CN114512769A - Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery - Google Patents
Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery Download PDFInfo
- Publication number
- CN114512769A CN114512769A CN202011145504.4A CN202011145504A CN114512769A CN 114512769 A CN114512769 A CN 114512769A CN 202011145504 A CN202011145504 A CN 202011145504A CN 114512769 A CN114512769 A CN 114512769A
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- phase monomer
- lithium
- chloride
- sulfur battery
- Prior art date
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- Granted
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 4
- 229920002647 polyamide Polymers 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 116
- 239000012071 phase Substances 0.000 claims description 92
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 42
- 238000012695 Interfacial polymerization Methods 0.000 claims description 38
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 30
- 239000001263 FEMA 3042 Substances 0.000 claims description 30
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 30
- 238000002791 soaking Methods 0.000 claims description 30
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 30
- 229940033123 tannic acid Drugs 0.000 claims description 30
- 235000015523 tannic acid Nutrition 0.000 claims description 30
- 229920002258 tannic acid Polymers 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 235000018553 tannin Nutrition 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- ONTRRCFTZOJJDL-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride;hydrochloride Chemical compound Cl.ClC(=O)C1=CC=CC(C(Cl)=O)=C1 ONTRRCFTZOJJDL-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 claims description 2
- PBWUKDMYLKXAIP-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCCC1(C(Cl)=O)C(Cl)=O PBWUKDMYLKXAIP-UHFFFAOYSA-N 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- TVWGIJDWKDJFDT-UHFFFAOYSA-N dimethyl 2,5-dicarbonochloridoylbenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(C(Cl)=O)=C(C(=O)OC)C=C1C(Cl)=O TVWGIJDWKDJFDT-UHFFFAOYSA-N 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- BCXWMIMRDMIJGL-UHFFFAOYSA-N naphthalene-1,5-disulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1S(Cl)(=O)=O BCXWMIMRDMIJGL-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- ZBJSGOMTEOPTBH-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(S(Cl)(=O)=O)=CC2=CC(S(=O)(=O)Cl)=CC=C21 ZBJSGOMTEOPTBH-UHFFFAOYSA-N 0.000 claims 1
- 229960001124 trientine Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 229920001021 polysulfide Polymers 0.000 abstract description 14
- 239000005077 polysulfide Substances 0.000 abstract description 14
- 150000008117 polysulfides Polymers 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000007873 sieving Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 64
- 239000010410 layer Substances 0.000 description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 210000004379 membrane Anatomy 0.000 description 20
- 239000012528 membrane Substances 0.000 description 20
- 239000012498 ultrapure water Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 18
- 230000001351 cycling effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YHXKXVFQHWJYOD-UHFFFAOYSA-N 1-biphenyl-2-ylmethanamine Chemical compound NCC1=CC=CC=C1C1=CC=CC=C1 YHXKXVFQHWJYOD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JJYJSKHTGGQVMD-UHFFFAOYSA-N [Li].[SH2]=N.FC(F)F.FC(F)F Chemical compound [Li].[SH2]=N.FC(F)F.FC(F)F JJYJSKHTGGQVMD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium-sulfur battery diaphragm, a preparation method thereof and a lithium-sulfur battery. The lithium-sulfur battery diaphragm comprises a hydrophilic modified polyolefin diaphragm and a confinement layer on the surface of the hydrophilic modified polyolefin diaphragm, wherein the confinement layer is a polyamide layer, the aperture of the confinement layer is 0.5-1 nm, and the thickness of the confinement layer is 50-80 nm. The ultra-thin confinement layer performs double confinement action on an intermediate polysulfide of the lithium-sulfur battery in the charging and discharging process by using the aperture sieving effect and the chemical adsorption effect, and relieves the shuttling effect of lithium polysulfide between a positive electrode and a negative electrode, thereby improving the electrochemical performance of the lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium-sulfur battery diaphragm, a preparation method thereof and a lithium-sulfur battery.
Background
The lithium-sulfur battery takes elemental sulfur with high specific capacity as a positive electrode material, and the theoretical energy density of the lithium-sulfur battery can reach 2600 Wh.kg-1. Meanwhile, the elemental sulfur also has the advantages of abundant reserves, low price, environmental friendliness and the like. Therefore, lithium sulfur batteries are considered as a novel battery system with great research value and development potential. However, polysulfide (Li) generated during cycling of the sulfur positive electrode in a lithium sulfur battery2Sx(x-4-8)) is very soluble in the electrolyte. The dissolved high valence polysulfide can migrate to the metallic lithium cathode under the action of concentration gradient and react with the metallic lithium cathode to be converted into short-chain polysulfide; the short-chain polysulfides diffuse back to the positive electrode and are again oxidized to form long-chain polysulfides, causing a "shuttling effect" within the cell. This shuttling effect causes a continuous depletion of the lithium negative electrode and active material, resulting in a lower coulombic efficiency, while severely affecting the high voltage plateau region in the charge-discharge curve.
Conventional lithium sulfur battery separators employ commercial polyolefin separators that have almost infinite domain capability for polysulfides and are not effective in suppressing the shuttling effect. In order to improve the cycling stability of the lithium-sulfur battery, researchers carry out a series of high-performance modification researches on the diaphragm, and the size sieving effect, the chemical adsorption effect and the electrostatic repulsion effect of the modified diaphragm are utilized to inhibit the transmembrane transmission of polysulfide, so that the cycling stability of the lithium-sulfur battery is improved. However, the conventional modification method still has certain defects: the interaction between the diaphragm substrate and the modified layer is weak, so that the problem of coating layer peeling exists in the long-term use process; the thickness of the modified layer is difficult to control; the preparation and the modification of the basement membrane are difficult to be industrially scaled up.
Disclosure of Invention
The invention provides a lithium-sulfur battery diaphragm and a preparation method thereof, and aims to overcome the defects and shortcomings of the prior art. Because commercial polyolefin membranes are inherently hydrophobic, the extent of aqueous phase reaction during interfacial polymerization is limited. Tannin as a plant polyphenol can form stronger adhesion with various matrixes similarly to dopamine, and is lower in price than the dopamine. Meanwhile, the tannin contains abundant polar groups, so that the chemical adsorption effect of the modified diaphragm on polysulfide is enhanced. The hydrophilization modification method is simple to operate, environment-friendly and safe. The obtained modified diaphragm can perform double confinement action on an intermediate product polysulfide of the lithium-sulfur battery in the charging and discharging process through aperture screening, chemical adsorption and the like, so that the shuttle effect of the lithium polysulfide between a positive electrode and a negative electrode is relieved, and the coulombic efficiency and the cycling stability of the lithium-sulfur battery are improved.
The second technical problem to be solved by the present invention is to provide a method for preparing the modified membrane for solving the first technical problem.
The invention aims to provide a lithium-sulfur battery diaphragm, which comprises a hydrophilic modified polyolefin diaphragm and a confinement layer on the surface of the hydrophilic modified polyolefin diaphragm, wherein the confinement layer is a polyamide layer, the pore diameter of the confinement layer is 0.5-1 nm, and the thickness of the confinement layer is 50-80 nm.
In the above technical solution, preferably, the aperture of the confinement layer is 0.6-0.8 nm, and the thickness is 55-75 nm.
In the above technical solution, preferably, the hydrophilic modified polyolefin membrane is a tannin modified polyolefin membrane.
In the above technical solution, preferably, the polyolefin diaphragm is one of a Polyethylene (PE) diaphragm, a polypropylene (PP) diaphragm, and a polypropylene/polyethylene/polypropylene (PP/PE/PP) diaphragm.
In the technical scheme, the confinement layer is obtained by performing interfacial polymerization on polyamine and polyacyl chloride on the surface of the hydrophilic modified polyolefin membrane.
The invention also aims to provide a preparation method of the lithium-sulfur battery diaphragm, which comprises the following steps:
step 1: carrying out hydrophilization modification on the polyolefin diaphragm by adopting a tannic acid solution in a vacuum filtration mode, and carrying out vacuum drying to obtain a hydrophilization modified polyolefin diaphragm;
step 2: and carrying out interfacial polymerization on a water-phase monomer and an oil-phase monomer on the surface of the hydrophilic modified polyolefin diaphragm to obtain the domain limiting layer.
In the above technical scheme, preferably, in the step 1, the concentration of the tannic acid is 0.5-1 g/L, and further the concentration of the tannic acid is 0.6-0.8 g/L.
In the step 1, if the concentration of tannic acid is too low, the hydrophilization modification effect of the polyolefin membrane is limited. If the concentration of tannic acid is too high, on the one hand, part of the oily monomers is consumed, and on the other hand, the molecules of tannic acid are self-crosslinked and settle.
In the above technical solution, preferably, in step 2, the water phase monomer and the oil phase monomer are respectively dissolved in the solvent to prepare a water phase monomer solution and an oil phase monomer solution; and (3) soaking the hydrophilic modified polyolefin diaphragm obtained in the step (1) in a water-phase monomer solution, removing the redundant solution on the surface, then soaking in an oil-phase monomer solution, and then carrying out heat treatment to obtain the confinement layer.
In the above technical solution, preferably, the water phase monomer is selected from polyamine, including but not limited to one or a mixture of more than one monomer of piperazine, bisphenol, triethylamine, m-phenylenediamine, triethanolamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 1, 4-butanediamine, diethylenetriamine, triethylenetetramine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane o-biphenylmethylamine, dimethylamine, o-phenylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 3-diethylaminopropylamine, 1, 2-cyclohexanediamine, 4, 5-dichloro-o-phenylenediamine; preferably one or more than one monomer of piperazine, ethylene diamine, m-phenylenediamine and p-phenylenediamine.
In the aqueous phase monomer solution, the mass fraction of the aqueous phase monomer is 0.05-3.5 wt%, preferably 0.1-3.0 wt%.
In the above technical solution, preferably, the oil phase monomer is selected from polyacyl chloride, including but not limited to one or a mixture of more than one monomer of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, pyromellitic chloride, succinoyl chloride, adipoyl chloride, cyclohexanetrioyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, 5-nitrobenzene-1, 3-diacid chloride, 2, 5-bis (methoxycarbonyl) terephthaloyl chloride, 1, 5-naphthalenedisulfonyl chloride, 1,3, 6-naphthalenedisulfonyl chloride; preferably one monomer or a mixture of more than one monomer of trimesoyl chloride, phthaloyl chloride, terephthaloyl chloride and isophthaloyl chloride.
In the oil phase monomer solution, the mass fraction of the oil phase monomer is 0.05-3.5 wt%, preferably 0.1-3.0 wt%.
In the above technical solution, preferably, in the oil phase monomer solution, the solvent includes but is not limited to at least one of n-hexane, cyclohexane, n-heptane, n-decane, benzene, toluene, xylene, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, and the like, or a combination thereof, and more preferably n-hexane.
In the above technical scheme, preferably, the soaking time of the aqueous monomer solution in the step 2 is 1-5 min.
In the above technical scheme, preferably, the soaking time of the oil phase monomer solution in the step 2 is 0.5-3 min.
In the above technical scheme, preferably, the heat treatment temperature in the step 2 is 60 to 90 ℃, and the heat treatment time is 1 to 10 min. More preferably, the heat treatment temperature in the step 2 is 60-80 ℃, and the heat treatment time is 5-10 min.
In the technical scheme, the aperture of the confinement layer with the nanoscale aperture prepared by the method is preferably 0.5-1 nm, and the thickness of the confinement layer is 50-80 nm, and more preferably, the aperture of the confinement layer is 0.6-0.8 nm, and the thickness of the confinement layer is 55-75 nm.
According to a preferred embodiment of the present invention, the method for preparing a separator for a lithium sulfur battery comprises the steps of:
step 1: carrying out hydrophilization modification on a commercial polyolefin diaphragm, specifically: dissolving a certain mass of tannic acid in water, carrying out hydrophilic modification on a polyolefin diaphragm in a vacuum filtration mode, and drying in vacuum for later use;
step 2: constructing an ultrathin confinement layer on the surface of the diaphragm prepared in the step 1 through interfacial polymerization, specifically: respectively dissolving a water-phase monomer and an oil-phase monomer in a solvent to prepare a water-phase monomer solution and an oil-phase monomer solution; and (2) soaking the diaphragm prepared in the step (1) in an aqueous phase monomer solution for 1-5 min, removing the redundant solution on the surface, then placing the obtained diaphragm in an oil phase monomer solution for soaking for 0.5-3 min, then performing heat treatment in an oven for 1-10 min to obtain an ultrathin limited zone layer, taking out, washing to remove unreacted monomers, and drying to obtain the modified diaphragm.
The inventor changes the interface reaction parameters including the water phase monomer concentration, the oil phase monomer concentration, the reaction time and the like to prepare the confinement layers with different pore sizes and thicknesses. The research on the effect finds that: if the aperture of the confinement layer is too low or the thickness of the confinement layer is too large, the migration resistance of lithium ions is seriously increased, and the conductivity of the lithium ions is further reduced; if the pore size of the confinement layer is too large, the effect on polysulfide inhibition is limited. The experimental result shows that the pore diameter and the thickness of the confinement layer significantly influence the effect of obtaining the modified diaphragm, and the modified diaphragm with good effect can be obtained only when the pore diameter and the thickness of the confinement layer are within the above ranges.
The invention also provides a lithium-sulfur battery, which comprises a positive electrode material, a negative electrode material, electrolyte and a diaphragm, wherein the diaphragm is the diaphragm obtained by the preparation method or the diaphragm obtained by the preparation method.
In the above technical solution, the electrode material, the negative electrode material, and the electrolyte are not particularly limited, and the electrode material, the negative electrode material, and the electrolyte that are generally used in the art may be used.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, tannic acid is adopted to carry out hydrophilic modification on the commercial polyolefin diaphragm, so that the interface impedance between the polyamide confinement layer and the base film is favorably reduced, the modification is lasting and effective, the operation is simple, the environment is protected and harmless, and meanwhile, the tannic acid contains rich polar groups, so that the inhibition of the modified diaphragm on the shuttle-threading effect is favorably strengthened;
(2) according to the invention, the confinement layer with the nano-grade aperture is formed by adopting an interface polymerization method, the migration of polysulfide can be inhibited by the dual confinement effects of aperture screening and chemical adsorption, the coulombic efficiency and the cycle stability of the lithium-sulfur battery are improved, and more excellent electrochemical performance is shown;
(3) the method has strong practicability, can quickly and accurately regulate and control the thickness and the aperture size of the ultrathin confinement layer by optimizing the interfacial polymerization process, is easy to popularize, and is favorable for accelerating the industrial application of the lithium-sulfur battery.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Assembling the modified diaphragm into a lithium-sulfur battery for electrochemical characterization, specifically: the S/CNT composite material is used as a positive electrode, a lithium sheet is used as a negative electrode, Celgard 2325 is used as an original diaphragm, the electrolyte is a mixed solution of glycol dimethyl ether and 1, 3-dioxolane containing 1.0mol/L bis (trifluoromethane) sulfimide lithium, and the volume ratio of the glycol dimethyl ether to the 1, 3-dioxolane is 1: 1.
[ example 1 ]
1. Preparation method
(1) Dissolving 0.6 tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving trimesoyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. Finally, the mixture is put into a vacuum oven to be dried for standby.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified diaphragm is 60nm, and the pore size is 1 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the diaphragms before and after modification. When the lithium-sulfur battery is charged and discharged at 0.5 ℃, the coulomb efficiency of the battery is reduced to 87.9 percent after the lithium-sulfur battery containing the diaphragm before modification is cycled for 100 times, and the discharge capacity retention rate is 85.7 percent; in contrast, the coulombic efficiency of the battery after the modified diaphragm prepared by the experimental example is cycled for 100 times is still maintained at about 90.5%, the discharge capacity retention rate is 92.8%, and the battery shows more excellent cycling stability.
[ COMPARATIVE EXAMPLE 1 ]
1. Preparation method
(1) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving trimesoyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. Soaking an unmodified polyolefin diaphragm in a water-phase monomer solution containing piperazine for 3min, then soaking the obtained diaphragm in an oil-phase monomer solution for 2min, and finally placing the obtained diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the unmodified separator was 35nm and the pore size was 5.0 nm.
(2) The lithium-sulfur battery assembled with the separator was subjected to cycle performance testing. The coulombic efficiency of the battery is still kept about 88.2% after the modified diaphragm prepared by the comparative example is cycled for 100 times, and the discharge capacity retention rate is 86.3%. Compared with the embodiment 1, the separator pretreated by the tannic acid shows more excellent electrochemical performance after the interfacial polymerization modification.
[ example 2 ]
1. Preparation method
(1) Dissolving 0.6g of tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving triethylamine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, dissolving trimesoyl chloride in n-hexane to obtain an oil-phase monomer solution, and the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing triethylamine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified membrane was 53nm, and the pore size was 0.9 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still maintained to be about 91.6% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 89.9%, and the excellent cycling stability is shown.
[ example 3 ]
1. Preparation method
(1) Dissolving 0.8 tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 3%, and dissolving trimesoyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified diaphragm is 60nm, and the pore size is 0.7 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still maintained to be about 91.2% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 92.7%, and the excellent cycling stability is shown.
[ example 4 ]
1. Preparation method
(1) Dissolving 0.8 tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified membrane was 77nm, and the pore size was 0.8 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still maintained to be about 91.5% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 93.8%, and the excellent cycling stability is shown.
[ example 5 ]
1. Preparation method
(1) Dissolving 0.6 tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 3%, and dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 3%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified membrane was 74nm and the pore size was 0.5 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still kept about 95.4% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 96.2%, and the excellent cycling stability is shown.
[ example 6 ]
1. Preparation method
(1) Dissolving 0.6g of tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 5min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 60 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified membrane was 68nm, and the pore size was 0.7 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still kept about 92.6% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 92.9%, and the excellent cycling stability is shown.
[ example 7 ]
1. Preparation method
(1) Dissolving 0.6g of tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 80 ℃, the interfacial polymerization time is 5min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified membrane was 75nm, and the pore size was 0.7 nm.
(2) And (3) carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still maintained to be about 91.4% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 93.6%, and the excellent cycling stability is shown.
[ example 8 ]
1. Preparation method
(1) Dissolving 0.6g of tannic acid in 1.0L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 0.15%, and dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, wherein the mass fraction of the oil-phase monomer is 0.35%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 3min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 70 ℃, the interfacial polymerization time is 10min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified diaphragm was 69nm, and the pore size was 0.5 nm.
(2) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still kept about 93.5% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 94.4%, and more excellent cycling stability is shown.
[ example 9 ]
1. Preparation method
(1) Dissolving 0.5g of tannic acid in 0.5L of high-purity water, and depositing the tannic acid on a polyolefin membrane for hydrophilic modification in a vacuum-pumping filtration mode.
(2) Dissolving piperazine in high-purity water to obtain a water-phase monomer solution, wherein the mass fraction of the water-phase monomer is 3%, dissolving terephthaloyl chloride in n-hexane to obtain an oil-phase monomer solution, and the mass fraction of the oil-phase monomer is 3%. And (2) soaking the diaphragm obtained in the step (1) in a water-phase monomer solution containing piperazine for 5min, then soaking the diaphragm in an oil-phase monomer solution for 2min, and finally placing the diaphragm in an oven for interfacial polymerization. The interfacial polymerization temperature is 80 ℃, the interfacial polymerization time is 10min, and after the reaction is finished, the product is taken out and washed by deionized water to remove unreacted monomers. And finally, putting the mixture into a vacuum oven to be dried for later use.
2. Product properties and characteristics:
(1) the thickness of the confinement layer of the modified diaphragm is 80nm, and the pore size is 0.5 nm.
(3) And carrying out cycle performance test on the lithium-sulfur battery assembled by the modified diaphragm. The coulombic efficiency of the battery is still kept about 95.5% after the modified diaphragm prepared by the experimental example is cycled for 100 times, the discharge capacity retention rate is 95.9%, and the excellent cycling stability is shown.
[ example 10 ]
The aperture and thickness of the ultra-thin confinement layer have important influence on the product performance
The preparation conditions of the diaphragm in the embodiment are the same as that in the step 1 in the embodiment 1, the zone limiting layers with different thicknesses and pore sizes are prepared by regulating the concentrations of the water phase monomer and the oil phase monomer in the step 2 in the embodiment 1, and the influence of the thickness and the pore size of the zone limiting layer on the product is examined, which is specifically shown in the following table 1.
TABLE 1 Effect of confinement layer thickness and pore size on product Properties
Claims (10)
1. A lithium-sulfur battery diaphragm comprises a hydrophilic modified polyolefin diaphragm and a confinement layer on the surface of the hydrophilic modified polyolefin diaphragm, wherein the confinement layer is a polyamide layer, the aperture of the confinement layer is 0.5-1 nm, and the thickness of the confinement layer is 50-80 nm; preferably, the aperture of the confinement layer is 0.6-0.8 nm, and the thickness of the confinement layer is 55-75 nm.
2. The lithium sulfur battery separator according to claim 1, wherein:
the hydrophilic modified polyolefin diaphragm is a tannin modified polyolefin diaphragm, and the polyolefin diaphragm is preferably one of a polyethylene diaphragm, a polypropylene diaphragm and a polypropylene/polyethylene/polypropylene diaphragm.
3. The lithium sulfur battery separator according to claim 1 or 2, wherein:
the domain limiting layer is obtained by carrying out interfacial polymerization on polyamine and polyacyl chloride on the surface of the hydrophilic modified polyolefin diaphragm.
4. A method of preparing a lithium-sulfur battery separator according to any one of claims 1 to 3, comprising the steps of:
step 1: carrying out hydrophilization modification on the polyolefin diaphragm by adopting a tannic acid solution in a vacuum filtration mode, and carrying out vacuum drying to obtain a hydrophilization modified polyolefin diaphragm;
step 2: and carrying out interfacial polymerization on a water-phase monomer and an oil-phase monomer on the surface of the hydrophilic modified polyolefin diaphragm to obtain the domain limiting layer.
5. The method of manufacturing a lithium sulfur battery separator according to claim 4, wherein:
in the step 1, the concentration of the tannic acid is 0.5-1 g/L, preferably 0.6-0.8 g/L; and/or the presence of a gas in the atmosphere,
the drying temperature is 60-80 ℃; the drying time is 6-12 h.
6. The method of manufacturing a lithium sulfur battery separator according to claim 4, wherein:
in step 2, soaking the hydrophilic modified polyolefin diaphragm obtained in the step 1 in a water-phase monomer solution, removing the redundant solution on the surface, then soaking the hydrophilic modified polyolefin diaphragm in an oil-phase monomer solution, and then carrying out heat treatment to obtain the confinement layer.
7. The method of manufacturing a lithium sulfur battery separator according to claim 6, wherein:
the water phase monomer is selected from polyamine, preferably at least one of piperazine, bisphenol, triethylamine, m-phenylenediamine, triethanolamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 1, 4-butanediamine, diethylenetriamine, triethylene tetramine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane-o-biphenylmethylamine, dimethylamine, o-phenylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 3-diethylaminopropylamine, 1, 2-cyclohexanediamine and 4, 5-dichloro-o-phenylenediamine; and/or the presence of a gas in the gas,
the oil phase monomer is selected from at least one of polybasic acyl chloride, preferably trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, pyromellitic chloride, succinoyl chloride, adipoyl chloride, cyclohexanetrioyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, 5-nitrobenzene-1, 3-diacid chloride, 2, 5-bis (methoxycarbonyl) terephthaloyl chloride, 1, 5-naphthalene disulfonyl chloride and 1,3, 6-naphthalene trisulfonyl chloride.
8. The method of manufacturing a lithium sulfur battery separator according to claim 6, wherein:
in the aqueous phase monomer solution, the mass fraction of the aqueous phase monomer is 0.05-3.5 wt%, preferably 0.1-3.0 wt%; and/or the presence of a gas in the gas,
in the oil phase monomer solution, the mass fraction of the oil phase monomer is 0.05-3.5 wt%, preferably 0.1-3.0 wt%.
9. The method of manufacturing a lithium sulfur battery separator according to claim 6, wherein:
in the step 2, soaking the aqueous phase monomer solution for 1-5 min; and/or the presence of a gas in the gas,
soaking the oil phase monomer solution for 0.5-3 min; and/or the presence of a gas in the gas,
the heat treatment temperature is 60-90 ℃, and the heat treatment time is 1-10 min.
10. A lithium-sulfur battery comprising a positive electrode material, a negative electrode material, an electrolyte and a separator, wherein the separator is the separator according to any one of claims 1 to 3 or the separator obtained by the preparation method according to any one of claims 4 to 9.
Priority Applications (1)
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