CN108155354A - By the anode active material particles from the polymerization of main chain Graft Method with SEI layers of synthesis - Google Patents
By the anode active material particles from the polymerization of main chain Graft Method with SEI layers of synthesis Download PDFInfo
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- CN108155354A CN108155354A CN201711248916.9A CN201711248916A CN108155354A CN 108155354 A CN108155354 A CN 108155354A CN 201711248916 A CN201711248916 A CN 201711248916A CN 108155354 A CN108155354 A CN 108155354A
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- Prior art keywords
- polymerization
- functional group
- group
- silane compound
- crown ether
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 204
- 239000002245 particle Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000006183 anode active material Substances 0.000 title claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 title abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 156
- -1 silane compound Chemical class 0.000 claims abstract description 130
- 125000000524 functional group Chemical group 0.000 claims abstract description 128
- 229910000077 silane Inorganic materials 0.000 claims abstract description 98
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 87
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 41
- 239000011149 active material Substances 0.000 claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 131
- 238000010526 radical polymerization reaction Methods 0.000 claims description 67
- 150000003983 crown ethers Chemical class 0.000 claims description 65
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- 239000000460 chlorine Substances 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 30
- 239000003505 polymerization initiator Substances 0.000 claims description 28
- 150000003254 radicals Chemical class 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000012546 transfer Methods 0.000 claims description 26
- 230000002441 reversible effect Effects 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- 125000004429 atom Chemical group 0.000 claims description 21
- 238000012711 chain transfer polymerization Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000005647 linker group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 12
- 150000005677 organic carbonates Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000005262 alkoxyamine group Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
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- 125000005605 benzo group Chemical group 0.000 claims description 5
- DOMLXBPXLNDFAB-UHFFFAOYSA-N ethoxyethane;methyl prop-2-enoate Chemical compound CCOCC.COC(=O)C=C DOMLXBPXLNDFAB-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- VIBRUMXTFSYBCG-UHFFFAOYSA-N [F].C=CCCCC Chemical class [F].C=CCCCC VIBRUMXTFSYBCG-UHFFFAOYSA-N 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001427 mPEG Polymers 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- 125000004149 thio group Chemical group *S* 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- CEWDRCQPGANDRS-UHFFFAOYSA-N 1-ethenyl-4-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(C=C)C=C1 CEWDRCQPGANDRS-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 1
- 241001614291 Anoplistes Species 0.000 claims 1
- 125000002009 alkene group Chemical group 0.000 claims 1
- 229910001507 metal halide Inorganic materials 0.000 claims 1
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- 238000002360 preparation method Methods 0.000 abstract description 12
- 150000002641 lithium Chemical class 0.000 abstract description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
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- 238000006482 condensation reaction Methods 0.000 description 14
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 12
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 10
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
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- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 6
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- 238000010792 warming Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 241000252073 Anguilliformes Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 101100425892 Danio rerio tpma gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CIKDGAZPCSNZPB-UHFFFAOYSA-N FC(C1=CC=C(C=C)C=C1)(F)F.C=C Chemical compound FC(C1=CC=C(C=C)C=C1)(F)F.C=C CIKDGAZPCSNZPB-UHFFFAOYSA-N 0.000 description 1
- BEDRPNAXDXDKBA-UHFFFAOYSA-N FC1=C(C=C)C(=C(C(=C1F)F)F)F.C=C Chemical compound FC1=C(C=C)C(=C(C(=C1F)F)F)F.C=C BEDRPNAXDXDKBA-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 101150048952 TPM-1 gene Proteins 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- BUTFCJGGGQXOQB-UHFFFAOYSA-N [4-(chloromethyl)phenyl]silane Chemical compound [SiH3]C1=CC=C(CCl)C=C1 BUTFCJGGGQXOQB-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003696 structure analysis method Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 present invention relates to by the anode active material particles from the polymerization of main chain Graft Method with SEI layers of synthesis.In particular it relates to the active material of positive electrode of lithium battery and/or lithium battery group, especially lithium ion battery and/or Li-ion batteries piles and/or the preparation method of anode and/or the preparation method of this lithium battery and/or lithium battery group.In order to improve the cyclical stability of lithium battery and/or lithium battery group, make that there is at least one polymerizable functional group and/or polymerization to cause at least one silane compound of functional group and/or polymerization control functional group in the method(2*)It is fixed on anode active material particles(1)Surface on, particularly on the surface of silicon particle, and add at least one polymerisable monomer(2).In addition, the present invention relates to active material of positive electrode, anode and lithium battery and/or lithium battery groups.
Description
Technical field
The present invention relates to lithium battery and/or lithium battery group, the especially anode of lithium ion battery and/or Li-ion batteries piles is lived
Property material and/or anode preparation method and/or the preparation method and anode of this lithium battery and/or lithium battery group activity
Material and anode and this lithium battery and/or lithium battery group.
Background technology
Active material of positive electrode currently used for lithium ion battery and-battery pack is mainly graphite.But graphite only has very little
Memory capacity.
Silicon can provide notable higher memory capacity as lithium ion battery and the active material of positive electrode of-battery pack.So
And in cycle violent volume change occurs for silicon, this leads to the SEI layers formed on a silicon surface by electrolyte decomposition products
(SEI, English:Solid Electrolyte Interphase;Solid electrolyte interface)It may be torn when silicon volume increases
Peeled off with when silicon volume reduces, so as to each cycle so that electrolyte contacted again with silicon face and SEI formation and
Electrolyte, which decomposes, constantly to carry out, this leads to lithium(And electrolyte)Irreversible loss and therefore significantly reduce cyclical stability and
Capacity.
2014/0248543 A1 of document US are related to the nanostructured silicon active material for Li-ion batteries piles.
2014/0248543 A1 of document US are related to the Li-ion batteries piles with anode and electrolyte, and wherein the anode has
There is at least one active material and the electrolyte includes at least one liquid polymers solvent and at least one polymer adds
Agent.
2015/0072246 A1 of document US are related to the non-aqueous liquid electrolyte for battery pack, and can include can gather
Monomer is closed as additive.
2010/0273066 A1 of document US describe a kind of lithium-air-battery pack, have based on the non-of organic solvent
Aqueous electrolyte, the electrolyte include lithium salts and the additive with alkylidene.
2012/0007028 A1 of document US are related to a kind of method for preparing polymer-silicon-composite material granular, wherein will
It is used to form the monomer of polymer substrate and silicon particle mixes and polymerize the mixture.
Document CN 104 362 300 is related to a kind of method for the silico-carbo-composite anode materials for preparing Li-ion batteries piles.
2014/0342222 A1 of document US are related to the particle with silicon core and block-copolymer shell, one of block
With compatibility relatively high to silicon and a block with the compatibility relatively low to silicon.
H. Zhao etc. describes the carbonic acid Asia of polymerization in J. Power Sources, 263,2014,288-295 pages
Purposes of the vinyl acetate as anode binder in Li-ion batteries piles.
J.-H. Min etc. is in Bull. Korean. Chem. Soc., volume 2013,34, number 4., 1296-1299
The SEI that synthesis is formed on silicon particle is described in page.
Document WO 2015/107581 is related to the battery anode material with non-aqueous electrolyte.
Invention content
Subject of the present invention is the sun of lithium battery and/or lithium battery group, especially lithium ion battery and/or Li-ion batteries piles
The preparation method and/or lithium battery of pole active material and/or anode and/or the preparation method of lithium battery group, particularly lithium ion
The preparation method of battery and/or Li-ion batteries piles.
In the method, particularly make to have at least one polymerizable functional group and/or polymerization cause functional group and/or
At least one silane compound of polymerization control functional group is fixed on the surface of anode active material particles, particularly silicon particle
On, particularly then, add at least one polymerisable monomer and particularly polymerize(It polymerize from main chain Graft Method
(graft-from-Polymerisation)).
Anode active material particles are particular it is understood that particle to include at least one active material of positive electrode.
The anode active material particles, such as can include or silicon particle and/or graphite particle and/or tin particles.
Silicon particle is particular it is understood that for the particle comprising silicon.For example, silicon particle can be understood as containing silicon
Grain.Therefore, silicon particle is especially it can be appreciated that based particles.For example, silicon particle can especially include pure or simple substance silicon,
Such as porous silicon, such as nano-structure porous silicon, such as with the pore size and/or nano-silicon in nanometer range, for example, with
Particle size and/or silicon-alloy substrate or silicon-alloy in nanometer range, such as wherein silicon insertion are active and/or nonactive
Matrix in and/or silico-carbo composite material and/or silica(SiOx)Or it is formed by it.For example, the silicon particle can be by
Particularly pure or simple substance silicon is formed.
Graphite particle is particular it is understood that for the particle comprising graphite.
Tin particles are particular it is understood that for the particle comprising tin.
Particularly, the anode active material particles can include either silicon particle.
The silane-functional of at least one silane compound can advantageously on the surface of anode active material particles,
Particularly on the surface of silicon particle, such as covalently combine.
By making that there is at least one polymerizable functional group and/or polymerization to cause functional group and/or polymerization control functional group
At least one silane compound be fixed on the surface of anode active material particles, particularly silicon particle, it can be advantageous to draw
Send out the polymerization on the surface of anode active material particles, particularly silicon particle.Therefore, it can be advantageous to realize the polymerization that surface is caused
(It polymerize from main chain Graft Method), such as the active free radical polymerization that surface is caused, as the atom transfer of surface initiation is active freely
Base polymerize(The ATRP that surface is caused;Multiphase ATRP polymerization)(ATRP, English:Atom Transfer Radical
Polymerization or Atomic Transfer Radical Polymerization)Or the stabilization that surface is caused is certainly
It is polymerize by base(The SFRP, multiphase SFRP that surface is caused)(SFRP, English:Stable Free Radical
Polymerization), such as the polymerization of the nitrogen oxides mediation of surface initiation(The NMP that surface is caused;Multiphase NMP polymerize)
(NMP, English:Nitroxide-mediated Polymerization)Or reversible addition-fracture-chain that surface is caused turns
Shifting-polymerization(The RAFT that surface is caused;Multiphase RAFT polymerize)(RAFT, English:Reversible Addition
Fragmentation Chain Transfer Polymerization)Or the iodine transfer polymerization that surface is caused(Cause on surface
ITP)(ITP, English:Iodine-Transfer Polymerization).By by anode active material particles, particularly
The polymerization that the surface of silicon particle starts, it can be advantageous in anode active material particles, particularly silicon particle and by polymerizeing shape
Into polymer between realize stable, particularly covalent and/or physical/mechanical combination and/or attachment, and therefore shape
Into the polymeric layer on anode active material particles, particularly silicon particle with improved adhesiveness.
For example, at least one polymerizable functional group of at least one silane compound, it particularly can at least one
Polymerized monomer and/or at least one polymer formed by least one polymerisable monomer, can be polymerize, example
Such as copolymerization.Pass through at least one silane compound at least one polymerizable functional group and the polymerizable list of at least one
The copolymerization of body, can be by silane-functional, such as covalently it is possible thereby to advantageously generate the copolymer with silane-functional
Ground combines on the surface of anode active material particles, particularly silicon particle.Silane at least one polymerizable functional group
Therefore compound can be advantageously used for adhesion promotor, particularly for by anode active material particles, particularly silicon
Polymerization on particle and the polymeric layer formed, and anode active material particles are formed in, have particularly on silicon particle and change
Into adhesiveness polymeric layer.
In this way it is possible to it is formed advantageously on anode active material particles, particularly silicon particle with improved
Adhesiveness, SEI layers of synthesis in the form of flexible polymer protective layer.By this in the form of flexible polymer protective layer
SEI layers of synthesis can advantageously inhibit electrolyte to decompose and be formed with continuous SEI, in this way because flexible polymer protective layer exists
With the anode active material particles occurred in cyclic process, particularly in the case of the volume change of silicon particle, such as can be with
Plastic elongation and/or compression, and be not destroyed herein, the particle, particularly silicon particle are thus passivated, and avoid that sun occurs
Pole surface of active material, particularly silicon face are reacted with electrolyte.Therefore, it and then can advantageously improve equipped with anode work
The lithium battery and/or-battery pack of property material, such as lithium ion battery and/or the cyclical stability of-battery pack(English:
Coulombic Efficiency).
In short, the active material of positive electrode with increased cyclical stability and memory capacity can be advantageously provided in this way,
Such as it can especially increase the reach of electric vehicle using it.
In one embodiment, in the method using at least two polymerisable monomers.It for example, in the method can be with
Use at least three kinds of polymerisable monomers.Copolymerization in this way is directed to especially by two kinds, three or more monomers
Property copolymerization desired characteristic can advantageously and be targetedly set, particularly synthesize SEI layers of desired characteristic, and
And it can for example cause SEI layers of matching these requirements or design SEI layers according to these requirements.It is used for for example, therefore can introduce
Adhesive enhances and/or for matching mechanical property, such as rheological properties, such as the polymer of intensity and/or tensility
Segment.
For example, the polymerization can be free radical polymerization and/or the polymerization and/or ionic polymerization by condensation reaction, example
Such as the polymerization of anion or cation.
For example, at least one that the polymerization can be free radical polymerization and/or at least one silane compound can
Polymer functional group can be polymerize and/or at least one polymerisable monomer by free radical polymerization, especially at least two kinds
Polymerisable monomer can be polymerize and/or at least one of at least one silane compound polymerize by free radical polymerization
Cause functional group's setting for causing free radical polymerization.
Particularly, the polymerization can be active free radical polymerization and/or at least one silane compound at least
A kind of polymerizable functional group can be polymerize and/or at least one polymerisable monomer by active free radical polymerization, especially
Being at least two polymerisable monomers can be polymerize and/or at least one silane compound by active free radical polymerization
At least one polymerization cause functional group's setting for causing active free radical polymerization and/or at least one silane chemical combination
At least one polymerization control functional group of object sets to control active free radical polymerization.
The active free radical polymerization is based on following principle, i.e., in the active material of relatively small amount(Promote oneself of growth
By base)Dynamic balance is generated between a large amount of deactivating materials.This can realize especially through free radical buffer, wherein
Free radical buffer can be captured in the form of deactivating materials and discharge active material again(That is free radical).Therefore, particularly exist
At least one free radical buffer can be used in polymerization.Therefore, this can greatly inhibit irreversible chain transfer reaction and chain
Reaction is terminated, these reactions may especially cause quantity of active material reduction and molecular weight distribution to broaden.The living radical
Polymerization is especially referred to as active free radical polymerization(LFRP;English:Living Free Radical
Polymerization)Or control(It is free)Free radical polymerization(CFRP;English:Controlled Free Radical
Polymerization)Or the active free radical polymerization of control.
The example of active free radical polymerization is atom transfer active free radical polymerization(ATRP, English:Atom Transfer
Radical Polymerization or Atomic Transfer Radical Polymerization), such as using passing through
Electronics shifts regenerated activator(ARGET-ATRP)(ARGET, English:Activators regenerated by
electron transfer), reversible addition-fracture-chain tra nsfer-polymerization(RAFT, English:Reversible Addition
Fragmentation Chain Transfer Polymerization), stable free radical polymerization(SFRP, English:Stable
Free Radical Polymerization), the particularly polymerization of nitrogen oxides mediation(NMP, English:Nitroxide-
mediated Polymerization)And/or the polymerization of Verdazyl- mediations(VMP, English:Verdazyl-mediated
Polymerization)And iodine transfer polymerization(ITP, English:Iodine-Transfer Polymerization).
By active free radical polymerization, gather especially by atom transfer active free radical polymerization and/or stabilized radical
It closes, such as the polymerization of nitrogen oxides mediation and/or the polymerization of Verdazyl- mediations, the polymerization that particularly nitrogen oxides mediates,
And/or reversible addition-fracture-chain tra nsfer-polymerization, it can be advantageous to realize Narrow Molecular Weight Distribution or low polydispersity(Molecular weight
The width of distribution)And/or improved polymer chain length control, and for example it is achieved in uniform polymer coating.Here, institute
Stating molecular weight distribution and/or polymer layer of thickness can be with, such as according to chemical concentration, such as monomer concentration and/or reaction time
And/or temperature is adjusted.
At least one polymerisable monomer, the polymerizations of especially at least two kinds polymerisable monomers can be with, such as by institute
State at least one silane compound at least one polymerization cause functional group and/or by(Such as pass through addition)At least one is poly-
Close initiator, for example, at least a kind of radical initiator and cause, particularly for causing free radical polymerization, such as causing
Active free radical polymerization, such as causing atom transfer active free radical polymerization and/or stable free radical polymerization, such as nitrogen oxidation
The polymerization of object mediation and/or polymerization and/or the reversible addition-fracture-chain tra nsfer-polymerization of Verdazyl- mediations.It therefore, can be with
Advantageously and targetedly cause polymerization, and cause anode active material particles, particularly silicon particle, advantageously and have needle
Property is disposed with, is particularly coated with the polymer formed by the polymerization.Therefore, it can be advantageous in anode activity material
By forming synthesizing for flexible polymer protective layer form by the polymer formed that polymerize on material particle, particularly silicon particle
SEI layers.
At least one polymerisable monomer, the polymerizations of especially at least two kinds polymerisable monomers can be with, such as by extremely
A kind of at least one polymerization control functional group of few silane compound and/or by(Such as pass through addition)At least one polymerization control
Preparation and control, particularly for controlling active free radical polymerization, such as controlling stable free radical polymerization, such as controlling
The polymerization of nitrogen oxides processed mediation and/or for controlling polymerization that Verdazyl- mediates and/or for controlling reversible addition-disconnected
Split-chain tra nsfer-polymerization.
In another embodiment, the polymerization is atom transfer active free radical polymerization(ATRP)And/or it is described extremely
A kind of at least one polymerizable functional group of few silane compound passes through atom transfer active free radical polymerization(ATRP)It and can
Polymerization and/or at least one polymerisable monomer, especially at least two kinds of polymerisable monomers are free by atom transfer activity
Base polymerize(ATRP)And it can polymerize and/or at least one polymerization of at least one silane compound causes functional group and sets
It puts to cause atom transfer active free radical polymerization(ATRP initiators).It, can be with by atom transfer active free radical polymerization
It is advantageously carried out Narrow Molecular Weight Distribution or low polydispersity(The width of molecular weight distribution)And/or improved polymer chain length control
System, and for example it is achieved in uniform polymer coating.
At least one polymerization of at least one silane compound causes functional group, is particularly used to cause atom transfer
Active free radical polymerization can especially be used at least one catalyst combination.
At least one polymerization of at least one silane compound causes functional group, particularly live for atom transfer
Free love base polymerize(ATRP initiators), such as can include or at least one halogen atom, such as chlorine(-Cl), bromine(-Br)
Or iodine(-I), preferred chlorine(-Cl)Or bromine(-Br), such as by least one halogen atom, such as chlorine(-Cl), bromine(-Br)Or iodine
(-I), preferred chlorine(-Cl)Or bromine(-Br)Substituted alkyl.
Alternatively, or in addition, the atom transfer active free radical polymerization can also be by(Such as pass through addition)With
In at least one polymerization initiator for causing atom transfer active free radical polymerization(ATRP initiators)And cause, particularly with extremely
A kind of few catalyst combination uses.In this case, at least one polymerization initiator can especially include alkyl halide
Object is formed by it.For example, at least one polymerization initiator can include or isobutyl bromide methyl esters and/or benzyl bromide
And/or acetic-alpha-brominated phenyl ester.
At least one catalyst can especially include transition metal halide, particularly copper halide, such as copper chloride
And/or copper bromide, such as copper bromide(I)And optionally at least one ligand, for example, at least a kind of, particularly multiple tooth, nitrogen is matched
Body(N-type ligand, English:N-type ligand), for example, at least a kind of amine, such as three [2-(Dimethylamino)Ethyl] amine
(Me6tren)And/or three(2- pyridylmethyls)Amine(TPMA)And/or 2,2'- bipyridyls and/or N, N, N', N'', N''- five
Methyl diethylenetriamines(PMDETA)And/or 1,1,4,7,10,10- hexamethyl triens(HMTETA)Or by it
It is formed.For example, at least one catalyst can be transient metal complex, particularly transition metal-nitrogen-complex.
Functional group and/or the alkyl halide are caused by least one polymerization of at least one silane compound,
The catalyst or complex and the monomer can form the free radical buffer or the deactivating materials.
In another alternative or additional embodiment, the polymerization is stable free radical polymerization(SFRP), example
The polymerization mediated such as nitrogen oxides(NMP)And/or the polymerization of Verdazyl- mediations(VMP), particularly nitrogen oxides mediation is poly-
It closes(NMP )And/or at least one polymerizable functional group of at least one silane compound is by stable free radical polymerization,
Such as by nitrogen oxides mediate polymerization or by Verdazyl- mediate polymerization, especially by nitrogen oxides mediation
Polymerization and can polymerize and/or at least one polymerisable monomer, especially at least two kinds of polymerisable monomers by stablize from
It is polymerize by base(SFRP), such as the polymerization mediated by nitrogen oxides(NMP)And/or the polymerization of Verdazyl- mediations(VMP),
The polymerization mediated especially by nitrogen oxides(NMP)And it can polymerize and/or wherein described at least one silane compound
At least one polymerization control functional group sets to control stable free radical polymerization(SFRP- mediators), such as controlling nitrogen oxygen
The polymerization of compound mediation(NMP- mediators)And/or the polymerization for Verdazyl- to be controlled to mediate(VMP- mediators), particularly it is used for
Control the polymerization of nitrogen oxides mediation(NMP- mediators).
At least one polymerization control functional group of at least one silane compound, particularly stablizes freely for controlling
Base polymerize(SFRP- mediators), such as the polymerization for nitrogen oxides to be controlled to mediate(NMP- mediators)And/or for controlling
The polymerization of Verdazyl- mediations(VMP- mediators), such as the polymerization for nitrogen oxides to be controlled to mediate(NMP- mediators), especially may be used
With at least one silane compound at least one polymerize initiation functional group and/or with(It is described)At least one polymer
Initiator is applied in combination.
At least one polymerization control functional group of at least one silane compound, particularly mediates for nitrogen oxides
Polymerization(NMP- mediators), can for example include or, especially straight chain or cricoid, nitroxide groups and/or alkoxyamine
Group, such as based on 2,2,6,6- tetramethyl-piperidyl oxygroups(TEMPO):
Or its sacrificial initiator(Opferinitiator), such as:
And/or based on 2,2,5- trimethyl -4- phenyl -3- aza-hexane -3- oxygroups (TIPNO):
Or its sacrificial initiator, such as:
And/or based on N- tert-butyl-n -s [1- diethyl phosphonyls-(2-2- dimethyl propylenes
Base) nitrogen oxides] (SG1*):
Or its sacrificial initiator.
Alternatively, or in addition, the stable free radical polymerization, for example, nitrogen oxides mediation polymerization and/or
The polymerization of Verdazyl- mediations, can also be by(Such as pass through addition)At least one polymerization control agent and control, the polymerization control
Preparation is used to control stable free radical polymerization, such as the polymerization for controlling nitrogen oxides mediation and/or for controlling
The polymerization of Verdazyl- mediations, the mediator of for example, at least a kind of nitrogen oxides base and/or Jie of at least one Verdazyl bases
Body, particularly at least one silane compound at least one polymerize initiation functional group and/or with(It is described)It is at least one poly-
Initiator is closed to be applied in combination.The mediator of at least one polymerization control agent or at least one nitrogen oxides base can for example including
Or especially straight chain or cricoid, nitrogen oxides.The mediator or nitrogen oxides of at least one nitrogen oxides base can be such as
Based on 2,2,6,6- tetramethyl-piperidyl oxygroups(TEMPO):
Or its sacrificial initiator, such as:
And/or based on 2,2,5- trimethyl -4- phenyl -3- aza-hexane -3- oxygroups (TIPNO):
Or its sacrificial initiator, such as:
And/or based on N- tert-butyl-n -s [1- diethyl phosphonyls-(2-2- dimethyl propylenes
Base) nitrogen oxides] (SG1*):
Or its sacrificial initiator.
At least one polymerization initiation official of at least one polymerization initiator and/or at least one silane compound
Can roll into a ball can especially set to cause stable free radical polymerization herein(SFRP- initiators), such as causing nitrogen oxides
The polymerization of mediation(NMP- initiators)And/or the polymerization for causing Verdazyl- mediations(VMP- initiators), particularly it is used for
Cause the polymerization of nitrogen oxides mediation(NMP- initiators).In this case, at least one polymerization initiator and/or institute
At least one polymerization for stating at least one silane compound causes functional group and can especially include or radical initiator, such as
Azo isobutyronitrile, such as azo are double(Isobutyronitrile)(AIBN)And/or benzoyl peroxide, such as dibenzoyl peroxide
(BPO), or derivatives thereof.
The free radical buffer or deactivating materials herein especially can be by active materials, i.e. free radical, and based on nitrogen
The reaction of the stabilized radical of the mediator of oxide groups and/or alkoxyamine groups or nitrogen oxides base and formed.
In another alternative or additional embodiment, the polymerization is reversible addition-fracture-chain tra nsfer-poly-
It closes(RAFT)And/or at least one polymerizable functional group of at least one silane compound by reversible addition-fracture-
Chain tra nsfer-polymerization(RAFT)And can polymerize and/or at least one polymerisable monomer, especially at least two kinds are polymerizable
Monomer passes through reversible addition-fracture-chain tra nsfer-polymerization(RAFT)And it can polymerize and/or at least one silane compound
At least one polymerization control functional group setting for controlling reversible addition-fracture-chain tra nsfer-polymerization(RAFT- reagents).
At least one polymerization control functional group of at least one silane compound, is particularly used to control reversible add
Into-fracture-chain tra nsfer-polymerization(RAFT- reagents), especially can polymerize initiation at least one of at least one silane compound
Functional group and/or with(It is described)At least one polymerization initiator is applied in combination.
At least one polymerization control functional group of at least one silane compound, particularly for reversible addition-disconnected
Split-chain tra nsfer-polymerization(RAFT- reagents), can include or such as thio group, such as trithiocarbonic acid ester group(-S-C=
S-S-)Or dithioesters group(-C=S-S-)Or dithiocarbamate groups group(-N-C=S-S-)Or xanthate group(-
C=S-S-).
Alternatively, or in addition, the reversible addition-fracture-chain tra nsfer-polymerization can also be by(Such as by adding
Enter)At least one is used to control reversible addition-fracture-chain tra nsfer-polymerization(RAFT- reagents)Polymerization control agent and control, should
Polymerization control agent is, for example, at least one thio-compounds, particularly polymerize at least one of at least one silane compound and draws
Send out functional group and/or with(It is described)At least one polymerization initiator is applied in combination.At least one polymerization control agent or at least
A kind of thio-compounds for example can be trithiocarbonate or dithioesters or dithiocarbamate or xanthic acid herein
Ester.
At least one polymerization initiation official of at least one polymerization initiator and/or at least one silane compound
Can roll into a ball can especially set to cause reversible addition-fracture-chain tra nsfer-polymerization herein(RAFT- initiators).In such case
Under, at least one polymerization of at least one polymerization initiator and/or at least one silane compound causes functional group
Can with particularly including or radical initiator, such as azo isobutyronitrile, such as azo it is double(Isobutyronitrile)(AIBN)And/or mistake
Benzoyl Oxide, such as dibenzoyl peroxide(BPO), or derivatives thereof.
The free radical buffer or deactivating materials herein especially can be by active materials, i.e. free radical, and based on sulphur
It is formed for the reaction of group or the stabilized radical of thio-compounds.
In another embodiment, at least one silane compound includes the silicon of at least one following chemical general formula
Hydride compounds:
,
R1, R2, R3 especially can respectively represent halogen atom, especially chlorine (- Cl) or alkoxy, especially methoxy independently of one another
Base (- OCH3) or ethyoxyl (- OC2H5) or alkyl, such as straight chained alkyl (- (CH2)x-CH3), wherein x >=0, especially first
Base (- CH3) or amino (- NH2,-NH-) or silazane group (- NH-Si-) or hydroxyl (- OH) or hydrogen (- H).For example,
R1, R2 and R3 can represent chlorine.
Y can especially represent the unit of linking group, i.e. bridging.Particularly, Y can include at least one alkylidene (-
CnH2n-) (Wherein n >=1)And/or at least one oxyalkylene group (- CnH2n-O-) (Wherein n >=1)And/or at least one
A carboxylate group (- C=O-O-) and/or at least one phenylene (- C6H4-)。
A can especially represent polymerizable functional group and/or polymerization causes functional group and/or polymerization control functional group.
Silane compound at least one polymerizable functional group can be advantageously used for adhesion promotor.
In an embodiment of the embodiment, A represents polymerizable functional group.Particularly, A can represent have extremely
The polymerizable functional group of a few polymerizable double bond.For example, A can represent the polymerizable official at least one carbon-to-carbon double bond
It can group.For example, A can represent vinyl or 1,1- ethenylidene or 1,2- ethenylidene or acrylate group or metering system
Acid esters group.
(Particularly promote bonding)Silane compound with polymerizable functional group can be for example logical with following chemistry
Formula:
In this case, R1, R2, R3 especially can respectively represent halogen atom, especially chlorine (- Cl) or alkane independently of one another
Oxygroup, especially methoxyl group (- OCH3) or ethyoxyl (- OC2H5) or alkyl, such as straight chained alkyl (- (CH2)x-CH3) (Its
Middle x >=0), especially methyl (- CH3) or amino (- NH2,-NH-) or hydrogen (- H).For example, SiR1R2R3 herein can be with table
Show single-, two- or trichlorosilane.A can especially represent the functional group at least one carbon-to-carbon double bond herein, especially represent second
Alkenyl or acrylate group or methacrylate group.Can be 1≤n≤20 in this case, preferably 1≤
N≤5, especially n=2 or 3.
(Particularly promote bonding)The example of silane compound with polymerizable functional group is methacrylic acid 3- (three
Chlorosilyl) propyl ester:
, especially wherein R1, R2 and R3 represent chlorine, A expression methacrylic acids
Ester and n=3.
In the another embodiment of the embodiment, A represents that polymerization causes functional group.Particularly, A herein can be with table
Show and cause functional group for causing the polymerization of atom transfer active free radical polymerization (ATRP- initiators).A herein especially can be with
Represent halogen atom, such as chlorine (- Cl) or bromine (- Br) or iodine (- I), especially chlorine (- Cl) or bromine (- Br).
Cause the silane compound of functional group with polymerization, particularly for causing atom transfer active free radical polymerization
(ATRP- initiators), can be for example with following chemical general formula:
In this case, R1, R2, R3 especially can respectively represent halogen atom, especially chlorine (- Cl) or alkane independently of one another
Oxygroup, especially methoxyl group (- OCH3) or ethyoxyl (- OC2H5) or hydrogen (- H).For example, SiR1R2R3 can be represented herein
Single-, two- or trichlorosilane.A can especially represent halogen atom, such as chlorine (- Cl), bromine (- Br) or iodine (- I) herein, excellent
Select chlorine (- Cl) or bromine (- Br).In such a case, it is possible to be 1≤n≤20, preferred 1≤n≤5, especially n=
1 or 2 and/or 0≤m≤20, preferably 0≤m≤5, especially m=0 or 1 or 2.
Cause the example of the silane compound of functional group with polymerization(Gather particularly for causing atom transfer living radical
It closes (ATRP- initiators))It is trichlorine [4- (chloromethyl) phenyl] silane or 4- (chloromethyl) phenyl trichlorosilane (CMPS):
, especially wherein R1, R2 and R3 and A represent chlorine and n=1 and m=0.
In the another embodiment of the embodiment, A represents polymerization control functional group.
In one embodiment, A represents the polymerization control of the polymerization mediated for nitrogen oxides (NMP- mediators) herein
Functional group processed.The polymerization control functional group A especially can be the mediator of nitrogen oxides base herein.For example, A herein can be with table
Show nitroxide groups and/or alkoxyamine groups, for example, based on 2,2,6,6- tetramethyl-piperidyl oxygroups (TEMPO) and/or
2,2,5- trimethyl -4- phenyl -3- aza-hexane -3- oxygroups (TIPNO) and/or N- tert-butyl-n -s [1- diethyl phosphonyls -
(2-2- dimethyl propyls) nitrogen oxides] (SG1*).
The example of silane compound with polymerization control functional group(Particularly for the polymerization (NMP- of nitrogen oxides mediation
Mediator))It is alkoxyamine-silane compound of 2,2,6,6- tetramethyl-piperidyls oxygroup-(TEMPO)-base:
And/or
,
Alkoxyamine-silane chemical combination of 2,2,5- trimethyl -4- phenyl -3- aza-hexane -3- oxygroups-(TIPNO)-base of following formula
Object:
And/or
The alcoxyl of N- tert-butyl-n -s [1- diethyl phosphonyls-(2-2- dimethyl propyls) nitrogen oxides]-(SG1)-base of following formula
Base amine-silane compound:
。
Instead of at least one silane compound of functional group being controlled to be used for nitrogen at least one polymerization by directly fixed
The polymerization (NMP- mediators) of oxide mediation, can be as follows so that anode active material particles, especially silicon particle functionalization be used for
The polymerization of nitrogen oxides mediation, wherein(First)Make at least one silane compound at least one polymerizable functional group,
Such as methacrylic acid 3- (trimethoxysilyl) propyl ester, it is fixed on the tables of anode active material particles, especially silicon particle
On face and make at least one silane compound(Then)With the mediator of at least one nitrogen oxides base, such as at least one
Kind of nitrogen oxides-or alkoxyamine compound, such as TEMPO and for example at least one polymerization initiator, especially free radical draws
Agent is sent out, as AIBN reacts.
In another embodiment, A is represented for reversible addition-fracture-chain tra nsfer-polymerization (RAFT- reagents)
Polymerization control functional group.The polymerization control functional group especially can be thio group herein.For example, A can represent three herein
Thiocarbonate group(-S-C=S-S-)Or dithioesters group(-C=S-S-)Or dithiocarbamate groups group(-N-C=
S-S-)Or xanthate group(-C=S-S-).
With polymerization control functional group silane compound, particularly for reversible addition-fracture-chain tra nsfer-polymerization
In the case of (RAFT- reagents), SiR1R2R3 can for example represent chlorosilane, methoxy silane, Ethoxysilane or silazane,
Dithioesters or dithiocarbamate or trithiocarbonate or xanthate are represented with A.
Silane compound with polymerization control functional group(Particularly for reversible addition-fracture-chain tra nsfer-polymerization
(RAFT- reagents))Example be trithiocarbonate-or dithioesters compound:
And/or
And/or
。
In another embodiment, at least one silane compound includes at least one of following chemical general formula
(Particularly crown ether base)Silane compound:
。
In this case, Q1, Q2, Q3 and Qk especially can respectively represent independently of one another oxygen (O) or nitrogen (N) or
Amine, such as secondary amine (NH) and/or tertiary amine, such as alkyl-or arylamine (NR).
G can especially represent at least one polymerizable functional group, for example, wherein one of carbon atom and/or Q1 and/or Q2 and/
Or Q3 and/or Qk are replaced by it.
Particularly, G can include at least one polymerizable double bond, for example, at least a carbon-to-carbon double bond, for example, at least one
Vinyl and/or 1,1- ethenylidene and/or 1,2- ethenylidene and/or pi-allyl, such as pi-allyl oxygroup alkyl, such as alkene
Propyl oxygroup methyl and/or at least one hydroxyl, such as alkylenehydroxyl, such as methylenehydroxy.
In addition, G can for example include one or more of the other group, be used for example as linking group, i.e., bridging unit or
Those of bridge section.For example, G can also include at least one benzo groups and/or hexamethylene and group
(Cyclohexanogruppe).
G can especially represent the quantity of polymerizable functional group G, and especially can with 1≤g, such as 1≤g≤5,
Such as 1≤g≤2.
K can especially represent the quantity of unit in bracket, and especially can with 1≤k, such as 1≤k≤3, such as
1 ≤ k ≤ 2。
Y' can especially represent the unit of linking group, i.e. bridging.For example, Y' can include at least one alkylidene (-
CnH2n-) (Wherein n >=0, especially n >=1)And/or at least one oxyalkylene group (- CnH2n-O-) (Wherein n >=
1)And/or at least one carboxylate group (- C=O-O-) and/or at least one phenylene (- C6H4-).For example, Y' herein may be used
To represent alkylidene-CnH2n-(Wherein 0≤n≤5, such as n=1 or 2 or 3).
S can especially be represented(It is combined particularly by linking group Y')The quantity of silane group (- SiR1R2R3), and
It and especially can be with 1≤s, such as 1≤s≤5, such as 1≤s≤2.
R1, R2, R3 especially can respectively represent halogen atom, especially chlorine (- Cl) or alkoxy independently of one another, especially
Its methoxyl group (- OCH3) or ethyoxyl (- OC2H5) or alkyl, such as straight chained alkyl (- (CH2)x-CH3)(Wherein x >=
0), especially methyl (- CH3) or amino (- NH2,-NH-) or silazane group (- NH-Si-) or hydroxyl (- OH) or hydrogen (-
H).For example, R1, R2 and R3 can represent chlorine.
Particularly, Q1, Q2, Q3 and Qk can represent oxygen.For example, at least one silane compound can include herein
At least one of following chemical general formula(Particularly crown ether base)Silane compound:
。
It is this(Particularly crown ether base)The example of silane compound is:
And/or
。
It is this(Particularly crown ether base)Silane compound can advantageous by the silane group, especially covalently,
Such as additionally by Van der Waals-and/or hydrogen bond, anode active material particles are incorporated in, especially on the surface of silicon particle, and
It is used for example as the adhesion promotor of silylation.
At least one silane compound at least one polymerizable functional group and/or at least one can gather
Close monomer can especially include at least one ion transmitable or ionic conductivity, especially lithium ion transmitable or
The polymerisable monomer of lithium-ion-conducting and/or at least one fluorinated polymerisable monomer, such as it has at least one be fluorinated
Alkyl and/or at least one fluorination alkoxy and/or at least one fluorinated alkenyl group and/or at least one fluorinated phenyl,
And/or at least one polymerisable monomer for being used to form gelatin polymer or ion transmitable or ionic conductivity
, especially lithium ion transmitable or lithium-ion-conducting and/or be fluorinated and/or setting is used to form gel and gathers
Close object.
The material of ion transmitable, such as the material of lithium ion transmitable, such as monomer or polymer, especially can be with
Such material, such as monomer or polymer are interpreted as, itself can be free of ion to be conducted, such as lithium ion, but suitable
For ion that will be to be conducted, such as the counter ion counterionsl gegenions of lithium ion and/or ion to be conducted, for example, lithium-conductive salt-the moon from
Son coordination and/or solvation, and for example by adding in ion to be conducted, for example, lithium ion and as lithium-ion-conducting
's.
By making list that is ion transmitable or ionic conductivity and/or fluorinated and/or forming gelatin polymer
Body polymerize, it can be advantageous in anode active material particles, synthetic polymer-SEI- protective layers are formed especially on silicon particle,
It is set as ion transmitable or ionic conductivity and/or fluorinated and/or is used to form gelatin polymer.Pass through ion
Transmitable or ionic conductivity polymer and/or gelatin polymer, it can be advantageous to realize equipped with anode activity material
The battery of material or the high efficiency of battery pack, and electricity is for example formed especially on silicon particle directly in anode active material particles
Solve matter coating or gel electrolyte coating.Fluoro-based polymers can have high thermodynamic stability and also especially have electrochemistry
Stability, and can be advantageously in the potential windows for lithium ion battery and/or-battery pack(Potentialfenster)In
It is particularly stable.
In another embodiment, at least one polymerizable functional group of at least one silane compound and/or
At least one polymerisable monomer include or described at least two, such as three kinds of polymerisable monomers(Respectively)Including
At least one polymerizable double bond, for example, at least a carbon-to-carbon double bond, especially at least a vinyl and/or at least one 1,2-
Ethenylidene and/or at least one 1,1- ethenylidenes and/or at least one pi-allyl, such as pi-allyl oxygroup alkyl, such as
Allyloxymethyl and/or at least one acrylate group and/or at least one methacrylate group and/or extremely
A few phenylethylene group (styryl) and/or at least one hydroxyl.It can be advantageously carried out by these functional groups
Polymerization.Particularly, at least one polymerizable functional group of at least one silane compound and/or at least one can gather
Close monomer or described at least two, such as three kinds of polymerisable monomers can be with(Respectively)Including or it is at least one polymerizable double
Key, for example, at least a carbon-to-carbon double bond, especially at least a vinyl and/or at least one 1,2- ethenylidenes and/or at least
One 1,1- ethenylidene and/or at least one pi-allyl, such as pi-allyl oxygroup alkyl, for example, allyloxymethyl and/
Or at least one acrylate group and/or at least one methacrylate group and/or at least one phenylethylene group
(styryl).This is proved to be polymerization particular by active free radical polymerization, such as polymerization of ATRP, NMP or RAFT
Particularly advantageous.By at least one hydroxyl, at least one polymerizable functionalities of at least one silane compound can be made
Group and/or at least one polymerisable monomer or at least two polymerisable monomer by condensation reaction or by the moon from
Son polymerize and polymerize or be copolymerized.
For example, at least one polymerizable functional group of at least one silane compound can include or at least one
Polymerizable double bond, for example, at least a carbon-to-carbon double bond, such as vinyl and/or 1,1- ethenylidene and/or 1,2- ethenylidene
And/or acrylate group and/or methacrylate group.
In another embodiment, at least one polymerisable monomer(Also)Including at least one(It is especially unfluorinated
's)Oxyalkylene group, such as ethylene oxide group, such as polyalkylene oxide groups, such as polyoxyethylene groups or poly- second two
Alcohol groups and/or at least one fluorinated oxyalkylene group and/or at least one fluorinated alkoxy and/or at least one fluorine
The alkyl of change and/or at least one fluorinated phenyl.
It is either formed comprising oxyalkylene group by oxyalkylene monomers or based on polyoxyalkylene(Such as polyethylene glycol oxide (PEO)
Or polyethylene glycol (PEG))Polymer, it can be advantageous to be ion transmitable, such as lithium ion transmitable.
Therefore, it can be advantageous on the particle, such as by being based on the poly- of polyethylene glycol oxide (PEO) or polyethylene glycol (PEG)
It closes object and forms ion transmitable, such as the synthesis SEI- protective layers of lithium ion transmitable.In at least one conductive salt, example
In the presence of lithium-conductive salt, there is oxyalkylene group or the polymer based on polyoxyalkylene, such as polyethylene glycol oxide (PEO)
Or polyethylene glycol (PEG), can be ionic conductivity, such as lithium-ion-conducting.It is disposed with, is particularly coated with
The anode active material particles of this polymer, especially silicon particle can be when battery-or battery pack assemble and at least one
Conductive salt, such as lithium-conductive salt contact, and become ionic conductivity in this way, such as lithium-ion-conducting.For
It realizes equipped with the battery of active material of positive electrode or the high efficiency of battery pack and particularly realizes that high ion can conduct
Property, it can will be arranged so as to, the anode active material particles particularly coated, especially silicon particle,(However particularly)Such as
With at least one conductive salt, such as lithium-conductive salt, such as lithium hexafluoro phosphate before battery-and/or battery pack assembling
(LiPF6), it is double(Fluoroform)Sulfimide lithium (LiTFSI) and/or lithium perchlorate (LiClO4) processing.It is in addition, this poly-
Closing object can be at least one electrolyte solvent or at least one liquid electrolyte(Such as based at least one conductive salt extremely
Solution in a kind of few electrolyte solvent)In the presence of, such as before or during battery-and/or battery pack assembling, formed solidifying
Glue and it is used for example as gel electrolyte.It may be thus possible, for example, to will be arranged so as to, the particle particularly coated, for example, battery-
And/or battery pack assembling before, at least one electrolyte solvent and/or at least one liquid electrolyte, especially by least
A kind of conductive salt, such as lithium-conductive salt, such as lithium hexafluoro phosphate (LiPF6), it is double(Fluoroform)Sulfimide lithium
(LiTFSI) and/or lithium perchlorate (LiClO4) and at least one electrolyte solvent form liquid electrolyte processing.Therefore,
It, can also advantageously directly especially except the synthesis SEI- protective layers of silicon particle in addition to being used for being passivated anode active material particles
In anode active material particles, electrolyte coating or gel electrolyte coating are formed especially on silicon particle.Notably, however,
If only anode active material particles, particularly silicon particle is coated with electrolyte coating or gel electrolyte coating, then the sun
At least one electrolyte, such as liquid electrolyte, such as the electrolyte based on carbonic ester can also extremely be included.
In an alternative or additional embodiment, at least one polymerisable monomer or described at least two
Kind, particularly three kinds of polymerisable monomers include or are selected from:
At least one polymerizable carboxylic acid, for example, acrylic acid and/or methacrylic acid and/or
At least one polymerizable carboxylic acid-derivative, particularly
At least polymerizable organic carbonate, such as vinylene carbonate and/or vinylethylene carbonate and/or acid anhydrides, especially
At least one carboxylic acid anhydrides, for example, maleic anhydride and/or
At least one carboxylate, for example, at least a kind of acrylate, for example, at least a kind of ether acrylate, such as poly- (second two
Alcohol) methyl ether acrylate and/or at least one methacrylate, such as methyl methacrylate and/or at least one
Acetic acid esters, for example, vinyl acetate and/or
At least one carboxylic acid nitriles, for example, acrylonitrile and/or
It is at least one(It is such as unfluorinated or fluorinated)Ether, especially at least a kind of crown ether and/or at least one crown ether-derivative
Object and/or at least one vinyl ethers, for example, trifluoro vinyl ether and/or
It is at least one(It is such as unfluorinated or fluorinated)Oxyalkylene, for example, ethylene oxide and/or
It is at least one(Such as aliphatic series or aromatics, it is such as unfluorinated or fluorinated)Unsaturated hydrocarbons, for example, at least a kind of alkene
Hydrocarbon, such as ethylene, such as vinylidene fluoride (vinylidene fluoride, vinylidene fluoride) and/or tetrafluoroethene (TFE) and/or
Propylene, such as hexafluoropropene and/or hexene, such as 3,3,4,4,5,5,6,6,6- nine fluorine hexenes and/or phenylethylene, such as 2,3,4,
5,6- pentafluorophenyl groups ethylene (2,3,4,5,6- pentafluorostyrenes) and/or 4- (trifluoromethyl) phenylethylene (4- (fluoroforms
Base) styrene) and/or styrene.
In one embodiment, at least one polymerisable monomer include or described at least two, especially
It is that three kinds of polymerisable monomers include at least one polymerizable carboxylic acid.
In an embodiment of the embodiment, at least one polymerisable monomer includes or described
Kind of the polymerisable monomer of at least two, particularly three includes acrylic acid:
And/or its derivative.
In another alternative or additional embodiment in the embodiment, at least one polymerisable monomer
Including or kind of the polymerisable monomer of described at least two, particularly three include methacrylic acid and/or its derivative.
By the polymerization of acrylic acid either methacrylic acid can be formed on the particle by be based on polyacrylic acid or
The synthesis SEI- protective layers that the polymer of polymethylacrylic acid is formed.In this case, it is described based on polyacrylic acid or poly-
The polymer of methacrylic acid is attached to the table of anode active material particles, especially silicon particle by carboxylic acid group (- COOH)
Hydroxyl on face, such as silicon hydroxide radicals or silanol (Si-OH), for example, by condensation reaction covalently and/
Or pass through Hydrogenbond.Except through the protective layer passivation being made of the polymer based on polyacrylic acid or polymethylacrylic acid
Except the particle, the polymer based on polyacrylic acid or polymethylacrylic acid can also be advantageously used for bonding enhancing
Agent and/or adhesive, and the adhesion characteristic of the active material of positive electrode is improved in this way.By in anode activity
The polymer based on polyacrylic acid or polymethylacrylic acid is prepared in the presence of material granule, especially silicon particle, compared to
Anode active material particles, especially silicon particle are mixed by the polyacrylic acid or polymethylacrylic acid that prepare ex situ,
Mixture evenly can also be advantageously generated.
In another embodiment, the polymer formed by least one polymerisable monomer, especially its carboxylic acid group
Group, at least partially at least one alkali metal hydroxide, such as lithium hydroxide (LiOH) and/or sodium hydroxide (NaOH)
And/or potassium hydroxide (KOH), particularly by formed alkali metal carboxylate, such as carboxylic acid lithium either carboxylic acid sodium or carboxylic acid potassium and
It neutralizes.Therefore, rheological properties can be improved and/or can be made particularly in the battery or electricity equipped with active material of positive electrode
Irreversible capacity loss in the first circulation of pond group minimizes.
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one polymerizable carboxylic acid-derivative.
In another embodiment, at least one polymerisable monomer include or described at least two, it is special
It is not that three kinds of polymerisable monomers include at least one polymerizable organic carbonate and/or acid anhydrides, especially at least a kind of carboxylic acid anhydrides.
Particularly, at least one polymerisable monomer can include or at least one polymerizable organic carbonate.Organic carbonate
Ester is proved to be particularly advantageous for forming SEI- layers of synthesis.In addition, organic carbonate ion can advantageously can conduct
Property, especially lithium ion transmitable.
In another embodiment, at least one polymerisable monomer includes or vinylene carbonate and/or carbon
Sour vinylethylene and/or maleic anhydride and/or its derivative.This is for forming(Especially ion transmitable, for example, lithium from
Sub- transmitable)SEI- layers of synthesis is proved to be advantageous.
In a particular implementation of the embodiment, at least one polymerisable monomer includes or carbonic acid is sub-
Vinyl acetate.Polymerized thylene carbonate vinyl acetate can especially be formed by the polymerization of vinylene carbonate, be used as to synthesize SEI- layers
Polymer be proved to be particularly advantageous.
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one carboxylate.
For example, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be with
Including or at least one acrylate, for example, at least a kind of ether acrylate, such as poly(ethylene glycol) methyl ether acrylate, example
Such as:
And/or at least one methacrylate, such as methyl methacrylate
Ester and/or at least one acetic acid esters, such as vinyl acetate and/or its derivative.
By acrylate, such as ether acrylate, such as poly(ethylene glycol) methyl ether acrylate and/or metering system
Acid esters such as the polymerization of methyl methacrylate (MMA), can be formed by being based on polyacrylate or gathering on the particle
The synthesis SEI- protective layers that the polymer of methyl methacrylate (PMMA) is formed.Polymer based on polyacrylate, example
Polymer or polymethyl methacrylate such as based on ether acrylate, it can be advantageous in the presence of following substance, such as
When battery-and/or battery pack assemble, form gel and be used for example as gel electrolyte:At least one electrolyte solvent, example
Such as organic carbonate of at least one liquid, such as ethylene carbonate (EC) and/or ethyl methyl carbonate (EMC) and/or carbonic acid
Dimethyl ester (DMC) and/or diethyl carbonate (DEC) or at least one liquid electrolyte, such as based at least one conductive
Salt, such as lithium hexafluoro phosphate (LiPF6) and/or it is double(Fluoroform)Sulfimide lithium (LiTFSI) and/or lithium perchlorate
(LiClO4) at least one electrolyte solvent, for example, at least a kind of organic carbonate of liquid, such as ethylene carbonate (EC)
And/or in ethyl methyl carbonate (EMC) and/or dimethyl carbonate (DMC) and/or diethyl carbonate (DEC)(Such as 1
M)Solution.Therefore, in addition to being used to be passivated the anode active material particles, especially except the synthesis SEI- protective layers of silicon particle,
Gel electrolyte coating can also be formed especially on silicon particle advantageously directly in the anode active material particles.In this way
In the battery of outfit or the first circulation of battery pack, the electrolyte may be in the polymer gel base of gel electrolyte coating
It decomposes, and causes in matter(Especially synthesis or naturally-produced)SEI- protective layers are mechanically stable.This can advantageously battery-
And/or do not have to during battery pack assembling(Especially to liquid electrolyte)Add SEI- stabilising additives, such as vinylene carbonate
(VC) or carbonic acid fluoroethylene (FEC).Based on the polymer of ether acrylate, such as poly(ethylene glycol) methyl ether acrylate, go back
Can be ion transmitable, such as lithium ion transmitable, and at least one conductive salt, such as lithium-conductive salt
In the presence of, such as by being contacted at least one conductive salt, such as lithium-conductive salt, and when battery-or battery pack assemble
It is ionic conductivity, such as lithium-ion-conducting.In order to realize battery or battery pack equipped with active material of positive electrode
High efficiency and particularly realize high ion transmitable, can will be arranged so as to, the anode activity material particularly coated
Expect particle, especially silicon particle,(However particularly)Such as at least one conductive salt is used before battery-and/or battery pack assembling,
Such as lithium-conductive salt, such as lithium hexafluoro phosphate (LiPF6), it is double(Fluoroform)Sulfimide lithium (LiTFSI) and/or high chlorine
Sour lithium (LiClO4) processing.
By the polymerization of vinyl acetate, can be formed on the particle by being based on polyvinyl acetate (PVAC)
The synthesis SEI- protective layers that polymer is formed.The polymer based on polyvinyl acetate then can such as saponification become poly-
Vinyl alcohol (PVAL).In order to avoid the side reaction with other electrode components, can for example be separated herein with other electrode components
The saponification of polymer that ground carries out the polymerization of at least one polymerisable monomer and is particularly consequently formed.It is described to be based on poly- second
The polymer of alkenyl alcohol can be advantageous by hydroxyl (- OH), such as silicon hydroxide radicals or silanol (Si-
OH the hydroxyl on) is attached to anode active material particles, especially on the surface of silicon particle, such as by condensation reaction covalently
And/or pass through Hydrogenbond.Except through the protective layer that is made of the polymer based on polyvinyl alcohol be passivated the particle it
Outside, the polymer based on polyvinyl alcohol can also be advantageously used for adhesiving reinforcing agent or adhesive, and with this side
Formula improves the adhesion characteristic of the active material of positive electrode.By in the anode active material particles, especially in the presence of silicon particle
The polymer based on polyvinyl alcohol is prepared, is lived compared to by the way that polyvinyl alcohol prepared by ex situ is mixed into anode
Property material granule, especially silicon particle, can also advantageously generate mixture evenly.
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one carboxylic acid nitriles.For example, at least one is polymerizable
Monomer or kind of the polymerisable monomer of described at least two, particularly three can include or acrylonitrile and/or its derivative.Pass through
The polymerization of acrylonitrile can form on the particle and synthesize SEI- by what the polymer for being based on polyacrylonitrile (PAN) was formed
Protective layer.Polymer based on polyacrylonitrile (PAN), it can be advantageous in the presence of following substance, such as battery-and/
Or during battery pack assembling, form gel and be used for example as gel electrolyte:At least one electrolyte solvent, it is for example, at least a kind of
The organic carbonate of liquid, such as ethylene carbonate (EC) and/or ethyl methyl carbonate (EMC) and/or dimethyl carbonate
(DMC) and/or diethyl carbonate (DEC) or at least one liquid electrolyte, such as based at least one conductive salt, such as
Lithium hexafluoro phosphate (LiPF6) and/or it is double(Fluoroform)Sulfimide lithium (LiTFSI) and/or lithium perchlorate (LiClO4)
At least one electrolyte solvent, for example, at least a kind of organic carbonate of liquid, such as ethylene carbonate (EC) and/or carbonic acid second
In base methyl esters (EMC) and/or dimethyl carbonate (DMC) and/or diethyl carbonate (DEC)(Such as 1 M)Solution.Therefore,
It, can also be advantageously especially except the synthesis SEI- protective layers of silicon particle in addition to being used for being passivated the anode active material particles
Directly in the anode active material particles, gel electrolyte coating is formed especially on silicon particle.In the battery being equipped in this way or
In the first circulation of person's battery pack, the electrolyte may decompose in the polymer gel matrices of gel electrolyte coating, and
And so that SEI- protective layers are mechanically stable.This can not have to advantageously when battery-and/or battery pack assemble(Especially to liquid
Electrolyte)SEI- stabilising additives are added, such as vinylene carbonate (VC) or carbonic acid fluoroethylene (FEC).
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one(It is such as unfluorinated or fluorinated)Ether.Especially
Ground, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be included or extremely
Few one kind(It is such as unfluorinated or fluorinated)Ether, which has at least one polymerizable functional group, especially at least one
Polymerizable double bond, such as at least one carbon-to-carbon double bond, such as at least one vinyl and/or pi-allyl and/or alkene
Propyl oxygroup alkyl, such as allyloxymethyl and/or at least one hydroxyl, such as alkylenehydroxyl, such as methylene
Base hydroxyl.
For example, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be with
Including or at least one crown ether and/or at least one crown ether-derivative and/or at least one vinyl ethers, such as trifluoro second
Alkene ether.
Particularly, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can
To include or at least one crown ether and/or at least one crown ether-derivative.
For example, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be with
Including or at least one crown ether and/or at least one crown ether-derivative, there is at least one polymerizable functional group, especially
With at least one polymerizable double bond, such as at least one carbon-to-carbon double bond, for example, at least one vinyl and/or
At least one 1,1- ethenylidenes and/or at least one 1,2- ethenylidenes and/or at least one pi-allyl, such as pi-allyl oxygen
Base alkyl and/or at least one acrylate group and/or at least one methacrylate group, such as at least one
A carbon-to-carbon double bond, such as at least one vinyl and/or at least one 1,1- ethenylidenes and/or at least one 1,2-
Ethenylidene and/or at least one pi-allyl, such as pi-allyl oxygroup alkyl, such as allyloxymethyl and/or with extremely
A few hydroxyl, such as alkylenehydroxyl, such as methylenehydroxy.
At least one polymerizable functional group of at least one crown ether and/or crown ether-derivative for example can be tied directly
Close crown ether or crown ether-derivative.However, particularly for the reason of the steric hindrance, it is also possible to advantageously in the hat
Between ether or crown ether-derivative and at least one polymerizable functional group(Such as in addition)Linking group or bridge are set
Section, such as phenyl ring or cyclohexane ring.It, especially can be with by least one polymerizable double bond, the especially polymerization of carbon-to-carbon double bond
Form main polymer chain, such as C-C- main polymer chains (C-C main chains), such as every have on a carbon atom crown ether-
The functional group of base.
By the polymerization of the crown ether with polymerizable functional group and/or crown ether-derivative, can be formed on the particle
SEI- protective layers are synthesized by what polymer was formed, the basic structural unit based on crown ether.Polymer based on crown ether can be with(It is special
It is not selectively)It is ion transmitable, especially lithium ion transmitable, and be advantageously alkali metal ion, especially
Its lithium ion provides best diffusion path.
Crown ether and/or crown ether-derivative can be advantageously in addition at least through Van der Waals-and/or Hydrogenbond described in
The surface of anode active material particles, especially silicon particle, and the polymeric layer being consequently formed therefore is improved in anode activity material
Expect particle, the especially adhesiveness on silicon particle.
At least one crown ether and/or at least one crown ether-derivative for example can be by free radical polymerizations, such as live
Free love base polymerize, such as atom transfer active free radical polymerization (ATRP) and/or stable free radical polymerization (SFRP), such as nitrogen
The polymerization (NMP) of oxide mediation and/or the polymerization (VMP) of Verdazyl- mediations and/or reversible addition-fracture-chain turn
Shifting-polymerization (RAFT) and/or by the polymerization of condensation reaction and/or by ionic polymerization, such as anion or cation
It polymerize and can polymerize and/or be polymerize or is copolymerized.
For example, at least one polymerizable functional group of at least one crown ether and/or crown ether-derivative can include or
It is at least one polymerizable double bond, a for example, at least carbon-to-carbon double bond, especially at least a vinyl and/or at least one 1,
2- ethenylidenes and/or at least one 1,1- ethenylidenes and/or at least one pi-allyl, such as pi-allyl oxygroup alkyl, example
Such as allyloxymethyl and/or at least one acrylate group and/or at least one methacrylate group and/or
At least one phenylethylene group (styryl) and/or at least one hydroxyl.It can be advantageously real by these functional groups
Now it polymerize.For example, at least one polymerizable functional group of at least one crown ether and/or crown ether-derivative can include or
It is at least one vinyl and/or at least one 1,2- ethenylidenes and/or at least one 1,1- ethenylidenes and/or at least one
A pi-allyl, such as pi-allyl oxygroup alkyl, for example, allyloxymethyl and/or at least one acrylate group and/or
At least one methacrylate group and/or at least one hydroxyl, especially alkylenehydroxyl.It can be with by least one hydroxyl
Make at least one polymerizable functional group of at least one crown ether and/or crown ether-derivative by condensation reaction or by
Anionic polymerisation and polymerize or be copolymerized.For example, at least one of at least one crown ether and/or crown ether-derivative can gather
Conjunction functional group can include or at least one polymerizable double bond, a for example, at least carbon-to-carbon double bond, especially at least an ethylene
Base and/or at least one 1,2- ethenylidenes and/or at least one 1,1- ethenylidenes and/or at least one pi-allyl, such as
Pi-allyl oxygroup alkyl, such as allyloxymethyl and/or at least one acrylate group and/or at least one methyl
Acrylate group and/or at least one phenylethylene group (styryl).This is for polymerizeing, particularly by activity certainly
It is polymerize by base, such as ATRP, NMP or RAFT, is proved to be particularly advantageous.
At least one crown ether and/or at least one crown ether-derivative and/or include at least one crown ether
And/or the polymer of crown ether-derivative can also have at least particularly other than at least one polymerizable functional group
A kind of silane group.Pass through at least one silane group, it can be advantageous to make at least one crown ether and/or it is described extremely
A kind of few crown ether-derivative and/or the polymer comprising at least one crown ether and/or crown ether-derivative(Such as covalently
Ground)The anode active material particles are attached to, especially on the surface of silicon particle.Therefore, it can be advantageous to be formed to have and improved
Adhesiveness polymeric layer.
Particularly, at least one crown ether and/or at least one crown ether-derivative can include or be based on
Crown ether, particularly
12-4- crown ethers:
And/or
15-5- crown ethers:
And/or
Aza-crown ether, such as (two -) aza-crown ether, such as azepine -12-4- crown ethers, such as 1- azepine -12-4- crown ethers, example
Such as:
And/or azepine -15-5- crown ethers, such as two-aza-crown ether, such as two-azepine -12-4- hats
Ether and/or two-azepine -15-5- crown ethers, such as:
And/or(Especially N- substitutions)(two -) aza-crown ether, such as N- alkyl-(two -) nitrogen
Miscellaneous -12-4- crown ethers and/or N- alkyl-(two -) azepine -15-5- crown ethers and/or
Benzo-crown ether, especially phendioxin 2-4- crown ethers and/or phendioxin 5-5- crown ethers, such as:
And/or, such as two-benzo-crown ether, example
Such as two-phendioxin 2-4- crown ethers, such as:
And/or two-phendioxin 5-5- crown ethers and/or hexamethylene simultaneously-crown ether,
Especially hexamethylene simultaneously -12-4- crown ethers and/or hexamethylene simultaneously -15-5- crown ethers, for example, two-hexamethylene simultaneously-crown ether, such as two-ring
Hexane simultaneously -12-4- crown ethers, such as:
And/or two-hexamethylene simultaneously -15-5- crown ethers.
In an embodiment of the embodiment, at least one crown ether and/or at least one crown ether-spread out
Biology includes the crown ether of following chemical general formula or crown ether-derivative:
。
In this case, Q1, Q2, Q3 and Qk especially can respectively represent independently of one another oxygen (O) or nitrogen (N) or
Amine, such as secondary amine (NH) and/or tertiary amine, such as alkyl-or arylamine (NR).
G can especially represent at least one polymerizable functional group, for example, wherein one of carbon atom and/or Q1 and/or Q2 and/
Or Q3 and/or Qk are replaced by it.
G can especially represent the quantity of polymerizable functional group G, and especially can with 1≤g, such as 1≤g≤5,
Such as 1≤g≤2.
K can especially represent the quantity of unit in bracket, and especially can with 1≤k, such as 1≤k≤3, such as
1 ≤ k ≤ 2。
Particularly, G can include at least one polymerizable double bond, for example, at least a carbon-to-carbon double bond, for example, at least one
Vinyl and/or at least one 1,1- ethenylidenes and/or at least one 1,2- ethenylidenes and/or at least one pi-allyl,
Such as pi-allyl oxygroup alkyl, such as allyloxymethyl and/or at least one hydroxyl, such as alkylenehydroxyl, such as it is sub-
Methylhydroxy.
In addition, G can be used for example as linking group for example including one or more other groups(The unit that bridges or
Bridge section)Group.For example, G can also include at least one benzo groups and/or hexamethylene and group.
Particularly, Q1, Q2, Q3 and Qk can represent oxygen.For example, at least one crown ether and/or at least one
Crown ether-derivative can include the crown ether of following chemical general formula or crown ether-derivative:
。
For example, at least one crown ether and/or at least one crown ether-derivative can include following chemical general formula
Crown ether or crown ether-derivative:
And/or
And/or
And/or
And/or
, especially wherein 0≤k', such as 0≤k'≤2, such as 0≤
k' ≤ 1。
By the polymerization of double bond, such as active free radical polymerization, can be formed with carbon-to-carbon main polymer chain (C-C master
Chain) and crown ether-or the polymer of crown ether-derivative-side group, such as:
。
It alternatively, or in addition, also for example can be with(Particularly directly)In the main polymer chain or described poly-
It closes and the polymer with crown ether-or crown ether-derivative-group is formed in object chain.This for example can by (two -) benzo-and/
Or (two -) hexamethylene simultaneously-crown ether and/or-crown ether derivative, such as at least two, optional four hydroxyls(Such as in the benzene
And-and/or hexamethylene simultaneously-ring on)Polymerization, such as by condensation reaction, such as be etherified and realize.
For example, at least one crown ether and/or at least one crown ether-derivative can include following chemical general formula
Crown ether or crown ether-derivative:
。
G' can especially represent at least one polymerizable functional group.Particularly, G' can include at least one polymerizable double
Key, for example, at least a carbon-to-carbon double bond, for example, at least a vinyl and/or at least one 1,1- ethenylidenes and/or at least
One 1,2- ethenylidene and/or at least one pi-allyl, such as pi-allyl oxygroup alkyl, for example, allyloxymethyl and/
Or at least one hydroxyl, such as alkylenehydroxyl, such as methylenehydroxy.
In addition, G' can be used for example as linking group for example including one or more other groups(The unit that bridges or
Bridge section)Group.For example, G' can also include at least one benzo groups and/or hexamethylene and group.
G' can especially represent the quantity of polymerizable functional group G', and especially can with 1≤g', such as 1≤g'≤
4, such as 1≤g'≤2.
For example, at least one crown ether and/or at least one crown ether-derivative can include following chemical general formula
Crown ether or crown ether-derivative:
And/or
。
By the polymerization of hydroxyl, such as by condensation reaction, especially it is etherified, can be in the polymer backbone formed particularly
Polymer benzo-crown ether, that there is crown ether-or crown ether-derivative-group based on etherificate, such as:
Or
。
This crown ether and/or crown ether-derivative can advantageous by with at least one polymerizable functional group extremely
Few a kind of reaction of silane compound, such as by condensation reaction, such as covalently, and anode active material particles, especially
Its silicon particle combines.
For example, the crown ether and silane compound of following chemical general formula can be reciprocally:
,
Wherein R1, R2, R3 especially respectively represent halogen atom, especially chlorine (- Cl) or alkoxy, especially methoxy independently of one another
Base (- OCH3) or ethyoxyl (- OC2H5) or alkyl, such as straight chained alkyl (- (CH2)x-CH3) (Wherein x >=0), especially
Methyl (- CH3) or amino (- NH2,-NH-) or silazane group (- NH-Si-) or hydroxyl (- OH) or hydrogen (- H), by
Condensation reaction, particularly by the hydroxyl of crown ether and reacting and particularly by silane compound for the chlorine atom of silane compound
R1, R2 and/or R3 in the anode active material particles, the especially hydroxyl on the surface of silicon particle, such as silicon hydroxide
The reaction of group or silanol (Si-OH), and with the anode active material particles, especially silicon particle, such as covalently
Ground, with reference to.
In another embodiment, at least one crown ether and/or at least one crown ether-derivative are particularly
Other than at least one polymerizable functional group, also there is at least one silane group.For example, at least one crown ether
And/or at least one crown ether-derivative can include the crown ether of following chemical general formula or crown ether-derivative:
。
In this case, Q1, Q2, Q3 and Qk especially can respectively represent independently of one another oxygen (O) or nitrogen (N) or
Amine, such as secondary amine (NH) and/or tertiary amine, such as alkyl-or arylamine (NR).
G can especially represent at least one polymerizable functional group, for example, wherein one of carbon atom and/or Q1 and/or Q2 and/
Or Q3 and/or Qk are replaced by it.Particularly, G can include at least one polymerizable double bond, a for example, at least carbon-to-carbon double bond,
A for example, at least vinyl and/or 1,1- ethenylidene and/or 1,2- ethenylidene and/or pi-allyl, such as pi-allyl oxygen
Base alkyl, such as allyloxymethyl and/or at least one hydroxyl, such as alkylenehydroxyl, such as methylenehydroxy.
In addition, G can be used for example as linking group for example including one or more other groups(The unit that bridges or
Bridge section)Group.For example, G can also include at least one benzo groups and/or hexamethylene and group.
G can especially represent the quantity of polymerizable functional group G, and especially can with 1≤g, such as 1≤g≤5,
Such as 1≤g≤2.
K can especially represent the quantity of unit in bracket, and especially can with 1≤k, such as 1≤k≤3, such as
1 ≤ k ≤ 2。
Y' can especially represent linking group, that is, the unit bridged.For example, Y' can include at least one alkylidene (-
CnH2n), wherein n >=0, especially n >=1 and/or at least one oxyalkylene group (- CnH2n- O-), wherein n >=1,
And/or at least one carboxylate group (- C=O-O-) and/or at least one phenylene (- C6H4-).For example, Y' herein can be with
Represent alkylidene-CnH2n, wherein 0≤n≤5, such as n=1 or 2 or 3.
S can especially be represented(It is combined particularly by linking group Y')The quantity of silane group (- SiR1R2R3),
It and especially can be with 1≤s, such as 1≤s≤5, such as 1≤s≤2.
R1, R2, R3 especially can respectively represent halogen atom, especially chlorine (- Cl) or alkoxy independently of one another, especially
Its methoxyl group (- OCH3) or ethyoxyl (- OC2H5) or alkyl, such as straight chained alkyl (- (CH2)x-CH3), wherein x >=0,
Especially methyl (- CH3) or amino (- NH2,-NH-) or silazane group (- NH-Si-) or hydroxyl (- OH) or hydrogen (- H).
For example, R1, R2 and R3 can represent chlorine.
Particularly, Q1, Q2, Q3 and Qk can represent oxygen.For example, at least one crown ether and/or at least one
Crown ether-derivative can include the crown ether of following chemical general formula or crown ether-derivative herein:
。
The example of crown ether or crown ether-derivative is:
And/or
。
This crown ether or crown ether-derivative can be attached to the anode activity material advantageous by the silane group
Expect particle, especially on silicon particle, and additionally may act as the adhesion promotor of silylation.
If at least one polymerisable monomer includes (two -) aza-crown ether-derivative, such as it is with vinyl
Functional group, then one or more NH- groups are substituted before the polymerization or are disposed with blocking group, such as be partially alkylated or alkylated, preferably
It is methylated.Therefore, one or more of NH- groups can be prevented to interfere the polymerization, for example, free radical (co) polymerization and/
Or anion (co) polymerization.In addition, the either tertiary amine-group or N-R- keys of substitution can be more stable for alkali metal.
Alternatively, however or additionally, for example, can also targetedly in the polymerization utilize (two -) azepine-
The reaction of one or more NH- groups of crown ether-derivative, such as so as to (two -) aza-crown ether-derivative for forming nitrogen-substituted
Object-polymer and/or block-copolymer, such as at least one by described at least one (two -) aza-crown ether-derivative
(Particularly end)Polymerizable double bond, such as vinyl-and/or pi-allyl, at least another polymerisable monomer or by it
At least one polymerizable double bond of the polymer of formation(Such as with styrene)Reaction.For example, (two -) nitrogen can be made thus
One or more NH- groups of miscellaneous-crown ether-derivative pass through (CH2)nBridge section especially by at least one α-ω-alkylene
The reaction of based compound and be coupled and/or using for example poly- positive alkylidene-two-aza-crown ether, such as following chemical general formula
α-ω-diamines, such as hexamethylene diamine, for synthesizing (two -) aza-crown ether-derivative-polymer:
, such as
,
Such as wherein 0≤i≤4.
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one, such as unfluorinated or fluorinated, oxyalkylene,
Such as ethylene oxide.
In another alternative or additional embodiment, it is described at least one polymerisable monomer include or or
At least two described in person, particularly three kinds of polymerisable monomers include at least one, for example, aliphatic series or aromatics, it is such as unfluorinated
Or fluorinated, unsaturated hydrocarbons.
For example, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be with
Including or at least one alkene, such as ethylene, such as vinylidene fluoride (vinylidene fluoride, vinylidene fluoride) and/or four
Vinyl fluoride (TFE) and/or propylene, such as hexafluoropropene and/or hexene, such as 3,3,4,4,5,5,6,6,6- nine fluorine hexenes and/
Or phenylethylene, such as 2,3,4,5,6- pentafluorophenyl group ethylene (2,3,4,5,6- pentafluorostyrene) and/or 4- (trifluoromethyl) benzene
Base ethylene (4- (trifluoromethyl) styrene) and/or styrene.
For example, at least one polymerisable monomer or kind of the polymerisable monomer of described at least two, particularly three can be with
Including or at least one fluorinated alkene, for example, at least a kind of fluorinated ethylene, such as vinylidene fluoride (1,1- difluoro second
Alkene, vinylidene fluoride) and/or tetrafluoroethene (TFE) and/or at least one fluorinated propylene, such as
Hexafluoropropene:
And/or at least one fluorinated hexene, such as 3,3,4,4,5,5,6,6,6- nine fluorine hexenes:
, such as with trade name Zonyl PFBE fluorine telomers intermediate obtain and/or
At least one fluorinated phenylethylene, such as
2,3,4,5,6- pentafluorostyrenes:
And/or
4- (trifluoromethyl) styrene:
And/or
At least one fluorinated vinyl ethers, such as
2- (perfluor propoxyl group) perfluoro propyl trifluoro vinyl ether:
。
By fluorinated alkene, such as the polymerization of vinylidene fluoride, it can be advantageous to be formed on the particle by being fluorinated
, such as the synthesis SEI- protective layers that the polymer based on polyvinylidene fluoride (PVdF) is formed.This polymer can be advantageous
Ground forms gel and is used for example as gel electrolyte in the presence of following substance, such as when battery-and/or battery pack assemble
Matter:At least one electrolyte solvent, for example, at least a kind of organic carbonate of liquid, such as ethylene carbonate (EC) and/or carbonic acid
Ethyl methyl esters (EMC) and/or dimethyl carbonate (DMC) and/or diethyl carbonate (DEC) or at least one liquid electrolytic
Matter, such as based at least one conductive salt, such as lithium hexafluoro phosphate (LiPF6) and/or it is double(Fluoroform)Sulfimide lithium
(LiTFSI) and/or lithium perchlorate (LiClO4) at least one electrolyte solvent, for example, at least a kind of organic carbonate of liquid
Ester, such as ethylene carbonate (EC) and/or ethyl methyl carbonate (EMC) and/or dimethyl carbonate (DMC) and/or carbonic acid diethyl
In ester (DEC)(Such as 1 M)Solution.Therefore, in addition to being used to being passivated the anode active material particles, especially silicon particle
It synthesizes except SEI- protective layers, can also be formed especially on silicon particle solidifying advantageously directly in the anode active material particles
Glue electrolyte coating.In the battery or the first circulation of battery pack being equipped in this way, the electrolyte may be in gel electrolyte
It is decomposed in the polymer gel matrices of matter coating, and so that SEI- protective layers are mechanically stable.This can advantageously battery-
And/or do not have to during battery pack assembling(Especially to liquid electrolyte)Add SEI- stabilising additives, such as vinylene carbonate
(VC) or carbonic acid fluoroethylene (FEC).
Alternatively, or in addition, at least one polymerisable monomer or described at least two, particularly three kind can
Polymerized monomer can be with, such as additionally, including or at least one unfluorinated alkene, for example, at least a kind of unfluorinated phenyl
Ethylene, such as styrene.
By using at least one(It is such as unfluorinated or fluorinated)Phenylethylene, such as styrene, particularly by with
It is copolymerized, it can be advantageous to, especially additionally, introduce(Such as based on polystyrene)Hard block, so as to for example improve needle
Stabilizer and/or improvement mechanical property to alkali and/or solvent, such as intensity.In this case, the copolymer can be with structure
As random copolymer or block copolymer, such as by polystyrene-hard segment and based on other soft segments, such as poly- hat
Ether-soft segment is formed.Poly-crown ether-polystyrene-block-copolymer can be advantageously thermoplastic elastomer (TPE) and can with high
Draftability.
In another embodiment, at least one polymerisable monomer polymerization or reaction at least one solvent
Middle progress.The molecular weight of polymer to be formed advantageously can be more preferably controlled by solvent polymeric or polymerisation in solution.Institute
After the polymerization or reaction of stating at least one polymerisable monomer, at least one solvent can be particularly removed again.
In another embodiment, provide lithium battery and/or lithium battery group, particularly lithium ion battery and/or lithium from
The preparation method of the anode of sub- battery pack.
It is described that there is at least one polymerizable functional group particularly so-called from the embodiment of main chain Graft Method
And/or polymerization cause functional group and/or polymerization control functional group at least one silane compound, especially add in described at least
Before a kind of monomer or at least two monomer, the anode active material particles can be fixed on, especially silicon particle
On surface.For example, at least one silane compound can by with the anode active material particles, especially silicon particle
Surfacing is formed(It is particularly covalent)Chemical bond and fix.It is then possible to add at least one polymerisable monomer or
At least two polymerisable monomer described in person.The fixation can be depending at least one silane compound and at least one
The lower progress of existence or non-existence of solvent.
At least one polymerisable monomer or at least two polymerisable monomer herein especially can be by freedom
Base polymerization is reacted with the fixed silane compound of at least one.The free radical polymerization can be herein(It is particularly simple
's)Free radical polymerization, such as only in the presence of at least one radical initiator, such as AIBN and/or BPO or particularly work
Free love base polymerize, such as ATRP, SFRP, such as NMP or RAFT.If use at least two polymerisable monomers and/or use
The combination of at least one polymerisable monomer and at least one silane compound at least one polymerizable functional group, then can be with
It is related to being copolymerized, particularly described at least two polymerisable monomer and/or at least one monomer and at least one silane
The copolymerization of at least one polymerizable functional group of compound.
If at least one(Particularly promote bonding)Silane compound has polymerizable functional group, then also special
Can be with, optionally at least one polymerisable monomer or at least two polymerisable monomers, such as carboxylic acid and/or carboxylic acid-
Derivative, such as vinylene carbonate and/or ether such as crown ether and/or crown ether-derivative together, add at least one polymerization and cause
Agent, such as radical initiator, such as AIBN or BPO(And/or optionally at least one solvent).Therefore, it can be advantageous to draw
Send out polymerization described.
If there is at least one silane compound polymerization to cause functional group(Particularly live for causing atom transfer
Free love base polymerize (ATRP- initiators)), then also especially can be with, optionally at least one polymerisable monomer or at least
Two kinds of polymerisable monomers, such as carboxylic acid and/or carboxylic acid-derivative, such as vinylene carbonate and/or ether, such as crown ether and/or hat
Ether-derivative together, adds at least one catalyst, for example, at least a kind of transition metal halide, such as copper halide and optionally
At least one ligand, such as nitrogen ligand (N-type-ligand), such as three [2- (dimethylamino) ethyl] amine).Therefore, Ke Yiyou
Cause the polymerization sharply.
If at least one silane compound has polymerization control functional group(Particularly it is used for stable free radical polymerization
(SFRP), for example, for nitrogen oxides mediation polymerization (NMP- mediators) and/or for Verdazyl- mediation polymerization
(VMP- mediators) or for reversible addition-fracture-chain tra nsfer-polymerization (RAFT- reagents)), then also especially can be with, optionally with
At least one polymerisable monomer or at least two polymerisable monomers, such as carboxylic acid and/or carboxylic acid-derivative, as carbonic acid Asia
Vinyl acetate and/or ether such as crown ether and/or crown ether-derivative together, add at least one polymerization initiator, such as free radical draws
Send out agent, such as AIBN or BPO.Therefore, it can be advantageous to cause the polymerization.For further preferably control polymerization, may be used also
To be optionally added at least one polymerization control agent, particularly for stable free radical polymerization (SFRP), such as nitrogen oxides
The polymerization (NMP- mediators) of mediation and/or for the polymerization (VMP- mediators) of Verdazyl- mediations and/or for reversible plus
Into-fracture-chain tra nsfer-polymerization (RAFT- reagents), for example, at least a kind of mediator of nitrogen oxides base, such as alkoxyamine form
Sacrificial initiator or at least one thio-compounds.
In another embodiment(Particularly wherein described at least one polymerisable monomer is equably lived with the anode
Property material granule, especially silicon particle polymerize, but dividually carried out with other electrode components(Method 1)), will be disposed with, especially
It is to be coated with the anode active material particles of polymer formed by the polymerization or reaction, especially silicon particle and at least one
The other electrode components mixing of kind, and anode is for example processed by blade coating.Therefore, it can be advantageous to and targetedly exist
SEI- layers of synthesis is formed on the anode active material particles, especially silicon particle, and for example so that for coating the anode
The amount of at least one polymerisable monomer needed for active material particle, especially silicon particle minimizes.
In an embodiment of the embodiment, the method includes following method and steps:
A) anode active material particles, especially silicon particle and at least one polymerisable monomer are mixed, especially mix anode activity material
Expect particle, especially silicon particle and at least one polymerisable monomer,
B) by(Such as pass through addition)At least one polymerization initiator, especially described at least one polymerization initiator and cause
The polymerization of at least one polymerisable monomer,
C) mixed-arrangement has, and is particularly coated with the anode active material particles of polymer formed by the polymerization, especially
Silicon particle and at least one other electrode component and
D) by the mixture(Such as pass through blade coating)It is processed into anode.
Mixing in method and step a) and the polymerization in method and step b) optionally can be at least one solvents
It carries out.After the polymerization or after method and step b), such as before method and step c) or in method and step d) mistakes
In journey or later, at least one solvent can and then be removed again.
In another embodiment(Particularly wherein described at least one polymerisable monomer is equably lived with the anode
Property material granule, especially silicon particle and other electrode components polymerization(Method 2)), by the anode active material particles, especially
Silicon particle is mixed at least one other electrode component and at least one polymerisable monomer.In this way it is possible to
It is in situ to carry out the polymerization, particularly directly mixing(Such as slurry)During, it is used to form anode.In such case
Under, it can be mutually mixed the anode active material particles, especially silicon particle, at least one other electrode component simultaneously
With at least one polymerisable monomer.It can also optionally, however be mutually mixed the anode active material particles first, especially
Its silicon particle and at least one electrode component and at least one polymerisable monomer is then added in into the mixture.
In an embodiment of the embodiment, after blending, it is described polymerization by(Such as pass through addition)Institute
It states at least one polymerization initiator and causes.Particularly, the polymerization herein can be by(Such as pass through addition)It is described at least
A kind of polymerization initiator and at least one catalyst and/or at least one polymerization control agent, such as described at least one
The mediator of kind of nitrogen oxides base and/or at least one thio-compounds and cause.In at least one polymerisable monomer
Polymerization after, then can by the mixture for example by blade coating be processed into anode.Therefore, it can be advantageous to reduce processing step
Rapid quantity and the method that simplifies in this way.In addition, the polymer formed by least one polymerisable monomer exists
This is also used as the adhesive of anode to be prepared.Optionally, other adhesive can not be had to add in herein as other
Electrode component.
For example, the method can include following method and step herein:
A' anode active material particles) are mixed, especially silicon particle and at least one other electrode component and at least one can gather
Monomer is closed, especially mixes the anode active material particles, especially silicon particle and at least one other electrode component and described
At least one polymerisable monomer,
B') by(Such as pass through addition)At least one polymerization initiator, especially described at least one polymerization initiator, such as by means of
It helps(Such as pass through addition)At least one polymerization initiator and at least one catalyst and/or at least one are poly-
Close controlling agent, for example, the mediator of at least one nitrogen oxides base and/or at least one thio-compounds and cause institute
State at least one polymerisable monomer polymerization and
C') by the mixture(Such as pass through blade coating)It is processed into anode.
Optionally, in method and step a') at least one polymerisable monomer can be added to active material of positive electrode
In particle, the especially mixture of silicon particle and at least one other electrode component.
In method and step a') in mixing and in method and step b') in polymerization especially can be at least one solvent
It carries out.After the polymerization or in method and step b') after, such as in method and step c') before or during or later,
At least one solvent can and then be removed again.
In another embodiment, by the anode active material particles, especially silicon particle with it is at least one other
It electrode component and is mixed at least one polymerisable monomer and at least one polymerization initiator, and by the mixture
Such as anode is processed by blade coating.The mixing and processing preferably carry out under the following conditions herein:Such as particularly low
At a temperature of and/or in the case of there is no light, wherein it is described at least one polymerization initiator(Especially at least substantially)
The polymerisation is not caused.After mixture is processed into anode, then cause polymerization, it is described mixed especially by radiating
Object is closed, such as is irradiated with ultraviolet light, such as with UV lamp and/or by warming or heating the mixture.
Therefore, it can be advantageous to be further reduced the quantity of procedure of processing and be further simplified the method.It is in addition, described
The polymer formed by least one polymerisable monomer may also serve as the adhesive of anode to be prepared herein.Optionally,
Therefore other adhesive can also not be had to add in herein as other electrode components.It in addition, in this way can be with processed
The form crossed forms the polymer, and curing is realized advantageously in the form of processed.
For example, the method can include following method and step herein:
A'' anode active material particles) are mixed, especially silicon particle, at least one other electrode component, at least one can gather
Monomer and at least one polymerization initiator are closed, particularly mixes the anode active material particles, especially silicon particle, it is at least one
Other electrode components, at least one polymerisable monomer and at least one polymerization initiator and for example described at least one
Kind of catalyst and/or at least one polymerization control agent, such as the mediator of at least one nitrogen oxides base and/or described
At least one thio-compounds;
B'') by the mixture(Such as pass through blade coating)It is processed into anode;With
C'' it) by radiating the mixture, is particularly irradiated with ultraviolet light and/or by warming or heating the mixture
And cause the polymerization of at least one polymerisable monomer.
For example, in method and step a'') in can be with(Such as first)By at least one polymerisable monomer and(Such as so
Afterwards)At least one polymerization initiator is added to anode active material particles, especially silicon particle and it is described it is at least one its
In the mixture of its electrode component.
In method and step a'') in mixing, in method and step b'') in processing and in method and step c'') in polymerization
It can especially be carried out at least one solvent.After the polymerization or in method and step c'') after, it can then again
Remove at least one solvent.
In the above-described embodiment, at least one other electrode component can include at least one carbon component, example
Such as graphite and/or conductive black and/or at least one(It is optionally other such as compatible)Adhesive, such as carboxymethyl cellulose
Plain (CMC) and/or carboxymethyl cellulose-salt, such as lithium-carboxymethyl cellulose (LiCMC) and/or sodium-carboxymethyl cellulose
(NaCMC) and/or potassium-carboxymethyl cellulose (KCMC) and/or polyacrylic acid (PAA) and/or polyacrylic acid-salt, as lithium-
Polyacrylic acid (LiPAA) and/or sodium-polyacrylic acid (NaPAA) and/or potassium-polyacrylic acid (KPAA) and/or polyvinyl
Alcohol (PVAL) and/or styrene-butadiene-rubber (SBR) and/or at least one solvent.
Particularly, at least one(It is optionally other)Adhesive can have carboxylic acid group (- COOH) and/or hydroxyl
Base (- OH).For example, at least one(It is optionally other)Adhesive can include or polyacrylic acid (PAA) and/or carboxylic
Methylcellulose (CMC) and/or polyvinyl alcohol (PVAL).
Particularly, at least one polymerisable monomer and/or the polymerization formed by least one polymerisable monomer
Object can have carboxylic acid group (- COOH) and/or hydroxyl (- OH) herein.For example, at least one polymerisable monomer can be with
Including or acrylic acid and/or vinyl acetate and/or the polymer formed by least one polymerisable monomer can wrap
It includes or polyacrylic acid (PAA) based polyalcohol that is obtained by acroleic acid polymerization and/or by vinyl acetate polyisocyanate polyaddition and then
The polyvinyl alcohol (PVAL) that saponification obtains.
If at least one(It is optionally other)Adhesive and at least one polymerisable monomer and/or it is described by
The polymer that at least one monomer is formed all comprising carboxylic acid group (- COOH) and/or hydroxyl (- OH), then can advantageously make
Be disposed with, such as the anode active material particles coated with the polymer, especially silicon particle by polycondensation reaction covalently with
At least one adhesive combines.By the condensation reaction between two carboxylic acid groups, acid anhydrides-chemical combination can be obtained herein
Object.By the condensation reaction between carboxylic acid group and hydroxyl, ester-compound can be obtained herein.By between two hydroxyls
Condensation reaction can obtain ether-compound herein.
For example, be disposed with the polymer based on polyacrylic acid silicon particle (Si-PAA) can according to the following formula with as viscous
The polyacrylic acid (PAA) and/or carboxymethyl cellulose (CMC) and/or polyvinyl alcohol (PVAL) of mixture are anti-by being condensed
It should covalently combine:
Si-PAA + PAA:- COOH+- COOH → acid anhydrides-compound
Si-PAA + CMC:- COOH+- COOH → acid anhydrides-compound
Si-PAA + PVAL:- COOH+- OH → ester-compound.
Optionally(Particularly in above-mentioned embodiment, wherein the polymer formed by polymerisable monomer can also be used
Make adhesive), can not have to add at least one(It is particularly other)Adhesive is as other electrode components or by institute
Stating at least one other electrode component can also optionally be configured to without adhesive.
However, it is also possible to(Such as in order to improve the mechanical stability of anode to be formed and/or transmitable)Using extremely
Few one kind(Such as it is other, it is particularly different from the polymer formed by the polymerisable monomer)Adhesive is as other
Electrode component.
Optionally, at least one solvent used in polymerization is also used as electrode component, such as be used to form
Electrode slurry.Therefore, other solvent can not optionally be had to add in as other electrode components.
Notably, however(For example, if remove at least one solvent again after the polymerization), then can use
It is at least one(It is particularly different from the solvent of the polymerization)Solvent is as other electrode components.
About other technical characteristics and advantage of the method for the present invention, herein referring specifically to the anode activity material with the present invention
The battery and/or battery pack of material, the anode of the present invention and the present invention are relevant to be illustrated and with reference to attached drawing and description of the drawings.
Other themes of the present invention are lithium battery and/or lithium battery group, particularly lithium ion battery and/or lithium ion battery
The active material of positive electrode and/or anode of group are prepared by the method for the present invention.
Active material of positive electrode of the invention or prepared in accordance with the present invention, for example, it is described by least one polymerisable monomer
The polymer of formation, for example, polymerized thylene carbonate vinyl acetate and/or the present invention's or anode prepared in accordance with the present invention can be as follows
Detection:Such as pass through nuclear magnetic resonance spectroscopy(NMR)And/or infra-red sepectrometry(IR)And/or Raman spectroscopy(Raman).This
Outside, active material of positive electrode either prepared in accordance with the present invention of the invention and/or the present invention or it is prepared in accordance with the present invention
Anode can detect as follows:Such as pass through surface analysis method, such as Auger electron spectroscopy(AES)And/or x-ray photoelectron energy
Spectrometry(XPS, English:X-ray Photoelectron Spectroscopy)And/or flight time-secondary ion-mass spectrography
(TOF-SIMS, English:Time-of-Flight Secondary Ion Mass Spectrometry)And/or energy dispersion X
Ray spectroscopy(EDX, English:Energy Dispersive X-ray Spectroscopy)And/or wavelength-dispersion type X ray
Spectroscopic methodology(WDX), such as EDX/WDX and/or pass through structure analysis method, such as transmission electron microscopy(TEM)And/or pass through
Cross-sectional analysis, such as scanning electron microscopy(REM)(SEM;English:Scanning Electron Microscope)And/or
Energy dispersion X-ray spectroscopic methodology(EDX, English:Energy Dispersive X-ray Spectroscopy), such as REM-
EDX and/or transmission electron microscopy(TEM)And/or electron energy loss spectroscopic methodology(EELS;English:Electron Energy
Loss Spectroscopy), such as TEM-EELS.Therefore, the mistake for example contained in ATRP- catalyst can mainly be detected
Cross the mediator of metal and/or nitrogen oxides base, such as TEMPO and/or RAFT- chemicals.
The other technical characteristics and advantage of the anode of the active material of positive electrode and present invention about the present invention, herein clearly
With reference to the relevant elaboration of battery and/or battery pack of the method with the present invention and the present invention and with reference to attached drawing and description of the drawings.
The invention further relates to lithium battery and/or lithium battery groups, especially lithium ion battery and/or Li-ion batteries piles, lead to
The method for crossing the present invention prepares and/or the anode including active material of positive electrode of the invention and/or the present invention.
About the present invention battery and/or battery pack other technical characteristics and advantage, herein referring specifically to this hair
The relevant elaboration of anode of bright method, the active material of positive electrode of the present invention and the present invention and with reference to attached drawing and description of the drawings.
Description of the drawings
The further advantage and advantageous embodiment of subject of the present invention shown by attached drawing, and in the following description into
Row is explained.It should be noted that attached drawing only has descriptive characteristics, it is not intended to limit the invention in any way.
Fig. 1 a show for show preparation in accordance with the present invention an embodiment flow chart;
Fig. 1 b show to be illustrated for being illustrated in the reaction of the embodiment of the preparation in accordance with the present invention shown in Fig. 1 a
Figure;With
Fig. 1 c schematically show the cross section of anode, the anode according in fig 1 a it is shown according to the method for the present invention
Embodiment and prepare.
Fig. 1 a are illustrated, in an embodiment according to the method for the present invention, such as in method and step A) in, will have
At least one polymerizable functional group and/or polymerization cause at least one silane chemical combination of functional group and/or polymerization control functional group
Object 2* is fixed on anode active material particles, especially on the surface of silicon particle 1.At least one silane compound 2*
The ATRP- initiators of vinyl silanes or silylation or the RAFT- of the NMP- mediators of silylation or silylation examinations can be such as related to
Agent.
Then to reaction product 12*, such as in method and step B) in, add at least one polymerisable monomer 2, such as carbon
Sour vinylene.In this case, from the surface of the anode active material particles, especially silicon particle, particularly from least
A kind of at least one functional group of silane compound 2* starts, and is formed by the polymerization of at least one polymerisable monomer 2
(co) polymer 12*2, and coated anode active material particle in this way, especially silicon particle 1.
The polymerization especially can be free radical polymerization herein.For example, vinyl silanes and/or vinylene carbonate
(VC) can by the ATRP- initiators of silylation and/or by adding in polymerization initiator, such as radical initiator, such as
Azo isobutyronitrile (AIBN) and/or benzoyl peroxide (BPO) by free radical polymerization, aggregate into such as polymerized thylene carbonate second
Enester, wherein under the specific condition of active free radical polymerization, such as ATRP, can by the ATRP- initiators of silylation and/or
Alkyl halide (RX) is used with the catalyst combination formed by transition metal halide (MX) and ligand (L), alternatively,
Such as NMP, it can be by the NMP- mediators of silylation and/or the mediator (TEMPO) and radical initiator of nitrogen oxides base, such as
AIBN is applied in combination, alternatively, such as RAFT, it can be by the RAFT- reagents and/or thio-compounds (Thio) of silylation and oneself
It is applied in combination by base initiator, such as AIBN:
。
The anode active material particles of coating, especially silicon particle 12*2 then can be with, such as in method and step C) in, with
One or more others electrode components, as graphite and/or conductive black 4 and adhesive 5 and/or solvent mix, and will be mixed
Close object 12*2,4,5, such as in method and step D) in, it is processed into(Such as it scratches into)Anode 100''.In this case, it uses
The polymer 2*2 formed by polymerisable monomer 2 can be optionally different from by making the adhesive 5 of other electrode components.
Fig. 1 b are illustrated, at least one silane compound 2*, such as 4- (chloromethyl) phenyl trichlorosilane herein, can be with
Such as in the anode active material particles, especially on the surface of silicon particle 1, by with hydroxyl, such as silicon hydroxide radicals
Or the condensation reaction of silanol (Si-OH), with anode active material particles, especially silicon particle 1 is formed(It is particularly common
Valency)Bonding, and the polymerization of at least one polymerisable monomer 2 can be caused since the surface of silicon particle 1.
Fig. 1 c are illustrated, and the anode 100'' accordingly prepared can include the anode activity material with polymer 2*2 coatings
Expect particle, especially silicon particle 1 and graphite-and/or conductive black-particle 4, they are embedded in other adhesive 5.
Claims (23)
1. it is used to prepare lithium battery and/or the active material of positive electrode and/or anode of lithium battery group(100''), particularly lithium ion
The active material of positive electrode and/or anode of battery and/or Li-ion batteries piles(100'')Method and/or be used to prepare lithium battery
And/or the method for lithium battery group, particularly lithium ion battery and/or Li-ion batteries piles, wherein,
Make that there is at least one polymerizable functional group and/or polymerization to cause functional group and/or polymerization control functional group at least
A kind of silane compound(2*)It is fixed on anode active material particles(1)Surface on, particularly on the surface of silicon particle and
Add at least one polymerisable monomer(2)And it is polymerize.
2. according to the method described in claim 1, wherein use at least two polymerisable monomers(2).
3. method according to claim 1 or 2, wherein at least one silane compound(2*)At least one can gather
Close functional group and/or at least one polymerisable monomer(2), especially at least two kinds of polymerisable monomers(2), include at least one
A polymerizable double bond and/or at least one hydroxyl.
4. according to the method in any one of claims 1 to 3,
Wherein, at least one silane compound(2*)At least one polymerizable functional group and/or at least one can
Polymerized monomer(2), especially at least two kinds of polymerisable monomers(2), by free radical polymerization, gather especially by living radical
Close and can polymerize and/or
Wherein, at least one silane compound(2*)At least one polymerization cause functional group's setting for causing free radical
Polymerization, particularly for cause active free radical polymerization and/or
Wherein, at least one silane compound(2*)At least one polymerization control functional group setting for control activity from
It is polymerize by base.
5. method according to any one of claim 1 to 4,
Wherein, at least one silane compound(2*)At least one polymerizable functional group and/or at least one can
Polymerized monomer(2), especially at least two kinds of polymerisable monomers(2), by atom transfer active free radical polymerization or by steady
Free radical polymerization is determined, especially by the polymerization of nitrogen oxides mediation or by reversible addition-fracture-chain tra nsfer-polymerization and energy
Enough polymerizations and/or
Wherein, at least one silane compound(2*)At least one polymerization cause functional group's setting and turn for causing atom
Move active free radical polymerization and/or
Wherein, at least one silane compound(2*)At least one polymerization control functional group setting for control stablize from
Polymerize by base, particularly for control nitrogen oxides mediate polymerization and/or for control reversible addition-fracture-chain tra nsfer-
Polymerization.
6. wherein described at least one silane compound the method according to any one of claims 1 to 5,(2*)At least
A kind of polymerizable functional group and/or at least one polymerisable monomer(2), especially at least two kinds of polymerisable monomers(2), packet
Containing at least one polymerizable double bond, in particular at least one carbon-to-carbon double bond.
7. method according to any one of claim 1 to 6, wherein at least one silane compound(2*)At least
A kind of initiation functional group that polymerize includes the alkyl replaced by least one halogen atom, particularly bromine or chlorine.
8. method according to any one of claim 1 to 7, wherein at least one silane compound(2*)At least
A kind of polymerization causes functional group and is used at least one catalyst combination, and particularly wherein described at least one catalyst included
It crosses metal halide and at least one ligand, particularly nitrogen ligand or is formed by it.
9. method according to any one of claim 1 to 8, wherein at least one silane compound(2*)At least
A kind of polymerization control functional group, the particularly polymerization for nitrogen oxides mediation include nitroxide groups and/or alkoxyamine
Group and/or particularly for reversible addition-fracture-chain tra nsfer-polymerization, includes thio group.
10. method according to any one of claim 1 to 9, wherein at least one silane compound(2*)Extremely
A kind of few polymerization control functional group at least one polymerization initiator and/or at least one silane compound(2*)At least one
Kind polymerization causes combination of functional groups and uses.
11. method according to any one of claim 1 to 10, wherein at least one polymerisable monomer(2), particularly extremely
Few two kinds of polymerisable monomers(2)Polymerization by least one silane compound(2*)At least one polymerization cause function
It rolls into a ball and/or by least one polymerization initiator, particularly causes by least one polymerization initiator is added in.
12. method according to any one of claim 1 to 11, wherein at least one silane compound(2*)Extremely
It is radical initiator that a kind of few polymerization, which causes functional group and/or at least one polymerization initiator,.
13. method according to any one of claim 1 to 12, wherein at least one silane compound is included at least
A kind of silane compound of following chemical general formula:
Wherein,
R1, R2, R3 respectively represent halogen atom or alkoxy or alkyl or amino or silazane group or hydroxyl independently of one another
Or hydrogen,
Y represents linking group, and particularly wherein Y is comprising at least one alkylidene and/or at least one oxyalkylene group and/or extremely
A few carboxylate group and/or at least one phenylene and
A represents polymerizable functional group and/or polymerization causes functional group and/or polymerization control functional group.
14. according to the method for claim 13,
Wherein, A represents the polymerizable functional group at least one polymerizable double bond, particularly vinyl or 1,1- ethenylidene
Or 1,2- ethenylidene or acrylate group or methacrylate group or
Wherein, A represent for cause the polymerization of atom transfer active free radical polymerization cause functional group, particularly bromine or chlorine or
Wherein, A represent for nitrogen oxides mediation polymerization polymerization control functional group, particularly nitroxide groups and/or
Alkoxyamine groups represent to control functional group, particularly thio group for the polymerization of reversible addition-fracture-chain tra nsfer-polymerization
Group.
15. the method according to any one of claim 1 to 14, wherein anode active material particles(1)Including or silicon
Particle and/or graphite particle and/or tin particles, particularly silicon particle.
16. the method according to any one of claim 1 to 15, wherein at least one polymerisable monomer(2), especially
It is at least two polymerisable monomer(2)Including:
At least one polymerizable carboxylic acid and/or
At least one polymerizable carboxylic acid derivates, particularly
At least polymerizable organic carbonate and/or acid anhydrides and/or
At least one carboxylate and/or
At least one carboxylic acid nitriles and/or
At least one ether, especially at least a kind of crown ether and/or at least one crown ether derivative and/or at least one vinyl
Ether and/or
The unsaturated hydrocarbons of at least one unsaturated hydrocarbons, especially at least a kind of aliphatic series or aromatics.
17. the method according to any one of claim 1 to 16, wherein at least one polymerisable monomer(2), especially
It is at least two polymerisable monomers(2)Also comprising at least one nonfluorinated oxyalkylene group and/or at least one fluorinated alkene
Group and/or at least one fluorination alkoxy and/or at least one fluorinated alkyl and/or at least one fluorinated phenyl.
18. the method according to any one of claim 1 to 17, wherein at least one polymerisable monomer(2), especially
It is at least two polymerisable monomers(2)Including or acrylic acid and/or methacrylic acid and/or vinylene carbonate and/or carbon
Sour vinylethylene and/or maleic anhydride and/or poly-(Ethylene glycol)Methyl ether acrylate and/or methyl methacrylate and/
Or vinyl acetate and/or acrylonitrile and/or at least one polymerizable functional group, particularly at least one polymerizable
Double bond and/or at least one crown ether at least one hydroxyl and/or at least one crown ether derivative and/or trifluoro-ethylene
Base ether and/or 1,1- difluoroethylenes and/or hexafluoropropene and/or nine fluorine hexenes of 3,3,4,4,5,5,6,6,6- and/or 2,3,4,
5,6- pentafluorophenyl groups ethylene and/or 4-(Trifluoromethyl)Phenylethylene and/or styrene and/or its derivative.
19. the method according to any one of claim 16 to 18, wherein at least one crown ether and/or at least one
Crown ether derivative includes the crown ether or crown ether derivative of following chemical general formula:
Wherein, Q1, Q2, Q3 and Qk respectively represent oxygen or nitrogen or amine, particularly oxygen independently of one another,
Wherein, G represents at least one polymerizable functional group, and particularly wherein G includes at least one vinyl and/or at least one
1,1- ethenylidene and/or at least one 1,2- ethenylidenes and/or at least one pi-allyl and/or at least one hydroxyl, it is special
It is not that wherein G further includes at least one benzo groups and/or hexamethylene and group,
Wherein, g represent polymerizable functional group G quantity and
Wherein, k represents the quantity of unit in bracket.
20. the method according to any one of claim 16 to 19, wherein at least one crown ether and/or at least one
Crown ether derivative includes the crown ether or crown ether derivative of following chemical general formula:
Wherein, G' represents at least one polymerizable functional group, in particular at least one vinyl and/or at least one 1,1- Asias second
Alkenyl and/or at least one 1,2- ethenylidenes and/or at least one pi-allyl and/or at least one hydroxyl and wherein 1≤
g'。
21. the method according to any one of claim 1 to 20, wherein at least one silane compound is included at least
A kind of crown ether base silane compound of following chemical general formula and/or at least one crown ether and/or at least one crown ether derive
Object includes the crown ether or crown ether derivative of following chemical general formula:
Wherein
R1, R2, R3 respectively represent halogen atom or alkoxy or alkyl or amino or silazane group or hydroxyl independently of one another
Or hydrogen,
Q1, Q2, Q3 and Qk respectively represent oxygen or nitrogen or amine independently of one another,
K represents the quantity of unit in bracket,
G represents at least one polymerizable functional group, and particularly wherein G includes at least one carbon-to-carbon double bond, in particular at least one
Vinyl and/or 1,1- ethenylidene and/or 1,2- ethenylidene and/or pi-allyl and/or at least one hydroxyl,
G represents the quantity of polymerizable functional group G,
Y' represents linking group, particularly-CnH2n, wherein n=1 or 2 or 3 and
S represents the quantity of silane group, especially by the quantity of the linking group Y' silane groups combined.
22. the active material of positive electrode and/or anode of lithium battery and/or lithium battery group(100''), particularly lithium ion battery and/
Or the active material of positive electrode and/or anode of Li-ion batteries piles(100''), by according to any one of claim 1 to 21
It is prepared by the method.
23. lithium battery and/or lithium battery group, particularly lithium ion battery and/or Li-ion batteries piles, by being wanted according to right
The method described in any one of 1 to 20 is asked to prepare and/or including active material of positive electrode according to claim 22 and/or sun
Pole(100'').
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CN114503311A (en) * | 2019-10-18 | 2022-05-13 | 株式会社村田制作所 | Negative electrode active material, negative electrode, and secondary battery |
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