CN117317415A - Carbon-coated lithium ferrate lithium supplementing additive and preparation method thereof - Google Patents
Carbon-coated lithium ferrate lithium supplementing additive and preparation method thereof Download PDFInfo
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- CN117317415A CN117317415A CN202311518070.1A CN202311518070A CN117317415A CN 117317415 A CN117317415 A CN 117317415A CN 202311518070 A CN202311518070 A CN 202311518070A CN 117317415 A CN117317415 A CN 117317415A
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- lithium
- carbon
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- ferrate
- ferric oxide
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 156
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 123
- 239000000654 additive Substances 0.000 title claims abstract description 47
- 230000000996 additive effect Effects 0.000 title claims abstract description 44
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 52
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000012298 atmosphere Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000013589 supplement Substances 0.000 claims description 15
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 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 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010426 asphalt Substances 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 102220043159 rs587780996 Human genes 0.000 description 27
- 238000001694 spray drying Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000004576 sand Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003801 milling Methods 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000002427 irreversible effect Effects 0.000 description 7
- 208000028659 discharge Diseases 0.000 description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 239000010410 layer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery lithium supplementing additives, and particularly discloses a carbon-coated lithium ferrate lithium supplementing additive and a preparation method thereof. Firstly, carrying out carbonization reaction on ferric oxide and a carbon source to obtain carbon-coated ferric oxide; then mixing the obtained carbon-coated ferric oxide with a lithium source, a dispersing agent and water, and sequentially grinding and granulating to obtain spherical carbon-coated lithium ferrate precursor powder; and sintering the spherical carbon-coated lithium ferrate precursor powder to obtain the carbon-coated lithium ferrate lithium supplementing additive. According to the invention, the carbon coating is introduced into the ferric oxide, so that the subsequent lithium ferrate generation rate can be reduced, the size can be controlled, and the storage stability of the lithium ferrate can be improved; the grinding operation can reduce the energy consumption of the subsequent reaction and improve the reaction degree and the phase purity of the lithium ferrate; in addition, nitrate is not needed to be added in the scheme of the invention, so that the cost can be reduced and the method is more environment-friendly.
Description
Technical Field
The invention relates to the technical field of lithium ion battery lithium supplementing additives, in particular to a carbon-coated lithium ferrate lithium supplementing additive and a preparation method thereof.
Background
With the continuous development of the fields of electric automobiles, large-scale energy storage power stations, portable electronic products and the like, the high-nickel ternary and lithium iron phosphate positive electrode materials become two main stream materials, and the energy density of the two main stream materials is improved to become a future development trend. It is known that in the first charge and discharge stage of a lithium ion battery, a solid electrolyte interface (SEI for short) mainly containing lithium salt is formed at the interface of a negative electrode material, and a certain amount of positive active lithium is irreversibly consumed in the process of forming an SEI film on the surface of the negative electrode. And further causes problems such as reduced first cycle coulombic efficiency (ICE), poor cycle life, etc. The irreversible capacity loss of the graphite cathode which is most widely used at present is between 5 and 10 percent, and the irreversible capacity of the silicon-carbon cathode is up to about 25 to 30 percent, so that the high gram capacity advantage of the silicon-carbon cathode is limited.
In order to further solve the problem of performance degradation of the battery caused by irreversible consumption of active lithium, lithium needs to be supplemented, so that the first charge and discharge loss of the battery is compensated, and the rate capability, capacity, cycle life and energy density of the battery are improved. At present, the lithium ion battery lithium supplementing method mainly comprises a negative electrode pre-lithiation method and a positive electrode lithium supplementing additive adding method, wherein the negative electrode pre-lithiation method realizes reduction lithium supplementing by utilizing chemical reaction of a negative electrode lithium supplementing material and a negative electrode material; the lithium supplementing material comprises lithium powder, lithium foil, high-temperature lithium hydroxide and the like, but the process is complex, the cost is high, and potential safety hazards can be caused by formation of lithium dendrites. The method of adding the lithium supplement additive into the positive electrode, namely adding a proper amount of the positive electrode lithium supplement additive into the positive electrode material in the homogenizing process, and irreversibly transferring excessive lithium ions in the positive electrode lithium supplement additive to the negative electrode to compensate the loss of active lithium in the negative electrode material when the lithium ion battery is charged for the first time, thereby improving the specific capacity and the capacity retention rate of the first time discharge, and having more relaxed requirements on environment and higher safety compared with the pre-lithiation of the negative electrode, thereby having more market prospect. The current energy storage battery can realize the cycle life of 7000-8000 times, and the positive electrode lithium supplementing agent can help to greatly improve the cycle life of the energy storage battery, and is hopeful to break through ten thousand times.
At present, more positive electrode lithium supplement additives are used and Li is contained 2 NiO 2 And Li (lithium) 5 FeO 4 Wherein Li is 5 FeO 4 The crystal structure belongs to an inverse fluorite structure and has high ion diffusion rate. The transition metal Fe with high ion diffusion rate and variable valence enables Li to be formed by 5 FeO 4 Li of (2) + Easy deintercalation and provides high lithium removal capacity. Li (Li) 5 FeO 4 The theoretical specific capacity corresponding to the extracted total lithium is 867mAh/g, and the theoretical specific capacity corresponding to the extracted 4 lithium reaches 693.6mAh/g. The lithium ion battery has high irreversible capacity, is compatible with the existing lithium ion battery binder system, and has good application prospect as a positive electrode lithium supplementing material. However, the research on lithium ferrate at the present stage has poor chemical stability (on moisture and CO in the air 2 More sensitive), poor conductivity of the material, excessive high residual alkali production on the surface and the like.
CN116470040a provides a carbon-coated lithium ferrite lithium supplementing agent, its preparation method and application. By adopting a sol-gel method, the iron source, the lithium source and the carbon source are mixed at the molecular level, so that uniformity is ensured. The formed lithium salt and ferric salt form a stable sol system in an aqueous solvent after the reactions such as hydrolysis, condensation and the like. After the sol is heated and aged, lithium salt and ferric salt colloidal particles slowly polymerize to form gel with a three-dimensional network structure, and the components in the system diffuse in the nanometer range, so that the reaction is easy to carry out, the sintering temperature is low, and a tightly-coated carbon coating layer is formed. However, the process adopts a sol-gel method, so that the process parameters are difficult to control, and the iron nitrate is used as an iron source, so that the method is not friendly to environmental pollution.
Therefore, how to provide a carbon-coated lithium ferrate lithium supplementing additive and a preparation method thereof, and the chemical stability and the material conductivity of the lithium supplementing additive are improved; meanwhile, the ferric nitrate is avoided as an iron source, and the pollution to the environment is prevented, so that the problem to be solved in the field is urgent.
Disclosure of Invention
In view of the above, the invention provides a carbon-coated lithium ferrate lithium supplementing additive and a preparation method thereof, which are used for solving the problems of poor chemical stability, poor conductivity, excessive surface residual alkali production and the like of the existing lithium supplementing additive, and the problems of environmental pollution and complex preparation steps of the existing lithium supplementing additive due to the fact that ferric nitrate is required to be used as an iron source.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a carbon-coated lithium ferrate lithium supplementing additive comprises the following steps:
1) Performing carbonization reaction on ferric oxide and a carbon source to obtain carbon-coated ferric oxide;
2) Mixing the carbon-coated ferric oxide obtained in the step 1) with a lithium source, a dispersing agent and water to obtain slurry, and sequentially grinding and granulating to obtain spherical carbon-coated lithium ferrate precursor powder;
3) And sintering the spherical carbon-coated lithium ferrate precursor powder to obtain the carbon-coated lithium ferrate lithium supplementing additive.
Preferably, the carbon source in the step 1) includes one or more of glucose, sucrose, citric acid, asphalt, polyethylene glycol and polyvinyl alcohol.
Preferably, the mass ratio of the ferric oxide to the carbon source in the step 1) is 100:3 to 15.
Preferably, the temperature of the carbonization reaction is 400-600 ℃, and the time of the carbonization reaction is 4-10 h.
Preferably, the lithium source in the step 2) includes one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate;
the dispersing agent in the step 2) comprises one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylonitrile and sodium carboxymethyl cellulose.
Preferably, the mass ratio of the total mass of the carbon-coated ferric oxide and the lithium source to the dispersing agent in the step 2) is 100:1 to 3;
the molar ratio of the iron element in the carbon-coated ferric oxide to the lithium element in the lithium source in the step 2) is 1:5 to 6;
the solid content of the slurry is 20-45%.
Preferably, the spherical carbon-coated lithium ferrate precursor powder obtained in step 2) has a particle size d50=4 to 10 μm.
Preferably, the sintering temperature in the step 3) is 700-900 ℃, and the sintering time is 12-20 h.
Preferably, the sintering in step 3) is performed under an inert atmosphere;
the inert atmosphere comprises one or more of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere and krypton atmosphere.
Another object of the present invention is to provide a carbon-coated lithium ferrate lithium supplementing additive prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the carbon coating is introduced into the ferric oxide, so that the subsequent lithium ferrate generation rate can be reduced, the size of lithium ferrate particles can be controlled, direct contact between the lithium ferrate and water or carbon dioxide in the air can be isolated, and the storage stability of the lithium ferrate can be improved; meanwhile, the nano-scale superfine grinding of the raw materials can reduce the energy consumption of subsequent reactions and improve the reaction degree and the phase purity of lithium ferrate; in addition, nitrate is not needed to be added in the scheme of the invention, and the prepared carbon-coated lithium ferrate lithium supplementing additive can reduce the cost and is more environment-friendly.
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 required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the carbon-coated lithium ferrate supplemental lithium additive prepared in example 1.
Detailed Description
The invention provides a preparation method of a carbon-coated lithium ferrate lithium supplementing additive, which comprises the following steps:
1) Performing carbonization reaction on ferric oxide and a carbon source to obtain carbon-coated ferric oxide;
2) Mixing the carbon-coated ferric oxide obtained in the step 1) with a lithium source, a dispersing agent and water to obtain slurry, and sequentially grinding and granulating the slurry to obtain spherical carbon-coated lithium ferrate precursor powder;
3) And sintering the spherical carbon-coated lithium ferrate precursor powder to obtain the carbon-coated lithium ferrate lithium supplementing additive.
In the present invention, the carbon source in the step 1) includes one or more of glucose, sucrose, citric acid, asphalt, polyethylene glycol and polyvinyl alcohol.
In the present invention, the ferric oxide is preferably battery grade ferric oxide.
In the invention, the mass ratio of the ferric oxide to the carbon source in the step 1) is 100:3 to 15, preferably 100:5 to 12, more preferably 100: 6-10, and the further preferable value is 100:8.
in the invention, the temperature of the carbonization reaction is 400-600 ℃, specifically 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃ and 580 ℃; the carbonization reaction time is 4-10 h, and can be specifically 5h, 6h, 7h, 8h and 9h.
In the present invention, the carbonization reaction is preferably performed under an inert atmosphere, and specifically, one or more of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, and a krypton atmosphere may be used.
In the present invention, the carbon-coated iron oxide obtained in step 1) may have a carbon coating amount of 0.5 to 2%, specifically 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%.
In the present invention, the lithium source in the step 2) includes one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate.
In the present invention, the dispersant in the step 2) includes one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylonitrile and sodium carboxymethyl cellulose.
In the present invention, the mass ratio of the total mass of the carbon-coated ferric oxide and the lithium source to the dispersant in the step 2) is 100:1 to 3, preferably 100:1.2 to 2.8, more preferably 100:1.5 to 2.5, and the further preferable value is 100:2.
in the present invention, the molar ratio of the iron element in the carbon-coated ferric oxide to the lithium element in the lithium source in the step 2) is 1:5 to 6, preferably 1:5.2 to 5.8, more preferably 1:5.4 to 5.6, and the further preferable step is 1:5.5.
in the present invention, the solid content of the slurry is 20 to 45%, specifically 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%.
In the present invention, the particle diameter d50=0.2 to 0.6 μm after grinding in the step 2) may be specifically 0.3 μm, 0.4 μm or 0.5 μm.
In the present invention, the granulation in the step 2) is preferably spray drying granulation, the spray drying equipment is preferably two-fluid spray drying, the inlet temperature of the spray drying is preferably 200-240 ℃, and specifically can be 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃; the outlet temperature is 90-130 ℃, and can be 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and 125 ℃; the particle diameter d50=4 to 10 μm after spray drying may be specifically 5 μm, 6 μm, 7 μm, 8 μm, or 9 μm.
In the present invention, the sintering temperature in the step 3) is 700 to 900 ℃, specifically 720 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, 860 ℃; the sintering time is 12-20 h, and can be specifically 14h, 15h, 16h and 18h.
In the present invention, the sintering in the step 3) is performed under an inert atmosphere.
In the present invention, the inert atmosphere includes one or more of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere.
In the invention, after the sintering of the spherical carbon coated lithium ferrate precursor powder is completed, the method further comprises a crushing step; the particle size of the crushed carbon-coated lithium ferrate lithium-supplementing additive is preferably d50=2 to 6 μm, and may specifically be 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm.
The invention also provides a carbon-coated lithium ferrate lithium supplementing additive prepared by the preparation method.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Example 1
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (Hebei Jinghuang nanometer, JH-505) and 60.0g glucose with a VC mixer, wherein the mixing parameters are 800rpm and 30min, then preserving heat for 6h at a temperature rising rate of 550 ℃ at 5 ℃/min under the condition of nitrogen, cooling to room temperature, and taking out to obtain the carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
An SEM image of the carbon-coated lithium ferrate supplemental lithium additive is shown in FIG. 1, and it can be seen from FIG. 1 that the carbon-coated lithium ferrate particle size is around 5 μm.
S4: coating carbon with lithium ferrate: PVDF: super P is prepared by the following components in percentage by mass: 15:15, mixing, dissolving and dispersing uniformly by using N-methyl pyrrolidone, coating on an aluminum foil, drying and rolling to prepare the pole piece. The pole piece is used as a working electrode, a metal lithium piece is used as a counter electrode and a reference electrode, and 1mol of LiPF is used 6 (EC: DMC: emc=1:1:1 v/v) as electrolyte, PP/PE as separator, in glove boxAnd assembling the battery. The assembled battery was subjected to charge and discharge test at 0.05C current, the charge and discharge range was set to 3.0 to 4.5V, and the test results are shown in table 1.
Example 2
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 60.0g glucose with a VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5 deg.C/min under nitrogen, cooling to room temperature, and taking out to obtain carbon-coated ferric oxide.
S2: dissolving 42.0g of PEG powder in 3900mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1511.7g of lithium carbonate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, performing two-fluid spray drying, and controlling the granularity of the spray drying at D50=7 mu m at the same time when controlling the inlet and outlet temperature to obtain carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 12 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
The test method was the same as in example 1.
Example 3
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 60.0g glucose with a VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5 deg.C/min under nitrogen, cooling to room temperature, and taking out to obtain carbon-coated ferric oxide.
S2: dissolving 77.4g of PEG powder in 7200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 3273.8g of lithium acetate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the granularity of spray drying to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 750 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
The test method was the same as in example 1.
Example 4
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 60.0g glucose with a VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5 deg.C/min under nitrogen, cooling to room temperature, and taking out to obtain carbon-coated ferric oxide.
S2: dissolving 68.3g of PEG powder in 6350mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 3273.8g of lithium nitrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the granularity of spray drying to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 20 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
The test method was the same as in example 1.
Example 5
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 60.0g glucose with a VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5 deg.C/min under nitrogen, cooling to room temperature, and taking out to obtain carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.5 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
Example 6
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 120.0g glucose with a VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5 deg.C/min under nitrogen, cooling to room temperature, and taking out to obtain carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
Example 7
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 130.0g glucose with VC mixer at 800rpm for 30min, maintaining the temperature at 550deg.C for 6h at 5deg.C/min under nitrogen,and cooling to room temperature, and taking out to obtain the carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
Example 8
S1: 1000.0g of battery grade Fe 2 O 3 Mixing the powder (same as in example 1) and 60.0g of sucrose by a VC mixer, wherein the mixing parameters are 800rpm and 30min, then preserving heat for 8h at a temperature rising rate of 5 ℃/min and 400 ℃ under the condition of nitrogen, cooling to room temperature, and taking out to obtain the carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=5 mu m of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
Example 9
S1: 1000.0g of battery grade Fe 2 O 3 Mixing powder (same as in example 1) and 60.0g of citric acid by a VC mixer, wherein the mixing parameters are 800rpm and 30min, then preserving heat for 5h at a temperature rising rate of 5 ℃/min and 600 ℃ under the condition of nitrogen, cooling to room temperature, and taking out to obtain the carbon-coated ferric oxide.
S2: dissolving 46.2g of PEG powder in 4200mL of deionized water, adding 600.0g of carbon-coated ferric oxide obtained in the step 1 and 1717.0g of lithium hydroxide monohydrate (wherein the molar ratio of Li to Fe is=5.5:1) after complete dispersion, transferring the slurry into a sand mill, controlling the sand milling granularity D50=0.3 mu m, then performing two-fluid spray drying, controlling the inlet and outlet temperature and controlling the spray drying granularity to D50=7 mu m at the same time, and obtaining carbon-coated lithium ferrate precursor powder;
s3: and (3) placing the carbon-coated lithium ferrate precursor powder in an argon atmosphere for sintering, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 16 hours, cooling, crushing by a jaw, and mechanically crushing to control the granularity D50=6μm of the product, thereby finally obtaining the carbon-coated lithium ferrate lithium supplement additive.
Comparative example 1
This comparative example differs from example 1 only in that: not to Fe 2 O 3 Carbon coating the powder with Fe 2 O 3 The powder replaces the carbon-coated ferric oxide in the step 2.
Comparative example 2
This comparative example differs from example 1 only in that: in step S2, the sanding grain size was controlled to d50=0.7 μm.
Comparative example 3
This comparative example differs from example 1 only in that: 1000.0g of battery grade Fe in step S1 2 O 3 The powder was mixed with 180.0g of glucose.
Comparative example 4
This comparative example differs from example 1 only in that: 1000.0g of battery grade Fe in step S1 2 O 3 The powder was mixed with 15.0g of glucose.
TABLE 1 specific first charge-discharge capacity
Examples 1-4 and comparative example 1 demonstrate that the preparation of carbon-coated lithium ferrate from different lithium sources all exhibits excellent irreversible capacity due to the carbon source coating at Fe 2 O 3 A layer of uniform protective film is formed on the surface of the material under the high temperature condition, so that the growth of particles of the material is prevented, the conductivity is improved, and the stability of an electrochemical interface is improved. Examples 1, 5 and comparative example 3 demonstrate that the larger the milling particle size, the lower the irreversible capacity, since the smaller the milling particle size, the smaller the lithium ferrate particle size, the more excellent the electrochemical performance; examples 1, 6-7 and comparative examples 3-4 demonstrate that decreasing the amount of carbon coating results in a decrease in irreversible capacity because the carbon coating is thinner and does not effectively inhibit lithium ferrate particle size growth. However, increasing the coating amount can obviously increase the coating layer thickness, reduce the reaction degree of the lithium ferrate and influence the electrochemical performance of the lithium ferrate.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the carbon-coated lithium ferrate lithium supplementing additive is characterized by comprising the following steps of:
1) Performing carbonization reaction on ferric oxide and a carbon source to obtain carbon-coated ferric oxide;
2) Mixing the carbon-coated ferric oxide obtained in the step 1) with a lithium source, a dispersing agent and water to obtain slurry, and sequentially grinding and granulating to obtain spherical carbon-coated lithium ferrate precursor powder;
3) And sintering the spherical carbon-coated lithium ferrate precursor powder to obtain the carbon-coated lithium ferrate lithium supplementing additive.
2. The method for preparing the carbon-coated lithium ferrate additive according to claim 1, wherein the carbon source in the step 1) comprises one or more of glucose, sucrose, citric acid, asphalt, polyethylene glycol and polyvinyl alcohol.
3. The method for preparing the carbon-coated lithium ferrate lithium supplementing additive according to claim 2, wherein the mass ratio of ferric oxide to carbon source in the step 1) is 100:3 to 15.
4. The method for preparing a carbon-coated lithium ferrate additive according to any one of claims 1-3, wherein the carbonization reaction is performed at a temperature of 400-600 ℃ for 4-10 hours.
5. The method for preparing a carbon-coated lithium ferrate lithium supplement additive according to claim 4, wherein the lithium source in step 2) comprises one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate, and lithium acetate;
the dispersing agent in the step 2) comprises one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylonitrile and sodium carboxymethyl cellulose.
6. The method for preparing a carbon-coated lithium ferrate lithium supplement additive according to claim 5, wherein the mass ratio of the total mass of carbon-coated ferric oxide and lithium source to the dispersant in the step 2) is 100:1 to 3;
the molar ratio of the iron element in the carbon-coated ferric oxide to the lithium element in the lithium source in the step 2) is 1:5 to 6;
the solid content of the slurry is 20-45%.
7. The method for preparing a carbon-coated lithium ferrate additive according to claim 5 or 6, wherein the spherical carbon-coated lithium ferrate precursor powder obtained in step 2) has a particle size d50=4-10 μm.
8. The method for preparing a carbon-coated lithium ferrate additive according to claim 7, wherein the sintering temperature in the step 3) is 700-900 ℃ and the sintering time is 12-20 h.
9. The method for preparing a carbon-coated lithium ferrate additive according to claim 8, wherein the sintering in step 3) is performed under an inert atmosphere;
the inert atmosphere comprises one or more of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere and krypton atmosphere.
10. The carbon-coated lithium ferrate lithium-supplementing additive prepared by the preparation method of any one of claims 1 to 9.
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| WO2023142666A1 (en) * | 2022-01-27 | 2023-08-03 | 广东邦普循环科技有限公司 | Lithium ion battery pre-lithiation agent, preparation method therefor, and application |
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| KR20220048347A (en) * | 2020-10-12 | 2022-04-19 | 주식회사 엘지에너지솔루션 | Additives for cathode, munufacturing method of the same, cathode including the same, and lithium rechargeable battery including the same |
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