphate positive electrode material with high tap density and the preparation method thereof are beneficial to improving the energy density of the battery and have important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a high tap density lithium iron phosphate positive electrode material, which aims to solve the problem that the existing lithium iron phosphate has low tap density and the energy density of a lithium iron phosphate battery is limited.
The second purpose of the invention is to provide a preparation method of the high tap density lithium iron phosphate positive electrode material, which improves the tap density and the electrochemical performance of the high tap density lithium iron phosphate positive electrode material by adopting the means of doping anions and cations and coating the carbon surface.
A third object of the present invention is to provide a positive electrode sheet.
A fourth object of the present invention is to provide a lithium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a high tap density lithium iron phosphate anode material, which comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material; the cations include at least one of titanium ions, zinc ions, manganese ions, aluminum ions, and vanadium ions; the anions include at least one of fluoride, silicate, and borate.
The lithium iron phosphate positive electrode material with high tap density provided by the invention has excellent electrochemical performance and high tap density.
The invention also provides a preparation method of the high tap density lithium iron phosphate anode material, which comprises the following steps:
mixing and grinding a lithium source, an iron source, a phosphorus source, a carbon source, a cationic dopant and an anionic dopant, and then spray-drying to obtain a precursor material;
sintering the precursor material to obtain the high tap density lithium iron phosphate anode material;
wherein the cationic dopant comprises one of tetrabutyl titanate, zinc oxide, manganese acetate tetrahydrate, aluminum oxide and ammonium metavanadate;
the anionic dopant includes at least one of lithium fluoride, silicic acid, and boric acid.
By adopting the preparation method, the ion conductivity of the positive electrode material can be improved, and the tap density of the positive electrode material can be improved, so that the prepared high tap density lithium iron phosphate positive electrode material has excellent electrochemical performance and high tap density.
The invention also provides a positive pole piece, which is mainly prepared from the high-tap-density lithium iron phosphate positive pole material prepared by the preparation method of the high-tap-density lithium iron phosphate positive pole material or the high-tap-density lithium iron phosphate positive pole material.
The positive electrode plate has excellent electrochemical performance.
The invention further provides a lithium ion battery, which comprises the positive electrode plate.
The lithium ion battery has excellent electrochemical performance, especially high energy density.
Compared with the prior art, the invention has the beneficial effects that:
(1) The lithium iron phosphate positive electrode material with high tap density provided by the invention has excellent electrochemical performance and high tap density.
(2) According to the preparation method of the high tap density lithium iron phosphate positive electrode material, provided by the invention, the tap density and the electrochemical performance of the high tap density lithium iron phosphate positive electrode material are both improved by adopting the means of doping anions and cations and coating the carbon surface.
(3) The preparation method of the lithium iron phosphate positive electrode material with high tap density provided by the invention can obtain high sphericity particles, has good fluidity, can further improve the tap density of the positive electrode material, and the tap density is more than or equal to 1.5g/cm 3 。
(4) The preparation method of the lithium iron phosphate positive electrode material with high tap density has the advantages of simplicity, easiness in implementation, short process flow, capability of realizing mass production and the like.
(5) The lithium iron phosphate positive electrode material with high tap density has good heteroelectrochemical performance and high tap density, and the positive electrode material provided by the invention comprises the lithium iron phosphate positive electrode material with high tap density, so that the positive electrode plate provided by the invention has excellent electrochemical performance.
(6) The lithium ion battery provided by the invention comprises the positive electrode plate, so that the lithium ion battery provided by the invention has excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a high tap density lithium iron phosphate positive electrode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a high tap density lithium iron phosphate positive electrode material prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the high tap density lithium iron phosphate positive electrode material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the charge and discharge at 0.1C of a battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in example 1 of the present invention;
FIG. 5 is a graph showing the charge and discharge of 1C of a battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in example 1 of the present invention;
FIG. 6 is a graph showing the charge and discharge at 0.1C of a battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in comparative example 1 of the present invention;
fig. 7 is a 1C charge-discharge graph of a battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in comparative example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the invention provides a high tap density lithium iron phosphate positive electrode material, which comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material.
Wherein the cations include at least one of titanium ions, zinc ions, manganese ions, aluminum ions, and vanadium ions.
According to the lithium iron phosphate positive electrode material with high tap density, provided by the invention, the diffusion rate of lithium ions can be effectively improved by carrying out cation doping, so that the ion conductivity of the lithium iron phosphate positive electrode material is improved.
The anions include at least one of fluoride, silicate, and borate.
The lithium iron phosphate positive electrode material with high tap density provided by the invention can be used as a fluxing agent in the sintering process by anion doping, so that the tap density of the positive electrode material can be improved, and the density of an active substance is higher.
Therefore, the lithium iron phosphate positive electrode material with high tap density provided by the invention has excellent electrochemical performance and high tap density.
In addition, the lithium iron phosphate positive electrode material with high tap density provided by the invention has the advantages of high sphericity, good particle consistency and good fluidity, so that the tap density of the positive electrode material is further improved.
In a preferred embodiment, the secondary particles of the high tap density lithium iron phosphate positive electrode material are spherical in shape.
The spherical particles have good fluidity, so that the materials are in closer contact, and the filling effect between the large particles and the small particles is good, thereby being beneficial to further improving the tap density of the positive electrode material.
In a preferred embodiment, the D50 particle size of the positive electrode material is optimized for the purpose of comprehensively considering the tap density of the material and the processability of the material, and the D50 particle size of the high tap density lithium iron phosphate positive electrode material is 8 to 15 μm, including but not limited to a point value of any one of 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or a range value between any two.
In a preferred embodiment, the thickness of the carbon coating layer is 2-5 nm, including but not limited to any one of the point values of 2nm, 3nm, 4nm and 5nm or any range between the two, and the carbon coating layer can improve the conductivity of the high tap density lithium iron phosphate positive electrode material, has an external coating protection effect on the lithium iron phosphate material, and does not hinder the deintercalation of lithium ions.
In a preferred embodiment, the secondary particles are mainly formed by aggregation of primary particles, and the D50 particle size of the primary particles is 200-300 nm, including but not limited to any one of 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, or a range between any two.
In a preferred embodiment, the tap density of the high tap density lithium iron phosphate positive electrode material is more than or equal to 1.5g/cm 3 Including but not limited to 1.6g/cm 3 、1.7g/cm 3 、1.75g/cm 3 、1.77g/cm 3 、1.79g/cm 3 、1.80g/cm 3 Any one of the point values or a range value between any two.
At present, the tap density of lithium iron phosphate is generally 0.8g/cm 3 ～1.2g/cm 3 . The tap density of the lithium iron phosphate anode material with high tap density prepared by the invention is more than or equal to 1.5g/cm 3 The tap density is obviously improved, and the energy density of the lithium battery is further improved.
In a preferred embodiment, the 0.1C charge gram capacity of the high tap density lithium iron phosphate positive electrode material is greater than or equal to 162mAh/g, including but not limited to a point value of any one of 163mAh/g, 164mAh/g, 165mAh/g, 166mAh/g, or a range of values between any two.
In a preferred embodiment, the 0.1C discharge gram capacity of the high tap density lithium iron phosphate positive electrode material is greater than or equal to 157mAh/g, including but not limited to a point value of any one of 158mAh/g, 159mAh/g, 160mAh/g, 161mAh/g, or a range of values between any two.
In a preferred embodiment, the 1C charge gram capacity of the high tap density lithium iron phosphate positive electrode material is greater than or equal to 145mAh/g, including but not limited to a point value of any one of 146mAh/g, 147mAh/g, 148mAh/g, 149mAh/g, 150mAh/g, 152mAh/g, 155mAh/g, 156mAh/g, 157mAh/g, 158mAh/g, or a range value therebetween.
In a preferred embodiment, the 1C discharge gram capacity of the high tap density lithium iron phosphate positive electrode material is greater than or equal to 137mAh/g, including but not limited to a point value of any one of 140mAh/g, 142mAh/g, 145mAh/g, 150mAh/g, or a range of values between any two.
In a preferred embodiment, the mass of the cations doped in the anion and cation co-doped lithium iron phosphate material is from 0.1% to 1% of the mass of the anion and cation co-doped lithium iron phosphate material, including but not limited to a point value of any one of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or a range of values between any two.
In a preferred embodiment, the mass of anions doped in the anion and cation co-doped lithium iron phosphate material is 0.1% to 1% of the mass of the anion and cation co-doped lithium iron phosphate material, including but not limited to a point value of any one of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or a range value between any two.
In a preferred embodiment, the mass of the carbon coating layer accounts for 0.1% -1.5% of the mass of the high tap density lithium iron phosphate positive electrode material, including but not limited to any one of the point values or any range between any two of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.4%.
In a second aspect, the invention provides a preparation method of the lithium iron phosphate positive electrode material with high tap density, comprising the following steps:
mixing and grinding a lithium source, an iron source, a phosphorus source, a carbon source, a cationic dopant and an anionic dopant, and then performing spray drying to obtain a precursor material.
And sintering the precursor material to obtain the high tap density lithium iron phosphate anode material.
Wherein the cationic dopant comprises one of tetrabutyl titanate, zinc oxide, manganese acetate tetrahydrate, aluminum oxide and ammonium metavanadate.
The anionic dopant includes at least one of lithium fluoride, silicic acid, and boric acid.
According to the invention, by adopting a means of co-doping anions and cations, the diffusion rate of lithium ions can be effectively increased after the cations are doped, the ion conductivity of the lithium ions is improved, the anions can be used as fluxing agent in the sintering process after being introduced, the tap density of the positive electrode material is improved, and the positive electrode material and the fluxing agent cooperate with each other, so that the finally obtained positive electrode material has excellent electrochemical performance and high tap density.
In addition, the spherical lithium iron phosphate positive electrode material with high tap density, which is obtained by adopting the preparation method provided by the invention, has regular microscopic morphology and good particle consistency, and the high sphericity particles have good fluidity, so that the materials are in closer contact, and the filling effect between the large particles is good, thereby further improving the tap density of the positive electrode material.
In addition, the preparation method of the lithium iron phosphate positive electrode material with high tap density provided by the invention is simple and feasible, has a short process flow, and is suitable for mass production.
In a preferred embodiment, the carbon source comprises at least one of glucose, polyethylene glycol, trimesic acid, white granulated sugar, citric acid, sucrose, activated carbon, carbon nanotubes and graphene.
The adoption of the carbon source of the type is beneficial to forming a uniform carbon coating layer, improving the electronic conductivity of the lithium iron phosphate anode material and increasing the conductivity of the material.
In a preferred embodiment, the mass of the carbon source is 0.1% to 1.5% of the sum of the masses of the lithium source, the iron source and the phosphorus source (i.e., the total mass of the lithium source, the iron source and the phosphorus source), including but not limited to a point value of any one of 0.1%, 0.5%, 1%, 1.5%, or a range value between any two.
In a preferred embodiment, the mass of the cationic dopant is 0.1% to 1% of the sum of the masses of the lithium source, the iron source, and the phosphorus source (i.e., the total mass of the lithium source, the iron source, and the phosphorus source), including, but not limited to, a dot value of any one of 0.1%, 0.5%, 1%, or a range value between any two.
In a preferred embodiment, the mass of the anionic dopant is 0.1% to 1% of the sum of the masses of the lithium source, the iron source, and the phosphorus source (i.e., the total mass of the lithium source, the iron source, and the phosphorus source), including, but not limited to, a point value of any one of 0.1%, 0.5%, 1%, or a range value between any two.
In a preferred embodiment, the lithium source comprises at least one of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium oxalate.
In a preferred embodiment, the iron source comprises at least one of iron phosphate, iron nitrate, and iron oxide.
In a preferred embodiment, the phosphorus source comprises at least one of iron phosphate, monoammonium phosphate, phosphoric acid, and ammonium phosphate.
It will be appreciated that when iron phosphate is included in the feedstock, the iron phosphate may serve as both an iron source and a phosphorus source.
In a preferred embodiment, the molar ratio of the iron element in the iron source to the lithium element in the lithium source is 1:1 to 1.1.
In a preferred embodiment, milling comprises ball milling or/and sanding.
In a preferred embodiment, the sanding is performed in a sand mill.
In a preferred embodiment, milling comprises wet milling, i.e., a solvent (i.e., dispersant) including, but not limited to, water is also added during mixing and milling.
In a preferred embodiment, the solids content of the mixture after addition of the solvent is 10% to 50%, including but not limited to any one of the point values of 20%, 30%, 40% or any range between the two.
In a preferred embodiment, the particles in the mixture are milled to a D50 particle size of 0.5 μm or less, including but not limited to a point value of any one of 0.4 μm, 0.3 μm, 0.2 μm, 0.1 μm or a range value between any two.
In a preferred embodiment, the rotational speed of the grinding is 1000 to 2400rpm, including but not limited to a point value of any one of 1200rpm, 1400rpm, 1500rpm, 1700rpm, 1900rpm, 2000rpm, 2200rpm, or a range value between any two.
In a preferred embodiment, the D50 particle size of the precursor material obtained after spray drying is 10-15 μm; including but not limited to a dot value of any one of 11 μm, 12 μm, 13 μm, 14 μm, or a range value between any two.
By controlling the D50 particle size of the precursor material, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density meeting the requirement can be obtained.
In a preferred embodiment, the spray-dried inlet air temperature is 240 to 300 ℃, including but not limited to any one of or a range of values between 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃.
In a preferred embodiment, the spray-dried outlet air temperature is 90-110 ℃, including, but not limited to, any one or a range of values between 92 ℃, 95 ℃, 98 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃.
In a preferred embodiment, the air source pressure of the spray equipment used for spray drying is from 0.3Mpa to 0.6Mpa, including but not limited to a point value of any one of 0.4Mpa, 0.45Mpa, 0.5Mpa, 0.55Mpa or a range of values between any two.
In a preferred embodiment, the feed rate of the spray-dried peristaltic pump is 20 to 40rpm, including but not limited to a point value of any one of 25rpm, 30rpm, 35rpm, or a range of values therebetween.
In a preferred embodiment, the sintering reaction temperature is optimized for a combination of material purity (avoiding the generation of more impurity phases) and its performance, and the sintering temperature is 700-770 ℃, including, but not limited to, any one of the point values or any range between any two of 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃.
In a preferred embodiment, the soak time for sintering is 15 to 20 hours, including but not limited to a point value of any one of 16 hours, 17 hours, 18 hours, 19 hours, or a range of values between any two.
In a preferred embodiment, the sintering is performed in an inert atmosphere, such as, but not limited to, nitrogen or/and argon.
In a third aspect, the invention provides a positive electrode plate, which is mainly prepared from the high tap density lithium iron phosphate positive electrode material prepared by the preparation method of the high tap density lithium iron phosphate positive electrode material or the high tap density lithium iron phosphate positive electrode material.
The positive electrode plate has excellent electrochemical performance.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet as above.
The lithium ion battery has excellent electrochemical properties, in particular, has high energy density.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a lithium iron phosphate positive electrode material with high tap density and a preparation method thereof.
The preparation method of the lithium iron phosphate positive electrode material with high tap density comprises the following steps:
step 01, li is adopted as a lithium source 2 CO 3 FePO is adopted as the iron source and the phosphorus source 4 The carbon source adopts glucose monohydrate, the cationic dopant adopts tetrabutyl titanate and ammonium metavanadate in a molar ratio of 1:1, and the anionic dopant adopts boric acid. Wherein the molar ratio of the iron element in the iron source to the lithium element in the lithium source is 1:1.05. The mass of the carbon source is 1% of the sum of the mass of the added phosphorus source, iron source and lithium source. The mass of the cationic dopant was 0.15% of the sum of the mass of the added phosphorus source, iron source and lithium source. The mass of the anionic dopant is 0.2% of the sum of the mass of the added phosphorus source, iron source and lithium source;
step 02, weighing the raw materials, adding the raw materials into deionized water, mixing, controlling the solid content to be 30%, grinding the mixed materials in a sand mill, controlling the particle diameter D50 in the ground slurry to be 320nm, then placing the ground slurry in spray equipment for spray drying, wherein the air inlet temperature of the spray drying is 250 ℃, the air outlet temperature is 95 ℃, the feeding rate of a peristaltic pump is 30rpm, and obtaining a pale yellow precursor material with the D50 particle diameter of 18 mu m;
step 03, the precursor material prepared above is put in a crucible, and is put in N 2 Sintering is carried out in atmosphere, the sintering temperature is 700 ℃, the heat preservation time is 16h, and after the heat preservation is finished and natural cooling is carried out, the lithium iron phosphate anode material with high tap density is obtained.
The high tap density lithium iron phosphate anode material comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material, the cations are titanium ions and vanadium ions, and the anions are borate ions.
The secondary particles of the lithium iron phosphate positive electrode material with high tap density prepared in the embodiment are spherical in shape, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density is 10 mu m, and the thickness of the carbon coating layer is 3nm.
The high tap density lithium iron phosphate positive electrode material prepared in this example 1 was XRD-characterized by using japanese physics-type X-ray powder diffractometer (XRD), and the result is shown in fig. 1. As can be seen from fig. 1, the XRD spectrum shows characteristic diffraction peaks of the lithium iron phosphate cathode material, and no impurity peaks.
Fig. 2 is an SEM image of the high tap density lithium iron phosphate cathode material prepared in this example 1. Fig. 3 is a TEM image of the high tap density lithium iron phosphate positive electrode material prepared in this example 1. As can be seen from fig. 2 and 3, the secondary particles of the high tap density lithium iron phosphate cathode material are well-defined in shape, have a spherical structure, and have a carbon coating layer.
Example 2
The preparation method of the positive electrode material provided in this example is basically the same as that of example 1, except that the anionic dopant-boric acid is replaced with lithium fluoride, but the amount of the anionic dopant is unchanged.
The high tap density lithium iron phosphate anode material comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material, the cations are titanium ions and vanadium ions, and the anions are fluoride ions.
The secondary particles of the lithium iron phosphate positive electrode material with high tap density prepared in the embodiment are spherical in shape, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density is 10 mu m, and the thickness of the carbon coating layer is 3nm.
Example 3
The preparation method of the positive electrode material provided in this example was substantially the same as that of example 1, except that the sintering temperature was replaced with 740 ℃.
The high tap density lithium iron phosphate anode material comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material, the cations are titanium ions and vanadium ions, and the anions are borate ions.
The secondary particles of the lithium iron phosphate positive electrode material with high tap density prepared in the embodiment are spherical in shape, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density is 10 mu m, and the thickness of the carbon coating layer is 3nm.
Example 4
The preparation method of the lithium iron phosphate positive electrode material with high tap density provided in this embodiment is basically the same as that of embodiment 1, except that the cationic dopant tetrabutyl titanate and ammonium metavanadate are replaced with aluminum oxide, but the dosage of the cationic dopant is unchanged.
The high tap density lithium iron phosphate anode material comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material, the cation is aluminum ion, and the anion is borate ion.
The secondary particles of the lithium iron phosphate positive electrode material with high tap density prepared in the embodiment are spherical in shape, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density is 10 mu m, and the thickness of the carbon coating layer is 3nm.
Example 5
The embodiment provides a lithium iron phosphate positive electrode material with high tap density and a preparation method thereof.
The preparation method of the lithium iron phosphate positive electrode material with high tap density comprises the following steps:
step 01, lithium source adopts LiOH, iron source and phosphorus source adopt FePO 4 The carbon source adopts citric acid, the cation doping agent adopts zinc oxide and tetrahydrate manganese acetate with the mol ratio of 1:1, and the anion doping agent adopts boric acid. Wherein the molar ratio of the iron element in the iron source to the lithium element in the lithium source is 1:1.1. The mass of the carbon source is 1% of the sum of the mass of the added phosphorus source, iron source and lithium source. The mass of the cationic dopant was 0.15% of the sum of the mass of the added phosphorus source, iron source and lithium source. The mass of the anionic dopant is 0.2% of the sum of the mass of the added phosphorus source, iron source and lithium source;
step 02, weighing the raw materials, adding the raw materials into deionized water, mixing, controlling the solid content to be 25%, grinding the mixed materials in a sand mill, controlling the particle diameter D50 of particles in the ground slurry to be 350nm, then placing the ground slurry in spray equipment for spray drying, wherein the air inlet temperature of the spray drying is 280 ℃, the air outlet temperature is 105 ℃, the feeding rate of a peristaltic pump is 30rpm, and obtaining a pale yellow precursor material with the D50 particle diameter of 18 mu m;
step 03, the precursor material prepared above is put in a crucible, and is put in N 2 Sintering is carried out in atmosphere, the sintering temperature is 760 ℃, the heat preservation time is 18h, and after the heat preservation is finished and natural cooling is carried out, the lithium iron phosphate anode material with high tap density is obtained.
The high tap density lithium iron phosphate anode material comprises a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material, cations are zinc ions and manganese ions, and anions are borate ions.
The secondary particles of the lithium iron phosphate positive electrode material with high tap density prepared in the embodiment are spherical in shape, the D50 particle size of the lithium iron phosphate positive electrode material with high tap density is 10 mu m, and the thickness of the carbon coating layer is 3nm.
Examples 6 to 10
The positive electrode sheets provided in examples 6, 7, 8, 9 and 10 include the high tap density lithium iron phosphate positive electrode materials prepared in examples 1, 2, 3, 4 and 5, respectively, and the preparation methods of the positive electrode sheets provided in examples 6 to 10 include the following steps:
the high tap density lithium iron phosphate anode materials prepared in examples 1-5 were mixed with conductive carbon powder and PVDF binder at 90:5:5, uniformly mixing, coating on an aluminum foil sheet, drying at 100 ℃, rolling by a pair of rollers, making a pole piece with the diameter of 14mm by a punching machine, weighing and deducting the mass of the copper foil to obtain the mass of the active substance. And drying the positive plate.
Examples 11 to 15
The lithium ion batteries provided in example 11, example 12, example 13, example 14 and example 15 respectively include the positive electrode sheets prepared in example 6, example 7, example 8, example 9 and example 10, and the preparation methods of the lithium ion batteries provided in examples 11 to 15 include the following steps:
the positive electrode sheets prepared in examples 6 to 10 were used, and CR2032 button half cells were assembled in a delane's unab type inert gas glove box, and assembled in the order of a negative electrode case, a lithium sheet, an electrolyte, a separator, an electrolyte, a electrode sheet, a gasket, a spring sheet, and a positive electrode case. Then, electrochemical performance tests are respectively carried out on each CR2032 button half cell by adopting a Wuhan blue electric CT2001A type cell test system, the voltage range is 2.0V-3.75V, and the test results are shown in Table 1.
Comparative example 1
The preparation method of the positive electrode material provided in this comparative example is substantially the same as that of example 1, except that no anionic dopant is added.
The positive electrode material prepared in this comparative example includes a carbon coating layer and a cation-doped lithium iron phosphate material disposed inside the carbon coating layer, and the cations are titanium ions and vanadium ions.
The secondary particles of the positive electrode material prepared in this comparative example were spherical in shape, and the D50 particle diameter of the positive electrode material was 10 μm.
Comparative example 2
The preparation method of the positive electrode material provided in this comparative example is substantially the same as that of example 1, except that no cationic dopant is added.
The positive electrode material prepared in this comparative example comprises a carbon coating layer and an anion-doped lithium iron phosphate material disposed inside the carbon coating layer, wherein the anion is borate ion.
The secondary particles of the positive electrode material prepared in this comparative example were spherical in shape, and the D50 particle diameter of the positive electrode material was 10 μm.
Comparative example 3
The preparation method of the positive electrode material provided in this comparative example is substantially the same as that of example 1, except that the anionic dopant and the cationic dopant are not added.
The positive electrode material prepared in this comparative example includes a carbon coating layer and lithium iron phosphate disposed inside the carbon coating layer.
The secondary particles of the positive electrode material prepared in this comparative example were spherical in shape, and the D50 particle diameter of the positive electrode material was 10 μm.
According to the preparation methods of the positive electrode plate and the button cell, the positive electrode materials prepared in comparative examples 1 to 3 are respectively prepared into positive electrode plates, and then the positive electrode plates are assembled into CR2032 button half cells, and electrochemical performance tests are carried out according to the detection methods, and the test results are shown in Table 1.
Table 1 electrochemical performance test results for each cell
The 0.1C charge-discharge curve of the battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in example 1 is shown in fig. 4, and the 1C charge-discharge curve of the battery assembled from the high tap density lithium iron phosphate positive electrode material prepared in example 1 is shown in fig. 5.
The 0.1C charge-discharge curve of the battery assembled from the high tap density lithium iron phosphate cathode material prepared in comparative example 1 is shown in fig. 6, and the 1C charge-discharge curve of the battery assembled from the high tap density lithium iron phosphate cathode material prepared in comparative example 1 is shown in fig. 7.
As can be seen from table 1, the tap density increase ratio of example 1 was 47.5% as compared with comparative example 1. Since the anionic dopant was not added in comparative example 1, the tap density was significantly reduced, and the charge and discharge capacity were also reduced. Therefore, the invention can obviously improve the tap density of the positive electrode material and improve the charge and discharge capacity by adding the anionic dopant.
As can be seen from the comparison of example 1 and comparative example 2, in comparative example 2, since the cationic dopant was not added, the charge-discharge capacity was significantly reduced, and the tap density was also reduced. Therefore, the invention can obviously improve the charge and discharge capacity and improve the tap density of the anode material by adding the cation doping agent.
Further, as is clear from comparative examples 1 and 1 to 3, the anionic dopant and the cationic dopant have synergistic effects, and can improve both electrochemical performance and tap density.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. The high tap density lithium iron phosphate positive electrode material is characterized by comprising a carbon coating layer and a lithium iron phosphate material arranged in the carbon coating layer, wherein the lithium iron phosphate material is an anion and cation co-doped material; the cations include at least one of titanium ions, zinc ions, manganese ions, aluminum ions, or vanadium ions; the anions include at least one of fluoride, silicate, or borate.
2. The high tap density lithium iron phosphate positive electrode material according to claim 1, wherein the secondary particles of the high tap density lithium iron phosphate positive electrode material are spherical in shape;
or/and the D50 particle size of the high tap density lithium iron phosphate positive electrode material is 8-15 mu m;
or/and the thickness of the carbon coating layer is 2-5 nm.
3. The high tap density lithium iron phosphate positive electrode material according to claim 1, wherein the tap density of the high tap density lithium iron phosphate positive electrode material is not less than 1.5g/cm 3 。
4. A method for preparing a high tap density lithium iron phosphate positive electrode material according to any one of claims 1 to 3, comprising the steps of:
mixing and grinding a lithium source, an iron source, a phosphorus source, a carbon source, a cationic dopant and an anionic dopant, and then spray-drying to obtain a precursor material;
sintering the precursor material to obtain the high tap density lithium iron phosphate anode material;
wherein the cationic dopant comprises one of tetrabutyl titanate, zinc oxide, manganese acetate tetrahydrate, aluminum oxide and ammonium metavanadate;
the anionic dopant includes at least one of lithium fluoride, silicic acid, and boric acid.
5. The method for preparing a lithium iron phosphate positive electrode material with high tap density according to claim 4, wherein the carbon source comprises at least one of glucose, polyethylene glycol, trimesic acid, white granulated sugar, citric acid, sucrose, activated carbon, carbon nanotubes and graphene;
or/and the mass of the carbon source is 0.1-1.5% of the sum of the mass of the lithium source, the mass of the iron source and the mass of the phosphorus source.
6. The method for preparing a high tap density lithium iron phosphate positive electrode material according to claim 4, wherein the mass of the cationic dopant is 0.1% to 1% of the sum of the mass of the lithium source, the iron source and the phosphorus source;
or/and, the mass of the anionic dopant is 0.1% -1% of the sum of the mass of the lithium source, the mass of the iron source and the mass of the phosphorus source.
7. The method for preparing a high tap density lithium iron phosphate positive electrode material according to claim 4, wherein the precursor material obtained after spray drying has a D50 particle size of 10 to 15 μm;
or/and the air inlet temperature of the spray drying is 240-300 ℃, and the air outlet temperature of the spray drying is 90-110 ℃.
8. The method for preparing a lithium iron phosphate positive electrode material with high tap density according to claim 4, wherein the sintering temperature is 700-770 ℃, and the sintering heat preservation time is 15-20 h.
9. The positive electrode plate is characterized by being prepared from the high tap density lithium iron phosphate positive electrode material according to any one of claims 1-3.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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| CN117208967A (en) * | 2023-11-07 | 2023-12-12 | 星恒电源股份有限公司 | Precursor material and preparation method thereof, lithium manganese iron phosphate positive electrode material and preparation method thereof, and lithium ion battery |
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| CN114759178A (en) * | 2022-04-25 | 2022-07-15 | 湖北万润新能源科技股份有限公司 | High-compaction lithium iron phosphate positive electrode material, preparation method thereof, positive electrode and battery |
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