CN111786017A - High-cohesiveness solid electrolyte prepared by in-situ curing, preparation method and application - Google Patents
High-cohesiveness solid electrolyte prepared by in-situ curing, preparation method and application Download PDFInfo
- Publication number
- CN111786017A CN111786017A CN202010302768.XA CN202010302768A CN111786017A CN 111786017 A CN111786017 A CN 111786017A CN 202010302768 A CN202010302768 A CN 202010302768A CN 111786017 A CN111786017 A CN 111786017A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid electrolyte
- slurry
- diaphragm
- cohesiveness
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910003002 lithium salt Chemical group 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical group 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 26
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 19
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 10
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 8
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 229910013461 LiZr2(PO4)3 Inorganic materials 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 4
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 4
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 claims description 4
- 229910010685 Li5La3M2O12 Inorganic materials 0.000 claims description 4
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 42
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002513 isocyanates Chemical group 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 229910052786 argon Inorganic materials 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 15
- 230000002238 attenuated effect Effects 0.000 description 13
- 239000008187 granular material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 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 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KPMKEVXVVHNIEY-NTSWFWBYSA-N (1s,4r)-bicyclo[2.2.1]heptan-3-one Chemical compound C1C[C@H]2C(=O)C[C@@H]1C2 KPMKEVXVVHNIEY-NTSWFWBYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a solid electrolyte, in particular to a high-cohesiveness solid electrolyte prepared by in-situ solidification, a preparation method and a secondary lithium battery formed by the high-cohesiveness solid electrolyte. The high-cohesiveness solid electrolyte is prepared by mixing and uniformly stirring a low polymer containing terminal hydroxyl, a compound containing terminal isocyanate and a lithium salt, adding the mixture into a cell, and carrying out in-situ polymerization and solidification under a heating condition. The electrolyte prepared by in-situ curing has high adhesive force, and is cured under heating, so that the positive electrode, the negative electrode and the electrolyte are tightly attached, the interface impedance between the electrolyte and the positive electrode and the negative electrode is reduced, and the effects of improving the multiplying power performance and the cycle performance of the battery are achieved. The preparation process of the solid-state lithium battery is greatly simplified, the interface contact is optimized, the risk of dislocation is prevented, and the safety of the battery is improved.
Description
Technical Field
The invention relates to a solid electrolyte, in particular to a high-cohesiveness solid electrolyte prepared by in-situ solidification, a preparation method and an application thereof in a secondary lithium battery.
Background
The lithium ion battery has the advantages of high voltage, low self-discharge rate, high energy density and the like, so the lithium ion battery gradually replaces the continuously expanded application field of the traditional battery. However, with the increasing energy density of lithium ion batteries and the upsizing of energy storage modules, the potential safety hazard of lithium ion batteries is always the first problem to be solved by researchers. The electrolyte is one of the key components of a high specific energy secondary lithium battery. Although the electrode material is a prerequisite for determining the energy density of a secondary lithium battery, the energy density is related to the reaction kinetics, the cycle stability and the safety thereof, which are directly related to the electrolyte. At present, the secondary lithium battery mainly uses liquid electrolyte, and the secondary lithium battery using the liquid electrolyte has potential safety hazards of internal short circuit, liquid leakage, combustion, even explosion and the like. In order to solve the above problems, researchers have proposed the idea of replacing the conventional liquid organic electrolyte with a solid electrolyte.
Solid state lithium batteries generally include two broad categories, the first category being inorganic solid state lithium batteries and the second category being solid state polymer lithium batteries. Solid electrolytes in solid polymer lithium batteries are mainly composed of polymers, lithium salts and fillers, for example, CN 104779415a provides an all-solid polymer electrolyte prepared by cross-linking polymerization of siloxane and polyethylene glycol under hot-pressing conditions; CN 102738510a provides a composite all-solid-state electrolyte, which comprises polyethylene oxide and/or polyethylene oxide derivatives, organic-inorganic hybrid framework compounds and lithium salts. All the solid polymer electrolytes are prepared by a method of preparing a polymer film in advance and then assembled into a battery together with positive and negative pole pieces of the battery in a winding or laminating mode, so that the solid/solid interface impedance between the pole pieces of the battery and the solid electrolyte is very large, and the charge and discharge performance, the multiplying power and the cycle performance of the solid battery are poor.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a high-cohesiveness solidified electrolyte prepared by in-situ solidification, a preparation method and application thereof in a secondary lithium battery.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the high-cohesiveness solid electrolyte is prepared by uniformly mixing and stirring a low polymer containing terminal hydroxyl, a compound containing terminal isocyanate and a lithium salt, adding the mixture into a cell, and carrying out in-situ polymerization and solidification under a heating condition.
The oligomer containing the terminal hydroxyl is one with any one of the following structural characteristics:
wherein n is an integer within 2-200, and m is an integer within 2-200;
R1，R2，R3is one of the following structures:
R4has a structural general formula of CnH2n+1N is an integer of 1-4;
the compound containing the terminal isocyanate group is one of the following structures:
wherein n is an integer within 1-20, and m is an integer within 1-20;
R1，R2and R3Is one of the following structures:
the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluorosulfonimide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium polyborate.
The mass fraction of the hydroxyl-terminated oligomer in the raw material is 30-80%, the mass fraction of the isocyanate-terminated compound in the raw material is 10-60%, and the mass fraction of the lithium salt in the raw material is 5-30%.
When the lithium salt contains at least one of lithium difluorooxalato borate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium dioxalate borate and lithium hexafluorophosphate, the high-adhesion solid electrolyte raw material needs to be added with a catalyst, and if the catalyst is not added, the high-adhesion solid electrolyte raw material cannot be cured and polymerized under a heating condition. The mass fraction of the catalyst in the raw material is 0.01-1%. Under the condition of using other lithium salts, the lithium salt can be directly cured by heating or by heating with a catalyst, wherein the mass fraction of the catalyst in the raw materials is 0-1%.
The catalyst is dibutyltin dilaurate, bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, organic bismuth or triazine trimerization catalyst.
The high-cohesiveness solid electrolyte raw material also comprises a filler and/or a micromolecular organic matter, wherein the mass fraction of the filler in the raw material is 0-20%, and the mass fraction of the micromolecular organic matter in the raw material is 0-20%.
The filler is Li7La3Zr2O12、Li10GeP2S12、Li5.5La3Nb1.75、In0.25O12、Li3N, LiX (X = Cl, Br or I), Li14Zn(GeO4)4、Li5La3M2O12(M = Ta or Nb), LiZr2(PO4)3The filler is in the shape of nanoparticles, and the particle size of the nanoparticles is 1 nm-1 mu m.
The micromolecular organic matter is one or more of succinonitrile, adiponitrile, ionic liquid, ethylene carbonate, methyl ethyl carbonate, propylene carbonate, vinylene carbonate, ethyl acetate, n-butyl acetate, fluorinated propylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, methyl ethyl sulfone, dimethyl sulfone and diethyl sulfone.
The invention also provides a preparation method of the high-cohesiveness solid electrolyte, which comprises the following steps:
a. adding lithium salt into the oligomer containing terminal hydroxyl groups for dissolving, then adding a compound containing terminal isocyanate groups, and stirring uniformly at room temperature to obtain slurry;
b. and (b) injecting the slurry obtained in the step (a) into a battery cell, and carrying out in-situ polymerization for 0.5-10h at the temperature of 20-90 ℃ for curing.
When the high-viscosity solid electrolyte raw material also comprises a filler and/or a small molecular organic matter, the step a is to add lithium salt into the oligomer containing terminal hydroxyl or the oligomer containing terminal hydroxyl and the small molecular organic matter for dissolving, sequentially add the compound containing terminal isocyanate group or the compound containing terminal isocyanate group and the filler, and stir the mixture evenly at room temperature to form slurry.
The oligomer containing the terminal hydroxyl is one with any one of the following structural characteristics:
wherein n is an integer within 2-200, and m is an integer within 2-200;
R1，R2，R3is one of the following structures:
R4has a structural general formula of CnH2n+1N is an integer of 1-4;
the compound containing the terminal isocyanate group is one of the following structures:
wherein n is an integer within 1-20, and m is an integer within 1-20;
R1，R2and R3Is one of the following structures:
the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluorosulfonimide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium polyborate;
the filler is Li7La3Zr2O12、Li10GeP2S12、Li5.5La3Nb1.75、In0.25O12、Li3N, LiX (X = Cl, Br or I), Li14Zn(GeO4)4、Li5La3M2O12(M = Ta or Nb), LiZr2(PO4)3The filler is in the shape of nanoparticles, wherein the particle size of the nanoparticles is 1 nm-1 mu m;
the micromolecular organic matter is one or more of succinonitrile, adiponitrile, ionic liquid, ethylene carbonate, methyl ethyl carbonate, propylene carbonate, vinylene carbonate, ethyl acetate, n-butyl acetate, fluoropropylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, methyl ethyl sulfone, dimethyl sulfone and diethyl sulfone;
the mass fraction of the hydroxyl-terminated oligomer in the slurry is 30-80%, the mass fraction of the isocyanate-terminated compound in the slurry is 10-60%, the mass fraction of the lithium salt in the slurry is 5-30%, the mass fraction of the filler in the slurry is 0-20%, and the mass fraction of the small molecular organic matter in the slurry is 0-20%.
The step a also comprises adding a catalyst, wherein the mass fraction of the catalyst in the slurry is 0-1%; when the lithium salt is at least one of lithium difluorooxalato borate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium dioxalate borate and lithium hexafluorophosphate, the mass fraction of the catalyst in the slurry is not zero.
A secondary lithium battery comprising a positive electrode, a negative electrode, a high-porosity separator and the above-mentioned high-adhesion solid electrolyte.
The positive electrode is prepared by mixing a positive electrode active material, polyvinylidene fluoride and conductive carbon black, wherein the positive electrode active material is one of lithium iron phosphate, lithium manganate, NCA, NCM ternary material, lithium cobaltate and lithium nickel manganese; the negative electrode is prepared by mixing a negative electrode active material, a binder and conductive carbon black, wherein the negative electrode active material is one of graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene and silicon carbon, and the negative electrode can also be a metal lithium sheet or a metal lithium alloy; the high-porosity diaphragm is one of a cellulose diaphragm, a high-porosity polyethylene diaphragm, a high-porosity polypropylene diaphragm, a glass fiber diaphragm, a polyimide diaphragm, a PEEK diaphragm, a polyolefin non-woven fabric diaphragm, a PVDF diaphragm and a ceramic particle composite non-woven fabric diaphragm, wherein the porosity of the diaphragm is more than 60%.
A method for preparing a secondary lithium battery includes the following steps: preparing a battery cell by winding or laminating a positive pole piece, a high-porosity diaphragm and a negative pole piece, then packaging the battery cell into an aluminum-plastic film, uniformly stirring the high-cohesiveness solid electrolyte raw material into slurry, injecting the slurry into the battery cell, vacuumizing for at least 30 minutes, standing for 24 hours, and carrying out in-situ polymerization for 0.5-10 hours at the temperature of 20-90 ℃ for curing.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Compared with the prior art, the invention has the following advantages:
firstly, the invention adopts the design concept of in-situ condensation polymerization curing, and the terminal hydroxyl-containing oligomer and the terminal isocyanate-containing compound are subjected to condensation reaction to generate a stable urethane bond, the structure has good electrochemical stability and a large amount of intermolecular hydrogen bonds, and has good cohesiveness, and meanwhile, the raw material adopts aliphatic polyol with strong adhesive force, so that the adhesive force of the cured and crosslinked electrolyte is greatly improved, the positive electrode material, the diaphragm and the negative electrode material are fully adhered together, the fragmentation of the active material caused by the change of the battery volume in the charging and discharging process of the battery is inhibited, and the long cycle performance of the battery is improved.
Secondly, the molecular structure of the oligomer containing terminal hydroxyl groups adopted by the invention has a plurality of functional groups for lithium salt dissociation, the transmission effect of lithium ions is improved, and the multiplying power performance of the solid electrolyte is greatly improved, wherein the room-temperature ionic conductivity of the cross-linked solid electrolyte can reach 1 × 10-4S/cm-1-9×10-3Scm-1The potential window reaches 5V.
Thirdly, the solid electrolyte raw material is injected into the battery core, is fully filled between the anode and cathode materials after standing, and greatly improves the interface contact between the anode and cathode active materials and the electrolyte and reduces the interface impedance through in-situ polymerization.
Fourthly, the scheme of in-situ curing is adopted, the preparation process of the solid-state battery is simplified, the consistency and the process stability of the battery are improved, and the production efficiency is greatly improved. Therefore, the battery has wide application prospect in the fields of power batteries and energy storage batteries.
Detailed Description
The present invention will be described in further detail below with reference to comparative examples and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The assembly and test of the secondary lithium battery comprise the following steps:
(1) preparation of positive plate
1) Polyvinylidene fluoride (PVDF) was dissolved in N, N-2-methylpyrrolidone at a solid content of 6%.
2) Mixing a positive active material, a PVDF solution and conductive carbon black according to a mass ratio of 95:2:3, and grinding for at least 3 hours, wherein the positive active material is one of lithium cobaltate, lithium iron phosphate, lithium manganese oxide, lithium nickel manganese oxide and NCM ternary materials.
3) Uniformly coating the obtained slurry on aluminum foil with a thickness of 50-100 μm, and oven drying at 80 deg.C until the content of active substance in positive electrode is less than 10 mg/cm2Rolling, drying in a 120 ℃ vacuum oven, punching, weighing, drying in the 120 ℃ vacuum oven, and putting in a glove box for later use.
4) And (5) cutting according to the size.
(2) Preparation of negative plate
1) Mixing a negative active material, an SBR adhesive and conductive carbon black in a mass ratio of 96:3:1, and grinding for at least 3 hours, wherein the negative active material is one of a metal lithium sheet, a metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene and a silicon carbon negative electrode.
2) Uniformly coating the slurry on copper foil with a thickness of 50-100 μm, drying at 80 deg.C to obtain negative active material with a content of less than 7 mg/cm2Rolling, drying in a 120 ℃ vacuum oven, punching, weighing, drying in the 120 ℃ vacuum oven, and putting in a glove box for later use.
3) And (5) cutting according to the size.
4) The cathode directly adopts lithium foil and is cut according to the size.
(3) Battery assembly
And preparing the battery cell by adopting a winding process or a lamination process. Packaging with an aluminum plastic film, injecting liquid, fully soaking the electrolyte under the vacuum condition, sealing and standing for 24 hours, extracting redundant electrolyte, and heating and curing.
(4) Testing of battery charging and discharging performance
The test method is as follows: and testing the charge and discharge performance of the secondary lithium battery by using a LAND battery charge and discharge instrument.
Examples of highly cohesive in-situ cured electrolytes are as follows:
example 1
In an argon-filled glove box, LiTFSI and LiPF were added6Dissolving the mixture in hydroxyl-terminated oligomer A1 and succinonitrile, stirring for 2 hours to completely dissolve the hydroxyl-terminated oligomer A1 and the succinonitrile, adding isocyanate-terminated compound B1 and porous PMMA particles, stirring fully and uniformly, and finally adding dibutyltin dilaurate, wherein the ratio of the components is shown in Table 1.
And quickly injecting the mixed electrolyte raw materials into the battery core, standing for 24 hours, extracting redundant electrolyte, and heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 850 circles when the capacity retention rate is attenuated to 80%.
TABLE 1
Example 2
In a glove box filled with argon, LiDFOB/LiPF6Dissolving the mixture in oligomer A2 containing terminal hydroxyl and succinonitrile, stirring for 2 hours to completely dissolve the oligomer, adding compound B2 containing terminal isocyanate group and porous PMMA particles, stirring fully and uniformly, and finally adding dibutyltin dilaurate, wherein the proportion of each component is shown in Table 2.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 850 circles when the capacity retention rate is attenuated to 80%.
TABLE 2
Example 3
In a glove box filled with argon, LiDFOB and LiPF6Dissolving the mixture in oligomer A3 containing terminal hydroxyl groups, EC and DEC, stirring for 2 hours to completely dissolve the oligomer, adding compound B2 containing terminal isocyanate groups and porous PMMA particles, stirring fully and uniformly, and finally adding dibutyltin dilaurate, wherein the ratio of the components is shown in Table 3.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle lasts 800 cycles when the capacity retention rate is attenuated to 80%.
TABLE 3
Example 4
In a glove box filled with argon, LiDFOB and LiPF6Dissolving the mixture in hydroxyl-terminated oligomer A4, stirring for 2 hours to completely dissolve the hydroxyl-terminated oligomer A4, adding isocyanate-terminated compound B2 and porous PMMA particles, stirring fully and uniformly, and finally adding dibutyltin dilaurate, wherein the ratio of the components is shown in Table 4.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle lasts 800 cycles when the capacity retention rate is attenuated to 80%.
TABLE 4
Example 5
In a glove box filled with argon, LiDFOB and LiPF6Dissolving in oligomer A5 containing terminal hydroxyl group, and stirring for 2 hr to completeDissolving, and adding the compound B3 containing terminal isocyanate group and Li7La3Zr2O12The granules were thoroughly stirred and homogenized, and finally dibutyltin dilaurate was added, the proportions of the components being shown in Table 5.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the capacity retention rate is attenuated to 80%, and the cycle is 1000 circles.
TABLE 5
Example 6
In a glove box filled with argon, LiDFOB was dissolved in the hydroxyl-terminated oligomer A6, and stirred for 2 hours to completely dissolve it, and then the terminal isocyanate-terminated compound B3 and Li were added7La3Zr2O12The granules were thoroughly stirred and homogenized, and finally dibutyltin dilaurate was added, the proportions of the components being shown in Table 6.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 1100 circles when the capacity retention rate is attenuated to 80%.
TABLE 6
Example 7
In a glove box filled with argon, LiDFOB and LiPF6Dissolving in oligomer A7 containing terminal hydroxyl group and DEC, stirring for 2 hr to dissolve completely, adding compound B4 containing terminal isocyanate group and Li7La3Zr2O12Granulating, stirring, and adding dilauric acidThe ratio of the components of butyltin is shown in Table 7.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at the temperature of 45 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 1500 circles when the capacity retention rate is attenuated to 80%.
TABLE 7
Example 8
In a glove box filled with argon, LiBOB and LiPF were added6Dissolving in oligomer A8 containing terminal hydroxyl group, stirring for 2 hr to dissolve completely, adding compound B4 containing terminal isocyanate group and Li7La3Zr2O12The granules, thoroughly stirred until homogeneous, were finally charged with dibutyltin dilaurate, the ratio of the components being given in Table 8, for example.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long-cycle performance of the NCM811 on the full cell of silicon carbon is tested, and when the capacity retention rate is attenuated to 80%, the cycle is 1200 circles.
TABLE 8
Example 9
In a glove box filled with argon, LiTFSI was dissolved in the hydroxyl-terminated oligomer a9, stirred for 2 hours to be completely dissolved, and then the isocyanate-terminated compound B4 and the porous PMMA particles were added and stirred sufficiently and uniformly, and the proportions of the components were as shown in table 9.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 3 hours at 70 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle lasts 800 cycles when the capacity retention rate is attenuated to 80%.
TABLE 9
Example 10
In a glove box filled with argon, LiDFOB and LiPF6Dissolving in oligomer A10 containing terminal hydroxyl group and tetraglyme, stirring for 2 hr to dissolve completely, adding compound B5 containing terminal isocyanate group and Li7La3Zr2O12The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being given in Table 10.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 1100 circles when the capacity retention rate is attenuated to 80%.
Watch 10
Example 11
In a glove box filled with argon, LiDFOB and LiPF6Dissolving in hydroxyl-terminated oligomer A11 and EMC, stirring for 2 hr to dissolve completely, adding isocyanate-terminated compound B2 and LiZr2(PO4)3The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being given in Table 11.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the capacity retention rate is reduced to 80%, and the cycle is 900 circles.
TABLE 11
Example 12
In an argon-filled glove box, LiTFSI and LiPF were added6Dissolving in oligomer A12 containing terminal hydroxyl group and succinonitrile, stirring for 2 hr to dissolve completely, adding compound B4 containing terminal isocyanate group and Li7La3Zr2O12The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being given in Table 12.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at the temperature of 45 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and when the capacity retention rate is attenuated to 80%, the cycle is 600 circles.
TABLE 12
Example 13
In a glove box filled with argon, LiTFSI was dissolved in the hydroxyl-terminated oligomer A13, stirred for 2 hours to completely dissolve the LiTFSI, and then the isocyanate-terminated compound B6 and Li were added7La3Zr2O12The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being shown in Table 13.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle is 500 circles when the capacity retention rate is attenuated to 80%.
Watch 13
Example 14
In a glove box filled with argon, lithium polyborate was dissolved in the oligomer A14 containing terminal hydroxyl groups and DEC, stirred for 2 hours to completely dissolve it, and then the compound B5 containing terminal isocyanate groups and Li were added7La3Zr2O12The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being given in Table 14.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the capacity retention rate is reduced to 80%, and the cycle is 900 circles.
TABLE 14
Example 15
In a glove box filled with argon, LiBF was put4And LiPF6Dissolving in oligomer A15 containing terminal hydroxyl group, stirring for 2 hr to dissolve completely, adding compound B7 containing terminal isocyanate group and Li7La3Zr2O12The granules were thoroughly stirred until homogeneous, and finally dibutyltin dilaurate was added, the proportions of the components being given in Table 15.
And quickly injecting the mixed electrolyte into the battery core, standing for 24 hours, extracting the redundant electrolyte, and then heating for 2 hours at 50 ℃.
The long cycle performance of the NCM811 on the full cell of silicon carbon is tested, and the cycle lasts 1150 circles when the capacity retention rate is attenuated to 80%.
Watch 15
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (14)
1. The high-cohesiveness solid electrolyte is characterized in that raw materials of the high-cohesiveness solid electrolyte comprise hydroxyl-terminated oligomer, isocyanate-terminated compound and lithium salt, and the high-cohesiveness solid electrolyte is prepared by uniformly mixing and stirring the hydroxyl-terminated oligomer, the isocyanate-terminated compound and the lithium salt, adding the mixture into a battery cell, and carrying out in-situ polymerization and solidification under heating conditions.
2. A highly adhesive solid electrolyte as defined in claim 1, wherein said hydroxyl terminated oligomer is one having any one of the following structural features:
wherein n is an integer within 2-200, and m is an integer within 2-200;
R1，R2，R3is one of the following structures:
R4has a structural general formula of CnH2n+1N is an integer of 1-4;
the compound containing the terminal isocyanate group is one of the following structures:
wherein n is an integer within 1-20, and m is an integer within 1-20;
R1，R2and R3Is one of the following structures:
the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluorosulfonimide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium polyborate.
3. The high-adhesiveness solid electrolyte according to claim 1, wherein the weight fraction of the hydroxyl-terminated oligomer in the raw material is 30% to 80%, the weight fraction of the isocyanate-terminated compound in the raw material is 10% to 60%, and the weight fraction of the lithium salt in the raw material is 5% to 30%.
4. The high-cohesiveness solid electrolyte of claim 2, wherein the raw material further comprises a catalyst, and the mass fraction of the catalyst in the raw material is 0% to 1%; when the lithium salt is at least one of lithium difluorooxalato borate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium dioxalate borate and lithium hexafluorophosphate, the mass fraction of the catalyst in the raw materials is not zero.
5. A highly binding solid electrolyte as claimed in claim 4, wherein said catalyst is dibutyltin dilaurate, bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine, organobismuth or triazine trimerization catalyst.
6. A high-adhesion solid electrolyte as claimed in any one of claims 1 to 5, wherein the raw material further comprises a filler and/or a small molecular organic substance, the mass fraction of the filler in the raw material is 0 to 20%, and the mass fraction of the small molecular organic substance in the raw material is 0 to 20%.
7. A highly adhesive solid electrolyte as defined in claim 6, wherein said filler is Li7La3Zr2O12、Li10GeP2S12、Li5.5La3Nb1.75、In0.25O12、Li3N, LiX (X = Cl, Br or I), Li14Zn(GeO4)4、Li5La3M2O12(M = Ta or Nb), LiZr2(PO4)3The filler is in the shape of nanoparticles, wherein the particle size of the nanoparticles is 1 nm-1 mu m; the micromolecular organic matter is one or more of succinonitrile, adiponitrile, ionic liquid, ethylene carbonate, methyl ethyl carbonate, propylene carbonate, vinylene carbonate, ethyl acetate, n-butyl acetate, fluorinated propylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, methyl ethyl sulfone, dimethyl sulfone and diethyl sulfone.
8. A method for producing a highly adhesive solid electrolyte as claimed in claim 1, comprising the steps of:
a. adding lithium salt into the oligomer containing terminal hydroxyl groups for dissolving, then adding a compound containing terminal isocyanate groups, and stirring uniformly at room temperature to obtain slurry;
b. and (b) injecting the slurry obtained in the step (a) into a battery cell, and carrying out in-situ polymerization for 0.5-10h at the temperature of 20-90 ℃ for curing.
9. The method of claim 8, wherein the step a comprises adding a lithium salt to the hydroxyl-terminated oligomer or the hydroxyl-terminated oligomer and the small organic molecule, dissolving, sequentially adding the isocyanate-terminated compound or the isocyanate-terminated compound and the filler, and stirring the mixture at room temperature to form a slurry.
10. A method for producing a high-adhesiveness solid electrolyte as claimed in claim 8 or 9, wherein said hydroxyl-terminated oligomer is one having any one of the following structural features:
wherein n is an integer within 2-200, and m is an integer within 2-200;
R1，R2，R3is one of the following structures:
R4has a structural general formula of CnH2n+1N is an integer of 1-4;
the compound containing the terminal isocyanate group is one of the following structures:
wherein n is an integer within 1-20, and m is an integer within 1-20;
R1，R2and R3Is one of the following structures:
the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluorosulfonimide, lithium dioxalate borate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium polyborate;
the filler is Li7La3Zr2O12、Li10GeP2S12、Li5.5La3Nb1.75、In0.25O12、Li3N, LiX (X = Cl, Br or I), Li14Zn(GeO4)4、Li5La3M2O12(M = Ta or Nb), LiZr2(PO4)3The filler is in the shape of nanoparticles, wherein the particle size of the nanoparticles is 1 nm-1 mu m;
the micromolecular organic matter is one or more of succinonitrile, adiponitrile, ionic liquid, ethylene carbonate, methyl ethyl carbonate, propylene carbonate, vinylene carbonate, ethyl acetate, n-butyl acetate, fluoropropylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, methyl ethyl sulfone, dimethyl sulfone and diethyl sulfone;
the mass fraction of the hydroxyl-terminated oligomer in the slurry is 30-80%, the mass fraction of the isocyanate-terminated compound in the slurry is 10-60%, the mass fraction of the lithium salt in the slurry is 5-30%, the mass fraction of the filler in the slurry is 0-20%, and the mass fraction of the small molecular organic matter in the slurry is 0-20%.
11. The method for preparing a high-cohesiveness solid electrolyte of claim 10, wherein the step a further comprises adding a catalyst, wherein the catalyst is present in the slurry in an amount of 0% to 1% by mass; when the lithium salt is at least one of lithium difluorooxalato borate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium dioxalate borate and lithium hexafluorophosphate, the mass fraction of the catalyst in the slurry is not zero.
12. A secondary lithium battery comprising a positive electrode, a negative electrode, a high porosity separator and the high adhesion solid electrolyte of any one of claims 1 to 7.
13. The secondary lithium battery of claim 12, wherein the positive electrode is prepared by mixing a positive active material, polyvinylidene fluoride and conductive carbon black, and the positive active material is one of lithium iron phosphate, lithium manganate, NCA, NCM ternary material, lithium cobaltate and lithium nickel manganate; the negative electrode is prepared by mixing a negative electrode active material, a binder and conductive carbon black, wherein the negative electrode active material is one of graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene and silicon carbon, and the negative electrode can also be a metal lithium sheet or a metal lithium alloy; the high-porosity diaphragm is one of a cellulose diaphragm, a high-porosity polyethylene diaphragm, a high-porosity polypropylene diaphragm, a glass fiber diaphragm, a polyimide diaphragm, a PEEK diaphragm, a polyolefin non-woven fabric diaphragm, a PVDF diaphragm and a ceramic particle composite non-woven fabric diaphragm, wherein the porosity of the diaphragm is more than 60%.
14. A method of manufacturing a secondary lithium battery as claimed in claim 12 or 13, characterized by comprising the steps of: preparing a battery cell by winding or laminating a positive pole piece, a high-porosity diaphragm and a negative pole piece, then packaging the battery cell into an aluminum-plastic film, uniformly stirring the high-cohesiveness solid electrolyte raw material of any one of claims 1 to 7 into slurry, injecting the slurry into the battery cell, vacuumizing for at least 30 minutes, standing for 24 hours, and carrying out in-situ polymerization for 0.5 to 10 hours at the temperature of between 20 and 90 ℃ for curing.
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