CN114551791B - 一种含单晶高镍正极材料的复合正极片及全固态电池 - Google Patents
一种含单晶高镍正极材料的复合正极片及全固态电池 Download PDFInfo
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- CN114551791B CN114551791B CN202110863686.7A CN202110863686A CN114551791B CN 114551791 B CN114551791 B CN 114551791B CN 202110863686 A CN202110863686 A CN 202110863686A CN 114551791 B CN114551791 B CN 114551791B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 57
- 239000002105 nanoparticle Substances 0.000 claims abstract description 58
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 238000001291 vacuum drying Methods 0.000 claims description 30
- -1 nitrile compound Chemical class 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000013310 covalent-organic framework Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000013384 organic framework Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 21
- 239000002608 ionic liquid Substances 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000002825 nitriles Chemical class 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical group C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- YSIIHTHHMPYKFP-UHFFFAOYSA-N 2,5-dimethoxyterephthalaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1C=O YSIIHTHHMPYKFP-UHFFFAOYSA-N 0.000 claims description 8
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical group N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 5
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000846 In alloy Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 229910013188 LiBOB Inorganic materials 0.000 claims description 4
- 229910010941 LiFSI Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 230000008569 process Effects 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000007086 side reaction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- LQZVAOGMFZWEMO-UHFFFAOYSA-N lithium difluorooxyborinate oxalic acid Chemical compound [Li+].B(OF)(OF)[O-].C(C(=O)O)(=O)O LQZVAOGMFZWEMO-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910008291 Li—B—O Inorganic materials 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZCMAPZIDPJAIJZ-UHFFFAOYSA-N [B]=O.[C].[Li] Chemical compound [B]=O.[C].[Li] ZCMAPZIDPJAIJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
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Abstract
本发明涉及电池正极材料技术领域,公开了一种含单晶高镍正极材料的复合正极片及全固态电池,所述复合正极片的制备方法为:通过二次加锂烧结法制备单晶高镍正极材料,经表面酸化、包覆Li2ZrO3纳米颗粒后,与含氟硼酸锂、锂盐、导电剂共混并涂覆在正极集流体上制得;所述全固态电池包括上述复合正极片和复合固体电解质。本发明中的二次加锂烧结法能够优化晶粒生长和晶体结构,得到具有良好粒度和低阳离子混排的单晶高镍正极材料;全固态电池能够有效稳定复合固体电解质和复合正极片间的界面性质,降低内阻,延长循环寿命,提高整体电化学性能。
Description
技术领域
本发明涉及电池正极材料技术领域,更具体地说,本发明是一种含单晶高镍正极材料的复合正极片及全固态电池。
背景技术
使用石墨负极的商业化液体锂离子电池能量密度已经接近极限,难以满足便携式电子设备、电动汽车和大型储能装置日益增长的能量密度需求,全固态电池被认为是最有前途的解决方案之一。而全固态电池的正极材料决定着全固态电池的能量密度,高镍正极材料因其高能量密度和高容量,已被广泛应用于全固态电池的制备中。但是,高镍正极材料中随着镍含量的增加,颗粒表面反应性增加,为了避免晶粒的过度生长,需要进一步降低比表面积。
另外,全固态电池中正极材料与固体电解质之间为固-固接触,当正极材料由于持续充放电过程累积的应力发生颗粒破碎,锂离子传输路径急剧减少,界面动力学性能变差,并且存在高界面阻抗,大大降低全固态电池的循环寿命。
为了解决这一问题,公开号为CN112289995A的中国发明专利公开了复合正极浆料与正极极片、固态电池,该复合正极浆料的制备方法包括以下步骤:将正极活性材料与锂碳硼氧化物混合并在660-700℃烧结后得到预制烧结料;将所得预制烧结料、固体电解质、导电剂、胶黏剂和锂盐溶于溶剂,混合后得到所述复合正极浆料;将复合正极浆料涂覆于正极集流体表面,干燥后得到所述正极极片。其不足之处在于并不能很好地解决正极活性材料与固体电解质间的高界面阻抗问题,正极活性材料的高比表面积以及界面间不可避免的副反应仍会阻碍电化学性能的发挥,并影响循环寿命。同时,胶黏剂为电化学惰性材料,其添加会降低正极活性材料的比例,进而降低电池的能量密度。
发明内容
本发明的目的在于提供了一种含单晶高镍正极材料的复合正极片及全固态电池,使用二次加锂烧结法制备单晶高镍正极材料,降低正极材料和固体电解质间的界面阻抗,减少副反应,提高正极片的电化学性能和循环寿命。
本发明的目的通过以下技术方案予以实现。
第一方面,本发明提供了一种含单晶高镍正极材料的复合正极片,其制备方法包括如下步骤:
(A)、单晶高镍正极材料的制备:将镍、钴、锰的摩尔比为x:y:(1-x-y)的镍源、钴源和锰源溶解于水中,加入碱溶液和络合剂直至溶液pH值为11-12,所得混合溶液在惰性气体气氛下搅拌,依次经过过滤、洗涤、干燥;加入锂源后有氧煅烧,锂元素与镍、钴和锰三种元素总量的摩尔比为0.35-0.45:1.0,然后冷却并球磨;将所得粉末再次加入锂源,使总反应物中锂元素与镍、钴和锰三种元素总量的摩尔比为1.1-1.2:1.0,之后烧结;将所得颗粒加入硼酸混合溶液中并超声混合,依次经洗涤、过滤、真空干燥和有氧烧结,制得单晶高镍正极材料;其中,0.9>x≥0.5,0.3≥y>0;
(B)、Li2ZrO3纳米颗粒包覆的单晶高镍正极材料的制备:将锆、锂的摩尔比为1:2的锆的化合物和锂源溶解于水中,添加辅助剂并调节pH值为6-7,在搅拌下加热蒸发;将所得凝胶依次经过真空干燥、研磨、加热和烧结后制得Li2ZrO3纳米颗粒;将Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料球磨后烧结,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料;(C)、含单晶高镍正极材料的复合正极片的制备:将步骤(B)中的Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、含氟硼酸锂、锂盐、导电剂加入有机溶剂中,搅拌后超声混合;所得浆液涂覆在正极集流体上,真空干燥后,制得含单晶高镍正极材料的复合正极片。
步骤(A)中,采用二次加锂烧结法制备单晶高镍正极材料,第一次烧结时锂源不足,为欠锂状态,因此无法生成多晶颗粒,在第二次烧结时,锂源的再次添加使反应物中的总锂源过量,并进行低温锂化,最终制得单晶高镍正极材料。通过二次加锂和锻烧,可以优化晶粒生长和晶体结构,得到具有良好粒度和低阳离子混排的单晶高镍正极材料,而且通过研磨减少了锻烧后的团聚,使得单晶高镍正极颗粒尺寸可控。
高镍正极材料中随着镍含量的增加,颗粒表面反应性增加,为了避免晶粒的过度生长,需要进一步降低比表面积,而单晶高镍正极材料相对于多晶高镍正极材料的比表面积低。并且多晶高镍正极颗粒在持续充放电过程中,由于晶胞体积变化导致二次颗粒的破裂使得电解液渗透到一次颗粒之间,生成CEI膜,消耗了活性锂,并增加了电荷转移阻抗,尤其是在全固态电池中,颗粒破裂后暴露出的新表面,极难与固体电解质颗粒重新接触,电池阻抗会急剧上升。相比之下,单晶高镍正极颗粒在循环后几乎没有裂纹,颗粒完整性保持得较好,可以显著改善固体电池的内阻和循环寿命。
另外,单晶高镍材料在制备过程中,由于反应不彻底表面会残存少量碳酸锂等杂质,对正极材料产生不利影响。杂质会吸收空气中的微量水导致材料表面pH升高,与电解液发生副反应,导致电池性能恶化产气引起安全隐患,同时残存的碳酸锂杂质在充放电过程中诱发“两相”行为,阻碍锂离子传输和电池电化学性能发挥。本发明使用硼酸混合溶液去除碳酸锂,硼酸混合溶液为将硼酸溶解于有机溶剂中得到,有机溶剂能够在后续洗涤、过滤、真空干燥和有氧烧结过程中完全去除,避免了二次杂质掺杂。
步骤(B)中,使用Li2ZrO3纳米颗粒包覆不仅能有效保护单晶高镍正极材料,避免被固体电解质PEO氧化,产生副反应,而且能提供更好的Li+传输通道,提高锂离子扩散速率,提高单晶高镍正极材料的结构稳定性和电化学性能。
步骤(C)中,锂盐可提高复合正极片的离子电导性,导电剂可提高复合正极片的电子电导性。在复合正极片的充放电过程,Li2ZrO3纳米颗粒包覆的单晶高镍正极材料的体积变化低,可以使正极颗粒表面始终与PEO保持紧密接触,显著降低界面电阻,并且副反应速度低,提高正极片的循环寿命。含氟硼酸锂中含有Li-B-O/C-O键,有效地促进复合正极片的电化学稳定性,以及其与正极集流体的润湿性。同时含有的氟元素和硼元素,在充放电过程中形成低界面阻抗的CEI(cathode electrolyte interface,正极电解质界面)膜,延长全固态电池的循环寿命。
作为优选,步骤(A)中,所述镍源为NiSO4,所述钴源为CoSO4,所述锰源为MnSO4;所述碱溶液为氢氧化钠水溶液,所述络合剂为氨水;所述锂源为碳酸锂、氢氧化锂或硝酸锂,优选为碳酸锂;步骤(B)中,所述锆的化合物为硝酸氧锆水合物、硫酸锆、四丙醇锆、四正丙基锆酸酯或乙酰丙酮合锆,优选为硝酸氧锆水合物;所述锂源为硝酸锂;所述辅助剂为尿素或氨水;步骤(C)中,所述含氟硼酸锂为LiODFB;所述锂盐为LiTFSI、LiClO4、LiBF4、LiAsF6、LiPF6、LiBOB、LiDFOB或LiFSI,优选为LiTFSI;所述导电剂为碳类导电剂;所述有机溶剂为无水乙腈、甲醇、四氢呋喃、二甲亚砜或N,N-二甲基甲酰胺,优选为无水乙腈。
尿素作为辅助剂,可以有效平衡反应速度,并提高反应的均匀性。
作为优选,步骤(A)中,所述氢氧化钠水溶液的浓度为5-8mol/L,所述氨水的浓度为0.5-1.0mol/L,氢氧化钠水溶液和氨水溶液的体积比为4-7:2.0-2.5;所述惰性气体为氮气或氩气,所述搅拌为在35-45℃下搅拌10-16h;所述洗涤为去离子水洗涤,所述干燥为在90-110℃空气中干燥20-26h;所述有氧煅烧为在氧气气氛下700-900℃锻烧4-7h,后以10-20℃/min的速度升温至900-950℃锻烧1-3h;所述球磨为在高能振动球磨机内球磨1-2h,球磨机为氧化锆材质,研磨球为钢球、碳化钨球和聚胺肽球中的一种,球料比为1-2.5:1.5-3.0;所述烧结为在700-800℃烧结2-5h;所述硼酸混合溶液为将硼酸溶解于有机溶剂中得到,浓度为0.1-1.0g/ml;所述有机溶剂为无水乙醇、丙酮、二甲亚砜、乙腈、乙二醇、丙三醇或异丙醇;所述超声混合为超声5-20min;所述真空干燥为在70-90℃真空干燥1-3h,所述有氧烧结为在氧气气氛下300-500℃下烧结2-4h。
作为优选,步骤(B)中,所述调节pH值为6-7的溶剂为柠檬酸、酒石酸、草酸、苹果酸或枸椽酸;所述加热蒸发的温度为60-65℃;所述真空干燥为在110-120℃下干燥12-16h;所述加热为在350-400℃下加热2-4h,所述烧结为在空气中600-650℃下烧结6-8h,升温速率为1-3℃/min;所述Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料的质量比为0.5-1.5:65-75;所述球磨时间为10-20min;所述烧结为在300-350℃下烧结1-2h。
作为优选,步骤(C)中,所述步骤(B)中的Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、含氟硼酸锂、锂盐、导电剂的质量比为40-65:2-4:8-12:8-12;所述搅拌的时间为10-15h;所述超声混合为在常温下超声3-6h;所述正极集流体为铝箔,厚度为15-40μm;所述真空干燥的温度为60-80℃,时间为10-25h。
第二方面,本发明还提供了一种全固态电池,包括上述的复合正极片。
作为优选,一种全固态电池包括复合固体电解质,所述复合固体电解质的制备方法包括如下步骤:
(a)、有机骨架COFs纳米颗粒的制备:将含双醛基芳香烃衍生物和含酰基或含氨基的芳香烃衍生物溶解于有机溶剂中并搅拌,接着加入酸溶液并加热搅拌,冷却至室温,依次经过过滤、洗涤和真空干燥,制得有机骨架COFs纳米颗粒;
(b)、复合固体电解质的制备:将PEO、锂盐、腈类化合物、离子液体、步骤(a)中的有机骨架COFs纳米颗粒和液体球磨助剂混合后球磨,将所得混合溶液涂覆于基板上,真空干燥后,制得复合固体电解质。
离子液体可以与聚合物固体电解质PEO部分接枝,形成杂化固体电解质,可以将阴离子[TFSI]-固定在电解质中促进锂盐的解离,并形成无序的锂离子迁移通道,有助于获得高的锂离子迁移数,大大提高PEO内锂离子的离子电导率。离子液体填充在有机骨架COFs中可以作为润湿剂,稳定复合固体电解质和复合正极片间的界面性质,并且可以直接在锂负极表面形成一层保护膜,延长固体电池循环寿命。
同时,COFs具有高比表面积和三维结构,有利于增加离子液体与PEO的接触面积,提高固体电解质的机械性能。COFs与PEO间有较好的界面相容性,能够有效抑制PEO的结晶,提高锂离子的传输性能。腈类化合物中含有氰基,优选为3,6-己烷三甲腈时,所含3个氰基具有较强的络合和吸附作用,可以抑制高压下PEO在单晶高镍正极材料表面的分解反应,提高电化学稳定性。
作为优选,步骤(a)中,所述含双醛基芳香烃衍生物为2,5-二甲氧基苯-1,4-二甲醛、对苯二甲醛或2,5-二羟基对苯二甲醛,优选为2,5-二甲氧基苯-1,4-二甲醛;所述含酰基或含氨基的芳香烃衍生物为1,3,5-三(4-氨基苯基)苯、1,3,5-三(4-(苯丙烯酰基)苯基)苯或2,4,6-三(4-氨基苯基)苯,优选为1,3,5-三(4-氨基苯基)苯;所述有机溶剂包括溶剂a和溶剂b,溶剂a为二氧环己酮、二甲基亚砜或1,4-二氧六环,优选为二氧环己酮,溶剂b为丁二醇、无水乙醇、丙三醇或正丁醇,优选为丁二醇;所述酸溶液为醋酸;步骤(b)中,所述锂盐为LiTFSI、LiClO4、LiBF4、LiAsF6、LiPF6、LiBOB、LiDFOB或LiFSI,优选为LiTFSI;所述腈类化合物为3,6-己烷三甲腈、己二腈、戊二腈、丁二腈、辛二腈、癸二腈或1,3,5-戊烷三甲腈,优选为3,6-己烷三甲腈;所述离子液体为咪唑基、链季铵盐基、吡咯烷基或哌啶基离子液体,优选为咪唑基离子液体;所述液体球磨助剂为乙腈、乙醇、丁二醇、丙三醇或正丁醇,优选为乙腈。
液体球磨助剂作为液体溶剂,有助于改善颗粒之间的摩擦力,提高球磨效率,优选为乙腈,也可以由醇类溶剂包括乙醇、丁二醇、丙三醇、正丁醇等低分子量醇类代替,高分子量的醇类粘度高,不利于球磨效果改善。
作为优选,步骤(a)中,所述含双醛基芳香烃衍生物和含酰基或含氨基的芳香烃衍生物的摩尔比为1.5-3.0:2.0-3.5;所述溶剂a和溶剂b的体积比为1-1.5:1.5-2.0;所述搅拌为常温下搅拌20-30min;所述醋酸与含双醛基芳香烃衍生物的摩尔比为0.3-0.6:10-20;所述加热搅拌为在50-65℃下搅拌1-3h;所述洗涤为用丙酮或无水乙醇洗涤3-6次;所述真空干燥的时间为6-8h。
作为优选,步骤(b)中,所述PEO、锂盐、腈类化合物、离子液体、步骤(a)中的有机骨架COFs纳米颗粒的质量比为(15-25):(1-2):(0.5-1.5):(1.0-1.5):(0.5-1.0);所述球磨为常温下于高能振动球磨机内球磨1-3h;所述基板为玻璃板或聚四氟乙烯板;所述涂覆的厚度为50-250μm;所述真空干燥为在40-60℃真空干燥10-25h。
与现有技术相比,本发明具有以下有益效果:
(1)使用二次加锂烧结法制备单晶高镍正极材料,能够优化晶粒生长和晶体结构,得到具有良好粒度和低阳离子混排的单晶高镍正极材料,在持续充放电循环过程中保持良好的颗粒完整性,显著改善固体电池的内阻和循环寿命;
(2)复合正极片中Li2ZrO3纳米颗粒包覆的单晶高镍正极材料以及添加的含氟硼酸锂,能够降低正极颗粒与固体电解质PEO界面内阻,提高正极片的电化学稳定性;
(3)复合固体电解质中3,6-己烷三甲腈、离子液体和有机骨架COFs纳米颗粒的添加,能够显著改善复合固体电解质的抗氧化性和机械强度;
(4)以复合正极片和复合固体电解质制备的全固态电池,能够有效稳定复合固体电解质和复合正极片间的界面性质,降低内阻,延长全固态电池的循环寿命。
具体实施方式
以下用具体实施例来说明本发明的技术方案,但本发明的保护范围不限于此:
总实施例
1.含单晶高镍正极材料的复合正极片的制备(A)、单晶高镍正极材料的制备:将镍、钴、锰的摩尔比为x:y:(1-x-y)(0.9≥x≥0.5,0.3≥y≥0)的NiSO4、CoSO4和MnSO4溶解于水中,加入浓度为5-8mol/L氢氧化钠水溶液和浓度为0.5-1.0mol/L氨水,氢氧化钠水溶液和氨水溶液的体积比为4-7:2.0-2.5,直至溶液pH值为11-12;所得混合溶液在氮气气氛下搅拌,于35-45℃下搅拌10-16h,之后过滤并用去离子水洗涤,在90-110℃空气中干燥20-26h;加入碳酸锂,锂元素与镍、钴、锰三种元素总量的摩尔比为0.35-0.45:1.0,在氧气气氛下700-900℃锻烧4-7h,后以10-20℃/min的速度升温至900-950℃锻烧1-3h,然后冷却并在高能振动球磨机内球磨1-2h,球磨机为氧化锆材质,研磨球为钢球,球料比为1-2.5:1.5-3.0;将所得粉末再次加入碳酸锂,使总反应物中锂元素与镍、钴、锰三种元素总量的摩尔比为1.1-1.2:1.0,之后在700-800℃烧结2-5h;将所得颗粒加入硼酸混合溶液中并超声混合5-20min,硼酸混合溶液为将硼酸溶解于无水乙醇中得到,浓度为0.1-1.0g/ml;洗涤并过滤后,在70-90℃真空干燥1-3h,再在氧气气氛下300-500℃下烧结2-4h,制得单晶高镍正极材料。
(B)、Li2ZrO3纳米颗粒包覆的单晶高镍正极材料的制备:将锆、锂的摩尔比为1:2的硝酸氧锆水合物和硝酸锂溶解于水中,添加尿素和柠檬酸,调节pH值为6-7,并在剧烈搅拌下将所得溶液保持在60-65℃使溶剂蒸发;将所得凝胶在110-120℃下干燥12-16h,研磨后在350-400℃下加热2-4h,再在空气中600-650℃下烧结6-8h,升温速率为1-3℃/min,制得Li2ZrO3纳米颗粒;将质量比为0.5-1.5:65-75的Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料球磨10-20min,之后在300-350℃下烧结1-2h,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料。
(C)、含单晶高镍正极材料的复合正极片的制备:将质量比为40-65:2-4:8-12:8-12的步骤(B)中的Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、LiODFB、LiTFSI、碳类导电剂加入无水乙腈中搅拌10-15h,在常温下超声3-6h;所得浆液涂覆在厚度为15-40μm的铝箔上,在60-80℃下真空干燥10-25h后,制得含单晶高镍正极材料的复合正极片。
2.复合固体电解质的制备(a)、有机骨架COFs纳米颗粒的制备:将摩尔比为1.5-3.0:2.0-3.5的2,5-二甲氧基苯-1,4-二甲醛、1,3,5-三(4-氨基苯基)苯溶解于体积比为1-1.5:1.5-2.0二氧环己酮和丁二醇中,常温下搅拌20-30min,接着加入醋酸,醋酸与含2,5-二甲氧基苯-1,4-二甲醛的摩尔比为0.3-0.6:10-20,在50-65℃下搅拌1-3h,冷却至室温后过滤,使用丙酮洗涤3-6次,真空干燥6-8h,制得有机骨架COFs纳米颗粒。
(b)、复合固体电解质的制备:将质量比为(15-25):(1-2):(0.5-1.5):(1.0-1.5):(0.5-1.0)的PEO、LiTFSI、3,6-己烷三甲腈、离子液体1-乙基-3-甲基咪唑四氟硼酸盐(EMImBF4)、步骤(a)中的有机骨架COFs纳米颗粒加入到乙腈中混合,常温下于高能振动球磨机内球磨1-3h,将所得混合溶液涂覆于聚四氟乙烯板上,涂覆厚度为50-250μm,在40-60℃真空干燥10-25h后,制得复合固体电解质,立即将复合固体电解质转移到手套箱中保存。
一种含有上述复合正极片和复合固体电解质的全固态电池。
实施例1
1.含单晶高镍正极材料的复合正极片的制备
x=0.6,y=0.2,加入碳酸锂,锂元素与镍、钴和锰三种元素总量的摩尔比为0.4:1.0,将所得粉末再次加入碳酸锂,使总反应物中锂元素与镍、钴和锰三种元素总量的摩尔比为1.15:1.0,制得单晶高镍正极材料。
Li2ZrO3纳米颗粒和单晶高镍正极材料的质量比为1.2:70,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料。
Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、LiODFB、LiTFSI、碳类导电剂的质量比为55:3:11:9,所得浆液涂覆在铝箔上,真空干燥后,制得含单晶高镍正极材料的复合正极片。
2.复合固体电解质的制备
2,5-二甲氧基苯-1,4-二甲醛、1,3,5-三(4-氨基苯基)苯的摩尔比为2:2.5,制得有机骨架COFs纳米颗粒。
PEO、LiTFSI、3,6-己烷三甲腈、离子液体1-乙基-3-甲基咪唑四氟硼酸盐(EMImBF4)、有机骨架COFs纳米颗粒的质量比为18:1.2:1.2:1.3:0.7,将所得混合溶液涂覆于聚四氟乙烯板上,真空干燥后,制得复合固体电解质,立即将复合固体电解质转移到手套箱中保存。
以锂铟合金片(锂原子比为50%)为负极,手套箱内在60个标准大气压下,将复合正极片、负极片分别压制在复合固体电解质两侧,组装得到2035型扣式半电池。
实施例2
1.含单晶高镍正极材料的复合正极片的制备
x=0.7,y=0.15,加入碳酸锂,锂元素与镍、钴和锰三种元素总量的摩尔比为0.35:1.0,将所得粉末再次加入碳酸锂,使总反应物中锂元素与镍、钴和锰三种元素总量的摩尔比为1.2:1.0,制得单晶高镍正极材料。
Li2ZrO3纳米颗粒和单晶高镍正极材料的质量比为0.5:65,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料。
Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、LiODFB、LiTFSI、碳类导电剂的质量比为40:4:8:12,所得浆液涂覆在铝箔上,真空干燥后,制得含单晶高镍正极材料的复合正极片。
2.复合固体电解质的制备
2,5-二甲氧基苯-1,4-二甲醛、1,3,5-三(4-氨基苯基)苯的摩尔比为1.5:2.0,制得有机骨架COFs纳米颗粒。
PEO、LiTFSI、3,6-己烷三甲腈、离子液体1-乙基-3-甲基咪唑四氟硼酸盐(EMImBF4)、有机骨架COFs纳米颗粒的质量比为15:1:1.5:1:1,将所得混合溶液涂覆于聚四氟乙烯板上,真空干燥后,制得复合固体电解质,立即将复合固体电解质转移到手套箱中保存。
以锂铟合金片(锂原子比为50%)为负极,手套箱内在60个标准大气压下,将复合正极片、负极片分别压制在复合固体电解质两侧,组装得到2035型扣式半电池。
实施例3
1.含单晶高镍正极材料的复合正极片的制备
x=0.5,y=0.3,加入碳酸锂,锂元素与镍、钴和锰三种元素总量的摩尔比为0.45:1.0,将所得粉末再次加入碳酸锂,使总反应物中锂元素与镍、钴和锰三种元素总量的摩尔比为1.1:1.0,制得单晶高镍正极材料。
Li2ZrO3纳米颗粒和单晶高镍正极材料的质量比为1.5:75,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料。
Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、LiODFB、LiTFSI、碳类导电剂的质量比为65:2:12:8,所得浆液涂覆在铝箔上,真空干燥后,制得含单晶高镍正极材料的复合正极片。
2.复合固体电解质的制备
2,5-二甲氧基苯-1,4-二甲醛、1,3,5-三(4-氨基苯基)苯的摩尔比为2.5:3.5,制得有机骨架COFs纳米颗粒。
PEO、LiTFSI、3,6-己烷三甲腈、离子液体1-乙基-3-甲基咪唑四氟硼酸盐(EMImBF4)、有机骨架COFs纳米颗粒的质量比为25:2:0.5:1.5:0.5,将所得混合溶液涂覆于聚四氟乙烯板上,真空干燥后,制得复合固体电解质,立即将复合固体电解质转移到手套箱中保存。
以锂铟合金片(锂原子比为50%)为负极,手套箱内在60个标准大气压下,将复合正极片、负极片分别压制在复合固体电解质两侧,组装得到2035型扣式半电池。
实施例4
与实施例1的区别在于:
步骤(A)中,x=0.8,y=0.1;
步骤(B)中,硝酸氧锆水合物代替为硫酸锆,并在剧烈搅拌下将所得溶液保持在65℃使溶剂蒸发,将所得凝胶转移到真空烘箱中并在120℃下干燥12h,研磨后在350℃下加热4h,再在空气中650℃下烧结6h,升温速率为3℃/min,制得Li2ZrO3纳米颗粒;将质量比为1.5:65的Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料球磨10min,之后在350℃下烧结2h,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料。
对比例1
与实施例1的区别在于:高镍正极材料采用常规商业化多晶高镍正极材料(x=0.6,y=0.2)。
对比例2
与实施例1的区别在于:单晶高镍正极材料未经过硼酸处理。
对比例3
与实施例1的区别在于:复合正极片不添加草酸二氟硼酸锂(LiODFB)。
对比例4
与实施例1的区别在于:单晶高镍正极材料未经过Li2ZrO3纳米颗粒包覆。
对比例5
与实施例1的区别在于:复合固体电解质中不含有锂盐LiTFSI。
对比例6
与实施例1的区别在于:复合固体电解质中不含有3,6-己烷三甲腈、离子液体和有机骨架COFs纳米颗粒。
对比例7
与实施例1的区别在于:复合固体电解质中不含有离子液体。
对比例8
与实施例1的区别在于:复合固体电解质中不含有机骨架COFs纳米颗粒。
对比例9
与实施例1的区别在于:复合固体电解质中不含有3,6-己烷三甲腈。
性能测试:
在40℃下,3.1-4.2V范围内,0.1C倍率测试该电池的实际放电倍率(以第二周放电容量为准);利用交流阻抗谱EIS测量电池的交流内阻,频率范围为1-106HZ,电压振幅为5mV;在相同温度和电压范围内,以0.1C倍率进行充放电循环,当电池出现明显短路时认为寿命终止(电压下降速度超过5mV/S)。
表1.不同条件制备的全固态电池性能测试对比
样品 | 放电容量(mAh) | 内阻(Ω) | 循环寿命(周) |
实施例1 | 3.94 | 79.4 | 488 |
实施例2 | 3.84 | 80.2 | 479 |
实施例3 | 3.87 | 79.9 | 475 |
实施例4 | 3.85 | 80.6 | 471 |
对比例1 | 3.99 | 74.2 | 312 |
对比例2 | 3.72 | 81.2 | 442 |
对比例3 | 3.89 | 81.9 | 437 |
对比例4 | 3.81 | 83.9 | 433 |
对比例5 | 3.85 | 81.3 | 427 |
对比例6 | 3.79 | 84.2 | 309 |
对比例7 | 3.78 | 82.4 | 417 |
对比例8 | 3.81 | 82.9 | 433 |
对比例9 | 3.84 | 81.7 | 409 |
具体结果见表1,结合实施例1-4,可以看出在本发明要求的技术范围内,制得的全固态电池的放电容量、内阻和循环寿命表现均较好,实施例1效果最佳。结合实施例1和对比例1-4,看出与常规多晶高镍正极材料相比,本发明制备的单晶高镍正极材料的循环寿命得到了显著提升,主要原因是单晶颗粒在循环过程中结构完整性较好,颗粒内部不会出现微裂纹,避免暴露的新表面引起不必要的副反应,同时单晶颗粒体积几乎没有变化,与聚合物固体电解质始终保持紧密的接触,延长了电池的循环寿命。另外,表面酸洗并包覆Li2ZrO3纳米颗粒后,降低界面阻抗进一步抑制单晶高镍正极颗粒表面的副反应。采用二次加锂烧结法制备单晶高镍正极材料,可以优化晶粒生长和晶体结构,得到具有良好粒度和低阳离子混排的单晶高镍正极材料,而且通过研磨减少了锻烧后的团聚,使得单晶高镍正极颗粒尺寸可控。复合正极片中添加草酸二氟硼酸锂,促进PEO电化学稳定性及其与正极的润湿性,同时含有氟和硼元素,在充放电过程中形成性能更优的CEI,进一步改善了电池的循环寿命。结合实施例1和对比例5-9,发现采用本发明制备的聚合物复合固体电解质,固体电池具有更优异的综合性能,具体机理是聚合物中添加了3,6-己烷三甲腈,多腈官能团提高了PEO聚合物的抗氧化性,改善了高压下PEO与高镍正极颗粒的界面稳定性,同时添加的有机骨架COFs纳米颗粒和离子液体,与PEO和锂盐之间的协同作用,大幅度增加了锂离子的传输性能和机械强度,因而延长了固体电池的循环寿命。上述结果说明,本发明提出的方法可以有效改善高镍正极材料和固体电解质PEO的界面稳定性,改善固体电池的循环寿命,为研究高性能固体电池提供了技术参考。
以上仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (8)
1.一种全固态电池的制备方法,其特征在于,包括如下步骤:以锂铟合金片为负极片,将复合正极片、负极片分别压制在复合固体电解质两侧,组装得到全固态电池;
所述复合正极片的制备方法包括如下步骤:
(A)、单晶高镍正极材料的制备:将镍、钴、锰的摩尔比为x:y:(1-x-y)的镍源、钴源和锰源溶解于水中,加入碱溶液和络合剂直至溶液pH值为11-12,所得混合溶液在惰性气体气氛下搅拌,依次经过过滤、洗涤、干燥;加入锂源后有氧煅烧,所述有氧煅烧为在氧气气氛下700-900℃锻烧4-7h,后以10-20℃/min的速度升温至900-950℃锻烧1-3h,锂元素与镍、钴和锰三种元素总量的摩尔比为0.35-0.45:1.0,然后冷却并球磨;将所得粉末再次加入锂源,使总反应物中锂元素与镍、钴和锰三种元素总量的摩尔比为1.1-1.2:1.0,之后烧结,所述烧结为在700-800℃烧结2-5h;将所得颗粒加入硼酸混合溶液中并超声混合,依次经洗涤、过滤、真空干燥和有氧烧结,制得单晶高镍正极材料;
其中,0.9>x≥0.5,0.3≥y>0;
(B)、Li2ZrO3纳米颗粒包覆的单晶高镍正极材料的制备:将锆、锂摩尔比为1:2的锆的化合物和锂源溶解于水中,添加辅助剂并调节pH值为6-7,在搅拌下加热蒸发;将所得凝胶依次经过真空干燥、研磨、加热和烧结后制得Li2ZrO3纳米颗粒;将Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料球磨后烧结,制得Li2ZrO3纳米颗粒包覆的单晶高镍正极材料;
(C)、含单晶高镍正极材料的复合正极片的制备:将步骤(B)中的Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、含氟硼酸锂、锂盐、导电剂加入有机溶剂中,搅拌后超声混合;所得浆液涂覆在正极集流体上,真空干燥后,制得含单晶高镍正极材料的复合正极片;
所述复合固体电解质的制备方法包括如下步骤:
(a)、有机骨架COFs纳米颗粒的制备:将含双醛基芳香烃衍生物和含酰基或含氨基的芳香烃衍生物溶解于有机溶剂中并搅拌,接着加入酸溶液并加热搅拌,冷却至室温,依次经过过滤、洗涤和真空干燥,制得有机骨架COFs纳米颗粒;
(b)、复合固体电解质的制备:将PEO、锂盐、腈类化合物、离子液体、步骤(a)中的有机骨架COFs纳米颗粒和液体球磨助剂混合后球磨,将所得混合溶液涂覆于基板上,真空干燥后,制得复合固体电解质;
所述腈类化合物为1,3,6-己烷三甲腈;所述离子液体为咪唑基、链季铵盐基、吡咯烷基或哌啶基离子液体。
2.如权利要求1所述全固态电池的制备方法,其特征在于,
步骤(A)中,所述镍源为NiSO4,所述钴源为CoSO4,所述锰源为MnSO4;所述碱溶液为氢氧化钠水溶液,所述络合剂为氨水;所述锂源为碳酸锂、氢氧化锂或硝酸锂;
步骤(B)中,所述锆的化合物为硝酸氧锆水合物、硫酸锆、四丙醇锆、四正丙基锆酸酯或乙酰丙酮合锆;所述锂源为硝酸锂;所述辅助剂为尿素或氨水;
步骤(C)中,所述含氟硼酸锂为LiODFB;所述锂盐为LiTFSI、LiClO4、LiBF4、LiAsF6、LiPF6、LiBOB、LiDFOB或LiFSI;所述导电剂为碳类导电剂;所述有机溶剂为无水乙腈、甲醇、四氢呋喃、二甲亚砜或N,N-二甲基甲酰胺。
3.如权利要求2所述全固态电池的制备方法,其特征在于,步骤(A)中,
所述氢氧化钠水溶液的浓度为5-8mol/L,所述氨水的浓度为0.5-1.0mol/L,氢氧化钠水溶液和氨水溶液的体积比为4-7:2.0-2.5;
所述惰性气体为氮气或氩气,所述搅拌为在35-45℃下搅拌10-16h;
所述洗涤为去离子水洗涤,所述干燥为在90-110℃空气中干燥20-26h;
所述球磨为在高能振动球磨机内球磨1-2h,球磨机为氧化锆材质,研磨球为钢球、碳化钨球和聚胺肽球中的一种,球料比为1-2.5:1.5-3.0;
所述硼酸混合溶液为将硼酸溶解于有机溶剂中得到,浓度为0.1-1.0g/ml;所述有机溶剂为无水乙醇、丙酮、二甲亚砜、乙腈、乙二醇、丙三醇或异丙醇;
所述超声混合为超声5-20min;
所述真空干燥为在70-90℃真空干燥1-3h,所述有氧烧结为在氧气气氛下300-500℃下烧结2-4h。
4.如权利要求2所述全固态电池的制备方法,其特征在于,步骤(B)中,
所述调节pH值为6-7的溶剂为柠檬酸、酒石酸、草酸、苹果酸或枸椽酸;
所述加热蒸发的温度为60-65℃;
所述真空干燥为在110-120℃下干燥12-16h;
所述加热为在350-400℃下加热2-4h,所述烧结为在空气中600-650℃下烧结6-8h,升温速率为1-3℃/min;
所述Li2ZrO3纳米颗粒和步骤(A)中的单晶高镍正极材料的质量比为0.5-1.5:65-75;
所述球磨时间为10-20min;
所述烧结为在300-350℃下烧结1-2h。
5.如权利要求2所述全固态电池的制备方法,其特征在于,步骤(C)中,
所述步骤(B)中的Li2ZrO3纳米颗粒包覆的单晶高镍正极材料、含氟硼酸锂、锂盐、导电剂的质量比为40-65:2-4:8-12:8-12;
所述搅拌的时间为10-15h;
所述超声混合为在常温下超声3-6h;
所述正极集流体为铝箔,厚度为15-40μm;
所述真空干燥的温度为60-80℃,时间为10-25h。
6.如权利要求1所述全固态电池的制备方法,其特征在于,
步骤(a)中,所述含双醛基芳香烃衍生物为2,5-二甲氧基苯-1,4-二甲醛、对苯二甲醛或2,5-二羟基对苯二甲醛;所述含酰基或含氨基的芳香烃衍生物为1,3,5-三(4-氨基苯基)苯、1,3,5-三(4-(苯丙烯酰基)苯基)苯或2,4,6-三(4-氨基苯基)苯;所述有机溶剂包括溶剂a和溶剂b,溶剂a为二氧环己酮、二甲基亚砜或1,4-二氧六环,溶剂b为丁二醇、无水乙醇、丙三醇或正丁醇;所述酸溶液为醋酸;
步骤(b)中,所述锂盐为LiTFSI、LiClO4、LiBF4、LiAsF6、LiPF6、LiBOB、LiDFOB或LiFSI;所述液体球磨助剂为乙腈、乙醇、丁二醇、丙三醇或正丁醇。
7.如权利要求6所述全固态电池的制备方法,其特征在于,步骤(a)中,
所述含双醛基芳香烃衍生物和含酰基或含氨基的芳香烃衍生物的摩尔比为1.5-3.0:2.0-3.5;
所述溶剂a和溶剂b的体积比为1-1.5:1.5-2.0;
所述搅拌为常温下搅拌20-30min;
所述醋酸与含双醛基芳香烃衍生物的摩尔比为0.3-0.6:10-20;
所述加热搅拌为在50-65℃下搅拌1-3h;
所述洗涤为用丙酮或无水乙醇洗涤3-6次;
所述真空干燥的时间为6-8h。
8.如权利要求6所述全固态电池的制备方法,其特征在于,步骤(b)中,
所述PEO、锂盐、腈类化合物、离子液体、步骤(a)中的有机骨架COFs纳米颗粒的质量比为(15-25):(1-2):(0.5-1.5):(1.0-1.5):(0.5-1.0);
所述球磨为常温下于高能振动球磨机内球磨1-3h;
所述基板为玻璃板或聚四氟乙烯板;所述涂覆的厚度为50-250μm;
所述真空干燥为在40-60℃真空干燥10-25h。
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