CN110828823A - Preparation method of lithium manganese borate/carbon composite material - Google Patents
Preparation method of lithium manganese borate/carbon composite material Download PDFInfo
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- CN110828823A CN110828823A CN201911137056.0A CN201911137056A CN110828823A CN 110828823 A CN110828823 A CN 110828823A CN 201911137056 A CN201911137056 A CN 201911137056A CN 110828823 A CN110828823 A CN 110828823A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- AJRRQFMRDLDKCO-UHFFFAOYSA-N lithium;manganese(2+);borate Chemical compound [Li+].[Mn+2].[O-]B([O-])[O-] AJRRQFMRDLDKCO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 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
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 lithium manganese borate compound Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229910014928 LiMnBO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium manganese borate/carbon composite material, which comprises the following steps: (1) weighing a carbon source, wherein the carbon source is PVP or a mixture of PVP and other carbon-containing substances, directly placing the carbon source in a ball milling tank with or without a dispersing agent, then preparing a lithium source, a manganese source and a boron source, adding the lithium source, the manganese source and the boron source, carrying out ball milling for 1-10 h at a rotating speed of 100-500 rpm, drying the mixture at 40-120 ℃, and then grinding to obtain precursor powder; (2) placing the precursor powder in an atmosphere furnace, heating to 350-800 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 5-30 h, then cooling to room temperature along with the furnace, introducing inert gas in the whole process to avoid Mn2+And oxidizing to obtain a black powdery final product, wherein the carbon content in the final product is 1-20 wt.%. The invention has simple process and easy large-scale production, and the prepared material has uniform particles and capacityHigh circulating performance and stable circulating performance.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery anode material, in particular to a method for synthesizing a lithium manganese borate/carbon composite material by using a simple solid phase method, and specifically relates to a preparation method of the lithium manganese borate/carbon composite material.
Background
The polyanion compound has the advantages of high safety, good reversibility, stable performance and the like as the anode material of the lithium ion battery, and is developed rapidly in recent years, in particular to polyanion phosphate LiFePO4The successful commercialization of these materials has led to a greater interest in such materials. LiFePO4The theoretical specific capacity of the lithium ion battery is 170mAh/g, and the output voltage (relative Li/Li)+) 3.4V; and lithium manganese borate (LiMnBO)3) The theoretical specific capacity of the lithium ion battery anode material is up to 222mAh/g, the output voltages of the two crystal forms are respectively 3.7V (monoclinic m type) and 4.1V (hexagonal h type), the energy density is higher, and the lithium ion battery anode material has application prospect. However, this material has a problem of low electrochemical activity, a small actual discharge capacity, and a serious polarization.
In order to improve the electrochemical activity of the lithium manganese borate material, the synthesis process can be improved, carbon coating is added, the particle size is reduced, and metal ions are doped. Patent CN102947984A discloses a lithium manganese borate compound and a preparation method thereof, wherein sucrose is used as a carbon source, and m-LiMnBO is obtained by long-time ball milling and secondary calcination3The discharge capacity of the/C material is 96mAh/g at the multiplying power of 0.05C. Patent CN105047873A discloses a method for preparing carbon-coated lithium manganese borate by a sol-gel method, but the synthesized material has low capacity, and the discharge from 0.1C to 1.0V is only 83 mAh/g. Patents CN102403505A, CN104064773A, CN102386408A and CN103833044A disclose different methods for preparing carbon-coated lithium manganese borate, respectively, and the synthesized material, although capable of releasing initial capacity over 170mAh/g, has serious electrode polarization, very fast decay, and low discharge voltage as low as 1.5V, even 1.0V, and is not an intercalation reaction of lithium ions.
Polyvinylpyrrolidone (PVP) is a synthetic high molecular compound, is soluble in water and most organic solvents, has film forming property, low toxicity and good physiological compatibility, and is widely applied to the fields of medicines, foods, cosmetics, textile printing and dyeing and the like. The molecular formula of PVP is (C)6H9NO)nThe manganese borate lithium ion battery material is decomposed at high temperature in an inert atmosphere, the residue is only carbon, and the manganese borate lithium ion battery material is suitable for being used as a carbon coating raw material in the preparation process of the lithium ion battery material, but no report is provided at present for the manganese borate lithium material.
Disclosure of Invention
The invention aims to solve the problem of low electrochemical activity of the lithium manganese borate material prepared by the prior art, and provides a preparation method for preparing a high-activity lithium manganese borate/carbon composite material.
In order to achieve the above object, the present invention provides a method for preparing a lithium manganese borate/carbon composite material, which is characterized by comprising the following steps:
(1) weighing a carbon source, wherein the carbon source is polyvinylpyrrolidone (PVP) or a mixture of PVP and other carbon-containing substances, directly placing the mixture in a ball milling tank with or without a dispersing agent, preparing a lithium source, a manganese source and a boron source, adding the lithium source, the manganese source and the boron source, ball milling for 1-10 hours at a rotating speed of 100-500 rpm, drying the mixture at 40-120 ℃, and then grinding to obtain precursor powder which is uniformly mixed;
(2) placing the precursor powder in an atmosphere furnace, heating to 350-800 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 5-30 h, cooling to room temperature along with the furnace, introducing inert gas in the whole process to avoid oxidation of Mn2+, and obtaining a black powdery manganese lithium borate/carbon composite material, namely a final product, wherein the carbon content in the final product is 1-20 wt.%.
Preferably, the carbon source weighing amount in the step (1) is 1-200 wt% of theoretical lithium manganese borate; the other carbon-containing substances are one or more of carbon black, sucrose, oxalic acid, glucose, citric acid, graphene and starch; the addition amount of the dispersing agent is 100-1000 ml of dispersing agent added per mol according to the amount of the carbon source; the preparation molar ratio of the lithium source, the manganese source and the boron source Li to Mn to B is 1-1.5 to 1.
Further preferably, the dispersant in step (1) is one or more of acetone, water, ethanol, or hydrocarbons, alcohols, amines, and fatty acids capable of dissolving PVP.
Further preferably, the lithium source in step (1) is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium metaborate; the manganese source is at least one of manganese carbonate, manganese acetate, manganese oxalate, manganese nitrate and manganese hydroxide; the boron source is at least one of boric acid, boron oxide, lithium metaborate, trimethyl borate, triethyl borate and tributyl borate.
Further preferably, the inert gas in step (2) is at least one of argon, nitrogen and carbon dioxide.
Compared with the prior art, the invention has the advantages that:
(1) the operation is simple, the controllability is good, and the product is obtained by only ball-milling and mixing raw materials and calcining for one time;
(2) PVP has good film forming property, precursor particles can be uniformly coated in a high-temperature molten state, on one hand, pyrolytic carbon can be uniformly coated on the surface of a product, on the other hand, crystal growth is inhibited, and a material with fine particles and uniform distribution can be obtained;
(3) the material prepared by the method has high capacity and stable cycle performance.
Drawings
FIG. 1 is an XRD and SEM spectra of a material prepared with PVP as the sole carbon source;
FIG. 2 is a charge-discharge curve of a material prepared with PVP, starch and sucrose as the sole carbon sources, respectively;
FIG. 3 is the cycling performance of materials prepared with PVP, starch and sucrose as the sole carbon sources, respectively.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention will be described in detail below by way of examples. In the following examples, the raw materials were commercially available analytical pure drugs of the national drug group, and the structure of the product was determined by X-ray powder diffraction (XRD) analysis.
Example 1
Weighing 11.11g of PVP, placing the PVP in a ball milling tank, adding 50ml of ethanol, then respectively weighing 3.69g of lithium carbonate, 11.49g of manganese carbonate and 6.18g of boric acid, ball milling for 7h at the rotation speed of 400rpm, drying the mixture at 80 ℃, placing the mixture in an atmosphere furnace after grinding, introducing argon, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 10h, and then cooling to the room temperature along with the furnace to obtain a black powdery product. XRD analysis confirms that the product is m-type LiMnBO3The particle size is less than 100nm and the distribution is uniform, as shown in figure 1.
Example 2
Weighing 11.11g of PVP, placing the PVP in a ball milling tank, adding 50ml of acetone, then respectively weighing 3.69g of lithium carbonate, 11.49g of manganese carbonate and 6.18g of boric acid, carrying out ball milling for 7h at the rotation speed of 400rpm, drying the mixture at 80 ℃, placing the mixture in an atmosphere furnace after grinding, introducing argon, heating to 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃ respectively at the heating rate of 5 ℃/min, preserving heat for 10h, and then cooling to room temperature along with the furnace to obtain a black or gray black powdery lithium manganese borate/carbon composite material, wherein reaction products at 400 ℃, 500 ℃ and 600 ℃ are monoclinic lithium manganese borate, and reaction products at 700 ℃ and 800 ℃ are hexagonal lithium manganese borate.
Example 3
Weighing 5.56g of PVP, placing the PVP in a ball milling tank, adding 50ml of deionized water, then weighing 4.28g of lithium hydroxide monohydrate, 24.51g of manganese acetate tetrahydrate and 3.48g of boron oxide respectively, ball milling for 10h at the rotating speed of 300rpm, drying the mixture at 80 ℃, placing the mixture in an atmosphere furnace after grinding, introducing argon, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 10h, and then cooling to room temperature along with the furnace to obtain the black powdery lithium manganese borate/carbon composite material.
Comparative example 1
The material was prepared as in example 1 except that PVP was replaced with starch when the raw materials were weighed.
Comparative example 2
A material was prepared as in example 1, except that PVP was replaced with sucrose when the material was weighed out.
The materials prepared in examples 1-3 and comparative examples 1-2 above at 500 ℃ were mixed with conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1, added with an appropriate amount of N-methylpyrrolidone (NMP) and stirred into a viscous state to be coated on an aluminum foil, heated in vacuum to remove NMP, and cut into disks as positive electrode sheets. And (3) stacking the positive plate, the diaphragm, the negative metal lithium plate and the foamed nickel in a glove box filled with high-purity argon in sequence, and dropwise adding a proper amount of electrolyte to assemble the button cell. The cells were tested for electrochemical performance in the blue and cell test system, charged and discharged at 0.05C, and the third cycle discharge results are shown in table 1.
TABLE 1500 ℃ specific discharge capacity of the samples prepared
As can be seen from the results in Table 1, the examples 1 to 3 according to the present invention have significantly better effects. Fig. 2 and 3 are graphs of charge-discharge curves and cycle performance of the material-assembled batteries prepared in example 1, comparative example 1 and comparative example 2, respectively, and it can be seen from the graphs that the electrode polarization of the PVP-coated material is smaller, the capacity is higher, and the cycle performance is more stable.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (5)
1. The preparation method of the lithium manganese borate/carbon composite material is characterized by comprising the following steps of:
(1) weighing a carbon source, wherein the carbon source is polyvinylpyrrolidone (PVP) or a mixture of PVP and other carbon-containing substances, directly placing the mixture in a ball milling tank with or without a dispersing agent, preparing a lithium source, a manganese source and a boron source, adding the lithium source, the manganese source and the boron source, ball milling for 1-10 hours at a rotating speed of 100-500 rpm, drying the mixture at 40-120 ℃, and then grinding to obtain precursor powder which is uniformly mixed;
(2) placing the precursor powder in an atmosphere furnace, heating to 350-800 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 5-30 h, then cooling to room temperature along with the furnace, introducing inert gas in the whole process to avoid Mn2+And oxidizing to obtain a black powdery lithium manganese borate/carbon composite material, namely a final product, wherein the carbon content in the final product is 1-20 wt.%.
2. The method of preparing a lithium manganese borate/carbon composite material according to claim 1, wherein: weighing the carbon source in the step (1) to obtain theoretical lithium manganese borate with the content of 1-200 wt.%; the other carbon-containing substances are one or more of carbon black, sucrose, oxalic acid, glucose, citric acid, graphene and starch; the addition amount of the dispersing agent is 100-1000 ml of dispersing agent added per mol according to the amount of the carbon source; the preparation molar ratio of the lithium source, the manganese source and the boron source Li to Mn to B is 1-1.5 to 1.
3. The method of preparing a lithium manganese borate/carbon composite material according to claim 2, wherein: the dispersant in the step (1) is one or more of acetone, water, ethanol or hydrocarbons, alcohols, amines and fatty acids capable of dissolving PVP.
4. The method of preparing a lithium manganese borate/carbon composite material according to claim 3, wherein: the lithium source in the step (1) is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium metaborate; the manganese source is at least one of manganese carbonate, manganese acetate, manganese oxalate, manganese nitrate and manganese hydroxide; the boron source is at least one of boric acid, boron oxide, lithium metaborate, trimethyl borate, triethyl borate and tributyl borate.
5. The method of preparing a lithium manganese borate/carbon composite material according to claim 4, wherein: the inert gas in the step (2) is at least one of argon, nitrogen and carbon dioxide.
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