CN108701819A - 多层组件 - Google Patents
多层组件 Download PDFInfo
- Publication number
- CN108701819A CN108701819A CN201780012180.7A CN201780012180A CN108701819A CN 108701819 A CN108701819 A CN 108701819A CN 201780012180 A CN201780012180 A CN 201780012180A CN 108701819 A CN108701819 A CN 108701819A
- Authority
- CN
- China
- Prior art keywords
- copolymer
- composition
- group
- multilayer module
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 59
- 229910052744 lithium Inorganic materials 0.000 claims description 51
- 229920001577 copolymer Polymers 0.000 claims description 46
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- -1 hydroxyl Chemical group 0.000 claims description 26
- 230000003252 repetitive effect Effects 0.000 claims description 24
- 239000002608 ionic liquid Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 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
- 239000010703 silicon Substances 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003235 pyrrolidines Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 20
- 210000001787 dendrite Anatomy 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 12
- 230000012010 growth Effects 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229940021013 electrolyte solution Drugs 0.000 description 7
- 229920001897 terpolymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000013047 polymeric layer Substances 0.000 description 3
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- WDEZYHHMIZHERM-UHFFFAOYSA-N 1,1-bis(fluoranyl)ethene Chemical compound FC(F)=C.FC(F)=C WDEZYHHMIZHERM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical class OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005138 cryopreservation Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 1
- 229960003132 halothane Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000009329 sexual behaviour Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
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Abstract
本发明提供了一种包含至少部分地涂覆有杂合无机/有机组合物的金属层的多层组件、其制备方法以及包含所述多层组件的电化学电池。
Description
相关申请的交叉引用
本申请要求于2016年2月19日提交的欧洲申请号EP 16156507.2的优先权,出于所有目的将所述申请的全部内容通过援引方式并入本申请。
技术领域
本发明提供了一种包含至少在一侧上涂覆有杂合无机/有机组合物的金属层的多层组件、用于制备所述组件的方法以及包含所述多层组件的电化学电池。
背景技术
包含锂金属或锂化合物作为阳极的原(非可再充电的)电池是非常有用的能量储存装置,其可以找到各种应用,包括大量的便携式电子装置到电动车辆。
锂(Li)金属还将由于其优异的电化学特性而是可再充电(二次)电池的理想的阳极材料。不幸地,在可再充电电池中固有的锂沉积/溶出期间不可控的树枝状生长和有限的库伦效率已经阻止了基于Li金属的可再充电电池以及相关装置在过去40年中的实际应用(参考文献:XU,W.等人,“Lithium metal anodes for rechargeable batteries[用于可再充电电池的锂金属阳极]”,Energy Environ.Sci.[能源与环境科学],2014,第7卷,第513-537页,以及其中所引用的参考文献)。
随着用于许多应用(范围从便携式电子装置到电动车辆)的后Li离子电池的出现,Li金属阳极的安全和有效运行已经成为使能技术,该技术可以决定下一代能量储存技术的命运,包括可再充电的Li–空气电池、Li–S电池以及使用插层化合物作为阴极的Li金属电池(参考文献:LIANG,Z.等人,“Polymer Nanofiber-Guided Uniform Lithium Depositionfor Battery Electrodes[用于电池电极的聚合物纳米纤维引导的均匀锂沉积]”,NanoLett.[纳米快报],2015,第15卷,第2910-2916页;UMEDA,G.A.等人,Protection oflithium metal surfaces using tetraethoxysilane[使用四乙氧基硅烷保护锂金属表面],J.Mater.Chem.[材料化学期刊],2011,第21卷,第1593页;LOVE,C.A.等人,“Observation of Lithium Dendrites at Ambient Temperature[在环境温度下观察锂枝晶]”,ECS Electrochemistry Letters[ECS电化学快报],2015,第4卷,第2期,第A24-A27页)。
在二次电池中使用Li金属阳极的主要问题与在重复充电/放电循环期间锂枝晶的生长有关,这最终导致差的使用寿命以及潜在的内部短路。
不受控的锂枝晶生长导致循环性能差以及严重的安全危害(参考文献:WU,H.等人,“Improving battery safety by early detection of internal shorting with abifunctional separator[通过使用双功能隔膜早期检测内部短路以提高电池安全性]”,Nat.Commun.[自然通讯],2014,第5卷,第5193页)。电化学循环时,锂离子向缺陷扩散,产生所谓的“热点”。众所周知,在电流密度局部显著增强的这些热点处,Li枝晶生长加速。所得的树状锂金属枝晶将刺穿隔膜并且引起内部短路,具有装置过热、着火以及潜在爆炸的风险。
可以通过在锂金属上添加聚合物层防止锂枝晶生长。这个层应均匀地粘附在锂金属上以获得均匀的锂沉积,并且还应具有良好的机械特性以抵抗枝晶生长、用于长寿命的适度溶胀、良好的离子电导率以避免性能损失以及界面处锂浓度的减少。然而,已知的涂层组合物(例如基于偏二氟乙烯聚合物)未将枝晶生长抑制到令人满意的水平并且降低了电化学电池的总效率。
目前,对耐用的、可靠的并且安全的基于锂金属阳极的可再充电的电化学电池的需求仍未得到满足。
发明内容
本发明提供了一种多层组件,该多层组件包括:
-金属层(a),该金属层基本上由锂金属、钠金属、镁金属、锌金属、它们与硅或锡的合金组成,所述金属层(a)包含第一表面和第二表面;
-涂层(b),该涂层粘附到金属层(a)的所述第一表面和第二表面中的至少一个上,
其中,(b)包含杂合无机/有机组合物,该组合物通过使以下项反应而获得:
i.具有式(I)的化合物(M)
X4-mAYm (I)
其中X是烃基,任选地包含一个或多个官能团,m是从1至4的整数,A是选自由Si、Ti和Zr组成的组的元素,并且Y是选自由烷氧基、酰氧基和羟基组成的组的可水解基团,以及
ii.至少一种氟共聚物(F),该氟共聚物包含衍生自偏二氟乙烯(VDF)的重复单元和至少衍生自具有至少一个基团–O-Rx和/或–C(O)O-Rx的单体(R1’)的重复单元,其中每个Rx任选地彼此独立地是氢基团或包含至少一个羟基的C1-C5烃基,
其中,通过所述化合物(M)与所述氟共聚物(F)的反应,衍生自化合物(M)缩聚的无机残基经由与共聚物(F)的基团-O-Rx和/或–C(O)O-Rx的反应而至少部分地化学键合到共聚物(F)上,并且其中(b)任选地包含:
iii.电解质盐(ES-1)和/或
iv.离子液体(IL-1)。
在实施例中,本发明涉及一种用于制备如以上定义的多层组件的方法,该方法包括以下步骤:
i.提供包含第一表面和第二表面的金属层(a);
ii.提供具有式(I)的化合物(M)
X4-mAYm (I)
其中X是烃基,任选地包含一个或多个官能团,m是从1至4的整数,A是选自由Si、Ti和Zr组成的组的元素,并且Y是选自由烷氧基、酰氧基和羟基组成的组的可水解基团;
iii.将(M),任选地呈与电解质盐(ES-1)和/或离子液体(IL-1)的混合物形式,与包含液体介质(L1)和至少一种氟共聚物(F)的组合物(C-1)混合以获得组合物(C),该氟共聚物包含衍生自偏二氟乙烯(VDF)的重复单元和至少衍生自具有至少一个基团–O-Rx和/或–C(O)O-Rx的单体(R1’)的重复单元,其中每个Rx任选地彼此独立地是氢基团或包含至少一个羟基的C1-C5烃基;
iv.用在步骤iii中获得的该组合物(C)涂覆层(a)的所述第一表面和第二表面中的至少一个,以便获得潮湿的涂层;
v.除去该液体介质(L1)以获得多层材料,其中衍生自化合物(M)的无机残基与衍生自共聚物(F)的–O-Rx和/或–C(O)O-Rx的基团键合。
本发明进一步提供了一种包含如以上定义的多层组件的电化学电池。
具体实施方式
诸位发明人出人意料地发现,用如上所述的组合物涂覆电极降低了或实际上抑制了电化学电池组件中枝晶的生长,同时维持了非常好的离子电导率。用所述组合物涂覆电极(尤其是在锂金属电极的情况下)的至少一侧,相对于用有机材料(例如基于偏二氟乙烯(VDF)的聚合物)涂覆,提供了在离子电导率、溶胀以及抵抗锂枝晶生长方面具有改进特性的电极。
优选地,在本发明的多层组件中,层(a)基本上由锂金属组成。有利地,可以将该锂金属层在未涂覆有组合物(b)的那侧层压到另一个金属层(优选地是铜)上,以增强该层的机械阻力。
在本发明的上下文中,术语“基本上由...组成”表示组合物或元件包含以重量计(相对于该组合物的总重量)超过95%的特定物质(例如锂金属)或由此种物质组成,前提是其可能包括在此种物质中通常或不可避免地存在的杂质和痕量的其他物质。
除非另外指明,否则在本发明的上下文中,组合物中组分的量被表示为在该组分的重量与该组合物的总重量之间的比率乘以100(还为:“wt%”)。
如在此使用的,术语“粘附”(“adheres”和“adhesion”)表示两个层经由它们的接触表面永久地彼此附着,例如在根据ASTM D3359测试方法B的横切测试中被分类为5B至3B。为清楚起见,其中将电极型层(a)和如上对于层(b)所述的层通过接触组装,例如通过将(a)和(b)压在一起而这两个层之间没有粘附的多层组合物不在本发明范围之内。
在本发明的上下文中,术语“氟聚合物杂合物”、“无机/有机组合物”以及“溶胶-凝胶杂合物”表示包含通过使衍生自化合物(M)的无机残基和衍生自共聚物(F)的-O-Rx和/或-C(O)O-Rx的基团交联而形成的有机/无机网络的组合物。该涂层(b)的溶胶-凝胶杂合物具有在WO 2011/121078 A(苏威苏莱克斯公司(SOLVAY SOLEXIS SPA))3/31/2011中描述的通用结构特征。
术语“多层组件”或“多层材料”在此旨在表示由一系列层(这些层经由至少一侧彼此粘附)中的两种或更多种物质形成的材料。
该涂层(b)的厚度可以取决于预期应用和其中待结合根据本发明的组件的装置的具体设计。优选地,涂层(b)的厚度是从1至100微米、优选地是2至50微米、更优选地是3至40、4至30、5至20或7至10微米、最优选地是从2至5微米。
为了本发明的目的,偏二氟乙烯(VDF)聚合物旨在表示包含衍生自偏二氟乙烯(通常也表示为偏二氟乙烯1,1-二氟乙烯,VDF)的重复单元的聚合物,即,衍生自包括偏二氟乙烯(VDF)的重复单元聚合的聚合物,这些重复单元以相对于该聚合物的总重量不小于40重量%的量存在于最终聚合物中。术语“氟共聚物”或“共聚物”通常表示VDF的共聚物,即,其中衍生自VDF的单元存在并形成小于100%全部重复单元的聚合物。
优选地,共聚物(F)包含不少于50wt%、更优选地不少于65wt%、或70wt%或85wt%的衍生自VDF的重复单元。
该共聚物(F)典型地包含衍生自至少一种具有以下式(II)的(甲基)丙烯酸类单体(MA)的重复单元(R1’):
其中:
-R1、R2和R3,彼此相同或不同,独立地选自氢原子和C1-C3烃基,并且
-ROH是氢原子或包含至少一个羟基的C1-C5烃部分。
共聚物(F)典型地包含至少0.01wt%、优选地至少0.02wt%、更优选地至少0.03wt%的衍生自至少一种具有如上所述的式(II)的(甲基)丙烯酸类单体(MA)的重复单元(R1’)。
共聚物(F)典型地包含至多10wt%、优选地至多5wt%、更优选地至多2wt%的衍生自至少一种具有如上所述的式(II)的(甲基)丙烯酸类单体(MA)的重复单元(R1’)。
该(甲基)丙烯酸类单体(MA)优选地符合以下式(III):
其中:
-R’1、R’2和R’3是氢原子,并且
-R’OH是氢原子或包含至少一个羟基的C1-C5烃部分。
(甲基)丙烯酸类单体(MA)的非限制性实例包括,值得注意地,丙烯酸、甲基丙烯酸、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟乙基己基酯。
该(甲基)丙烯酸类单体(MA)更优选地选自以下项:
-具有下式的丙烯酸羟乙酯(HEA):
-具有以下任一式的丙烯酸2-羟丙酯(HPA):
-以及其混合物。
(甲基)丙烯酸类单体(MA)甚至更优选地是丙烯酸羟乙酯(HEA)。
共聚物(F)优选地包含按摩尔计至少0.05、更优选按摩尔计至少0.1%(即相对于(F)中的这些重复单元的总摩尔数的摩尔数),甚至更优选按摩尔计至少0.2%的衍生自如以上定义的具有式(I)的所述单体(MA)的重复单元。
共聚物(F)优选地包含按摩尔计至多10%、更优选地按摩尔计至多7.5%、甚至更优选地按摩尔计至多5%或按摩尔计至多3%的衍生自如以上定义的具有式(I)的所述单体(MA)的重复单元。
诸位发明人已经发现,当共聚物(F)是直链半结晶共聚物时,获得最佳结果。
术语半结晶旨在表示具有可检测的熔点的聚合物。一般理解为半结晶聚合物具有根据ASTM D 3418确定的熔解热,该熔解热有利地是至少0.4J/g、优选地至少0.5J/g、更优选地至少1J/g。
诸位发明人已经发现,亲水性(甲基)丙烯酸类单体(MA)在共聚物(F)的聚偏二氟乙烯主链内的基本上随机分布有利地最大化了改性单体(MA)对所得共聚物的粘附性和/或亲水性行为二者的作用(甚至在组合物中的亲水性(甲基)丙烯酸类单体(MA)低水平的情况下)而没有损害偏二氟乙烯聚合物的其他出色的特性,例如热稳定性和机械特性。
共聚物(F)可以有利地是直链共聚物,也就是说它可以由来自VDF单体和(MA)单体的重复单元的基本上直链序列制成的大分子构成;共聚物(F)因此可与接枝的和/或梳状聚合物区分开。
共聚物(F)有利地具有改进的耐热性。特别地,聚合物(F)在超过350℃、优选地超过360℃、更优选地超过380℃的温度下,按照ISO 11358标准,在氮气下在TGA分析中经受1%wt的重量损失。
除了衍生自如上定义的单体(R1’)的那些之外,共聚物(F)可以包含至少衍生自另一种单体(R2’)的重复单元。
此种单体(R2’)可以包括至少一种常规使用的与偏二氟乙烯可共聚的单体,例如但不限于氟乙烯、三氟乙烯、三氟氯乙烯(CTFE)、四氟乙烯(TFE)、六氟丙烯(HFP)以及氟烷基乙烯基醚及其混合物。在任何情况下,优选的是偏二氟乙烯在共聚物(F)中的量是至少70mol%,以便不会损害偏二氟乙烯树脂的优异特性,例如耐化学性、耐气候性、以及耐热性。共聚单体(R2)的量相对于共聚物(F)中的重复单元的总摩尔数是优选地低于10mol%、更优选地低于5mol%或低于2mol%。更优选地,共聚物(F)是由如以上定义的偏二氟乙烯(VDF)、HFP以及HEA的重复单元形成的三元共聚物。
除了共聚物(F)和电解质盐(ES-1)、如以上定义的具有式(I)的化合物(M)、以及离子液体(IL-1)之外,组合物(C)还可以任选地包含至少一种其他组分。优选地,所述至少一种任选的组分选自消泡剂、表面活性剂、抗菌剂、填充剂以及其混合物。典型地,当存在时,此类任选的组分的量是相对于组合物(C)的重量低于15wt%、优选地低于10wt%、7wt%、5wt%或3wt%。
在优选的实施例中,金属层(a)由锂金属或锂金属合金组成,包括被层压在铜上、例如铜箔上的锂金属。
优选地,根据本发明的多层组件,层(b)衍生自以下反应,其中化合物(M)是烷氧基硅烷(任选地在烷氧基链上带有官能团),其中每个X基团可以与其他X基团相同或不同并且是C1-C8烷基链,更优选地其中(M)是四甲氧基硅烷(TMOS)、四乙氧基硅烷(TEOS)、3-(三乙氧基甲硅烷基)丙基异氰酸酯(TSPI)或其混合物。最优选地,该化合物(M)是3-(三乙氧基甲硅烷基)丙基异氰酸酯(TSPI)或TSPI与TEOS的混合物。
优选地,在本发明的多层组合物中,带有官能团的烷氧基硅烷(更优选是TSPI)的摩尔量是在多层组合物中存在的共聚物(F)的(MA)单体的从80%至120%。
在本发明的上下文中,术语“官能团”表示与烷基链和芳环不同的化学部分,该化学部分可以是原子、或者原子团,每当其在不同化合物中存在时具有相似化学特性,定义了有机化合物族的特征物理和化学特性(根据第2版国际纯粹与应用化学协会金皮书(IUPACGold Book 2nd Edition)的定义),并且该化学部分可以任选地反应以形成官能化的或交联的物种。官能团的非限制性实例是异氰酸酯、氰酸酯、氰基、酯、酰胺、羧酸、胺、卤化物。优选地,在根据本发明的多层组件中,(b)包含至少一种选自以下项的固体无机填充剂:无机氧化物(优选SiO2、TiO2、ZnO、Al2O3和混合氧化物),碱金属或碱土金属硫酸盐,碳酸盐,硫化物或其混合物。
优选地,在根据本发明的多层组件中,电解质盐(ES-1)(当存在时)是锂盐、优选双三氟甲烷磺酰亚胺锂和/或双(氟磺酰)亚胺锂。
优选地,在根据本发明的多层组件中,离子液体(IL)选自以下那些:包含锍离子或咪唑鎓、吡啶鎓、吡咯烷鎓或哌啶鎓环作为阳离子,所述环任选地在氮原子上被取代,并且包含选自卤素阴离子、全氟化阴离子和硼酸根的那些作为阴离子,优选地其中(IL)是Pyr13TFSI(N-丙基-N-甲基吡咯烷鎓双(三氟甲烷磺酰)亚胺)。
在另一个实施例中,本发明提供了一种用于制备如以上定义的多层组件的方法,该方法包括以下步骤:
i.提供金属层(a),该金属层基本上由锂金属、钠金属、镁金属、锌金属、或它们与硅或锡的合金组成;
ii.提供具有式(I)的化合物(M)
X4-mAYm (I)
其中X是烃基,任选地包含一个或多个官能团,m是从1至4的整数,A是选自由Si、Ti和Zr组成的组的元素,并且Y是选自由烷氧基、酰氧基和羟基组成的组的可水解基团;
iii.将(M),任选地呈与电解质盐(ES-1)和/或离子液体(IL-1)的混合物形式,与包含液体介质(L1)和至少一种氟共聚物(F)的组合物(C-1)混合以获得组合物(C),该氟共聚物包含衍生自偏二氟乙烯(VDF)的重复单元和至少衍生自具有至少一个基团–O-Rx和/或–C(O)O-Rx的单体(R1’)的重复单元,其中每个Rx任选地彼此独立地是氢基团或包含至少一个羟基的C1-C5烃基;
iv用在步骤iii.中获得的该组合物(C)涂覆层(a)的至少一侧;
v.除去该液体介质(L1)以获得多层材料,其中衍生自化合物(M)的无机残基与衍生自共聚物(F)的–O-Rx和/或–C(O)O-Rx的基团键合。
典型地使用溶剂体系来将聚合物粘合剂分散在用于涂覆金属层的组合物中,该溶剂体系一般包含极性非质子有机溶剂或至少含有极性非质子有机溶剂的混合物。
优选地,在本发明的方法中,组合物(C-1)至少包含非质子有机溶剂,该非质子有机溶剂包括但不限于环醚和线性醚例如四氢呋喃(THF),二甲亚砜(DMSO),碳酸亚烷基酯例如碳酸亚乙酯或碳酸亚丙酯,乙二醇或丙二醇的烷基醚(“二醇醚”或“甘醇二甲醚”),以及其混合物。
优选地,在步骤iii中将电解质盐(ES-1)与离子液体(IL-1)和化合物(M)混合以获得电解质组合物(EC-1)。
可以根据本领域技术人员已知的任何方法进行金属层(a)的涂覆,例如流延、刮刀涂覆(doctor blading)、模涂(die coating)、逆辊涂覆、凹版涂覆、喷涂、迈耶(Mayer)棒涂覆以及本领域技术人员已知的相似技术。
在另一个实施例中,如以上定义的多层组件与通常用于电化学装置中的隔膜的多孔基底组合使用,以提供适用于电化学装置的隔膜和如上所述的涂覆有层(b)的金属层(a)的组件。
在另一个实施例中,本发明提供了一种包含如以上定义的多层组件的电化学电池。
优选地,所述电化学电池呈可再充电的锂金属电池或锂金属原电池的形式。
术语“电化学电池”在此旨在表示电化学组件,该电化学组件包括正极,负极和液态、固态或凝胶态电解质,以及置于所述电极之间的单层或多层隔膜。
合适的电化学装置的非限制性实例值得注意地包括二次电池、尤其是碱金属或碱土金属二次电池,如锂离子电池,以及电容器,尤其是锂离子基电容器和双电层电容器(“超级电容器”)。
如果通过援引方式并入本申请的任何专利、专利申请、和公开物的披露内容与本申请的说明相冲突到了可能导致术语不清楚的程度,则本说明应该优先。
提供以下实例以说明本发明的实际实施例,而不旨在限制其范围。
实验部分
原材料
-锂金属萡(西格玛公司(Sigma)),厚度0.38mm,纯度99.9%
-锂盐:双(三氟甲烷磺酰)亚胺锂(LiTFSI)(苏威公司(Solvay)),纯度>99.9%
-原硅酸四乙酯(西格玛公司),纯度≥99.0%
-甲酸(西格玛公司),纯度≥98%
–离子液体:N-丙基-N-甲基吡咯烷鎓双(三氟甲烷磺酰)亚胺纯度99.5%
-3-(三乙氧基甲硅烷基)丙基异氰酸酯(TSPI)(西格玛公司),纯度>94.5%
-乙酰丙酮锰(III)(西格玛公司),工业级
-THF四氢呋喃(卡劳尔巴公司(Carlo Erba)),>99.9%
-DMSO二甲亚砜(西格玛公司),>99.9%
-DMF N,N-二甲基甲酰胺(西格玛公司),>99.8%
-丙酮(卡劳尔巴公司),>99.6%
-LFP(LiFePO4)LifeP2(菲斯特克公司(Phostec)),LFP>90%,碳0-4%
-SuperC65(伊美瑞公司(Imerys))碳含量>99.5wt.%
-PVDF-HFP-HEA(三元共聚物)
用于将离子杂合的(ionobrid)或杂合的PVDF涂覆在锂金属上的通用程序
体系I:杂合的PVDF三元共聚物(溶胶-凝胶)+电解质溶液
体系H:仅杂合的PVDF三元共聚物(溶胶-凝胶)
F聚合物溶液(5wt%)的制备
将分子筛放置在THF中以去除任何痕量的水。在回流下在45℃将PVDF三元共聚物PVDF-HFP-HEA(F)溶解在THF中。然后将该溶液冷却至室温。然后添加Mn(III)AA(TSPI在PVDF-HEA上的联接反应的催化剂)并且在室温(RT)下混合10min。添加TSPI并且将该溶液在回流下在60℃下加热90min,并且然后将其冷却至室温(RT)。
20g的PVDF溶液包含:
表1
PVDF | THF | TSPI | Mn(III)AA | |
重量(g) | 1.0 | 19.00 | 0.043 | 0.006 |
电解质溶液的制备
电解质溶液:在PYR13TFSI中0.5M LiTFSI
在手套箱内的玻璃瓶中制备该电解质溶液。将PYR13TFSI和LiTFSI储存在该手套箱中。离子液体通常在将其引入手套箱之前脱气。一旦制备好,在环境气氛下储存该电解质溶液。如此获得的电解质溶液在25℃下具有2.4×10-3S/cm的离子电导率。
体系I和H的制备
将如上所述获得的F聚合物溶液放置在手套箱内的瓶中。将TEOS和(仅用于体系I)电解质添加到该溶液中并在RT下混合15min。
体系I
表2
F聚合物溶液 | TEOS | ES | |
重量(g) | 10.782 | 0.490 | 1.000 |
体系H
表3
F聚合物溶液 | TEOS | |
重量(g) | 20.00 | 0.909 |
溶液在锂金属上的流延
在手套箱或干燥室中制备此第三部分。将该溶液在锂金属上流延,在室温下将其干燥10min并且然后在100℃下加热20min。
实例
实例1:涂覆于锂上的5μm离子混杂的膜。体系I[75/25]/64包含64vol%电解质溶液和两种硅烷TSPI+TEOS。PVDF与无机-有机杂合物(从溶胶-凝胶反应中获得)的含硅无机部分的体积比是75:25。
实例2:涂覆于锂上的5μm杂合的PVDF薄膜。体系H[75/25]/0包含两种硅烷TSPI+TEOS(无电解质溶液)。PVDF与无机-有机杂合物(从溶胶-凝胶反应中获得)的含硅无机部分的体积比是75:25。
对比实例1:涂覆于锂上的5μm PVDF致密层。仅PVDF三元共聚物(无硅烷)
对比实例2:在锂金属阳极上无保护层
离子电导率的测量
将独立式聚合物层浸入SelectilyteTMLP30电解质碳酸亚乙酯/碳酸二甲酯1:1LiPF61M电解质中持续24h。然后将其放置在1/2英寸不锈钢世伟洛克(Swagelok)电池原型中。测量该聚合物层的电阻并且使用以下方程获得离子电导率
其中d是薄膜的厚度,Rb是体电阻并且S是不锈钢电极的面积。
用玻璃电池(glass cell)测量锂枝晶生长
锂枝晶测试的目的是在对锂枝晶形成和穿透的抵抗性方面区分不同的聚合物锂涂层。该测试是在两电极玻璃电池中进行的,该电池具有聚合物涂覆的锂圆盘工作电极(直径14mm)和锂对电极(锂源);将东燃(Tonen)聚丙烯标准Li离子电池隔膜(厚度20微米)放置在工作电极上并且通过用金属螺丝闭合该电池而将其紧固在该电极上;用电解质碳酸亚乙酯/碳酸二甲酯1:1LiPF61M浸渍该隔膜。在距离约10mm处放置对电极。将该对电极、工作电极以及隔膜浸入附加的电解质碳酸亚乙酯/碳酸二甲酯1:1LiPF6 1M中,以便使所有电池部件能够离子接触。在这两个电极之间施加-10mA的恒定电流,使锂沉积在工作电极上。因为该电池是由玻璃制成的,所以可以通过目视检查评估锂枝晶通过隔膜的演变。当锂枝晶从隔膜表面变得可见时停止该测试:更长的测试持续时间与更有抵抗力的涂层相关。
锂枝晶生长
对于不同的锂电极,枝晶穿透该隔膜是可见的之前的时间(以小时计)在表1中报告。
表4
表4中的数据表明在根据本发明的电池中,枝晶的生长显著低于包含未涂覆的锂金属阳极的电池中的枝晶的生长。
钮扣电池测试
电池的制造
电池是由受保护的锂金属、隔膜、电解质和正极构成。
该隔膜是由型F20BMU制成的微孔膜。在将该膜用于电池之前,将其在80℃在真空下干燥18小时。
LFP(正极):82%LiFePO4/10%super C65/8%5130PVDF,负载=0.6mAh/cm2。Super C65:碳粉
将该正极在130℃下在真空下干燥持续一夜。
将电极和隔膜放置在氩气氛中(无氧,0%湿度)。将150μL电解质SelectilyteTMLP30(碳酸亚乙酯/碳酸二甲酯1:1LiPF61M)添加到该隔膜中。
然后将膜放置在钮扣电池中的该正极与该涂覆的锂金属层(在对比实例2中未涂覆的)之间,并且在室温下对其进行测试。
表5
IC=离子电导率
钮扣电池测试(平均放电)
表6
表6中的数据表明,根据本发明的电池的性能与包含未涂覆的锂金属阳极的电池的性能是可比较的。在高C-倍率下,用本发明获得的性能显著好于用PVDF聚合物涂覆的阳极。
Claims (13)
1.一种多层组件,该多层组件包括:
-金属层(a),该金属层基本上由锂金属、钠金属、镁金属、锌金属、它们与硅或锡的合金组成,所述金属层(a)包含第一表面和第二表面;
-涂层(b),该涂层粘附到金属层(a)的所述第一表面和第二表面中的至少一个上,
其中,(b)包含杂合无机/有机组合物,该组合物通过使以下项反应而获得:
i.具有式(I)的化合物(M)
X4-mAYm (I)
其中X是烃基,任选地包含一个或多个官能团,m是从1至4的整数,A是选自由Si、Ti和Zr组成的组的元素,并且Y是选自由烷氧基、酰氧基和羟基组成的组的可水解基团,以及
ii.至少一种氟共聚物(F),该氟共聚物包含衍生自偏二氟乙烯(VDF)的重复单元和至少衍生自具有至少一个基团–O-Rx和/或–C(O)O-Rx的单体(R1’)的重复单元,其中每个Rx任选地彼此独立地是氢基团或包含至少一个羟基的C1-C5烃基,
其中,通过所述化合物(M)与所述氟共聚物(F)的反应,衍生自化合物(M)缩聚的无机残基经由与共聚物(F)的基团-O-Rx和/或–C(O)O-Rx的反应而至少部分地化学键合到共聚物(F)上,并且其中(b)任选地包含:
iii.电解质盐(ES-1)和/或
iv.离子液体(IL-1)。
2.根据权利要求1所述的多层组件,其中,层(b)是通过使共聚物(F)与化合物(M)反应获得的,该化合物(M)是烷氧基硅烷、任选地在烷氧基链上带有官能团,优选地四甲氧基硅烷(TMOS)、四乙氧基硅烷(TEOS)、3-(三乙氧基甲硅烷基)丙基异氰酸酯(TSPI)或其混合物。
3.根据前述权利要求中任一项所述的多层组件,其中,(b)包含至少一种选自以下项的固体无机填充剂:无机氧化物,优选地SiO2、TiO2、ZnO、Al2O3和混合氧化物,碱金属或碱土金属硫酸盐,碳酸盐,硫化物或其混合物。
4.根据前述权利要求中任一项所述的多层组件,其中,该单体(R1’)是具有式(II)的(甲基)丙烯酸类单体:
其中,R1、R2和R3中的每一个,彼此相同或不同,独立地是氢原子或C1-C3烃基,并且RX是氢原子或包含至少一个羟基的C1-C5烃部分。
5.根据前述权利要求中任一项所述的多层组件,其中,该氟共聚物(F)进一步至少包含不同于(R1’)的单体(R2’)。
6.根据权利要求5所述的多层组件,其中,该共聚物(F)中的该至少一种单体(R2’)选自氟乙烯、三氟乙烯、三氟氯乙烯、四氟乙烯、六氟丙烯、氟烷基乙烯基醚以及它们的混合物。
7.根据前述权利要求中任一项所述的多层组件,其中,该电解质盐(ES-1)是锂盐,优选地是双三氟甲烷磺酰亚胺锂和/或双(氟磺酰)亚胺锂。
8.根据前述权利要求中任一项所述的多层组件,其中,该离子液体(IL)选自以下那些:包含锍离子或咪唑鎓、吡啶鎓、吡咯烷鎓或哌啶鎓环作为阳离子,所述环任选地在氮原子上被取代,并且包含选自卤素阴离子、全氟化阴离子和硼酸根的那些作为阴离子,优选地其中(IL)是Pyr13TFSI(N-丙基-N-甲基吡咯烷鎓双(三氟甲烷磺酰)亚胺)。
9.一种用于制备根据前述权利要求中任一项所述的多层组件的方法,该方法包括以下步骤:
i.提供包含第一表面和第二表面的金属层(a);
ii.提供具有式(I)的化合物(M)
X4-mAYm (I)
其中X是烃基,任选地包含一个或多个官能团,m是从1至4的整数,A是选自由Si、Ti和Zr组成的组的元素,并且Y是选自由烷氧基、酰氧基和羟基组成的组的可水解基团;
iii.将(M),任选地呈与电解质盐(ES-1)和/或离子液体(IL-1)的混合物形式,与包含液体介质(L1)和至少一种氟共聚物(F)的组合物(C-1)混合以获得组合物(C),该氟共聚物包含衍生自偏二氟乙烯(VDF)的重复单元和至少衍生自具有至少一个基团–O-Rx和/或–C(O)O-Rx的单体(R1’)的重复单元,其中每个Rx任选地彼此独立地是氢基团或包含至少一个羟基的C1-C5烃基;
iv.用在步骤iii中获得的该组合物(C)涂覆层(a)的所述第一表面和第二表面中的至少一个,以便获得潮湿的涂层;
v.除去该液体介质(L1)以获得多层材料,其中衍生自化合物(M)的无机残基与衍生自共聚物(F)的–O-Rx和/或–C(O)O-Rx的基团键合。
10.如权利要求9所述的方法,其中,该组合物(C-1)至少包含非质子有机溶剂,该非质子有机溶剂包括环醚和线性醚例如四氢呋喃(THF),二甲亚砜(DMSO),碳酸亚烷基酯例如碳酸亚乙酯或碳酸亚丙酯,乙二醇或丙二醇的烷基醚,及其混合物。
11.如权利要求9或10所述的方法,其中,在步骤iii.中,将该组合物(C-1)与电解质盐(ES-1)、离子液体(IL-1)或(ES-1)与(ES-2)的混合物的电解质组合物(EC-1)混合。
12.一种电化学电池,包括如权利要求1-8所述的多层组件。
13.根据权利要求12所述的电化学电池,该电化学电池呈可再充电的锂金属电池或锂金属原电池的形式。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1359165A (zh) * | 2000-12-13 | 2002-07-17 | 住友电气工业株式会社 | 形成无机固体电解质薄膜的方法 |
CN101501897A (zh) * | 2006-08-10 | 2009-08-05 | 奥克斯能源有限公司 | 带有金属锂电极的电池或电池组以及用于该电池或电池组的电解质 |
CN102315420A (zh) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | 具有保护层的金属负极结构及其制备方法 |
CN102881862A (zh) * | 2011-07-12 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | 保护性金属阳极结构及其制备方法 |
CN102918070A (zh) * | 2010-04-02 | 2013-02-06 | 索尔维特殊聚合物意大利有限公司 | 基于氟聚合物的杂化有机/无机复合物 |
CN103620819A (zh) * | 2011-06-23 | 2014-03-05 | 索尔维特殊聚合物意大利有限公司 | 用于制造电池部件的方法 |
CN103748154A (zh) * | 2011-07-15 | 2014-04-23 | 索尔维特殊聚合物意大利有限公司 | 用于多层组件的氟聚合物组合物 |
WO2014086906A1 (en) * | 2012-12-05 | 2014-06-12 | Solvay Specialty Polymers Italy S.P.A. | Solid composite fluoropolymer layer |
CN104321922A (zh) * | 2012-04-23 | 2015-01-28 | 索尔维公司 | 含氟聚合物膜 |
CN104520341A (zh) * | 2012-08-06 | 2015-04-15 | 索尔维特殊聚合物意大利有限公司 | 混杂的含氟聚合物组合物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6537701B1 (en) | 1998-09-03 | 2003-03-25 | Polyplus Battery Company, Inc. | Coated lithium electrodes |
JP2007226974A (ja) | 2006-02-21 | 2007-09-06 | Pionics Co Ltd | リチウムイオン二次電池 |
FR2942235B1 (fr) * | 2009-02-13 | 2011-07-22 | Centre Nat Rech Scient | Gels conducteurs ioniques, leur procede de preparation et leur utilisation comme electrolyte |
JP5702362B2 (ja) * | 2010-03-19 | 2015-04-15 | 第一工業製薬株式会社 | イオン液体を用いたリチウム二次電池 |
JP5545728B2 (ja) * | 2010-05-07 | 2014-07-09 | 国立大学法人三重大学 | リチウム二次電池及びリチウム二次電池用の複合負極 |
US20120082901A1 (en) * | 2010-09-30 | 2012-04-05 | Basf Se | Lithium-based anode with ionic liquid polymer gel |
KR102005448B1 (ko) * | 2012-09-13 | 2019-07-31 | 삼성전자주식회사 | 리튬전지 |
MY187115A (en) | 2014-05-07 | 2021-09-02 | Solvay | Hybrid fluoropolymer composites |
-
2017
- 2017-02-14 CN CN201780012180.7A patent/CN108701819B/zh active Active
- 2017-02-14 US US15/999,644 patent/US11777081B2/en active Active
- 2017-02-14 WO PCT/EP2017/053225 patent/WO2017140649A1/en active Application Filing
- 2017-02-14 KR KR1020187026107A patent/KR20180114112A/ko unknown
- 2017-02-14 EP EP17704029.2A patent/EP3417501B1/en active Active
- 2017-02-14 JP JP2018543592A patent/JP7254516B2/ja active Active
-
2022
- 2022-03-08 JP JP2022035319A patent/JP2022088424A/ja active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1359165A (zh) * | 2000-12-13 | 2002-07-17 | 住友电气工业株式会社 | 形成无机固体电解质薄膜的方法 |
CN101501897A (zh) * | 2006-08-10 | 2009-08-05 | 奥克斯能源有限公司 | 带有金属锂电极的电池或电池组以及用于该电池或电池组的电解质 |
CN102918070A (zh) * | 2010-04-02 | 2013-02-06 | 索尔维特殊聚合物意大利有限公司 | 基于氟聚合物的杂化有机/无机复合物 |
CN102315420A (zh) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | 具有保护层的金属负极结构及其制备方法 |
CN103620819A (zh) * | 2011-06-23 | 2014-03-05 | 索尔维特殊聚合物意大利有限公司 | 用于制造电池部件的方法 |
CN102881862A (zh) * | 2011-07-12 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | 保护性金属阳极结构及其制备方法 |
CN103748154A (zh) * | 2011-07-15 | 2014-04-23 | 索尔维特殊聚合物意大利有限公司 | 用于多层组件的氟聚合物组合物 |
CN104321922A (zh) * | 2012-04-23 | 2015-01-28 | 索尔维公司 | 含氟聚合物膜 |
CN104520341A (zh) * | 2012-08-06 | 2015-04-15 | 索尔维特殊聚合物意大利有限公司 | 混杂的含氟聚合物组合物 |
WO2014086906A1 (en) * | 2012-12-05 | 2014-06-12 | Solvay Specialty Polymers Italy S.P.A. | Solid composite fluoropolymer layer |
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