CN113871709A - Positive pole piece and solid-state battery comprising same - Google Patents
Positive pole piece and solid-state battery comprising same Download PDFInfo
- Publication number
- CN113871709A CN113871709A CN202111130497.5A CN202111130497A CN113871709A CN 113871709 A CN113871709 A CN 113871709A CN 202111130497 A CN202111130497 A CN 202111130497A CN 113871709 A CN113871709 A CN 113871709A
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- China
- Prior art keywords
- substituted
- unsubstituted
- polymer
- positive electrode
- compound
- Prior art date
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- CLJIGLPOBRSBNU-UHFFFAOYSA-N 5-bromo-1h-pyrimidin-6-one Chemical compound OC1=NC=NC=C1Br CLJIGLPOBRSBNU-UHFFFAOYSA-N 0.000 description 1
- ZXZUZJTXCUZSPM-UHFFFAOYSA-N 5-fluoro-3h-1,3-benzothiazol-2-one Chemical compound FC1=CC=C2SC(=O)NC2=C1 ZXZUZJTXCUZSPM-UHFFFAOYSA-N 0.000 description 1
- WAIKTAFMGLVRJC-UHFFFAOYSA-N 5-isocyanato-2,3-dihydro-1-benzofuran Chemical compound O=C=NC1=CC=C2OCCC2=C1 WAIKTAFMGLVRJC-UHFFFAOYSA-N 0.000 description 1
- LVOYSBZJJWPUBD-UHFFFAOYSA-N 6-(trifluoromethyl)-1h-pyrimidin-4-one Chemical compound OC1=CC(C(F)(F)F)=NC=N1 LVOYSBZJJWPUBD-UHFFFAOYSA-N 0.000 description 1
- KDVBYUUGYXUXNL-UHFFFAOYSA-N 6-aminopyridine-3-carbonitrile Chemical compound NC1=CC=C(C#N)C=N1 KDVBYUUGYXUXNL-UHFFFAOYSA-N 0.000 description 1
- SSPYSWLZOPCOLO-UHFFFAOYSA-N 6-azauracil Chemical compound O=C1C=NNC(=O)N1 SSPYSWLZOPCOLO-UHFFFAOYSA-N 0.000 description 1
- MLPWRGALYUWZEV-UHFFFAOYSA-N 6-fluoro-8-isocyanato-4h-1,3-benzodioxine Chemical compound C1OCOC2=C1C=C(F)C=C2N=C=O MLPWRGALYUWZEV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- HGVRLVNTOALLMR-UHFFFAOYSA-N C1C=C(C=CN1N)Cl Chemical compound C1C=C(C=CN1N)Cl HGVRLVNTOALLMR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VLJNHYLEOZPXFW-BYPYZUCNSA-N L-prolinamide Chemical compound NC(=O)[C@@H]1CCCN1 VLJNHYLEOZPXFW-BYPYZUCNSA-N 0.000 description 1
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- 229910012097 LiSbF Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CYFCVGAYSILWBF-UHFFFAOYSA-N N=C=O.ClC1=CC=CC=C1Cl Chemical compound N=C=O.ClC1=CC=CC=C1Cl CYFCVGAYSILWBF-UHFFFAOYSA-N 0.000 description 1
- YLHOUEPSWORKCF-UHFFFAOYSA-N N=C=O.N#CC1=CC=CC=C1 Chemical compound N=C=O.N#CC1=CC=CC=C1 YLHOUEPSWORKCF-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 229910006180 NixCoyAl1-x-yO2 Inorganic materials 0.000 description 1
- YFYTYOSYQUYIJL-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Si+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Si+4].[Li+] YFYTYOSYQUYIJL-UHFFFAOYSA-K 0.000 description 1
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KNAHARQHSZJURB-UHFFFAOYSA-N Propylthiouracile Chemical compound CCCC1=CC(=O)NC(=S)N1 KNAHARQHSZJURB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- UGTTVSAWRDLYRO-UHFFFAOYSA-N [N+](#[C-])CCCN=C=O Chemical compound [N+](#[C-])CCCN=C=O UGTTVSAWRDLYRO-UHFFFAOYSA-N 0.000 description 1
- NKLLZZNEDKQOOB-UHFFFAOYSA-N [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] Chemical compound [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] NKLLZZNEDKQOOB-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XVBZFXZNJAFCHL-UHFFFAOYSA-N ethyl 2-aminopyridine-4-carboxylate Chemical compound CCOC(=O)C1=CC=NC(N)=C1 XVBZFXZNJAFCHL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- JNQQEOHHHGGZCY-UHFFFAOYSA-N lithium;oxygen(2-);tantalum(5+) Chemical compound [Li+].[O-2].[O-2].[O-2].[Ta+5] JNQQEOHHHGGZCY-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- ATFKBWNEVZUSKC-UHFFFAOYSA-N methyl 2-isocyanatobenzoate Chemical compound COC(=O)C1=CC=CC=C1N=C=O ATFKBWNEVZUSKC-UHFFFAOYSA-N 0.000 description 1
- SKYDNLJVNFYBGY-UHFFFAOYSA-N methyl 3-isocyanatothiophene-2-carboxylate Chemical compound COC(=O)C=1SC=CC=1N=C=O SKYDNLJVNFYBGY-UHFFFAOYSA-N 0.000 description 1
- FQDDBYGPHUUTRN-UHFFFAOYSA-N methyl 4-isocyanatobenzoate Chemical compound COC(=O)C1=CC=C(N=C=O)C=C1 FQDDBYGPHUUTRN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XSNZNZJXEGKLQG-UHFFFAOYSA-N n-(2-methylpyridin-4-yl)acetamide Chemical compound CC(=O)NC1=CC=NC(C)=C1 XSNZNZJXEGKLQG-UHFFFAOYSA-N 0.000 description 1
- ZBAMQLFFVBPAOX-UHFFFAOYSA-N n-(pyridin-4-ylmethyl)ethanamine Chemical compound CCNCC1=CC=NC=C1 ZBAMQLFFVBPAOX-UHFFFAOYSA-N 0.000 description 1
- KTHDTJVBEPMMGL-GSVOUGTGSA-N n-acetylalanine Chemical compound OC(=O)[C@@H](C)NC(C)=O KTHDTJVBEPMMGL-GSVOUGTGSA-N 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- ZNPWYAMBOPRTHW-UHFFFAOYSA-N naphthalene-1,2-dicarbonitrile Chemical compound C1=CC=CC2=C(C#N)C(C#N)=CC=C21 ZNPWYAMBOPRTHW-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960002662 propylthiouracil Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- BZVJOYBTLHNRDW-UHFFFAOYSA-N triphenylmethanamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(N)C1=CC=CC=C1 BZVJOYBTLHNRDW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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 provides a positive pole piece and a solid-state battery comprising the same. The positive electrode sheet of the present invention includes a solid electrolyte including a polymer including a structural unit derived from an olefin compound having a substituted or unsubstituted ureido group, the olefin compound further including at least one cyclic group. The positive pole piece disclosed by the invention can effectively improve the interface impedance between the positive pole piece and the solid electrolyte by limiting the composition of the polymer in the positive pole piece.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a positive pole piece and a solid-state battery comprising the same.
Background
Compared with the traditional liquid lithium ion battery, the solid-state battery has the most outstanding advantages of safety, non-flammability, high temperature resistance, corrosion resistance, non-volatility and the like, can prevent the phenomena of electrolyte leakage, battery short circuit and the like in the traditional lithium ion battery, and greatly improves the safety performance of the battery. Then, the traditional mode of contacting the liquid electrolyte with the positive electrode and the negative electrode is liquid/solid contact, the interface wettability is good, compared with the mode of contacting the solid electrolyte with the positive electrode and the negative electrode in a solid interface mode, the contact area is small, the contact tightness with a pole piece is poor, the interface impedance is high, and the transmission of lithium ions between the interfaces is blocked.
The solid-state battery positive pole piece mainly comprises a positive active substance, a conductive agent, a solid electrolyte, a binder and the like, and the solid-state battery has large interface resistance with the solid electrolyte in the charging and discharging process, so that the cycle performance of the solid-state battery is directly influenced. Therefore, how to improve the solid-solid interface contact performance of the positive electrode plate and the solid electrolyte in the solid-state battery is a technical problem to be solved in the field.
Disclosure of Invention
The invention provides a positive pole piece, which can effectively improve the interface impedance of the positive pole piece and a solid electrolyte by enabling the positive pole piece to comprise the solid electrolyte and limiting the composition of a polymer in the solid electrolyte.
The invention also provides a solid-state battery which comprises the positive pole piece, and the solid-state battery has excellent cycle performance due to small interface impedance between the positive pole piece and the solid electrolyte.
The invention provides a positive electrode plate, which comprises a solid electrolyte, wherein the solid electrolyte comprises a polymer, the polymer comprises a first structural unit from an olefin compound containing a substituted or unsubstituted ureido group, and the olefin compound containing the substituted or unsubstituted ureido group further comprises at least one cyclic group.
The positive electrode sheet as described above, wherein the substituted or unsubstituted ureido group-containing olefin compound has a structure represented by formula 1:
wherein R is1、R3、R4Each independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted amino of (a); r2Selected from the group consisting of carbonyl, substituted or unsubstituted (hetero) aryl, ester, substituted or unsubstituted C1～12Alkylene, carboxyl, or a chemical bond; m1Selected from H, carbonyl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, hydroxy, halogen, amino, nitro, trifluoromethyl, alkylthio, substituted or unsubstituted (hetero) aryl; m2、M3Each independently selected from hydrogen, substituted or unsubstituted C4～60(hetero) aryl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, carbonyl, substituted or unsubstituted C containing a heterocyclic atom2～12Cycloalkyl, acyl, carboxyl, ester, or M2、M3Bonding to form a ring; r1～R4And M1～M3Wherein at least one cyclic group is present.
The positive electrode plate is characterized in that the number average molecular weight of the polymer is 2000-50000, and the mass ratio of the first structural unit in the polymer is not less than 30%.
The positive pole piece comprises, by mass, 60-95% of a polymer, 5-30% of a lithium salt and 0-20% of an auxiliary agent.
The positive electrode plate comprises, by mass, 70-95 wt% of a positive active material, 2-15 wt% of a solid electrolyte, 3-15 wt% of a conductive agent, and 0-10 wt% of a binder.
The positive pole piece is characterized in that the molar ratio of the sum of oxygen and nitrogen in the polymer to lithium in the lithium salt is (5-25): 1.
The positive pole piece is characterized in that the crystallinity of the polymer is less than or equal to 40%.
The positive electrode sheet as described above, wherein the polymer further comprises a second structural unit derived from an olefin compound, and the second structural unit is different from the first structural unit.
The positive electrode sheet as described above, wherein the olefin compound containing a substituted or unsubstituted ureido group is prepared according to a method comprising:
reacting a solvent system comprising a first isocyanate compound and a first amine compound, or a solvent system comprising a second isocyanate compound and a second amine compound to obtain the olefin compound containing a substituted or unsubstituted ureido group; wherein the first isocyanate compound satisfies the structure shown in formula 2a, the first amine compound satisfies the structure shown in formula 3a, and the first amine compound is a primary amine or a secondary amine compound; the second amine compound satisfies the structure shown in formula 2b, the second isocyanate compound satisfies the structure shown in formula 3b, and in the formula 3b, MxIs M2Or M3，
The invention provides a solid-state battery, which comprises the positive pole piece.
The positive pole piece comprises a solid electrolyte, the solid electrolyte comprises a polymer, the polymer comprises a first structural unit from an olefin compound containing substituted or unsubstituted ureido groups, the olefin compound further comprises at least one cyclic group, the olefin compound containing the cyclic group and the ureido groups has enough space for receiving lithium ions and enabling the lithium ions to move freely, and the lithium ions from the solid electrolyte can be efficiently transmitted into the positive pole piece, so that the interface impedance between the positive pole piece and the solid electrolyte is improved.
The solid-state battery comprises the positive pole piece, and the interface contact performance between the positive pole piece and the solid electrolyte is good, so that the solid-state battery has excellent cycle performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a positive electrode plate, which comprises a solid electrolyte, wherein the solid electrolyte comprises a polymer, the polymer comprises a first structural unit from an olefin compound containing a substituted or unsubstituted ureido group, and the olefin compound containing the substituted or unsubstituted ureido group further comprises at least one cyclic group.
The polymer in the positive electrode sheet comprises substituted or unsubstituted ureido groups, wherein the structure of the ureido groups which are not substituted by the substituent groups is as follows:
substituted ureido groups refer to ureido groups in which one hydrogen is substituted with a substituent R or both hydrogens are substituted with a substituent R and have the formula:
the substituent of the ureido group in the present invention is not limited, and for example, R may be acyl, carboxyl, substituted or unsubstituted C1-C36Alkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted alkoxy, etcWhen substituents are present in these groups, the substituents are each independently selected from halogen, cyano, nitro, amino, C1-C10Alkyl of (C)2-C6Alkenyl of, C1-C6Alkoxy or thioalkoxy of C6-C30Aryl of (C)3-C30One or more of the heteroaryl groups of (a).
Specifically, the polymer is obtained by polymerizing monomers, and the present invention is not limited to a specific form of polymerization, and for example, the polymer may be obtained by homopolymerization of one monomer, or the polymer may be obtained by copolymerization of two or more different monomers. Of course, when the monomers participating in the polymerization are two or more, the present invention is not limited to the number of the olefin compounds including a substituted or unsubstituted ureido group as the monomers, and all the monomers participating in the polymerization may be the olefin compounds including a substituted or unsubstituted ureido group, or a part of the monomers may be the olefin compounds including a substituted or unsubstituted ureido group.
The polymer may be mixed with other substances (for example, a positive electrode active material, a binder, a conductive agent, and the like) in the positive electrode active layer to form a positive electrode active layer, or a functional layer of the polymer may be formed on the surface of the positive electrode active layer including the positive electrode active material, the binder, the conductive agent, and the like, or the polymer may be coated on a part of the surface of the positive electrode active material as a shell material to form a core-shell material and then mixed with the conductive agent, the binder, and the like to form the positive electrode active layer, or at least two of the above may be performed.
The inventor researches and discovers that when the positive pole piece contains the polymer with the structure, the positive pole piece has higher lithium ion conductivity and good solid-solid interface contact performance, and the reason may be that: the olefin compound containing the cyclic group and the carbamido group has enough space to receive lithium ions and can enable the lithium ions to move freely, and the lithium ions from the solid electrolyte can be efficiently transmitted into the positive pole piece, so that the interface impedance between the positive pole piece and the solid electrolyte is improved.
In one particular embodiment, the olefin compound containing a substituted or unsubstituted ureido group has the structure shown in formula 1:
wherein R is1、R3、R4Each independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted amino of (a); r2Selected from the group consisting of carbonyl, substituted or unsubstituted (hetero) aryl, ester, substituted or unsubstituted C1～12Alkylene, carboxyl, or a chemical bond; m1Selected from H, carbonyl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, hydroxy, halogen, amino, nitro, trifluoromethyl, alkylthio, substituted or unsubstituted (hetero) aryl; m2、M3Each independently selected from hydrogen, substituted or unsubstituted C4～60(hetero) aryl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, carbonyl, substituted or unsubstituted C containing a heterocyclic atom2～12Cycloalkyl, acyl, carboxyl, ester, or M2、M3Bonding to form a ring; r1～R4And M1～M3Wherein at least one cyclic group is present.
Specifically, when R is1、R3、R4When substituted, the substituent may be selected from the group consisting of halogen, nitro, cyano, hydroxy, trifluoromethyl, C1～12Hydrocarbon sulfur groups, etc.;
R2is carbonyl RCO- (. R is substituted or unsubstituted C)1～12Alkyl of (A), substituted or unsubstituted C3～12Cycloalkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted C4～60(hetero) aryl group,Substituted or unsubstituted hydroxy, the substituent being C4～60(hetero) aryl, halogen, nitro, amino, cyano, etc.), substituted or unsubstituted (hetero) aryl (the carbon (or hetero) atom on the (hetero) aryl group and the N atom in the ureido group being bonded directly, or the substituent on the (hetero) aryl group and the N atom in the ureido group being bonded directly, the substituent being C1～12Alkyl of (C)1～12Alkoxy, nitro, halogen, amino, carboxyl, ester group, acyl, etc.), ester group-COOR (R is substituted or unsubstituted C1～12Alkyl of (A), substituted or unsubstituted C3～12The substituent of the cycloalkyl group is cyano, nitro, amino, halogen, etc.), a chemical bond (i.e., a direct bond between a double-bonded carbon atom and a nitrogen atom in the urea group), and substituted or unsubstituted C1～12Alkylene (the substituent is cyano, nitro, amino, halogen, etc.), carboxyl RCOOH (R is substituted or unsubstituted C)1～12Alkyl or alkenyl radicals directly bonded to both the N atom and the doubly-bound carbon atom of the ureido radical, the substituent being C1～12Alkoxy, halogen, cyano, nitro, amino, halogen, etc.). Wherein "-" represents a chemical bond directly bonded to the N atom in the urea group, and "-" represents a chemical bond directly bonded to the double-bonded carbon atom;
M1selected from H, substituted or unsubstituted C1～20Alkyl (substituent is C)1～12Alkoxy group of (C)4～30Hetero (aryl) group of (a), halogen, amino group, carboxyl group, ester group, acyl group, etc.), substituted or unsubstituted C1～20Alkoxy (substituent is C)1～12Alkyl of (C)4～30Hetero (aryl) group of (a), nitro, halogen, amino, carboxyl, ester, acyl, etc.), hydroxyl, halogen, amino, nitro, trifluoromethyl, alkylthio, substituted or unsubstituted (hetero) aryl (as defined with R)2Wherein the same), carbonyl RCO- (R is defined as R)2Wherein "-" represents a chemical bond directly bonded to the N atom in the urea group;
M2、M3each independently selected from hydrogen, substituted or unsubstituted C4～60(hetero) aryl (as defined for R)2Same as in (1), substituted or unsubstituted C1～20Alkyl (definition and M)1Same as in (1), substituted or unsubstituted C1～20Alkoxy (definition of and M)1Wherein the same), carbonyl RCO- (R is as defined for M)1Same as in (1), substituted or unsubstituted C containing a heterocyclic atom2～12Cycloalkyl (substituent is C)1～12Alkoxy group of (C)4～30Hetero (aryl) group of (a), halogen, amino group, carboxyl group, ester group, acyl group, etc.), acyl group RCO- (R is substituted or unsubstituted C1～12Alkyl or alkenyl, halogen, amino, etc., the substituent being C1～12Alkoxy, halogen, cyano, nitro, amino, etc.), carboxyl RCOOH (R is substituted or unsubstituted C1～12Alkyl or alkenyl radicals directly bonded to the N atom of the ureido radical, the substituents being C1～12Alkoxy, halogen, cyano, nitro, amino, halogen, etc.), ester group RCOOR- (R is substituted or unsubstituted C1～12Alkyl or alkenyl, the substituents being C1～12Alkoxy, halogen, cyano, nitro, amino, halogen, etc.), ester group-RCOOR- (R is substituted or unsubstituted C1～12Alkyl or alkenyl, the substituents being C1～12Alkoxy, halogen, cyano, nitro, amino, halogen, etc.) or M2、M3Bonded to form a ring (e.g. substituted or unsubstituted C4～30Cycloalkyl, substituted or unsubstituted C4～30Cycloalkenyl, substituted or unsubstituted C4～30Aryl, etc., further, the ring-forming atoms further include hetero atoms, and the substituent is C1～12Alkyl of (C)1～12Alkoxy, nitro, halogen, trifluoromethyl, amino, hydroxyl, methylthio, carboxyl, ester, acyl, carbonyl, etc.), wherein "-" and "-" each represent a bond directly bonded to the N atom in the urea group.
Further, the molecular weight of the olefin compound containing a substituted or unsubstituted ureido group is 100 to 5000. The molecular weight is in a proper range, so that the phenomena that the boiling point of an olefin compound is low and the olefin compound is easy to volatilize in the processing process due to too low molecular weight can be avoided, and the phenomena that the polymerization difficulty is high and a sample with stable performance cannot be prepared due to too high molecular weight can be avoided. The molecular weight of the olefin compound having a substituted or unsubstituted ureido group is more preferably 150 to 1500.
In a specific embodiment, the number average molecular weight of the polymer is 2000 to 50000, wherein the mass proportion of the first structural unit in the polymer is not less than 30%. When the polymer has the number average molecular weight and the first structural unit has the mass ratio in the polymer, the polymer can have more space for receiving and transmitting lithium ions, so that the lithium ions can be efficiently transmitted into the solid-state battery from the solid-state electrolyte, and the interface impedance between the positive electrode plate and the solid-state electrolyte is further improved.
It is understood that the solid electrolyte includes lithium salts and auxiliaries in addition to the above-mentioned polymers. In a specific embodiment, the solid electrolyte comprises, by mass, 60 to 95% of a polymer, 5 to 30% of a lithium salt, and 0 to 20% of an auxiliary agent.
The lithium salt in the solid electrolyte is not particularly limited in the present invention, and any lithium salt commonly used in the art may be used, and may be specifically selected from lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) difluoroborate (LiDFOB), lithium bis (difluorosulfonimide) (LiFSI), lithium bis (trifluoromethylsulfonimide) (LiTFSI), lithium (trifluoromethylsulfonate) (LiCF)3SO3) Bis (malonic) boronic acid (LiBMB), lithium oxalatoborate malonate (LiMOB), lithium hexafluoroantimonate (LiSbF)6) Lithium difluorophosphate (LiPF)2O2) Lithium 4, 5-dicyano-2-trifluoromethylimidazole (LiDTI), lithium bis (trifluoromethylsulfonyl) imide (LiN (SO)2CF3)2)、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2At least one of (1).
The assistant in the solid electrolyte as described above is selected from at least one of an oxide electrolyte, a nanofiller, and an organic assistant.
Specifically, the oxide electrolyte may be at least one selected from the group consisting of lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicon phosphate, and lithium lanthanum titanate.
The nanofiller may be selected from at least one of alumina, magnesia, boehmite, barium sulfate, barium titanate, zinc oxide, calcium oxide, silica, silicon carbide, nickel oxide.
The organic auxiliary agent can be selected from nitrogen-containing organic micromolecule compounds, and when the boiling point of the nitrogen-containing micromolecule compounds is higher than 200 ℃, the electrolyte processing window is improved, and electrolyte component change in the processing process is avoided.
Specifically, the nitrogen-containing organic small molecule compound can be at least one selected from succinonitrile, N-methylacetamide, 3-cyano-7-azaindole, 7-azaindole-4-carbonitrile, 3' -azotoluene, 5-methylbenzotriazole, 3,4, 5-trifluorophenylacetonitrile, 3,4,5, 6-tetrafluorophthalonitrile, 1, 2-naphthalenedinitrile, 2-amino-4, 5-imidazoldinitrile and 5-methylbenzotriazole.
In a specific embodiment, when the solid electrolyte comprises a polymer and a lithium salt, the molar ratio of the sum of oxygen and nitrogen in the polymer to lithium in the lithium salt is (5-25): 1. Illustratively, the molar ratio of the sum of the oxygen and nitrogen elements to the lithium element in the polymer can be 5:1, 10:1, 15:1, 20:1, 25:1, and the like. Controlling the molar ratio of the sum of the oxygen element and the nitrogen element in the polymer to the lithium element in the lithium salt in the above range is favorable for the transmission of lithium ions.
In a specific embodiment, the positive electrode sheet of the present invention includes a current collector and a positive active layer disposed on at least one functional surface of the current collector, and the positive active layer includes, by mass: 70-95 wt% of positive electrode active material, 2-15 wt% of solid electrolyte, 3-15 wt% of conductive agent and 0-10 wt% of binder.
The positive active material in the positive active layer is not particularly limited in the present invention, and any positive active material commonly used in the art can be used, including but not limited to lithium iron phosphate (LiFePO)4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (Li)zNixCoyMn1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0<x+y<1) Lithium manganate (LiMnO)2) Lithium nickel cobalt aluminate (Li)zNixCoyAl1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0.8≤x+y<1) Lithium nickel cobalt manganese aluminate (Li)zNixCoyMnwAl1-x-y-wO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，w>0，0.8≤x+y+w<1) Nickel-cobalt-aluminum-tungsten material, lithium-rich manganese-based solid solution positive electrode material (xLi)2MnO3·(1-x)LiMO2Where M ═ Ni/Co/Mn), lithium nickel cobalt oxide (LiNi)xCoyO2Wherein x is>0，y>0, x + y ═ 1), lithium nickel titanium magnesium oxide (LiNi)xTiyMgzO2Wherein x is>0，y>0，z>0, x + y + z ═ 1), lithium nickelate (Li)2NiO2) Spinel lithium manganate (LiMn)2O4) And nickel-cobalt-tungsten material.
Also, the conductive agent and the binder are not particularly limited in the present invention, and the binder and the conductive agent commonly used in the art may be used, for example, the conductive agent may be at least one selected from the group consisting of conductive carbon black, ketjen black, conductive fibers, conductive polymers, acetylene black, carbon nanotubes, graphene, flake graphite, conductive oxides, and metal particles, and the binder may be at least one selected from the group consisting of polyvinylidene fluoride (PVDF) and derivatives thereof, Polytetrafluoroethylene (PTFE) and derivatives thereof, polyvinylidene fluoride-hexafluoropropylene and derivatives thereof, and lithium polyacrylate (PAA-Li) and derivatives thereof.
The inventors also found that the crystallinity of the polymer also has a certain effect on the improvement of the interfacial contact property of the positive electrode sheet with the solid electrolyte. When the crystallinity is less than or equal to 40 percent, the interface contact performance of the positive plate and the solid electrolyte is more excellent. Specifically, the crystallinity of the polymer can be controlled by controlling the kind of the added monomer, the quality of the monomer, the kind of the initiator, the temperature, the time, and the like, thereby achieving the above-mentioned requirement for crystallinity.
In the invention, the method for detecting the crystallinity specifically comprises the following steps: and (3) testing the degree of crystallization of the polymer by adopting an X-ray diffraction technology, and separating the crystallization scattering from the non-crystallization scattering on a diffraction diagram based on that the X-ray scattering intensity is in direct proportion to the mass of a scattering substance, wherein the crystallinity Xc is A/(A + B), wherein A is the scattering intensity of a crystal phase, and B is the scattering intensity of an amorphous phase.
As described above, the polymer in the positive electrode sheet of the present invention may include, in addition to the first structural unit containing a substituted or unsubstituted ureido group, other structural units not containing a substituted or unsubstituted ureido group, and such structural units not containing a substituted or unsubstituted ureido group are referred to as second structural units, which are different from the first structural units. The second structural unit is derived from an olefin compound having an olefinic bond capable of participating in polymerization, more specifically, an olefin compound not containing a substituted or unsubstituted ureido group. The second structural unit referred to in the present invention means a unit containing no substituted or unsubstituted ureido group, and therefore, the polymer may contain a plurality of different second structural units. For example, the olefin compound not containing a substituted or unsubstituted ureido group may be selected from at least one of acrylic acid, acrylic acid ester, polyethylene glycol methacrylate, methyl methacrylate, acrylonitrile, amino acrylic acid ester, trimethylolpropane trimethacrylate, vinyl silicone material.
In a specific embodiment, the compound represented by the above formula 1 is prepared according to a method comprising the following steps:
reacting a solvent system containing a first isocyanate compound and a first amine compound (primary amine or secondary amine) to obtain an olefin compound containing a substituted or unsubstituted ureido group, i.e., a compound represented by formula 1. Wherein the first isocyanate compound satisfies the structure shown in formula 2a, and the first amine compound satisfies the structure shown in formula 3 a. For the groups in the structures of formula 2a and formula 3a, reference is made to the foregoing.
In the compound represented by the formula 1 prepared by the preparation method, M1Is a hydrogen atom.
The first isocyanate-based compound satisfying formula 2a may be, for example, at least one selected from among acryl-based isocyanate, and acryl-based isocyanate and derivatives thereof. Specifically, the isocyanate is at least one selected from the group consisting of methacryloyl isocyanate, 3-isopropenyl- α, α -dimethylbenzyl isocyanate, isocyanate ethyl acrylate, isocyanoethyl methacrylate, vinyl isocyanate, 3-isocyanopropyl isocyanate, and 3-ethoxy-2-acryloyl isocyanate.
The first amine compound satisfying formula 3a may be selected from, for example, 2-aminopyrimidine-5-carboxylic acid, 2-amino-3-iodo-5-methylpyridine, N- (4-picolyl) ethylamine, 3-methylthiophene-2-carboxamide, 2-bromo-3-amino-4-methylpyridine, 6-azauracil, 3-chloro-4-fluorobenzylamine, 2-amino-5, 7-difluorobenzothiazole, 3, 4-pyridinediimide, morpholine, 2, 4-dichloroaniline, 3-aminophthalic anhydride, 2-amino-3-hydroxymethylpyridine, 3-amino-4-chloropyridine, triphenylmethylamine, 1, 3-benzothiazol-5-amine, 1-amino-4-chloropyridine, and mixtures thereof, 2-amino-5-cyanopyridine, 4-aminoisoxazole, ethyl 2-aminoisonicotinate, dimethylpyridinamine, 1, 2-dimethylpiperazine, L-prolinamide, propylthiouracil, 5-fluoro-2- (3H) -benzothiazolone, 5-bromopyrimidin-4-one, N-acetyl-D-alanine, (S) -4-isopropyl-2-oxazolidinone, 1- (2-piperazin-1-ylacetyl) pyrrolidine, 2-methyl-4-acetamidopyridine, 2-chloromethyl-6-methyl-thieno [2,3-D ] pyrimidin-4- (3H) -one, 2-hydroxy-4-methylpyridine, N-methyl-pyridimine, N-methyl-2-methyl-pyridimine, N-acetyl-D-aminothiazoline, N-methyl-2-methyl-pyridone, N-methyl-4-oxazolidinone, N-methyl-thieno [2,3-D ] pyrimidin-4- (3H) -one, N-methyl-2-4-pyridines, N-methyl-one, N-methyl-pyridone, N-methyl-2-methyl-4-one, N-methyl-2-one, N-methyl-4-one, N-methyl-one, N-one, N-one, N-, At least one of tristhiocyanic acid, 2-methylthio-4, 6-dihydroxypyrimidine, 4-hydroxy-6-trifluoromethylpyrimidine, (1,4,7, 10-tetraaza-cyclododec-1-yl) -allyl acetate, (S) - (-) -2-amino-4-pentenoic acid, Fmoc-L-allylglycine, Fmoc-D-allylglycine, DL-2-amino-4-pentenoic acid, and D-2-amino-4-bromopentenoic acid.
In another embodiment, the compound represented by the above formula 1 may be further prepared according to a method comprising the following steps:
reacting a solvent system comprising a second isocyanate compound and a second amine compound to obtain the olefin compound containing a substituted or unsubstituted ureido group; wherein the second amine is of the groupThe compound satisfies the structure shown in formula 2b, the second isocyanate compound satisfies the structure shown in formula 3b, and in the formula 3b, MxIs M2Or M3. For the groups in the structures of formula 2b and formula 3b, reference is made to the foregoing.
In the compound represented by the formula 1 prepared by the preparation method, M2Or M3Is a hydrogen atom.
The second amine-based compound satisfying formula 2b may be, for example, at least one selected from the group consisting of pentenoic-acid-type primary or secondary amine group-containing olefin compounds, glycine-type primary or secondary amine group-containing olefin compounds, and carboxylic acid ester-type primary or secondary amine group-containing olefin compounds. Specifically, the compound is at least one selected from the group consisting of (1,4,7, 10-tetraaza-cyclododec-1-yl) -allyl acetate, (S) - (-) -2-amino-4-pentenoic acid, Fmoc-L-allylglycine, Fmoc-D-allylglycine, DL-2-amino-4-pentenoic acid and D-2-amino-4-bromopentenoic acid.
The second isocyanate-based compound satisfying the formula 3b may be selected from, for example, p-methoxybenzyl isocyanate, 3, 4-dichlorobenzene isocyanate, 4-methoxybenzyl isocyanate, 2-phenethyl isocyanate, 4-bromo-3-tolyl isocyanate, 2- (methoxycarbonyl) phenyl isocyanate, 4-bromo-2-chlorophenyl isocyanate, 2,3, 5-dimethylphenyl isocyanate, 2-methoxy-4-nitrobenzene isocyanate, 4-chloro-3-nitrobenzene isocyanate, 2-chloro-5- (trifluoromethyl) phenyl isocyanate, 2, 5-difluorophenyl isocyanate, 4-cyanobenzene isocyanate, 6-fluoro-1H-1, 3-benzodioxin-8-yl isocyanate, 4-isocyano-3-methyl-5-phenylisoxazole, benzyl α -methylisocyanate, nitrobenzene 2-methyl-3-isocyanate, 4-trifluoromethylthiophenyl isocyanate, 2-nitrophenol isobutyrate, methyl 4-isocyanatobenzoate, benzyl 4-isothiocyanato-1- (2H) -picolinate, 2-thiophenylisocyanate, 3-chloro-4-methoxyphenyl isocyanate, 2, 3-dihydro-1-benzofuran-5-yl isocyanate, 2-fluoro-4-isocyanato-1-methoxybenzene, methyl 3-isocyanatothiophene-2-carboxylate, methyl 4-isocyanato-5-isocyanate, methyl 2-isocyanato-2-carboxylate, methyl 2-isocyanato-2-isocyanate, and mixtures thereof, 3-bromophenyl isocyanate, 4- (methylthio) phenyl isocyanate.
In the above two preparation embodiments, the reaction system includes a solvent in addition to the isocyanate compound and the amine compound. The reaction solvent can be at least one of water, N-methyl pyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, xylene and toluene.
In the reaction process, in order to fully perform the reaction and avoid the generation of other impurities, the molar ratio of the isocyanate compound to the amine compound is controlled to be 1: 1.
It is understood that, in order to increase the efficiency of the preparation of the compound represented by formula 1, the reaction may be carried out after the two raw materials are sufficiently mixed by controlling the stirring speed. The mixing can be carried out at a rotating speed of 200-2000 r/min, the mixing time can be controlled to be 30-400 min, and the mixing can be carried out in an inert atmosphere.
In a specific embodiment, the isocyanate compound and the amine compound can be reacted at 30-60 ℃, and the reaction time is generally 2-30 h.
In order to have the safety performance and the energy density of the lithium ion battery, the thickness of a current collector in the positive pole piece is set to be 8-20 microns, and the thickness of a positive active material layer is set to be 20-80 microns. And the positive active material layer can be arranged on one side or both sides of the current collector according to different design requirements of the lithium ion battery.
The invention is not limited to the preparation method of the positive pole piece, and in a first optional embodiment, the positive pole piece can be prepared by adopting the following method:
mixing a positive active substance, a polymer monomer, a conductive agent, a lithium salt, an initiator and a solvent, and initiating a polymerization reaction to obtain a positive slurry; and coating the positive electrode slurry on one or two functional surfaces of the positive electrode current collector, and drying to obtain the positive electrode piece.
In a second alternative embodiment, the positive electrode sheet of the present invention can be prepared by the following method:
mixing a polymer monomer and an initiator and initiating a polymerization reaction to prepare a polymer; and mixing the prepared polymer, the positive active substance, the conductive agent, the lithium salt and the second solvent to obtain positive active layer slurry, coating the positive active layer slurry on one or two functional surfaces of a positive current collector, and drying to obtain the positive pole piece.
In the first alternative embodiment, the preparation of the polymer, the preparation of the solid electrolyte and the preparation of the positive electrode slurry are performed simultaneously, wherein the polymerization reaction of the polymer monomer is initiated by the initiator to form the polymer. The lithium salt and the auxiliary agent can be fully and physically mixed with the polymer while the polymer is formed, so that the polymer, the lithium salt and the auxiliary agent in the solid electrolyte are uniformly distributed.
Furthermore, the solvents in the above two methods for preparing the positive electrode plate can be respectively and independently selected from at least one of N-methyl pyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, xylene, and toluene.
Furthermore, the addition amount of the initiator is 0.05-0.5% of the total mass of the polymer monomers.
The initiator may be at least one initiator commonly used in the art, including but not limited to azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, ethyl 4- (N, N-dimethylamino) benzoate, and methyl o-benzoylbenzoate.
Further, after the positive electrode slurry is prepared, a process of sieving the positive electrode slurry is also included, and specifically, the positive electrode slurry can be sieved by a sieve with 200 meshes.
The mixing in the preparation process of the anode slurry can be completed by stirring at a rotating speed of 200-2000 r/min for 2-15 hours, and after the reaction is completed, the reaction is dried in an inert atmosphere to remove redundant solvent, wherein the drying temperature is 60-100 ℃, and the drying time is 6-36 hours. Preferably, the drying may be performed under vacuum.
In a second aspect, the invention provides a solid-state battery comprising the positive electrode plate provided in the first aspect of the invention.
It is understood that the solid-state battery of the present invention includes an electrolyte and a negative electrode tab in addition to the positive electrode tab. According to the solid-state battery, the positive pole piece, the electrolyte and the negative pole piece can be laminated to obtain the solid-state battery cell, and the solid-state battery can be obtained after welding and packaging.
The invention also provides an application of the solid-state battery in an electrical device. The invention is not limited to specific types of electrical devices, including but not limited to digital appliances, power tools, energy storage devices, unmanned planes, household appliances, energy storage products, electric vehicles, electric tools, and the like.
The present invention will be described in further detail with reference to specific examples. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The method for manufacturing the solid-state battery of the present embodiment includes the steps of:
1) preparation of positive pole piece
The preparation method of the positive pole piece comprises the following steps:
s1: adding a first monomer preparation raw material into dimethyl sulfoxide for full reaction to obtain a first monomer, adding the first monomer and a second monomer into a polymerization solvent for uniform mixing, adding an initiator for mixing, and initiating a polymerization reaction to obtain a polymer.
S2: mixing and dispersing a positive active material, a polymer, a lithium salt, an auxiliary agent, a conductive agent, a binder and the like in a solvent to obtain positive slurry; and coating the positive slurry on two functional surfaces of the aluminum foil, drying for 24 hours at 100 ℃, rolling and slitting to obtain the positive pole piece.
2) Preparation of negative pole piece
Taking 50-micron copper-based composite lithium provided by lithium industry in Tianjin as a negative electrode, wherein the thickness of a copper foil is 10 microns, and the thickness of a lithium layer is 20 microns;
3) preparation of solid electrolyte
5 g of polyethylene oxide (molecular weight 100W), 2 g of LITFSI and 100g of anhydrous acetonitrile were uniformly mixed, coated on a smooth surface, the solvent was removed in a drying chamber (dew point-50 ℃ C.), and hot-pressed to obtain a solid electrolyte with a thickness of 200 μm.
4) Assembly of lithium ion batteries
And preparing the positive pole piece, the solid electrolyte and the negative pole piece into a solid battery cell in a lamination mode, and performing processes such as packaging to obtain the lithium ion battery.
Comparative example 1a
Comparative examples 1a correspond to the foregoing examples 1 one to one, respectively, and differ from example 1 in the polymer.
Comparative example 1b
Comparative examples 1b correspond to the foregoing examples 1 one to one, respectively, and differ from example 1 in that the polymer used in example 1 was replaced with polyethylene oxide PEO of the same molecular weight.
Example 2
The method for manufacturing the solid-state battery of the present embodiment includes the steps of:
1) preparation of positive pole piece
The preparation method of the positive pole piece comprises the following steps:
mixing and dispersing a positive active material, a polymer monomer, an initiator, a lithium salt, an auxiliary agent, a conductive agent and a binder in a solvent to obtain positive slurry; and coating the positive slurry on two functional surfaces of the aluminum foil, polymerizing at 55 ℃ for 3h, and drying the positive slurry at 100 ℃ for 24h to obtain the positive pole piece.
2) Preparation of negative pole piece
Taking 50-micron copper-based composite lithium provided by lithium industry in Tianjin as a negative electrode, wherein the thickness of a copper foil is 10 microns, and the thickness of a lithium layer is 20 microns;
3) preparation of solid electrolyte
5 g of polyethylene oxide (molecular weight 100W), 2 g of LITFSI and 100g of anhydrous acetonitrile were uniformly mixed, coated on a smooth surface, the solvent was removed in a drying chamber (dew point-50 ℃ C.), and hot-pressed to obtain a solid electrolyte with a thickness of 200 μm.
4) Assembly of lithium ion batteries
And preparing the positive pole piece, the solid electrolyte and the negative pole piece into a solid battery cell in a lamination mode, and performing processes such as packaging to obtain the lithium ion battery.
Comparative example 2a
Comparative example 2a is substantially identical to example 2, except that the polymer monomer used is different.
Comparative example 2b
Comparative example 2b is substantially identical to example 2 except that the difference from each example is that the polymer monomer used in the examples is replaced with polyethylene oxide PEO of the same mass as the polymer monomer, wherein the molecular weight of PEO is identical to the number average molecular weight of the polymer obtained after polymerization of the polymer monomer.
Examples 3 to 5
The solid electrolyte and the lithium ion battery in examples 3 to 5 are prepared by referring to example 1, and the main differences are that the types of the polymer monomers, the contents of the components, the types of the components and the preparation process in the preparation of the solid electrolyte are different from those in example 1, and the specific details are shown in tables 1,2, 3 and 4.
For the sake of comparison, the raw materials and reaction parameters of the solid electrolyte preparation processes of example 1, comparative example 1a, and comparative example 1b are also listed together in tables 1,2, and 3.
Comparative examples 3a to 5a
Comparative examples 3a to 5a correspond one-to-one to the foregoing examples 3 to 5, respectively, and the difference from each example is that the polymers are different.
Comparative examples 3b to 5b
Comparative examples 3b-5b correspond one-to-one to the previous examples 3-5, respectively, and differ from the respective examples in that the polymers used in the examples were replaced with polyethylene oxide PEO of the same molecular weight.
Examples 6 to 9
The solid electrolyte and the lithium ion battery in examples 6 to 9 are prepared by referring to example 2, and the main differences are that the types of the polymer monomers, the contents of the components, the types of the components and the preparation process in the preparation of the solid electrolyte are different from those in example 2, and the specific details are shown in tables 1,2, 3 and 4.
Comparative examples 6a to 8a
Comparative examples 6a to 8a correspond one-to-one to the foregoing examples 6 to 8, respectively, and the difference from each example is that the polymer monomer used is different.
Comparative examples 6b to 9b
Comparative examples 6b to 9b correspond to the previous examples 6 to 9, respectively, one-to-one, except that the difference from each example is that the polymer monomer used in the examples is replaced with polyethylene oxide PEO having the same mass as the polymer monomer, wherein the molecular weight of PEO is identical to the number average molecular weight of the polymer obtained after polymerization of the polymer monomer.
For the sake of comparison, the raw materials and reaction parameters of the solid electrolyte preparation processes of example 2, comparative example 2a, and comparative example 2b are also listed together in table 1, table 2, and table 3.
The composition-related parameters of the positive electrode sheets of the above examples and comparative examples are referred to table 1, and the thickness of the positive electrode active layer of the positive electrode sheet of the above examples and the related information of the polymer are referred to table 4, wherein the thicknesses of the positive electrode active layers of the examples 1 to 9 and the comparative examples of examples 1 to 9 correspond to each other, and are not listed in table 4.
TABLE 1
In table 1, the preparation method of polymer 1 in example 1 includes the following steps:
s1: under inert atmosphere, adding isocyanate ethyl acrylate and 3-chloro-4-fluorobenzylamine into dimethyl sulfoxide, fully reacting, and removing the solvent to obtain a first monomer (an olefin compound containing a ureido group), wherein the structure of the first monomer is shown in Table 3.
S2: adding the first monomer in S1, polyethylene glycol monomethyl ether alkenoic acid ester (second monomer) and azobisisoheptonitrile into a closed container under inert atmosphere, uniformly mixing the mixture, and reacting at 60 ℃ for 2h to obtain the polymer 1.
In table 1, the method of preparing the polymer 1a in comparative example 1a comprises the following steps:
s1: under inert atmosphere, polyethylene glycol monomethyl ether acrylate (second monomer) and azobisisoheptonitrile with the same mass as the monomer for preparing the polymer 1 are added into a closed container and react for 2h at 60 ℃ to obtain a polymer 1 a.
The polymer preparation method steps in the other examples and comparative examples were substantially similar to those of polymer 1 and polymer 1a, respectively, except for the selection of the preparation raw material of the first monomer, the second monomer and the initiator, and the polymerization process, as shown in table 2.
The structural formula of the first monomer in all examples in table 2 is shown in table 3.
TABLE 2
TABLE 3
The polymers of the embodiments 1 to 9 are tested for the number average molecular weight and the crystallinity, wherein the polymers of the embodiments 2 and 6 to 9 are mixed with the preparation of the positive active layer during the preparation, before the test, the positive pole piece is treated in tetrahydrofuran at 60 to 100 ℃ for 10 to 60 hours, and the supernatant is obtained after suction filtration, and then the supernatant is subjected to column chromatography separation to obtain the polymer. The number average molecular weight and crystallinity were measured as follows:
polymer number average molecular weight test method: dissolving the polymer in a solvent to form a uniform liquid system, carrying out suction filtration on the uniform liquid system, taking a sample, detecting the sample in a Nippon Shimadzu GPC-20A gel chromatograph, and collecting molecular weight information. The test results are shown in Table 4.
And (3) detecting the crystallinity of the polymer: the polymer is ground into powder, an Shimadzu XRD-7000 type X-ray diffractometer is adopted, a theta/theta scanning mode is adopted, a sample is horizontally placed, and the crystallinity of the polymer is tested. The crystallinity of a polymer, based on the X-ray scattering intensity being proportional to the mass of the scattering material, separates crystalline scattering from amorphous scattering on the diffraction diagram, with the crystallinity Xc ═ a/(a + B), where a is the crystalline phase scattering intensity and B is the amorphous phase scattering intensity. The test results are shown in Table 4.
TABLE 4
Test examples
The above examples and comparative examples were subjected to the following two parameter tests:
testing the interface impedance of the positive pole piece and the solid electrolyte: the interface impedance of the positive pole piece and the solid electrolyte is tested by adopting an alternating current impedance method (EIS), and the used instrument is an electrochemical workstation of model CHI660E of Shanghai Chenghua apparatus Co. Preparing a solid electrolyte membrane: and coating the solid electrolyte precursor on the surface of the flat plate in an argon glove box, and treating at 70 ℃ until the solid electrolyte forms a film. In an argon glove box, a polymer film is attached to the surface of the single-sided anode of the embodiment and the comparative example, electricity is buckled by adopting a gasket, a stainless steel sheet, an anode pole piece, a solid electrolyte and a stainless steel sheet structure, and the electricity is buckled under the condition of 30 ℃ to carry out an EIS test. The specific results are shown in Table 5.
And (3) detecting the cycle performance of the lithium ion battery: and (3) placing the lithium ion battery on a blue battery charging and discharging test cabinet to carry out charging and discharging cycle test, wherein the test conditions are 30 ℃, 0.5C/0.5C charging and discharging, the charging and discharging starting and stopping voltage is 3.0-4.20V, and the cycle times when the capacity is attenuated to 80% of the first discharging capacity are recorded. The specific results are shown in Table 5.
TABLE 5
As can be seen from the data in table 5, the positive electrode sheet of the present invention has lower internal resistance, and the lithium ion battery assembled by using the positive electrode sheet of the present invention has better cycle performance. Taking example 1 and comparative examples 1 a-1 b as examples, compared with example 1, comparative example 1a adopts only the second monomer for polymerization, has no alkenyl ureido structure, has large interface impedance between the positive pole piece and the solid electrolyte, increases side reactions in the battery, and has poor cycle performance. In the comparative example 1b, polyethylene oxide is used as the solid electrolyte, the conductivity and electrochemical stability of polyethylene oxide are relatively low, the molecular weight is large, the chain length is long, the interface impedance of the prepared positive pole piece and the solid electrolyte is large, and the assembled solid battery has more side reactions on the interface, so that the performance of the solid battery is attenuated too fast. The comparison between examples 2 to 9 and their corresponding comparative examples is identical to that between example 1 and comparative examples 1a to 1b, and no further analysis is carried out here.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A positive electrode sheet comprising a solid state electrolyte, wherein the solid state electrolyte comprises a polymer comprising a first structural unit derived from an olefin compound containing a substituted or unsubstituted ureido group, wherein the olefin compound containing a substituted or unsubstituted ureido group further comprises at least one cyclic group.
2. The positive electrode sheet according to claim 1, wherein the olefin compound having a substituted or unsubstituted ureido group has a structure represented by formula 1:
wherein R is1、R3、R4Each independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted amino of (a); r2Selected from the group consisting of carbonyl, substituted or unsubstituted (hetero) aryl, ester, substituted or unsubstituted C1～12Alkylene, carboxyl, or a chemical bond; m1Selected from H, carbonyl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, hydroxy, halogen, amino, nitro, trifluoromethyl, alkylthio, substituted or unsubstituted (hetero) aryl; m2、M3Each independently selected from hydrogen, substituted or unsubstituted C4～60(hetero) aryl, substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C1～20Alkoxy, carbonyl, substituted or unsubstituted C containing a heterocyclic atom2～12Cycloalkyl, acyl, carboxyl, ester, or M2、M3Bonding to form a ring; r1～R4And M1～M3Wherein at least one cyclic group is present.
3. The positive electrode sheet according to claim 1 or 2, wherein the number average molecular weight of the polymer is 2000 to 50000, and the mass ratio of the first structural unit in the polymer is not less than 30%.
4. The positive electrode plate as claimed in any one of claims 1 to 3, wherein the solid electrolyte comprises, by mass, 60 to 95 wt% of the polymer, 5 to 30 wt% of the lithium salt, and 0 to 20 wt% of the additive.
5. The positive electrode plate as claimed in any one of claims 1 to 4, wherein the positive active layer of the positive electrode plate comprises, by mass, 70 to 95 wt% of a positive active material, 2 to 15 wt% of a solid electrolyte, 3 to 15 wt% of a conductive agent, and 0 to 10 wt% of a binder.
6. The positive electrode sheet according to claim 4, wherein the molar ratio of the sum of oxygen and nitrogen in the polymer to the lithium in the lithium salt is (5-25): 1.
7. The positive electrode sheet according to any one of claims 1 to 6, wherein the polymer has a crystallinity of 40% or less.
8. The positive electrode sheet according to any one of claims 1 to 7, wherein the polymer further comprises a second structural unit derived from an olefinic compound, and the second structural unit is different from the first structural unit.
9. The positive electrode sheet according to claim 2 or 3, wherein the olefin compound having a substituted or unsubstituted ureido group is prepared according to a method comprising:
reacting a solvent system comprising a first isocyanate compound and a first amine compound, or a solvent system comprising a second isocyanate compound and a second amine compound to obtain the olefin compound containing a substituted or unsubstituted ureido group; wherein the first isocyanate compound satisfies the structure shown in formula 2a, the first amine compound satisfies the structure shown in formula 3a, and the first amine compound is a primary amine or a secondary amine compound; a second amine compound satisfying the structure of formula 2b, a second isocyanoThe acid ester compound satisfies the structure shown in formula 3b, wherein in the formula 3b, MxIs M2Or M3，
10. A solid-state battery comprising the positive electrode sheet according to any one of claims 1 to 9.
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