CN103700850B - 锂离子电池正极复合材料 - Google Patents
锂离子电池正极复合材料 Download PDFInfo
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- CN103700850B CN103700850B CN201210373325.5A CN201210373325A CN103700850B CN 103700850 B CN103700850 B CN 103700850B CN 201210373325 A CN201210373325 A CN 201210373325A CN 103700850 B CN103700850 B CN 103700850B
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- Prior art keywords
- lithium ion
- ion battery
- composite material
- positive active
- anode composite
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 claims abstract description 76
- 239000011247 coating layer Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910013612 LiCo0.75Ni0.25O2 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000003746 solid phase reaction Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010671 solid-state reaction Methods 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 4
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 4
- 238000010606 normalization Methods 0.000 description 4
- 150000003901 oxalic acid esters Chemical class 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020855 Co0.75Ni0.25(OH)2 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- NRTAIOMPJNZURJ-UHFFFAOYSA-N [Tc+4].[O-2].[O-2].[Ti+4] Chemical compound [Tc+4].[O-2].[O-2].[Ti+4] NRTAIOMPJNZURJ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 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 description 1
- OYFUIMQYZOLBMZ-UHFFFAOYSA-J tetrachloromanganese Chemical compound Cl[Mn](Cl)(Cl)Cl OYFUIMQYZOLBMZ-UHFFFAOYSA-J 0.000 description 1
- PJYXVICYYHGLSW-UHFFFAOYSA-J tetrachloroplumbane Chemical compound Cl[Pb](Cl)(Cl)Cl PJYXVICYYHGLSW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/22—Plumbates; Plumbites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- 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
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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Abstract
本发明涉及一种锂离子电池正极复合材料,其包括正极活性物质及包覆于该正极活性物质表面的包覆层,该正极活性物质为层状锂-过渡金属复合氧化物,该包覆层的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物。
Description
技术领域
本发明涉及一种锂离子电池正极复合材料。
背景技术
锂离子电池是一种新型的绿色化学电源,与传统的镍镉电池、镍氢电池相比具有电压高、寿命长、容量和能量密度大、体积小、自放电率低等优点。自1990年初次进入市场以来,使用范围越来越广,已经被广泛用于各种便携式电子设备。随着新能源汽车的兴起,锂离子电池以其优异的特性,被认为是新能源汽车理想的储能设备之一。
目前,锂离子电池的制约因素在于其循环过程中伴随的容量衰减,以及由此导致的较差的循环寿命。容量衰减的原因一方面是正极活性物质的本征结构随着循环的进行逐渐发生不可逆改变,另外一方面是当正极活性物质脱锂时,氧化性增强,容易与有机电解液发生反应,从而使正极活性物质损失,导致容量衰减。因此,如何提高正极活性物质在电池循环过程中的稳定性,降低电极副反应程度,是提高锂离子电池循环寿命的关键。
对锂离子电池正极活性物质的颗粒表面采用其它材料包覆,是现有技术中对正极活性物质进行改性的常用方法。例如,在磷酸铁锂的颗粒表面包覆一层碳可以有效解决磷酸铁锂导电性较差的问题,使包覆有碳层的磷酸铁锂具有较好的导电性。然而,现有技术中对钴酸锂在电池循环过程中的稳定性的改进问题并没有得到很好的解决。
发明内容
有鉴于此,确有必要提供一种具有较好的循环稳定性的锂离子电池正极复合材料。
一种锂离子电池正极复合材料,其包括正极活性物质及包覆于该正极活性物质表面的包覆层,该正极活性物质为层状锂-过渡金属复合氧化物,该包覆层的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物。
一种锂离子电池正极复合材料,其包括正极活性物质及包覆于该正极活性物质表面的包覆层,该正极活性物质为层状锂-过渡金属复合氧化物,该包覆层的材料为Li2TiO3、Li2MnO3、Li2SnO3、Li2PbO3、Li2TeO3、Li2RuO3、Li2HfO3及Li2ZrO3中的至少一种。
相较于现有技术,本发明提供的正极复合材料中,该正极活性物质为层状锂-过渡金属复合氧化物,该包覆层的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物,该包覆层的氧化物是一个层状结构的化合物,层间具有二维的锂离子通道,并且在晶体C轴方向上存在一维的锂离子通道,因此具有良好的锂离子传导能力,从而可以使该正极复合材料具有较好的倍率性能。另外,由于该锂-金属复合氧化物的化学性质稳定,不与锂离子电池电解液反应,从而阻断了层状锂-钴镍锰复合氧化物和电解液的直接接触,抑制电池循环过程中副反应的发生,使锂离子电池具有较好的循环稳定性和电池寿命。
附图说明
图1为本发明实施例正极复合材料的结构示意图。
图2为本发明实施例正极复合材料的制备方法的过程示意图。
图3为本发明实施例复合前驱体的制备方法的过程示意图。
图4为本发明实施例1包覆有Co离子掺杂Li2TiO3的LiCoO2的XRD图谱。
图5为图4的局部放大图。
图6为本发明实施例1与对比例的电池循环性能测试图。
图7为本发明实施例1与对比例的电池倍率性能测试图。
图8为本发明实施例2包覆有Ni离子和Co离子掺杂Li2TiO3的LiCo0.75Ni0.25O2的XRD图谱。
图9为本发明实施例2的电池循环性能测试图。
图10为本发明实施例2的电池倍率性能测试图。
主要元件符号说明
正极复合材料 | 10 |
正极活性物质 | 12 |
包覆层 | 14 |
复合前驱体 | 100 |
正极活性物质前驱体 | 120,120’ |
包覆层前驱体 | 140 |
包覆试剂 | 144 |
锂源化合物 | 160 |
结晶水 | 180 |
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的锂离子电池正极复合材料作进一步的详细说明。
请参阅图1,本发明实施例提供一种锂离子电池正极复合材料10,其包括正极活性物质12及包覆于该正极活性物质12表面的包覆层14。
【正极活性物质】
该正极活性物质12为锂-过渡金属复合氧化物,该锂-过渡金属复合氧化物晶体结构为α-NaFeO2型层状结构,化学式为LixLO2,其中0.1≤x≤1.1,L为一种或多种过渡金属元素,如该过渡金属元素可以列举为镍、钴以及锰中的一种或多种。该层状锂-过渡金属复合氧化物的化学式可以为LixL1-yRyO2,其中0≤y<1,优选地,0≤y≤0.5。其中,R为掺杂元素,选自碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡族元素及稀土元素中的一种或多种,优选地,R选自Co、Ni、Mn、Cr、V、Ti、Sn、Cu、Al、Fe、B、Sr、Ca、Nd、Ga及Mg中的至少一种。更为具体地,该层状锂-过渡金属复合氧化物的化学式可以为LixNi1-yRyO2,LixCo1-yRyO2或LixMn1-yRyO2。
更为优选地,该正极活性物质12为LiCoO2、LiCo0.75Ni0.25O2以及LiNi0.5Mn0.5O2中的至少一种。
【包覆层】
该包覆层14的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物,通式可以是Li2AO3,其中A为具有+4价的金属元素,优选为Ti、Sn、Mn、Pb、Te、Ru、Hf及Zr中的至少一种,如Li2TiO3、Li2MnO3、Li2SnO3、Li2PbO3、Li2TeO3、Li2RuO3、Li2HfO3及Li2ZrO3。
另外,该锂-金属复合氧化物也可以是掺杂的Li2AO3,归一化通式可以写作[Li1-2aMa?a][Li1/3-2b-cMbN3cA2/3-2c?b]O2,其中M及N为掺杂元素,“?”代表Li+位空穴,0≤2a<1,0≤2b+c<1/3,且0≤2c<2/3。该归一化通式中Li1-2aMa?a位于层间八面体位点,Li1/3-2b-cMbN3cA2/3-2c?b位于层内八面体位点。具体来说,未掺杂的Li2AO3归一化通式可以写作[Li]α[Li1/3A2/3]βO2,[]α表示[]内的元素位于层间的八面体位点,为Li+所占据;[]β表示[]内的元素位于层内的八面体位点,被Li+和A4+占据,且比例为1:2。当掺杂元素M取代一定量层间和层内的Li+时,同时还产生等量的空穴(?)。这些空穴有助于锂离子在该包覆层14中迁移。另外,掺杂元素N可以同时取代一定量层内的Li+和A4+。
具体地,M及N优选为碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡族元素及稀土元素中的一种或多种,进一步优选地,M及N选自Co、Ni、Mn、Cr、V、Ti、Sn、Cu、Al、Fe、B、Sr、Ca、Nd、Ga及Mg中的至少一种。
另外,该掺杂的Li2AO3中的掺杂元素M及N中的至少一个可以来自该层状锂-过渡金属复合氧化物,即M及N中的至少一个可以与该正极活性物质12中的层状锂-过渡金属复合氧化物的过渡金属元素相同。举例来说,当该正极活性物质12的过渡金属元素为Ni和Co,如LiCo0.75Ni0.25O2时,该归一化通式可以为[Li1-2aAa?a][Li1/3-2b-cNibCo3cA2/3-2c?b]O2。
该包覆层14优选为连续的锂-金属复合氧化物层。更为优选地,该包覆层14具有均匀的厚度。在本实施例中,该包覆层14为原位生成在该正极活性物质12表面,具有均匀厚度的连续的锂-金属复合氧化物层。
该包覆层14在该正极复合材料10中的质量百分含量为0.05%至7%,优选地,为1%至7%,更为优选为5%。该包覆层14的厚度为2纳米至20纳米,优选地,该厚度为2纳米至10纳米。可以理解,锂离子电池的正极中可以包括大量该正极活性物质12,该包覆层14为单独包覆在该单个正极活性物质12的表面。在优选的实施例中,在锂离子电池的正极中,每个正极活性物质12的表面均包覆有该包覆层14。该包覆层14优选为完整的包覆在该正极活性物质12的整个表面。该正极活性物质12的粒径不限,可根据需要进行选择,优选为1微米至500微米。该正极活性物质12的形状不限,可以为球状、棒状、针状、片状、不规则形状或它们的组合。该包覆层14单独包覆在该正极活性物质12表面,从而使该正极复合材料10仍然对应的具有球状、棒状、针状、片状、不规则形状等与该正极活性物质12相同或相似的形状。
【正极复合材料的制备方法】
本发明实施例提供一种正极复合材料的制备方法,其包括以下步骤:
S1,制备一复合前驱体,该复合前驱体包括正极活性物质前驱体及包覆于该正极活性物质前驱体表面的包覆层前驱体;
S2,将该复合前驱体与锂源化合物反应,使该复合前驱体中的包覆层前驱体及正极活性物质前驱体同时锂化,从而生成该正极复合材料。
该正极活性物质前驱体为可以与该锂源化合物反应生成所述层状锂-过渡金属复合氧化物的化合物,具体可以为所述过渡金属元素的含氧化合物。该过渡金属元素的含氧化合物具体可以选自氢氧化物、含氧酸盐及氧化物中的至少一种。该过渡金属元素的含氧酸盐可以举例为草酸盐、乙酸盐、碳酸盐及碱式氧化物。具体地,该过渡金属元素的含氧化合物可举例为氢氧化钴、氢氧化镍、氢氧化锰、钴镍的氢氧化物、镍锰的氢氧化物、锰钴的氢氧化物、草酸镍、草酸锰、草酸钴、钴镍的草酸盐、镍锰的草酸盐、锰钴的草酸盐、碱式氧化锰、碱式氧化钴、碱式氧化镍、钴镍的氧化物、镍锰的氧化物、锰钴的氧化物、碳酸锰、碳酸镍、碳酸钴、钴镍的碳酸盐、镍锰的碳酸盐以及锰钴的碳酸盐中的至少一种。该过渡金属元素的含氧化合物可进一步带有结晶水。
该包覆层前驱体可以是具有+4价的金属元素的金属氧化物或金属氢氧化物,具体可以举例为二氧化钛(TiO2)、二氧化锡(SnO2)、二氧化锰(MnO2)、二氧化铅(PbO2)、二氧化锝(TeO2)、二氧化钌(RuO2)、二氧化铪(HfO2)及二氧化锆(ZrO2)中的至少一种。
该锂源化合物可选择为氢氧化锂、氯化锂、硫酸锂、硝酸锂、磷酸二氢锂以及醋酸锂中的一种或多种。
请参阅图2,上述方法可以用于制备该正极复合材料10,该复合前驱体100包括包覆层前驱体140及正极活性物质前驱体120。包覆层前驱体140是可以与锂源化合物反应生成该包覆层14的前驱体。也就是说,该包覆层前驱体140是可以与该锂源化合物反应生成具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物的化合物。该正极活性物质前驱体120是可以与锂源化合物反应生成该正极活性物质12的前驱体。该包覆层前驱体140为原位生成在该正极活性物质前驱体120表面的连续层状结构。该锂源化合物160同时与该正极活性物质前驱体120及该包覆层前驱体140反应,生成该正极活性物质12及该包覆于该正极活性物质12表面的包覆层14。该包覆层前驱体140优选为单独包覆在单个所述过渡金属元素的含氧化合物的表面。
在本实施例中,该步骤S1可以包括以下步骤:
S11,将该正极活性物质前驱体分散于一液相溶剂,以形成一固液混合物,且该正极活性物质前驱体不溶于该液相溶剂;
S12,向该固液混合物中加入一包覆试剂;
S13,通过加热该加入有包覆试剂的固液混合物,使该包覆试剂在该正极活性物质前驱体表面生成该包覆层前驱体,得到该复合前驱体。
在本实施例中,当所述过渡金属元素的含氧化合物选自氢氧化物及含氧酸盐中的至少一种,或者该过渡金属元素的含氧化合物进一步带有结晶水时,该液相溶剂可以仅为有机溶剂。该氢氧化物、含氧酸盐或带有的结晶水可通过加热缓慢释放出水,与该包覆试剂进行反应。该有机溶剂可以选择为甲醇、乙醇、丙醇、异丙醇、乙二醇、丙酮、二氯乙烷或氯仿等常用有机溶剂。
该包覆试剂优选为液态或溶液,或者可溶于该液相溶剂。该包覆试剂可以包括金属卤化物及金属有机酯中的至少一种,具体可以是具有+4价的金属元素的金属卤化物或金属有机酯,具体可以举例为钛酸四乙酯、钛酸四丁酯、锆酸四丁酯、锡酸四丁酯、铪酸四丁酯、四氯化钛、四氯化锆、四氯化锡、四氯化铪、四氯化铅、四氯化锝、四氯化钌及四氯化锰。
在该步骤S11中,可以通过超声振荡或机械搅拌等方法,将正极活性物质前驱体均匀分散于该液相溶剂中。
在该步骤S12中,该包覆试剂加入的摩尔量优选为该正极活性物质前驱体的0.1%至20%。该包覆试剂加入该固液混合物后可进一步包括一将该包覆试剂与该固液混合物均匀混合的步骤。具体可以通过超声振荡或机械搅拌的方式,使该包覆试剂与该固液混合物充分均匀混合。
在该步骤S13中,该加入有包覆试剂的固液混合物可直接在开放环境中加热或放入水热釜中进行加热。该水热釜可以为一密封高压釜,在该加热反应过程中提供大于1个大气压的压力。该加热温度根据压力条件及包覆试剂的不同而变化,可以选择为80℃至200℃。该加热时间根据加热温度及包覆试剂的量而变化,可以选择为10分钟至12小时。在该步骤S13的加热过程中,该包覆试剂发生水解反应,在该正极活性物质前驱体表面生成该包覆层前驱体。
请参阅图3,当该正极活性物质前驱体120含有结晶水180时,该加热步骤使该结晶水180逐渐脱出,并与该包覆试剂144发生反应,形成包覆层前驱体140包覆在结晶水脱出的正极活性物质前驱体120表面。
通过采用无水的液相溶剂,仅靠正极活性物质前驱体提供水,使包覆试剂发生反应,可以使反应易于控制且生成形貌更好,更为均匀的包覆层前驱体。
在另一实施例中,该步骤S1可包括以下步骤:
S11’,将该正极活性物质前驱体分散于一液相溶剂,以形成一固液混合物,且该正极活性物质前驱体不溶于该液相溶剂;
S12’,向该固液混合物中加入一包覆试剂;
S13’,使该包覆试剂与水反应并发生分解,在该正极活性物质前驱体表面生成该包覆层前驱体,得到该复合前驱体。
上述步骤S11’-S13’与S11-S13基本相同,区别仅在当该正极活性物质前驱体120本身不带结晶水或为氧化物时,可通过外加水的步骤使该包覆试剂与水反应产生分解。具体地,该液相溶剂可为有机溶剂和少量水形成的混合溶剂。当该液相溶剂中仅含有有机溶剂时,该步骤S13’中可进一步包括一向该固液混合物中加入水的步骤。该加入的水的量可以由该包覆试剂的加入量加以确定。总之,该固液混合物中可以有少量水,该固液混合物中水与有机溶剂的体积比优选小于或等于1:10,更为优选小于1:50。另外,该固液混合物中水的量可以由该包覆试剂的加入量加以确定。
在该步骤S2中,该复合前驱体与该锂源化合物可进行高温固相反应,具体可以先将该复合前驱体与该锂源化合物均匀混合形成固相混合物,再将该固相混合物在固相反应温度下加热。具体地,该复合前驱体与该锂源化合物可先通过机械搅拌或球磨的方式均匀混合。该高温固相反应的温度可以根据该复合前驱体的材料而定,具体可以为400℃至900℃,反应时间可以为2至12小时。另外,在将该固相混合物在该高温固相反应温度下加热之前,可预先将该固相混合物在一较低温度下预烧结,以使复合前驱体充分分解,该较低温度可以为350℃至400℃,时间可以为0.5小时至1小时。在预烧结之后,可不经过降温,直接将温度升至该高温固相反应温度。该锂源化合物与该复合前驱体的比例可以根据该正极活性物质前驱体及该包覆层前驱体分别生成正极活性物质及包覆层所需要的锂的量加以确定,另外,由于锂在高温加热时易挥发,因此该锂源化合物相对于该复合前驱体可以为化学计量比过量,例如该锂源化合物与该复合前驱体的化学计量比可以大于1:1,例如为1.2:1。在正极活性物质前驱体锂化并生成正极活性物质的同时,该锂源化合物也和该包覆层前驱体反应,直接在该正极活性物质表面生成该包覆层,由于该高温固相反应过程中该包覆层前驱体与该正极活性物质前驱体共同进行高温处理,且均形成锂化物,因此该生成的正极活性物质及包覆层之间存在较强的化学键合力,从而使该包覆层结构致密连续,且厚度均匀。
可以理解,该包覆试剂可以含有不止一种该+4价的金属元素,从而可以最终形成具有多种锂-金属复合氧化物混合的包覆层14。
本发明实施例提供的正极复合材料中,该包覆层的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物,在晶体C轴方向上存在一维的锂离子通道,因此具有良好的锂离子传导能力,从而可以使该正极复合材料具有较好的倍率性能。另外,由于该锂-金属复合氧化物的化学性质稳定,不与锂离子电池电解液反应,从而阻断了该层状锂-过渡金属复合氧化物和电解液的直接接触,抑制电池循环过程中副反应的发生。
进一步地,本发明实施例通过先制备一核-壳结构的前驱体,再将该核-壳结构的前驱体的核及壳同时锂化,一次形成该正极复合材料。上述原位包覆的方法形成的包覆层并非将包覆材料松散的堆积在正极活性物质表面,而是连续的包覆材料层,具有均匀的厚度和连续的晶体结构,包覆层和层状锂-过渡金属复合氧化物之间的结合牢固致密,有效的减少了晶错,提高了锂离子在包覆层中的迁移率,从而使该正极复合材料具有较好的循环稳定性。
【实施例】
实施例1
称取0.25克Co(OH)2,超声分散或搅拌分散于10mL乙醇中,得到固液混合物。向该固液混合物中加入钛酸四丁酯,加入的钛酸四丁酯的摩尔量为Co(OH)2的10%。继续超声振荡或搅拌后,将该固液混合物转入干洁的水热釜中,在150℃下加热3小时后取出,得到均匀的非晶TiO2层形成于Co(OH)2表面。将该复合前驱体与化学计量比的LiOH?H2O混合,并使乙醇完全蒸干,然后以3℃/分钟的升温速率升温至800℃,并在800℃下焙烧5小时,自然降温,得到产物为包覆有Co离子掺杂Li2TiO3的LiCoO2。请参阅图4,将该产物进行XRD测试,显示得到了纯相的LiCoO2。请参阅图5,局部放大该XRD图,可见Li2TiO3特征峰,并且,Li2TiO3在23度附近的特征峰消失,说明形成的Li2TiO3中存在Co3+掺杂。
将该实施例1制备的正极复合材料与导电剂、粘结剂混合设置在正极集流体表面,形成正极,负极采用金属锂,将正极及负极通过隔膜间隔并以电解液浸润组装成锂离子电池,进行充放电性能测试。
作为与实施例1的对比,采用未包覆的钴酸锂(LiCoO2)替换上述正极复合材料,其它条件不变,组装锂离子电池,进行充放电性能测试。
请参阅图6,将上述两种锂离子电池在室温下以1C电流进行恒流充放电,从图6中明显可以看到采用Co离子掺杂Li2TiO3的LiCoO2的锂离子电池具有更高的首次放电比容量(约140mAh/g),及良好的容量保持率,在100次循环后电池容量几乎不衰减。而未包覆的钴酸锂的锂离子电池首次放比电容量只有约128mAh/g,且经过100次充放电循环后容量减少至90mAh/g以下。
请参阅图7,将上述两种电池以不同倍率的电流进行倍率性能测试,可以看到,未包覆的钴酸锂的锂离子电池以1C、2C、3C、4C、5C及10C倍率进行恒流充放电,随着电流倍率逐渐提高,比容量迅速衰减,到10C电流时放电比容量仅有约110mAh/g。而采用Co离子掺杂Li2TiO3的LiCoO2的锂离子电池以1C、5C、10C、15C、20C及25C倍率进行很硫充放电,随着电池倍率的提高,比容量下降缓慢,10C时电池的放电比容量仍然可以达到约137mAh/g,25C时电池的放电比容量仍比未包覆的钴酸锂的电池10C时的放电比容量高。
实施例2
与实施例1条件完全相同,区别仅在于Co(OH)2替换为Co0.75Ni0.25(OH)2,得到的产物为Co离子和Ni离子掺杂Li2TiO3的LiCo0.75Ni0.25O2。
请参阅图8,将实施例2的产物进行XRD测试,从图中无法观察到Li2TiO3的特征峰,这是因为Co和Ni在Li2TiO3中的掺杂所导致的。
与实施例1的条件相同,将该实施例2制备的正极复合材料与导电剂、粘结剂混合设置在正极集流体表面,形成正极,负极采用金属锂,将正极及负极通过隔膜间隔并以电解液浸润组装成锂离子电池,进行充放电性能测试。
请参阅图9,将实施例2的锂离子电池在室温下以2C电流进行恒流充放电,从图中可以看出,采用Co离子和Ni离子掺杂Li2TiO3的LiCo0.75Ni0.25O2的锂离子电池具有较高的首次放电比容量以及较好的容量保持率,在100循环后,电池容量衰减较少。
请参阅图10,将实施例2锂离子电池以不同倍率的电流进行倍率性能测试,可以看到,采用Co离子和Ni离子掺杂Li2TiO3的LiCo0.75Ni0.25O2的锂离子电池以0.5C、1C、2C、3C、4C、5C、7C、10C以及20C倍率进行恒流放电,随着电池倍率的提高,比容量的下降比较缓慢。
实施例3
与实施例1条件完全相同,区别仅在于将该钛酸四丁酯替换为锆酸四丁酯,得到的产物为包覆有Ni离子和Co离子掺杂Li2ZrO3的LiCo0.75Ni0.25O2。
另外,本领域技术人员还可在本发明精神内做其他变化,当然,这些依据本发明精神所做的变化,都应包含在本发明所要求保护的范围之内。
Claims (17)
1.一种锂离子电池正极复合材料,其包括正极活性物质,该正极活性物质为层状锂-过渡金属复合氧化物,其特征在于,进一步包括包覆于该正极活性物质表面的包覆层,该包覆层的材料为具有单斜晶系结构、空间群为C2/c的锂-金属复合氧化物,该包覆层的材料的通式为[Li1-2aMa□a][Li1/3-2b-cMbN3cA2/3-2c□b]O2,其中A为具有+4价的金属元素,M及N为掺杂元素,“□”代表Li+位空穴,0<2a<1,0<2b+c<1/3,且0<2c<2/3,该掺杂元素M及N中的至少一个来自该正极活性物质。
2.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该金属元素A为Ti、Sn、Mn、Pb、Te、Ru、Hf及Zr中的至少一种。
3.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该M及N为碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡元素中的一种或多种。
4.如权利要求3所述的锂离子电池正极复合材料,其特征在于,该掺杂元素M及N选自Co、Ni、Mn、Cr、V、Ti、Sn、Cu、Al、Fe、B、Sr、Ca、Nd、Ga及Mg中的至少一种。
5.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层的材料的通式为[Li1-2aNia□a][Li1/3-2b-cNibCo3cA2/3-2c□b]O2。
6.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层厚度均匀且连续。
7.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层为原位生成在该正极活性物质表面。
8.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层在该正极复合材料中的质量百分含量为0.05%至7%。
9.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层的厚度为2纳米至20纳米。
10.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层为单独包覆在单个该正极活性物质颗粒的表面。
11.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层为完整的包覆在该正极活性物质的整个表面。
12.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该正极活性物质的粒径为1微米至500微米。
13.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该正极活性物质的形状为球状、棒状、针状、片状、不规则形状或它们的组合。
14.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该正极复合材料对应的具有与该正极活性物质相同的形状。
15.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该层状锂-过渡金属复合氧化物的化学式为LixLO2,其中0.1≤x≤1.1,L为过渡金属元素。
16.如权利要求1所述的锂离子电池正极复合材料,其特征在于,所述层状锂-过渡金属复合氧化物的化学式为LixL1-yRyO2,其中0.1≤x≤1.1,0≤y<1,其中,L为过渡金属元素,R为掺杂元素,R选自碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡元素中的一种或多种。
17.如权利要求1所述的锂离子电池正极复合材料,其特征在于,该包覆层与正极活性物质之间通过化学键合力结合。
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