CN112820873A - Polymer-coated lithium battery positive electrode material and preparation method thereof - Google Patents
Polymer-coated lithium battery positive electrode material and preparation method thereof Download PDFInfo
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- CN112820873A CN112820873A CN202011631795.8A CN202011631795A CN112820873A CN 112820873 A CN112820873 A CN 112820873A CN 202011631795 A CN202011631795 A CN 202011631795A CN 112820873 A CN112820873 A CN 112820873A
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- lithium battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 98
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 claims description 47
- 239000002033 PVDF binder Substances 0.000 claims description 31
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 229920002472 Starch Polymers 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000008107 starch Substances 0.000 claims description 12
- 235000019698 starch Nutrition 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- 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
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- 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
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Abstract
The invention provides a polymer-coated lithium battery positive electrode material and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing a lithium battery positive electrode material with a polymer solution, wherein the solvent of the polymer solution is an organic solvent; heating and pressurizing for reaction, coating the polymer on the surface of the lithium battery positive electrode material, carrying out solid-liquid separation, and sintering the obtained solid at 80-300 ℃ in an inert atmosphere to obtain the polymer-coated lithium battery positive electrode material. In the preparation method provided by the invention, the lithium battery anode material is not contacted with water and carbon dioxide in the whole process, and no carbonized layer is formed finally.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a polymer-coated lithium battery anode material and a preparation method thereof.
Background
With the rapid development of energy storage technology, the use of portable digital devices and vehicle-mounted power supplies is increasing, people have higher and higher requirements on the energy density of batteries, and the development of secondary batteries with large capacity, long service life and high safety is imperative.
During the first charge and discharge process of the lithium ion battery, an SEI film is formed on the interface of a negative electrode material, and researches show that the SEI mainly comprises LiF and Li2CO3、R-COOLi、R-CH2OLi and the like. SEI formation is an irreversible process, Li used to form SEI+Can not be embedded into the anode material during the discharge process, resulting in the loss of battery capacity. Therefore, this capacity loss can be compensated by pre-replenishing lithium.
The lithium pre-supplement technology is mainly divided into two types, one is a lithium supplement technology for a negative electrode material, the technology has higher requirements on the operating environment, and lithium supplement agents are generally metal lithium foil and inert lithium powder; the other is a lithium supplement technology of the anode material, the technical requirement is relatively low, the method is simple, and the lithium supplement agent generally adopts a lithium-rich anode material Li with a reverse fluorite structureXMO4(M ═ Fe, Co, Mn). Among them, lithium ferrate (Li)5FeO4) The lithium supplement agent has the advantages of simple synthesis process, low material price and high lithium supplement safety, and is the lithium supplement agentThe preference of (1). However, part of the positive electrode material (such as lithium ferrate) is easy to react with water and carbon dioxide in the air, and the stability of the material is poor, so that the material needs to be coated with inert gas to realize good application.
In the existing coating technology of the anode material of the lithium ion battery, a process of firstly carrying out heat treatment by using an aqueous solution containing a carbon source and then carrying out sintering is mostly adopted, and the process has the advantages of simple operation and suitability for mass production. However, for lithium ferrate, both water and carbon dioxide are not allowed to be present in the coating process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polymer-coated lithium battery positive electrode material and a preparation method thereof. The preparation method does not contact water and carbon dioxide in the whole process, and finally no carbonized layer is formed, so that compared with the existing high-temperature carbon coating, the preparation method is beneficial to improving the stability of lithium iron oxide and other lithium battery anode materials which are easy to react with water and carbon dioxide and easy to reduce, and the energy consumption is lower.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polymer-coated lithium battery positive electrode material, the method comprising the steps of:
uniformly mixing a lithium battery positive electrode material with a polymer solution, heating and pressurizing to react so that the polymer is coated on the surface of the lithium battery positive electrode material, carrying out solid-liquid separation, and sintering the obtained solid in an inert atmosphere at 80-300 ℃ (for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 150 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 250 ℃, 260 ℃, 280 ℃ or 300 ℃ and the like) to obtain a polymer-coated lithium battery positive electrode material;
wherein the solvent of the polymer solution is an organic solvent.
The polymer and the lithium battery anode material react in an organic solvent under the conditions of heating and pressurizing, so that the polymer is coated on the surface of the lithium battery anode material, and then the polymer is sintered at low temperature (80-300 ℃) to shrink, thereby obtaining the polymer-coated lithium battery anode material. In the preparation method, the lithium battery anode material does not contact water and carbon dioxide in the whole process, and no carbonized layer is formed finally, which is beneficial to ensuring the stability of the lithium battery anode material.
In the invention, the sintering temperature needs to be kept in the range of 80-300 ℃; when the sintering temperature is lower than 80 ℃, the polymer is not completely shrunk, and the coating effect is poor; when the sintering temperature is higher than 300 ℃, the polymer coating layer is easily carbonized, and the high-temperature carbonized layer easily reduces the lithium battery cathode material which is easy to reduce, such as lithium ferrite.
In an embodiment of the invention, the polymer is selected from one or a combination of at least two of starch, cellulose, PVDF (polyvinylidene fluoride), PVP (polyvinylpyrrolidone) and PEO (polyethylene oxide).
In one embodiment of the present invention, the organic solvent is selected from one or a combination of at least two of ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and dioxane.
In one embodiment of the invention, the concentration of the polymer solution is 0.1 to 20 wt%; for example, it may be 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 13 wt%, 15 wt%, 16 wt%, 18 wt%, or 20 wt%, etc.
In one embodiment of the present invention, the positive electrode material for lithium batteries includes lithium ferrate.
In one embodiment of the present invention, the lithium battery positive electrode material includes lithium ferrate (Li)5FeO4) One or a combination of at least two of lithium iron phosphate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate.
In an embodiment of the present invention, the lithium battery positive electrode material includes lithium iron oxide, and further includes one or a combination of at least two of lithium iron phosphate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate, and lithium nickel cobalt aluminate.
In one embodiment of the present invention, the particle size of the lithium battery positive electrode material is 0.2 to 20 μm; for example, it may be 0.2. mu.m, 1. mu.m, 3. mu.m, 5. mu.m, 8. mu.m, 10. mu.m, 12. mu.m, 15. mu.m, 18. mu.m, or 20 μm.
In one embodiment of the invention, the polymer coating layer in the polymer-coated lithium battery cathode material is 0.5-5 wt%; for example, it may be 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, etc.
In the invention, the thickness of the coating layer can be adjusted by controlling the mass ratio of the lithium battery anode material to the polymer. When the ratio of the polymer to the lithium battery anode material is too low, the lithium battery anode material is not completely coated; when the proportion of the polymer to the lithium battery anode material is more than 5%, the polymer proportion is continuously increased, the thickness of the coating layer is not obviously increased, and the polymer is wasted.
In one embodiment of the invention, the temperature of the reaction is 60-200 ℃; for example, the temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃.
In one embodiment of the invention, the pressure of the reaction is 1-14 MPa; for example, it may be 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa or 14 MPa.
In one embodiment of the invention, the reaction time is 6-20 h; for example, it may be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, or 20 h.
In the invention, the coating uniformity and the bonding strength of the polymer coating layer on the lithium battery cathode material can be adjusted by controlling the reaction temperature and the reaction time. When the reaction temperature is too low or the reaction time is too short, the bonding strength is insufficient; when the reaction temperature exceeds 200 ℃ or the reaction time exceeds 20 hours, the bonding strength is not increased significantly any more. The coating strength can be adjusted by controlling the pressure. When the pressure intensity is too low, the coating strength is insufficient, and the coating effect is poor; when the pressure exceeds 14MPa, the pressure is continuously increased, and the change of the coating strength is not obvious.
In one embodiment of the present invention, the sintering time is 5-20 h; for example, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, or the like may be used.
In one embodiment of the present invention, the rate of temperature rise before reaching the sintering temperature is 1-20 ℃/min; for example, it may be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 13 ℃/min, 15 ℃/min, 16 ℃/min, 18 ℃/min or 20 ℃/min, etc.
In one embodiment of the present invention, the gas of the inert atmosphere is nitrogen and/or argon.
In one embodiment of the present invention, the preparation method comprises the steps of:
(1) dissolving a polymer in an organic solvent to prepare a polymer solution with the concentration of 0.1-20 wt%;
(2) mixing a lithium battery anode material with the polymer solution obtained in the step (1), placing the mixture in a high-pressure reaction kettle, adjusting the temperature to be 60-200 ℃, the pressure to be 1-14MPa, reacting for 6-20h to ensure that the polymer is coated on the surface of the lithium battery anode material, and carrying out solid-liquid separation to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 80-300 ℃ at a heating rate of 1-20 ℃/min in an inert atmosphere, and sintering for 5-20h in a heat preservation manner to obtain the polymer-coated lithium battery positive electrode material.
In a second aspect, the invention provides a polymer-coated lithium battery positive electrode material prepared by the preparation method of the first aspect.
In a third aspect, the invention provides a lithium battery comprising the polymer-coated lithium battery positive electrode material of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the polymer and the lithium battery anode material react in an organic solvent under the conditions of heating and pressurizing, so that the polymer is coated on the surface of the lithium battery anode material, and then the polymer is sintered at low temperature (80-300 ℃) to shrink, thereby obtaining the polymer-coated lithium battery anode material. In the preparation method provided by the invention, the lithium battery anode material does not contact water and carbon dioxide in the whole process, and no carbonization zone is formed finally, so that the reduction effect of a high-temperature carbonization zone on ferric ions is avoided, and the activity of the anode material is reduced. Compared with the existing high-temperature carbon coating, the preparation method provided by the invention is beneficial to ensuring the stability of lithium iron oxide and other lithium battery anode materials which are easy to react with water and carbon dioxide and easy to reduce, and has lower energy consumption.
Drawings
FIG. 1 is an SEM photograph of lithium ferrate used in the examples of the present invention;
FIG. 2 is an SEM photograph of PVDF-coated lithium ferrate provided in example 1 of the present invention;
fig. 3 is a voltage-specific capacity graph of batteries using PVDF-coated lithium ferrite and lithium ferrite, respectively, provided in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the embodiment of the invention, part of the materials are as follows:
PVDF: suwei PVDF 5130;
PVP: purchased from alatin reagent net, model: p110611, number average molecular weight 100000;
PEO: purchased from the alatin reagent net, model P101334: number average molecular weight 300000.
Example 1
The embodiment provides a preparation method of PVDF-coated lithium ferrite, which comprises the following specific steps:
(1) dissolving 1.0g of PVDF in 99.0g N-methyl pyrrolidone to prepare a 1 wt% PVDF solution;
(2) 5.0g of lithium ferrate (Li) was taken5FeO4) Slowly adding into the PVDF solution, placing in a high-pressure reaction kettle, adjusting the temperature to 150 ℃, the pressure to 5MPa, reacting for 10h to coat the PVDF on ironFiltering the lithium surface to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 200 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and carrying out heat preservation sintering for 10 hours to obtain the PVDF-coated lithium ferrite.
The content of the PVDF coating layer in the PVDF-coated lithium ferrite is calculated to be 5.49 wt% according to the mass change before and after the lithium ferrite coating.
The surface morphology of the lithium ferrite used in this example and the obtained PVDF-coated lithium ferrite was characterized by Scanning Electron Microscopy (SEM), and the results are shown in fig. 1 and fig. 2, respectively. As can be seen from the figure, the particle size of the uncoated lithium ferrite was about 1 μm, and the particle size of the PVDF-coated lithium ferrite was not substantially changed.
Example 2
The embodiment provides a preparation method of starch-coated lithium ferrite, which comprises the following specific steps:
(1) dissolving 0.1g of starch in 99.9g of ethanol to prepare 0.1 wt% of starch solution;
(2) 1.0g of lithium ferrate (Li) was taken5FeO4) Slowly adding the starch solution into the starch solution, then placing the starch solution into a high-pressure reaction kettle, adjusting the temperature to be 60 ℃, the pressure to be 1MPa, reacting for 20 hours to enable the starch to be coated on the surface of the lithium ferrite, and filtering to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 300 ℃ at the heating rate of 20 ℃/min in the nitrogen atmosphere, and carrying out heat preservation sintering for 5 hours to obtain the starch-coated lithium ferrite.
The content of the starch coating layer in the starch-coated lithium ferrite is 1.36 wt% according to the mass change before and after the coating of the lithium ferrite.
Example 3
The embodiment provides a preparation method of PVP coated lithium ferrite, which comprises the following specific steps:
(1) dissolving 20.0g of PVP in 80.0g N-methyl pyrrolidone to prepare a 20 wt% PVP solution;
(2) 20.0g of lithium ferrate (Li) was taken5FeO4) Slowly adding into the PVP solution, placing in a high pressure reaction kettle, adjusting temperature to 200 deg.C and pressure to 14MPa, reacting for 6 hr to make PVP bagCovering the surface of lithium ferrite, and filtering to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 80 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and carrying out heat preservation sintering for 20h to obtain the PVP coated lithium ferrite.
The content of the PVP coating layer in the PVP coated lithium ferrite is calculated to be 14.37 wt% according to the mass change before and after the coating of the lithium ferrite.
Example 4
The embodiment provides a preparation method of PEO-coated lithium ferrite, which comprises the following specific steps:
(1) dissolving 5.0g of PEO in 95.0g N, N-dimethylformamide to prepare 5 wt% PEO solution;
(2) slowly adding 10.0g of lithium ferrite into the PEO solution, then placing the PEO solution into a high-pressure reaction kettle, adjusting the temperature to be 100 ℃, the pressure to be 3MPa, reacting for 15 hours to enable PEO to be coated on the surface of the lithium ferrite, and filtering to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 150 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and carrying out heat preservation sintering for 12h to obtain the PEO-coated lithium ferrite.
The content of the PEO coating layer in the PEO-coated lithium ferrite is 5.62 wt% according to the mass change before and after the lithium ferrite coating.
Example 5
This example provides a method for preparing PVDF-coated lithium ferrite, which is different from example 1 in that the reaction temperature in step (2) is 50 ℃.
The content of the PVDF coating layer in the PVDF-coated lithium ferrite is calculated to be 2.76 wt% according to the mass change before and after the lithium ferrite coating.
In example 5, the PVDF coating layer of the obtained PVDF-coated lithium ferrate was not uniformly coated with lithium ferrate and had lower bonding strength than example 1 due to the lower reaction temperature in step (2).
Comparative example 1
This example provides a method for producing PVDF-coated lithium ferrite, which is different from example 1 in that the reaction in step (2) is carried out under normal pressure.
The content of the PVDF coating layer in the PVDF-coated lithium ferrite is calculated to be 3.67 wt% according to the mass change before and after the lithium ferrite coating.
Compared with example 1, the reaction pressure in step (2) of comparative example 1 is lower, and thus the obtained PVDF-coated lithium ferrite coating layer is looser and has lower coating strength.
Comparative example 2
There is provided a method for preparing PVDF-coated lithium ferrite, which is different from example 1 in that the sintering temperature in step (3) is 60 ℃.
The content of the PVDF coating layer in the PVDF-coated lithium ferrite is calculated to be 5.41 wt% according to the mass change before and after the lithium ferrite coating.
The sintering temperature in step (3) of comparative example 2 was lower, the shrinkage of the polymer was incomplete, and thus the coating strength was lower, compared to example 1.
Comparative example 3
A method for producing PVDF-coated lithium ferrite is provided, which is different from example 1 in that the sintering temperature in step (3) is 320 ℃.
In comparison with example 1, in comparative example 3, the sintering temperature exceeded 300 ℃, the polymer coating layer was also partially carbonized, and the effect of dense coating was lost.
The polymer-coated lithium battery positive electrode material provided in the above examples and comparative examples, and lithium ferrate were used to assemble a battery as follows:
the positive electrode materials are mixed according to the mass ratio of NMP to Super P-Li to PVDF to the positive electrode material of 25:8:1:1 (the positive electrode material refers to the polymer coated lithium battery positive electrode material or lithium ferrite provided in examples 1-5 and comparative examples 1-3), and are subjected to homogenate-coating-drying-cutting operation to prepare a positive electrode sheet, and the positive electrode sheet is baked in a vacuum oven at 100 ℃ to remove trace water. And assembling the prepared positive plate assembled button cell in an inert atmosphere glove box according to the assembling sequence of the negative electrode shell, the stainless steel gasket, the lithium metal sheet, the diaphragm, the electrolyte, the positive plate and the positive plate. The button cell comprises a button cell shell (comprising a negative electrode shell, a stainless steel gasket and a positive electrode shell), wherein the model of the button cell shell is CR2032, and the manufacturer is Korea; the lithium metal sheet is a lithium metal sheet with the diameter of 16mm which can be produced in the lithium industry in Tianjin; electrolyte solutionLiPF of 1mol/L6A solution, wherein a solvent consists of EC (ethylene carbonate) and DEC (diethyl carbonate) according to a volume ratio of 1: 1; the diaphragm is a PE diaphragm produced by Shanghai Enjie. After the battery is assembled, the first charge-discharge specific capacity of the battery is tested according to the following method:
charging to 4.5V at 0.05C, and keeping the voltage at 4.5V until the current is less than 0.01C; discharging to 2.5V at 0.05C, testing the first charge-discharge specific capacity, and using a battery testing instrument of a LANHE-CT3001A battery testing cabinet produced by blue-electron limited company in Wuhan City.
The results of the above performance tests are shown in table 1 below:
TABLE 1
Fig. 3 shows the voltage-specific capacity curves of the batteries using the PVDF-coated lithium ferrite and the lithium ferrite provided in example 1. As can be seen from the test results in table 1 and fig. 3, compared with lithium ferrite, the charge-discharge specific capacity of the polymer-coated lithium ferrite is significantly improved, which indicates that the polymer coating layer plays a role in protecting the lithium ferrite from water and carbon dioxide.
Compared with the example 1, the reaction temperature in the step (2) of the example 5 is lower, the reaction pressure in the step (2) of the comparative example 1 is lower, the sintering temperature in the step (3) of the comparative example 2 is lower, the coating layer of the obtained polymer-coated lithium battery positive electrode material is uneven or the coating strength is lower, so that part of lithium ferrate reacts with water and carbon dioxide in the air to be deactivated, and the charge-discharge specific capacity of the obtained polymer-coated lithium battery positive electrode material is reduced.
Compared with the embodiment 1, in the comparative example 3, because the sintering temperature exceeds 300 ℃, the polymer coating layer is partially carbonized and cracked, so that part of the material is exposed, the effect of dense coating is lost, and part of lithium ferrite is in contact with the external environment to deteriorate, so that the charge-discharge specific capacity of the obtained polymer-coated lithium battery cathode material is obviously reduced.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a polymer-coated lithium battery positive electrode material is characterized by comprising the following steps:
uniformly mixing a lithium battery positive electrode material with a polymer solution, heating and pressurizing to react so that the polymer is coated on the surface of the lithium battery positive electrode material, carrying out solid-liquid separation, and sintering the obtained solid at 80-300 ℃ in an inert atmosphere to obtain the polymer-coated lithium battery positive electrode material;
wherein the solvent of the polymer solution is an organic solvent.
2. The method according to claim 1, wherein the polymer is selected from one or a combination of at least two of starch, cellulose, polyvinylidene fluoride, polyvinylpyrrolidone, and polyethylene oxide.
3. The production method according to claim 1 or 2, wherein the organic solvent is one or a combination of at least two selected from the group consisting of ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and dioxane;
and/or the concentration of the polymer solution is 0.1 to 20 wt%.
4. The production method according to any one of claims 1 to 3, wherein the positive electrode material for a lithium battery comprises lithium ferrate;
preferably, the lithium battery positive electrode material comprises one or a combination of at least two of lithium ferrite, lithium iron phosphate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate;
preferably, the lithium battery positive electrode material comprises lithium ferrite, and further comprises one or a combination of at least two of lithium iron phosphate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate;
and/or the particle size of the lithium battery positive electrode material is 0.2-20 μm.
5. The production method according to any one of claims 1 to 4, wherein the content of the polymer coating layer in the polymer-coated lithium battery positive electrode material is 0.5 to 5 wt%.
6. The method according to any one of claims 1 to 5, wherein the reaction temperature is 60 to 200 ℃;
and/or the pressure of the reaction is 1-14 MPa;
and/or the reaction time is 6-20 h.
7. The method according to any one of claims 1 to 6, wherein the sintering time is 5 to 20 hours;
and/or the heating rate is 1-20 ℃/min before reaching the sintering temperature.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) dissolving a polymer in an organic solvent to prepare a polymer solution with the concentration of 0.1-20 wt%;
(2) mixing a lithium battery anode material with the polymer solution obtained in the step (1), placing the mixture in a high-pressure reaction kettle, adjusting the temperature to be 60-200 ℃, the pressure to be 1-14MPa, reacting for 6-20h to ensure that the polymer is coated on the surface of the lithium battery anode material, and carrying out solid-liquid separation to obtain filter residue;
(3) and (3) heating the filter residue obtained in the step (2) to 80-300 ℃ at a heating rate of 1-20 ℃/min in an inert atmosphere, and sintering for 5-20h in a heat preservation manner to obtain the polymer-coated lithium battery positive electrode material.
9. A polymer-coated lithium battery positive electrode material, characterized by being produced by the production method according to any one of claims 1 to 9.
10. A lithium battery comprising the polymer-coated lithium battery positive electrode material of claim 9.
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