CN116936767A - Preparation method of high-capacity water system processed lithium iron phosphate anode - Google Patents
Preparation method of high-capacity water system processed lithium iron phosphate anode Download PDFInfo
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- CN116936767A CN116936767A CN202311017633.9A CN202311017633A CN116936767A CN 116936767 A CN116936767 A CN 116936767A CN 202311017633 A CN202311017633 A CN 202311017633A CN 116936767 A CN116936767 A CN 116936767A
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- iron phosphate
- lithium iron
- lithium
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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 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 230000001681 protective effect Effects 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 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 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052744 lithium Inorganic materials 0.000 abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 230000006378 damage Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- 239000002243 precursor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000013473 artificial intelligence Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 150000004713 phosphodiesters Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/626—Metals
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention discloses a preparation method of a high-capacity water system processed lithium iron phosphate anode, which comprises the following steps: step S1: mixing and dispersing a component Li source, a Fe source, a C source, a P source, metatitanic acid and a component A in deionized water according to a proportion, weighing the components by using a precise balance, and obtaining the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A; step S2: carrying out spray drying treatment on the slurry A to obtain powder; step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water system processed lithium iron phosphate anode powder; step S4: coating lithium iron phosphate anode powder to obtain a lithium iron phosphate anode; along with the progress of discharge, the zero strain of lithium titanate avoids the damage of the structure caused by the back and forth expansion of electrode materials, thereby improving a voltage platform, prolonging the discharge time of the partially formed lithium titanate, and finally obviously improving the specific discharge capacity.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a high-capacity water system processed lithium iron phosphate anode.
Background
With miniaturization of electronic products, popularity of electric automobiles, mobile phones and intelligent portable terminals is improved year by year, and a power battery having the characteristics of quick charging, large capacity, long service life, low price, good safety and the like is urgently needed. The lithium battery has the advantages of quick charge and discharge, long endurance time, good low-temperature performance and the like, and meets the requirements. The lithium battery type comprises ternary lithium batteries, lithium iron phosphate batteries and lithium cobalt oxide batteries, and the lithium iron phosphate batteries are mainly applied to new energy automobiles, energy storage batteries and the like. Lithium iron phosphate batteries, which use lithium iron phosphate as a positive electrode material for power cells, have gained widespread acceptance in the capital market in terms of cost, life and safety.
CN108706564a discloses a preparation method of high-compaction lithium ion battery anode material lithium iron phosphate, which comprises the following steps: s1, mixing a composite iron source, a phosphorus source and a carbon source which are composed of a lithium source, ferric orthophosphate and metal iron powder according to a certain proportion, putting the mixture into a dispersion kettle, adding a solvent for dispersion, coarse grinding and fine grinding to obtain uniformly mixed slurry, and carrying out spray drying on the slurry to obtain spherical precursor powder; s2, tabletting, granulating and densifying the obtained precursor powder to obtain a granular precursor; s3, sintering the obtained granular precursor at high temperature under the protection of inert gas, naturally cooling to room temperature, and crushing to obtain a high-compaction lithium iron phosphate product. The invention adopts a composite iron source, the density of the metal iron powder is higher, and the metal iron powder is matched with nanoscale ferric orthophosphate, so that the synthesized lithium iron phosphate has excellent electrochemical performance and higher tap density; and tabletting, granulating and densifying the precursor powder obtained by spray drying, so that the sintering production efficiency and the density of the lithium iron phosphate material are improved.
However, the battery process has a larger environmental protection problem in the preparation technology, as the environmental protection requirements of customers at home and abroad on the battery are more and more strict, a few manufacturers start to try to develop a water system processing lithium iron phosphate anode, and a few manufacturers already develop the lithium iron phosphate anode which can use water as a solvent for battery assembly processing in order to meet the environmental protection requirements of water system processing, for example, CN108878878A discloses a high-capacity high-magnification water system lithium iron phosphate battery and a preparation method thereof. The battery comprises an anode, a cathode, a diaphragm, electrolyte and a shell, and is characterized in that: the positive electrode slurry is formed by mixing carbon-coated lithium iron phosphate, graphene composite slurry, a conductive agent and an aqueous binder, the positive electrode current collector is carbon-coated aluminum foil, the negative electrode is artificial graphite, and the diaphragm is a PP ceramic diaphragm. The lithium iron phosphate has the advantages of no toxicity, no pollution, good safety performance and the like, while the graphene has excellent conductivity and electron transmission channels, can improve the content of main materials, can obviously improve the conductivity of the electrode, and reduces the consumption of the conductive agent. The carbon-coated aluminum foil is used as the positive current collector, so that the performance of a lithium battery product can be improved, the discharge multiplying power can be improved, the internal resistance of the battery can be reduced, the adhesion with active substances can be improved, and the processability of lithium iron phosphate can be improved. Compared with NMP, the water is used as solvent, which can reduce the harm to human body and reduce the environmental pollution.
However, the aqueous processed lithium iron phosphate positive electrode manufactured by the process has certain capacity loss, so that the electrical performance of the aqueous processed lithium iron phosphate positive electrode needs to be improved to improve the electronic conductivity of the lithium iron phosphate, thereby improving the discharge capacity of the material. Lithium iron phosphate positive electrodes are a very important component in lithium ion batteries. Improving the capacity of the lithium iron phosphate positive electrode has important significance for improving the performance of the lithium ion battery.
At present, the preparation method of the high-capacity water-based lithium iron phosphate anode mainly comprises the following directions:
1. the utilization rate of lithium ions in the precursor is improved, and the capacity of the lithium iron phosphate anode can be improved by adjusting the content of the lithium ions in the precursor, taking measures to improve the conversion rate of the lithium ions and other methods.
2. The stability of the phosphate is improved, namely, the phosphate is easy to generate hydrolysis, phosphodiester and other reactions in the preparation process, so that the capacity of the lithium iron phosphate anode is reduced. Therefore, by controlling the preparation conditions of the phosphate, the stability of the lithium iron phosphate positive electrode can be improved, thereby improving the capacity thereof.
3. Optimizing the processing course, namely the processing course of the lithium iron phosphate anode has important influence on the performance. The capacity of the lithium iron phosphate anode can be improved by optimizing the processing process, such as controlling parameters of temperature, time, pressure and the like.
4. And introducing functional groups, namely introducing functional groups such as conductive groups, hydroxide ions and the like, so that the surface energy of the lithium iron phosphate anode can be improved, and the charge and discharge performance of the lithium ion battery can be improved.
5. And combining an artificial intelligence technology, namely optimizing the preparation process of the lithium iron phosphate anode by applying the artificial intelligence technology, and improving the preparation efficiency and capacity of the lithium iron phosphate anode.
Research in these directions has been progressed, but there are still some challenges such as the influence of the electrolyte solution concentration of the lithium ion solution on the capacity thereof, difficulty in phosphate crystallization, and the like. Accordingly, the present invention is directed to a new approach to increasing the capacity of lithium iron phosphate anodes.
Disclosure of Invention
The invention aims to provide a preparation method of a high-capacity water system processed lithium iron phosphate anode, which improves the conductivity of a material and improves the discharge platform of the material by doping metal into the lithium iron phosphate, thereby improving the capacity of the material.
In order to achieve the above object, the present invention provides a method for preparing a high-capacity water-based processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing a component Li source, a Fe source, a C source, a P source, metatitanic acid and a component A in deionized water according to a proportion, weighing the components by using a precise balance, and obtaining the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water system processed lithium iron phosphate anode powder;
step S4: coating lithium iron phosphate anode powder to obtain a lithium iron phosphate anode;
the component A is one or more of ethanol, glycol, polyethylene glycol and glycerol.
Preferably, in the step S1, the Li source includes one or more of lithium carbonate, lithium hydroxide, lithium phosphate, and lithium nitrate;
preferably, in the step S1, the Fe source is one or more of iron oxide, iron hydroxide, ferrous oxalate, and iron phosphate;
preferably, in the step S1, the P source is one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate, and lithium phosphate;
preferably, in the step S1, the C source is one or more of glucose, galactose, carbon nanotubes, citric acid, sucrose, and polyethylene glycol;
preferably, in the step S1, the metatitanic acid is nano-scale metatitanic acid with a main content of 98% or more and a D50 of 30 to 100 nm;
preferably, in the step S2, the spray drying inlet temperature is set to 250-300 ℃ and the spray drying outlet temperature is set to 80-110 ℃;
preferably, in the step S3, the protective atmosphere is one or more of N2, ar, CO2, and H2;
preferably, in the step S3, the sintering temperature is 600-790 ℃ and the sintering time is 6-12 hours;
preferably, in the step S3, the carbon content of the lithium iron phosphate positive electrode is 1.1% to 1.5%.
As the discharge proceeds, the meta-titanic acid forms lithium titanate with lithium, and the greatest feature of lithium titanate Li4Ti5O12 is its "zero strain". By "zero strain" is meant that the crystal has little change in lattice constant and volume, less than 1%, upon intercalation or deintercalation of lithium ions. In the charge-discharge cycle, the zero strain can avoid the structural damage caused by the back-and-forth expansion of the electrode material, thereby improving the cycle performance and the service life of the electrode, reducing the specific capacity attenuation caused by the cycle and having very good overcharge and overdischarge resistance. Therefore, the voltage platform is improved, the discharge time of the lithium titanate formed by the lithium titanate is prolonged, and the discharge specific capacity is obviously improved finally.
The invention has the beneficial effects that: compared with the prior art, the invention has the following effects:
1. the lithium source in the step S1 can improve the supply amount of lithium, thereby improving the performance of the lithium ion battery; the iron source can improve the stability of lithium iron phosphate and reduce the volatilization loss of lithium; the phosphorus source can provide phosphorus to promote the oxidation-reduction reaction of lithium; the sugar source can provide more charge carriers for the lithium ion battery and improve the capacitance of the battery.
2. The protective atmosphere in the S3 comprises one or more of N2, ar, CO2 and H2, and can prevent lithium ions from being oxidized at high temperature, so that the performance of the lithium ion battery is improved; the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the performance and stability of the lithium ion battery can be effectively improved; the carbon content of the lithium iron phosphate product is between 1.1 and 1.5 percent, which is beneficial to prolonging the cycle life of the lithium ion battery.
3. According to the invention, the lithium titanate is formed by the meta-titanic acid and lithium in the S1, and the zero-strain property of the lithium titanate can avoid the structural damage caused by the back and forth expansion of the electrode material, so that the cycle performance and the service life of the electrode are improved, the specific capacity attenuation caused by the cycle is reduced, and the lithium titanate has very good overcharge and overdischarge resistant characteristics. Therefore, the voltage platform is improved, the discharge time of the lithium titanate formed by the lithium titanate is prolonged, and the discharge specific capacity is obviously improved finally.
Drawings
FIG. 1 is a schematic diagram of a preparation method of the present invention;
FIG. 2 is a schematic diagram of a charge-discharge curve according to the present invention;
fig. 3 is an SEM image of sample 1 prepared in the example of the present invention.
Detailed Description
In order that the objects and advantages of the invention will become more apparent, the invention will be further described with reference to the following examples; it should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are merely for explaining the technical principles of the present invention, and are not intended to limit the scope of the present invention.
It should be noted that, in the description of the present invention, terms such as "upper," "lower," "left," "right," "inner," "outer," and the like indicate directions or positional relationships based on the directions or positional relationships shown in the drawings, which are merely for convenience of description, and do not indicate or imply that the apparatus or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those skilled in the art according to the specific circumstances.
As shown in fig. 1:
example 1, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium carbonate, ferric oxide, glucose, phosphoric acid, metatitanic acid and ethanol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, the components are weighed by using an accurate balance, and the proportions of the elements are as follows: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared in example 1 was designated as sample 1.
Example 2, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium hydroxide, ferric hydroxide, galactose, ammonium phosphate, metatitanic acid and ethylene glycol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, and weighing the components by using an accurate balance to obtain the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared in example 2 was designated as sample 2.
Example 3, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium phosphate, ferrous oxalate, carbon nano tubes, metatitanic acid and polyethylene glycol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, and weighing the components by using an accurate balance to obtain the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared in example 3 was designated as sample 3.
Example 4, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium phosphate, ferric phosphate, carbon nano tubes, metatitanic acid and glycerol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, and the components are weighed by using an accurate balance to obtain the components with the following proportions: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared in example 4 was designated as sample 4.
Example 5, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium nitrate, ferric phosphate, sucrose, metatitanic acid and glycerol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, the components are weighed by using an accurate balance, and the proportions of the elements are as follows: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared from example 5 was designated as sample 5.
Example 6, a method for preparing a high capacity aqueous processed lithium iron phosphate positive electrode, comprising the steps of:
step S1: mixing and dispersing components of lithium nitrate, ferric phosphate, monoammonium phosphate, citric acid, metatitanic acid and ethylene glycol into deionized water according to a proportion, wherein the metatitanic acid is nano-scale metatitanic acid with the main content of more than 98% and the D50 of 30-100 nm, and weighing the components by using a precise balance to obtain the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder, wherein the inlet temperature of spray drying is set to be 250-300 ℃ and the outlet temperature is set to be 80-110 ℃;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water-system processed lithium iron phosphate anode powder, wherein the protective atmosphere is one or more of N2, ar, CO2 and H2, the sintering temperature is 600-790 ℃, the sintering time is 6-12 hours, and the carbon content of the lithium iron phosphate anode is 1.1-1.5%.
Step S4: and coating the lithium iron phosphate positive electrode powder to obtain the lithium iron phosphate positive electrode.
The lithium iron phosphate positive electrode prepared from example 6 was designated as sample 6.
The LI, fe, P, ti components of samples 1-6 prepared from examples 1-6 were compared to Table 1 (1 as P):
TABLE 1
The lithium iron phosphate positive electrode powders of samples 1 to 6 prepared from examples 1 to 6 shown in FIG. 2 were prepared as follows in Table 2
TABLE 2
Compared with the performance of the lithium battery of the conventional positive electrode material, as can be seen from fig. 2, 3 and table 2, the lithium iron phosphate positive electrode material prepared by the invention has higher compaction density and specific surface area, improves a voltage platform, and finally obviously improves the specific discharge capacity.
Thus far, the technical solution of the present invention has been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of protection of the present invention is not limited to these specific embodiments. Equivalent modifications and substitutions for related technical features may be made by those skilled in the art without departing from the principles of the present invention, and such modifications and substitutions will be within the scope of the present invention.
Claims (10)
1. The preparation method of the lithium iron phosphate anode processed by the high-capacity water system is characterized by comprising the following steps:
step S1: mixing and dispersing a component Li source, a Fe source, a C source, a P source, metatitanic acid and a component A in deionized water according to a proportion, weighing the components by using a precise balance, and obtaining the components with the proportion of Li: fe: p: ti=1.00-1.03:0.90-1.10:1: 0.001-0.006, and then sanding to obtain slurry A;
step S2: carrying out spray drying treatment on the slurry A to obtain powder;
step S3: calcining the powder in a protective atmosphere, and then crushing to obtain high-capacity water system processed lithium iron phosphate anode powder;
step S4: coating lithium iron phosphate anode powder to obtain a lithium iron phosphate anode;
the component A is one or more of ethanol, glycol, polyethylene glycol and glycerol.
2. The method for producing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S1, preferably, the Li source in the step S1 includes one or more of lithium carbonate, lithium hydroxide, lithium phosphate, and lithium nitrate.
3. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S1, the Fe source is one or more of iron oxide, iron hydroxide, ferrous oxalate, and iron phosphate.
4. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S1, the P source is one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate, and lithium phosphate.
5. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S1, the C source is one or more of glucose, galactose, carbon nanotubes, citric acid, sucrose, and polyethylene glycol.
6. The method for preparing a high-capacity water-based processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S1, the main content of the metatitanic acid is 98% or more, and the D50 is 30-100 nm.
7. The method for preparing a high-capacity water-based processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S2, the spray-drying inlet temperature is set to be 250-300 ℃, and the outlet temperature is set to be 80-110 ℃.
8. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S3, the protective atmosphere is one or more of N2, ar, CO2, and H2.
9. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S3, the sintering temperature is 600-790 ℃ and the sintering time is 6-12 hours.
10. The method for preparing a high-capacity aqueous processed lithium iron phosphate positive electrode according to claim 1, wherein in the step S3, the carbon content of the lithium iron phosphate positive electrode is 1.1% -1.5%.
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