CN112811471B - Silver, cobalt and nickel doped lithium manganate positive electrode material of lithium ion battery and preparation method thereof - Google Patents
Silver, cobalt and nickel doped lithium manganate positive electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN112811471B CN112811471B CN202011579459.3A CN202011579459A CN112811471B CN 112811471 B CN112811471 B CN 112811471B CN 202011579459 A CN202011579459 A CN 202011579459A CN 112811471 B CN112811471 B CN 112811471B
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- Prior art keywords
- cobalt
- silver
- nickel
- ion battery
- lithium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 144
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 84
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010941 cobalt Substances 0.000 title claims abstract description 66
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 66
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 66
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 title claims description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000010405 anode material Substances 0.000 claims abstract description 27
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 229940100890 silver compound Drugs 0.000 claims abstract description 6
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 5
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 5
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 5
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- -1 li 2 O Chemical compound 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 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 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 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
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 64
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 238000000498 ball milling Methods 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 10
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 37
- 239000013078 crystal Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 229910020630 Co Ni Inorganic materials 0.000 description 16
- 229910002440 Co–Ni Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000003746 solid phase reaction Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910013733 LiCo Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000593 microemulsion method Methods 0.000 description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Chemical group 0.000 description 2
- 229910021641 deionized water Chemical group 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000005287 template synthesis Methods 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical class [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
- H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the fields of lithium ion battery anode materials, lithium ion batteries and the like, in particular to a silver, cobalt and nickel doped lithium manganate anode material of a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: A. mixing manganese compound, nickel compound, cobalt compound, lithium compound, silver compound and oxidant, fully grinding or ball milling to obtain reaction mixture, and transferring into a reaction kettle; B. mixing surfactant, organic alkane, surfactant auxiliary agent and water to prepare microemulsion; C. adding the microemulsion into a reaction kettle, fully mixing, sealing and placing the mixture into an oven for reaction; D. slowly adding the mixture obtained in the step C into alcohol, stirring, filtering, washing the filtrate with distilled water, and drying to obtain the final product. The advantages are that: the particle size is uniform; particle size, morphology, silver, cobalt, nickel doping amount and the like of the particles are easy to control; can be widely applied to manufacturing of various lithium ions and the like; simple process, low cost and easy mass production.
Description
Technical Field
The invention relates to the fields of lithium ion battery anode materials, lithium ion batteries and the like, in particular to a silver, cobalt and nickel doped lithium manganate anode material of a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are one of the most widely used batteries in modern human life. The raw materials for manufacturing the lithium ion battery mainly comprise a positive electrode active material (positive electrode material), a negative electrode active material (negative electrode material), an electrolyte, a positive and negative electrode current collector, a positive and negative electrode adhesive, a conductive agent and the like. The positive electrode active material occupies the highest specific gravity, usually 30 to 40%, among the manufacturing costs of lithium ion batteries. The importance of the positive electrode material for lithium ion battery fabrication is seen.
Besides the manufacturing cost factors of the positive electrode material of the lithium ion battery, the comprehensive electrochemical performance of the lithium ion battery is also mainly limited by the positive electrode material. Such as core indexes of lithium ion battery capacity, cycle performance, multiplying power performance, safety performance and the like. Therefore, the positive electrode material of the lithium ion battery is important for the production and application of the lithium ion battery. Therefore, the synthesis technology of the positive electrode material of the lithium ion battery, the development of the material, and the like are one of the important contents of the research and development of the related technology.
The lithium ion battery anode materials are various in variety, and the synthesis method and the technology are also rich. The reported positive electrode materials mainly comprise the following four and three categories. (1) Co, ni, mn-based compounds and doping-modified compounds thereof, e.g. LiCoO 2 、LiNiO 2 、LiMnO 2 、LiCo x Ni y Mn 1-x-y O 2 、Li 2 Mn 2 O 4 、LiCo x Ni y Mn 2-x-y O 4 Of these, the most typical, most studied, most mature and most widely used is ternary positive electrode material LiCo x Ni y Mn 2-x-y O 4 . (2) Phosphoric acid, vanadate-based compoundsDoping-modified compounds, e.g. LiFePO 4 、LiMnPO 4 、LiCoPO 4 、LiMn x Fe 1-x PO 4 、LiV 3 O 8 、Li 3 V 2 (PO 4 ) 3 . Of these, the most representative, most widely used and most mature technology is LiFePO 4 And a positive electrode material. (3) Other elemental-based compounds and doping-modified compounds thereof, e.g. LiMnBO 3 、LiFeBO 3 、LiNiBO 3 、LiCoBO 3 、Li 2 MnSiO 4 、Li 2 FeSiO 4 、Li 2 MnTiO 4 、LiNi x Co y Al 1-x-y O 2 、LiNi x Mn y Zr 1-x-y O 2 。
The synthesis technology of the lithium ion battery anode material is mainly divided into two major categories, namely a solid phase synthesis technology and a liquid phase synthesis technology. The solid phase synthesis technology mainly adopts high-temperature solid phase reaction, uses corresponding metal oxide, hydroxide, carbonate, acetate, metal organic compound and the like as raw materials, and synthesizes corresponding anode materials through the high-temperature reaction. LiCo as ternary compound x Ni y Mn 2-x-y O 4 Synthesis, usually in LiOH, coCO 3 、MnO 2 、Ni(OH) 2 And the like are used as raw materials, and are synthesized by reaction at 650-950 ℃ after ball milling, mixing and compression molding. LiFePO 4 The positive electrode material generally uses Li 2 CO 3 、FeSO 4 ·7H 2 O、NH 4 H 2 PO 4 And ball milling, mixing, pressing and forming, roasting at low temperature of 350-450 ℃, and then carrying out solid phase reaction under Ar atmosphere and 650-950 ℃ to synthesize the composite material. The liquid phase synthesis generally uses metal salt as raw material, uses sodium hydroxide and ammonia water as precipitant and matching reagent, firstly prepares hydroxide precursor by precipitation method, and then synthesizes corresponding positive electrode material by high temperature solid phase reaction. The liquid phase method also comprises the technologies of a microemulsion method, a hydrothermal method and the like. The microemulsion method has a relatively complex technical flow and aims at controlling the morphology, the particle size and the like of the synthesized cathode material. The microemulsion method generally synthesizes carbonate or hydroxide precursor with specific morphology first, and then pyrolyzes the precursor to obtain metal oxideFinally, oxidizing the metal with a specific shape into a material which reacts with lithium hydroxide or lithium oxide through a solid phase reaction to finally synthesize the anode material. The lithium ion battery anode material is prepared by the reaction of corresponding raw materials under hydrothermal conditions or the precursor is prepared by hydrothermal method, and then the anode material is synthesized by the solid phase reaction of the precursor. In fact, many reported liquid phase synthesis techniques are a combination of liquid phase synthesis techniques and solid phase synthesis techniques. In addition, "rheological phase" synthesis techniques typically employ at least one insoluble reactant, the reactant being formulated with a small amount of solvent to form a "rheological phase", and the use of insoluble reactant cracking to further break down the synthesized nanomaterial.
The prior lithium ion battery anode material and the prior synthesis technology have respective advantages and disadvantages. The main defects of the existing positive electrode material are poor rate performance and cycle performance and insufficient specific capacity. The most important defects of the prior synthesis technology are high production cost, lower production efficiency, poor consistency of synthetic materials and the like. If the high-temperature solid phase reaction has high energy consumption and long reaction time, the consistency of the synthesized anode material is poor. The reaction yield of the hydrothermal synthesis technology and the rheological phase synthesis technology is lower, and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery and a preparation method thereof, and aims to provide the silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery.
The technical scheme for solving the technical problems is as follows: a preparation method of a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery comprises the following steps:
A. mixing 0.5-0.8 mole of manganese compound, 0.05-0.15 mole of cobalt compound, 0.15-0.35 mole of nickel compound, lithium compound with lithium mole amount of 1.05-1.1 mole, silver compound solid (hereinafter referred to as compound) accounting for 0.01-0.08 times of the total mole amount of manganese, nickel and cobalt and 1.05-1.2 mole of oxidant, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with polytetrafluoroethylene lining;
B. mixing 12-20g of surfactant, 180-250 mL of water, 50-100 mL of surfactant auxiliary agent and 100-150 mL of alkane to prepare microemulsion;
C. adding the microemulsion of the step B into the reaction kettle mixture of the step A, uniformly mixing, sealing, placing in a baking oven at 95-165 ℃ for reacting for 12-36 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step C, fully mixing and washing with 0.5L-1L of alcohol, filtering, washing the filtered solid with distilled water until no sulfate radical is detected, and drying at 65-105 ℃ to obtain the catalyst.
Based on the technical scheme, the invention can also make the following further specific selection.
Specifically, the preferred manganese compound in the step A is any one or a mixture of a plurality of manganese sulfate, manganese nitrate and manganese acetate.
Specifically, the cobalt compound preferred in the step A is any one or a mixture of a plurality of cobalt sulfate, cobalt nitrate and cobalt acetate.
Specifically, the preferred nickel compound in the step A is any one or a mixture of a plurality of nickel sulfate, nickel nitrate and nickel acetate.
Specifically, preferred lithium compounds for step A are LiOH, li 2 O, lithium acetate, lithium sulfate, lithium nitrate.
Specifically, the preferred silver compound for step A is AgNO 3 Mixing of any one or more of AgF.
Specifically, the preferred oxidant in step A is any one of potassium peroxodisulfate, sodium peroxodisulfate and ammonium peroxodisulfate.
Specifically, the preferred surfactant in step B is any one or more of CTAB (cetyltrimethylammonium bromide), DTAB (dodecyltrimethylammonium bromide), SDS (dodecylsulfonic acid), ABS (dodecylbenzenesulfonic acid).
Specifically, the alkane preferred in the step B is any one of cyclohexane, n-heptane and octane.
Specifically, the surfactant auxiliary agent preferred in the step B is any one or a mixture of more of n-butanol, amyl alcohol and isoamyl alcohol.
Specifically, the water preferred in the step B is any one of distilled water, secondary distilled water and deionized water.
Specifically, the preferred alcohol for step D is 95wt% alcohol or absolute alcohol.
Specifically, the detection of sulfate-free ions in step D means that the concentration of sulfate in the eluate is less than 0.1mg/L. The method used for detection is a rapid test of saturated barium chloride solution.
In addition, the invention also provides a silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery, which is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
1. the technology of the invention has better synthesis efficiency. Because the invention adopts a brand new synthesis technology which is a synthesis technology combining a hydrothermal synthesis method and a template synthesis between a solid phase reaction and a liquid phase reaction, the invention is called as a micro-emulsion thermosetting liquid phase synthesis technology (see the synthetic reaction principle of the specification as shown in a schematic diagram 1). The technology of the invention is different from the existing common solid-phase and liquid-phase synthesis technology, and has better synthesis efficiency and more accurate control on chemical composition, particle size, morphology and the like of the synthetic material (see later description of the specification for details). Different from the solid phase synthesis technology, the technology adopts the saturated solution (microemulsion) phase of reactants and the solid phase reaction technology, the contact between the reactants is tighter, the proportion of the reactants to the solvent (microemulsion), the reaction temperature and the reaction time are accurately controlled, the composition, the particle size and the morphology of the synthesized material product can be effectively controlled, and the synthesis efficiency is high. Because the microemulsion of the invention technology can provide a reaction template environment similar to the template synthesis technology, has a crystal growth system of a hydrothermal (solvothermal) synthesis technology, has the characteristic of rapid replenishment of reactants of a solid phase reaction, and remarkably improves the synthesis efficiency of the material while better controlling the composition, the particle size and the morphology of the synthesized material.
2. The silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery synthesized by the invention can better control the morphology of the synthesized material because of adopting a brand-new micro-emulsion hydrothermal liquid-solid mixed phase synthesis technology, and the synthesized positive electrode material is a sphere, an ellipsoid, a double sphere and the like (see the specific embodiments of the invention and the accompanying drawings 1 to 8 of the specification for details);
3. the silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery prepared by the technology adopts a brand-new synthesis technology and adopts a reaction temperature of 95-165 ℃, so that initial nano crystal particles of the synthesized material are larger, the nano particles are agglomerated and form an obvious porous structure (see the attached figures 1-8 for details), the efficiency of wetting the positive electrode material by electrolyte and the intercalation and deintercalation of lithium ions are improved, and further the charge and discharge efficiency and the high-rate discharge performance of the lithium ion battery are improved;
4. the silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery prepared by the technology has higher tap density due to the adoption of a brand new synthesis technology and the doping of silver, and the tap density of a sample of the typical positive electrode material is measured to be 2.53-2.61 g/cm 3 The higher tap density is further beneficial to improving the volume specific capacity and specific energy of the lithium ion battery while improving the charge and discharge efficiency and high-rate discharge performance of the lithium ion battery;
5. the particle size distribution of the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery synthesized by the invention is uniform, the particle size distribution range of the particles is between 0.4 and 2.0 mu m, the average particle size is about 1.0 to 1.5 mu m, the particle size of initial crystallization particles is about 30 to 200nm, and the crystal structures are lamellar crystals (see the specific embodiments of the invention, the accompanying drawings 1 to 8 and the accompanying drawings 9 in the specification);
6. the particle size, the doping amount of silver, nickel and cobalt and the like of the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery prepared by the technology are easy to control, and the production process parameters can be changed in time according to different electrochemical performance requirements and lithium ion batteries with different purposes to prepare the anode material with different doping amounts of silver, nickel and cobalt, different particle sizes and electrochemical performances; the impurity amount of silver, nickel and cobalt is easy to control; the lithium content (Li: mn molar ratio) is relatively high, about 124 to 210:100 (see examples, table 1 for details);
7. the silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery prepared by the technology has higher specific discharge capacity, the first specific discharge capacity is 196.5mAh/g at the highest, and the highest specific discharge capacity is 216.9mAh/g (see example 3, example 5 and specification table 2 for details);
8. the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery prepared by the technology has higher conductivity and good structural stability due to the doping of silver, so that the manufactured lithium ion battery has good high-rate charge-discharge performance and cycle performance, and the charge-discharge capacity retention rate of 10C rate and 500 th week charge-discharge cycle is more than 80 percent and is up to 90.9 percent (see each embodiment and specification table 2 for details);
9. the silver, cobalt and nickel doped lithium manganate positive electrode material of the lithium ion battery prepared by the technology has good high-rate charge-discharge cycle performance, and the 1058 th Zhou Chong discharge capacity of 1C rate is kept up to 90%; the cycle life at 5C rate exceeds 750 weeks (charge and discharge cycles with a battery capacity retention rate higher than 85% of the design capacity); the cycle life at 10C was over 580 weeks (see example 5, fig. 11 for details);
10. the synthesis technology of the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery prepared by the synthesis technology has flexible process, simple steps, high production efficiency, simple equipment, cheap and easily available raw materials, low comprehensive production cost of raw materials and easy realization of large-scale industrial production;
11. the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery prepared by the invention can be widely applied to the fields of manufacturing various types of lithium ion batteries and the like, and has good economic and social benefits.
Drawings
Fig. 1 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 1.
Fig. 2 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 2.
Fig. 3 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 3.
Fig. 4 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 4.
Fig. 5 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 5.
Fig. 6 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 6.
Fig. 7 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 7.
Fig. 8 is an SEM photograph of a silver, cobalt and nickel doped lithium manganate cathode material of a lithium ion battery prepared in example 8.
Fig. 9 is an XRD diffraction pattern of a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery prepared in an exemplary embodiment.
Fig. 10 is a graph showing the 10C rate charge-discharge and 500 cycle capacity retention of a 1000mAh lithium ion battery made of a lithium ion battery silver, cobalt and nickel doped lithium manganate positive electrode material of each example.
Fig. 11 shows the charge-discharge cycle performance of 1000mAh lithium ion batteries 1C, 5C, and 10C made of a silver, cobalt, and nickel doped lithium manganate cathode material of a lithium ion battery of exemplary embodiment 5.
FIG. 12 is a schematic diagram of the reaction principle of the synthesis technology of the present invention.
Detailed Description
The following description of the embodiments of the present invention further refers to the accompanying drawings, which are included to illustrate and not to limit the scope of the invention.
The methods used in the examples below are conventional in the art unless otherwise specified, and the raw materials, reagents and the like used are commercially available products unless otherwise specified.
Example 1:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. uniformly mixing, grinding or ball-milling 0.8 mol of manganese sulfate, 0.05 mol of cobalt acetate, 0.15 mol of nickel nitrate, 0.51 mol of LiOH, 0.01 mol of silver fluoride and 1.1 mol of potassium peroxodisulfate to form a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely sequentially adding 250mL of distilled water, 100mL of surfactant auxiliary agent isoamyl alcohol and 150mL of cyclohexane into 20g of surfactant CTAB to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a baking oven at 95 ℃ for reacting for 36 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step C, carrying out suction filtration, washing the filtered solid with 500mL of 95wt% alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 65 ℃ to obtain the Ag-Co-Ni doped lithium manganate anode material powder.
The morphology, particle size, doping amount of silver, cobalt and nickel and crystal structure of the synthesized material are analyzed and tested by using a Scanning Electron Microscope (SEM), EDS and XRD, the lithium content is measured by using an atomic absorption spectrum, and the tap density is measured by using a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly a double sphere and sphere agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range of the particles is 0.5-1.0 mu m, the average particle size is about 0.8 mu m, and the particle size of initial crystallization particles is about 30-50 nm; tap density of about 2.53g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) is about 1:80, the cobalt doping amount (Co: mn molar ratio) is about 1:16, and the nickel doping amount (Ni: mn molar ratio) is about 3:16; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 99:80; the crystal is a lamellar structure crystal. The positive electrode material prepared in the embodiment is used for manufacturing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the 0.5C multiplying power of the lithium ion battery is 189.6mAh/g in initial discharge specific capacity, and the highest discharge specific capacity is 203.3mAh/g.10C timesThe rate charge-discharge cycle 500 weeks discharge efficiency (compared with the 0.5C rate maximum discharge specific capacity) was 81.8% (see Table 1, table 2, FIG. 1, FIG. 9, FIG. 10 for details).
Example 2:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. 0.375 mole of manganese nitrate, 0.375 mole of manganese acetate, 0.1 mole of nickel sulfate, 0.1 mole of nickel acetate, 0.025 mole of cobalt nitrate, 0.025 mole of cobalt acetate, 0.135 mole of Li 2 Mixing O, 0.27 mol of lithium acetate, 0.01 mol of silver nitrate and 0.95 mol of sodium peroxodisulfate, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely sequentially adding 220mL of deionized water, 80mL of surfactant auxiliary agent n-butanol and 130mL of n-heptane into 18g of surfactant SDS to prepare a microemulsion which is transparent or semitransparent;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a baking oven at 105 ℃ for reacting for 32 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, leaching the filtered solid with 600mL of absolute ethyl alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 75 ℃ to obtain Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly a double sphere and sphere agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range of the particles is 0.5-1.0 mu m, the average particle size is about 0.8 mu m, and the particle size of initial crystallization particles is about 30-50 nm; tap density of about 2.53g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) is about 1:80, the cobalt doping amount (Co: mn molar ratio) is about 1:16, and the nickel doping amount (Ni: mn molar ratio) is about 3:16; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 101:70; the crystals are lamellar structure crystals (see in detailTable 1, fig. 2, fig. 9). The positive electrode material prepared by the embodiment is used for manufacturing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the initial discharge specific capacity of 0.5C multiplying power is 183mAh/g, and the highest discharge specific capacity is 199.9mAh/g. The 10C rate charge-discharge cycle had a 500-week discharge efficiency (compared to the 0.5C rate maximum discharge specific capacity) of 83.6% (see Table 2, FIG. 10 for details).
Example 3:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.3 mol of manganese sulfate, 0.3 mol of manganese acetate, 0.325 mol of nickel nitrate, 0.075 mol of cobalt acetate, 0.305 mol of lithium sulfate, 0.305 mol of lithium nitrate, 0.03 mol of silver nitrate and 1.0 mol of ammonium peroxodisulfate, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely mixing 16g of surfactant ABS with 200mL of distilled water, 60mL of surfactant additive amyl alcohol and 120mL of octane in sequence to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a 115 ℃ oven for reacting for 28 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, leaching the filtered solid with 800mL of 95% alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 85 ℃ to obtain Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly a sphere and a double sphere agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range of the particles is 0.6-1.2 mu m, the average particle size is about 1.0 mu m, and the particle size of initial crystallization particles is about 60-80 nm; tap density of about 2.54g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) was about 3:70, the cobalt doping amount (Co: mn molar ratio) was about 1:7, and the nickel doping amount (Ni: mn molar ratio) was about1:35; the lithium content (Li: mn molar ratio) as measured by atomic absorption spectrometry is about 101 to 70; the crystal is a lamellar structure crystal. The positive electrode material prepared in the embodiment is used for manufacturing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the 0.5C multiplying power of the lithium ion battery is 196.5mAh/g of initial discharge specific capacity, and the highest discharge specific capacity is 205.5mAh/g. The 10C rate charge-discharge cycle had a 500-week discharge efficiency (compared to the 0.5C rate maximum discharge specific capacity) of 85.4% (see Table 1, table 2, FIG. 3, FIG. 9, FIG. 10 for details).
Example 4:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.2 mole of manganese sulfate, 0.2 mole of manganese nitrate, 0.2 mole of manganese acetate, 0.1 mole of nickel sulfate, 0.1 mole of nickel nitrate, 0.1 mole of nickel acetate, 0.05 mole of cobalt sulfate, 0.05 cobalt acetate, 0.51 lithium nitrate, 0.03 mole of silver nitrate and 1.05 mole of oxidant ammonium peroxodisulfate, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle lined with polytetrafluoroethylene;
B. stirring, namely sequentially mixing 12g of surfactant DTAB with 180mL of distilled water and 50mL of surfactant auxiliary agent n-butanol and 100mL of cyclohexane to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a 125 ℃ oven for reacting for 24 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, leaching the filtered solid with 800mL of 95% alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 105 ℃ to obtain Ag-Co-Ni doped lithium manganate anode material powder.
The morphology, particle size, doping amount of silver, cobalt and nickel and crystal structure of the synthesized material are analyzed and tested by using a Scanning Electron Microscope (SEM), EDS and XRD, the lithium content is measured by using an atomic absorption spectrum, and the tap density is measured by using a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material mainly comprises double spheres, ellipsoids and spheres agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range is 0.8-1.2 mu m, the average particle size is about 1 mu m, and the initial particle size is about 1 mu mThe grain size of the primary crystallization particles is about 50-100 nm; tap density of about 2.55g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) is about 3:70, the cobalt doping amount (Co: mn molar ratio) is about 1:70, and the nickel doping amount (Ni: mn molar ratio) is about 1:70; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 102:70; the crystal is a layered structure crystal (see table 1, fig. 4, fig. 9 for details). The positive electrode material prepared in the embodiment is used for manufacturing a lithium ion battery to determine the electrochemical performance of the battery, the initial discharge specific capacity of 0.5C multiplying power is 188.9mAh/g, and the highest discharge specific capacity is 210.3mAh/g. The 10C rate charge-discharge cycle has a 500-week discharge efficiency (compared with the 0.5C rate maximum discharge specific capacity) of 86.7% (see Table 2, FIG. 10 for details).
Example 5:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.55 mol of manganese sulfate, 0.35 mol of nickel sulfate, 0.1 mol of cobalt sulfate, 0.525 mol of lithium nitrate, 0.05 mol of silver nitrate and 0.65 mol of potassium peroxodisulfate, fully grinding or ball-milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely mixing 20g of surfactant CTAB with 200mL of distilled water, 100mL of n-butanol and 150mL of n-heptane in sequence to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a baking oven at 135 ℃ for reacting for 20 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, washing the filtered solid with 1L of 95wt% alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 85 ℃ to obtain the Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly double spheres and spheres agglomerated by nano particles, the agglomerated particles have a porous structure, and the particles areThe grain diameter range is 0.8-1.5 mu m, the average grain diameter is about 1.2 mu m, and the grain diameter of the primary crystallization grain is about 50-150 nm; tap density of about 2.56g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Silver doping (Ag: mn molar ratio) of about 1:12, cobalt doping (Co: mn molar ratio) of about 1:4, nickel doping (Ni: mn molar ratio) of about 5:12; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 51:30; the crystal is a layered structure crystal (see table 1, fig. 5, fig. 9 for details). The positive electrode material prepared in the embodiment is used for manufacturing a lithium ion battery to determine the electrochemical performance of the battery, wherein the 0.5C multiplying power first discharge specific capacity is 193.3mAh/g, and the highest discharge specific capacity is 216.9mAh/g. The 10C rate charge-discharge cycle had a 500-week discharge efficiency (compared to the 0.5C rate maximum discharge specific capacity) of 87.5% (see Table 2, FIG. 10 for details). The prepared lithium ion battery has excellent high-rate discharge of 1000mAh sample, the capacity (capacity excess coefficient is 1.1, the charging amount of the positive electrode active material is 10% greater than that of the designed capacity), the 1C rate first discharge capacity is 1095mAh, and the 1058-week circulation capacity retention rate is 90%;5C rate first discharge capacity 1054mAh, and cycle capacity retention rate of 755 weeks of 85%; the initial discharge capacity 959mAh at 10C rate and the 584-week cycle capacity retention rate are 85% (see FIG. 11 for details).
Example 6:
a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.55 mol of manganese nitrate, 0.325 mol of nickel sulfate, 0.125 mol of cobalt sulfate, 0.26 mol of lithium nitrate, 0.05 mol of silver nitrate and 1.05 mol of oxidant ammonium peroxodisulfate, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely sequentially mixing 20g of surfactant CTAB with 200mL of distilled water, 80mL of n-butanol and 150mL of cyclohexane to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a baking oven at 145 ℃ for reacting for 16 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, washing with 500mL of 95wt% alcohol for one time, washing with distilled water until no sulfate radical is detected, and drying at 85 ℃ to obtain Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly a nanoparticle agglomerated ellipsoid, sphere and double sphere, wherein the agglomerated particles have a porous structure, the particle size range is 0.8-1.5 mu m, the average particle size is about 1.2 mu m, and the initial crystal particle size is about 80-200 nm; tap density of about 2.57g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Silver doping (Ag: mn molar ratio) of about 1:12, cobalt doping (Co: mn molar ratio) of about 1:4, nickel doping (Ni: mn molar ratio) of about 5:12; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 103:60; the crystal is a layered structure crystal (see table 1, figure 6 and figure 9 for details). The positive electrode material prepared by the embodiment is used for manufacturing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the initial discharge specific capacity of 0.5C multiplying power is 192.5mAh/g, and the highest discharge specific capacity is 208.7mAh/g. The 10C rate charge-discharge cycle has a 500-week discharge efficiency (compared with the 0.5C rate maximum discharge specific capacity) of 90.1% (see Table 2, FIG. 10 for details).
Example 7
A silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.35 mole of manganese sulfate, 0.1 mole of manganese nitrate, 0.1 mole of manganese acetate, 0.1 mole of nickel sulfate, 0.1 mole of nickel nitrate, 0.1 mole of nickel acetate, 0.15 mole of cobalt sulfate, 1.1 mole of LiOH, 0.04 mole of silver nitrate, 0.04 mole of AgF and 0.55 mole of potassium peroxodisulfate, 0.3 mole of sodium peroxodisulfate and 0.2 mole of ammonium peroxodisulfate, fully grinding or ball milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely sequentially mixing 20g of surfactant CTAB with 200mL of distilled water, 100mL of n-butanol and 150mL of cyclohexane to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a 155 ℃ oven for reacting for 14 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, washing with 800mL of 95wt% alcohol once, washing with distilled water until no sulfate radical is detected, and drying at 85 ℃ to obtain Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly spheres, double spheres and ellipsoids agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range is 0.8-1.8 mu m, the average particle size is about 1.5 mu m, and the particle size of initial crystallization particles is about 100-200 nm; tap density of about 2.59g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) is about 4:25, the cobalt doping amount (Co: mn molar ratio) is about 2:5, and the nickel doping amount (Ni: mn molar ratio) is about 3:5; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 21:10; the crystal is a layered structure crystal (see table 1, fig. 7, fig. 9 for details). The positive electrode material prepared by the embodiment is used for preparing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the initial discharge specific capacity of 0.5C multiplying power is 190.6mAh/g, and the highest discharge specific capacity is 215.6mAh/g. The 10C rate charge-discharge cycle had a 500-week discharge efficiency (compared to the 0.5C rate maximum discharge specific capacity) of 91.8% (see Table 2, FIG. 10 for details).
Example 8
A silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery is prepared by the following specific steps:
A. mixing 0.5 mol of manganese sulfate, 0.35 mol of nickel sulfate, 0.15 mol of cobalt sulfate, 1.05-1.2 mol of lithium nitrate, 0.08 mol of silver nitrate and 1.05 mol of oxidant ammonium peroxodisulfate, fully grinding or ball-milling to obtain a reaction mixture, and transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
B. stirring, namely sequentially mixing 20g of surfactant CTAB with 200mL of distilled water, 80mL of n-butanol and 150mL of cyclohexane to prepare transparent or semitransparent microemulsion;
C. adding the microemulsion of the step B into the reaction kettle of the step A, uniformly mixing, sealing, placing in a baking oven at 165 ℃ for reacting for 12 hours, and cooling;
D. and C, taking out the mixture after the reaction in the step, filtering, stirring and washing once by using 1L of 95wt% of alcohol, then washing by using distilled water until no sulfate radical is detected, and drying at 85 ℃ to obtain the Ag-Co-Ni doped lithium manganate anode material powder.
The particle size, the doping amount of silver, cobalt and nickel and the crystal structure of the synthesized material are tested by scanning electron microscope SEM, EDS and XRD analysis, the lithium content is measured by atomic absorption spectrometry, and the tap density is measured by a vibrating pile method. The obtained Ag-Co-Ni doped lithium manganate positive electrode material is mainly a double sphere and sphere agglomerated by nano particles, wherein the agglomerated particles have a porous structure, the particle size range of the particles is 1.0-2.0 mu m, the average particle size is about 1.5 mu m, and the particle size of the initial crystallization particles is about 100-200 nm; tap density of about 2.61g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The silver doping amount (Ag: mn molar ratio) is about 4:25, the cobalt doping amount (Co: mn molar ratio) is about 2:5, and the nickel doping amount (Ni: mn molar ratio) is about 3:5; the lithium content (Li: mn molar ratio) as determined by atomic absorption spectrometry was about 21:10; the crystal is a layered structure crystal (see table 1, fig. 8, fig. 9 for details). The positive electrode material prepared in the embodiment is used for manufacturing a lithium ion battery, and the electrochemical performance of the battery is measured, wherein the 0.5C multiplying power of the lithium ion battery is 189.4mAh/g in initial discharge specific capacity, and the highest discharge specific capacity is 211.5mAh/g. The 10C rate charge-discharge cycle has a 500-week discharge efficiency (compared with the 0.5C rate maximum discharge specific capacity) of 90.9% (see Table 2, FIG. 10 for details).
TABLE 1 chemical composition and fitting chemical formula of the cathode material prepared by the invention
TABLE 2 tap Density and charge-discharge Property of the cathode Material prepared according to the invention
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the silver, cobalt and nickel doped lithium manganate anode material of the lithium ion battery is characterized by comprising the following specific steps:
A. mixing and grinding each 0.5-0.8 mole of manganese compound, 0.05-0.15 mole of cobalt compound, 0.15-0.35 mole of nickel compound, lithium compound with lithium mole amount of 1.05-1.1 mole, silver compound and 1.05-1.2 mole of oxidant into a reaction mixture, and transferring the mixture into a reaction kettle, wherein the mole amount of the silver compound is 0.01-0.08 times of the mole total amount of manganese, nickel and cobalt;
B. mixing 12-20g of surfactant, 180-250 mL of water, 50-100 mL of surfactant auxiliary agent and 100-150 mL of alkane to prepare microemulsion;
C. adding the microemulsion obtained in the step B into the reaction kettle in the step A, uniformly mixing, sealing, placing in a baking oven at 95-165 ℃ for reacting for 12-36 hours, and cooling;
D. taking out the mixture obtained after the reaction in the step C, filtering, leaching the solid obtained by filtering by using 0.5L-1L of alcohol, washing by using distilled water until no sulfate radical is detected, and drying at 65-105 ℃ to obtain the catalyst;
the surfactant in the step B is any one of CTAB, DTAB, SDS, ABS;
the surfactant auxiliary agent in the step B is any one or a mixture of more of n-butanol, n-amyl alcohol and isoamyl alcohol;
the alkane in the step B is any one of cyclohexane, n-heptane and n-octane.
2. The method for preparing the silver, cobalt and nickel doped lithium manganate cathode material of the lithium ion battery according to claim 1, wherein the manganese compound in the step A is any one or a mixture of a plurality of manganese sulfate, manganese acetate and manganese nitrate.
3. The method for preparing the silver, cobalt and nickel doped lithium manganate cathode material of the lithium ion battery according to claim 1, wherein the nickel compound in the step A is any one or a mixture of a plurality of nickel sulfate, nickel acetate and nickel nitrate.
4. The method for preparing the silver, cobalt and nickel doped lithium manganate cathode material of the lithium ion battery according to claim 1, wherein the cobalt compound in the step A is any one or a mixture of a plurality of cobalt sulfate, cobalt acetate and cobalt nitrate.
5. The method for preparing a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery according to claim 1, wherein the lithium compound in the step A is LiOH, li 2 O, lithium acetate, lithium sulfate, lithium nitrate.
6. The method for preparing the silver, cobalt and nickel doped lithium manganate cathode material of the lithium ion battery according to claim 1, wherein the oxidant in the step A is any one or a mixture of more of potassium peroxodisulfate, sodium peroxodisulfate and ammonium peroxodisulfate.
7. The method for preparing a silver, cobalt and nickel doped lithium manganate positive electrode material of a lithium ion battery according to claim 1, wherein the silver compound in the step A is AgNO 3 Either AgF.
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| CN103274454A (en) * | 2013-05-19 | 2013-09-04 | 吉林大学 | Hydrothermal synthesis method of micro-emulsion of nano lithium titanate |
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| CN103274454A (en) * | 2013-05-19 | 2013-09-04 | 吉林大学 | Hydrothermal synthesis method of micro-emulsion of nano lithium titanate |
| CN105118983A (en) * | 2015-09-16 | 2015-12-02 | 湖北宇电能源科技股份有限公司 | Method for preparing lithium nickel manganese oxide anode material |
| CN107634195A (en) * | 2017-08-31 | 2018-01-26 | 福建师范大学 | Mix the preparation method of the nickel-cobalt-manganese ternary material of monovalent cation |
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