CN116063601B - Water-soluble polyion liquid and application thereof in lithium-sulfur battery - Google Patents
Water-soluble polyion liquid and application thereof in lithium-sulfur battery Download PDFInfo
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920001021 polysulfide Polymers 0.000 claims abstract description 26
- 239000005077 polysulfide Substances 0.000 claims abstract description 26
- 150000008117 polysulfides Polymers 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 96
- 239000000178 monomer Substances 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 238000004821 distillation Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims description 45
- 159000000002 lithium salts Chemical class 0.000 claims description 43
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- -1 fluorosulfonyl imide Chemical class 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 24
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 125000002883 imidazolyl group Chemical group 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000011403 purification operation Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005349 anion exchange Methods 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002955 isolation Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 239000002608 ionic liquid Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 34
- 239000011244 liquid electrolyte Substances 0.000 description 28
- 239000005518 polymer electrolyte Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 24
- 239000011541 reaction mixture Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 101710134784 Agnoprotein Proteins 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- 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 13
- 238000000926 separation method Methods 0.000 description 13
- ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 4-chlorobutanenitrile Chemical compound ClCCCC#N ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 0.000 description 12
- 230000008901 benefit Effects 0.000 description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- 229910004761 HSV 900 Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- GNHMRTZZNHZDDM-UHFFFAOYSA-N 3-chloropropionitrile Chemical compound ClCCC#N GNHMRTZZNHZDDM-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
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- 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
- H01M10/0566—Liquid materials
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- 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
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- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
- H01M2300/0025—Organic electrolyte
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a water-soluble polyion liquid, which is prepared by introducing polar groups into the polyion liquid through molecular design and polymerizing to form the water-soluble polyion liquid, so that the polarity of the polyion liquid is increased, and the polyion liquid can be dissolved in aqueous solution with larger polarity and can not be dissolved in ether electrolyte with smaller polarity. The polyion liquid is coated on the negative plate, is insoluble in electrolyte, does not swell, and has excellent polysulfide isolation capability, so that the shuttle effect of polysulfide ions can be reduced through the water-soluble polyion liquid, and the long-cycle performance of the lithium-sulfur battery is improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a water-soluble polyion liquid and application thereof as an electrolyte in a lithium-sulfur battery.
Background
In the current energy storage field, lithium ion batteries occupy most of market share, but the need for improved energy density, rare lithium resources and cobalt resources limit the large-scale application of lithium ion batteries. Therefore, it is important to develop a next generation rechargeable battery with high specific energy, long life, low toxicity and low cost. Lithium sulfur batteries are receiving wide attention from the scientific community and industry due to the advantages of high specific energy, low cost, abundant resources and the like. Besides the very high energy density, lithium sulfur batteries have other advantages, on the one hand, the production cost is relatively low; on the other hand, it also has the advantage of being environmentally friendly.
The polysulfide generated in the charge and discharge process of the lithium sulfur battery is dissolved in the electrolyte, so that the cycle utilization frequency of the lithium sulfur battery is low. The current recycling times of the lithium sulfur battery are far lower than that of a common lithium iron phosphate battery, so that the use cost of the lithium sulfur battery is greatly increased.
In order to solve the problem of polysulfide shuttling in lithium sulfur batteries, article Ion-Inserted Metal-Organic Frameworks Accelerate the Mass Transfer Kinetics in Lithium-Sulfur Batteries(Small,2021,2104367,DOI:10.1002/smll.202104367) blocks polysulfide transport by preparing a metal organic framework layer capable of blocking ion transport, but cannot meet practical application due to difficult preparation and high cost. In the invention patent with the publication number of CN105845965A, a polymer membrane material capable of transmitting ions is prepared, and has good barrier effect on polysulfide ions, but the specific capacity of the polymer membrane material only has 600mAh/g, and the advantage of high specific energy of sulfur cannot be exerted.
The polyionic liquid has the advantages of excellent thermal stability, incombustibility, wide electrochemical stability window and the like, and also has the advantages of excellent processability and flexibility, thus being a very promising material. However, conventional polyionic liquids are swelled or even dissolved in ether electrolyte, and cannot inhibit polysulfide migration.
Disclosure of Invention
The invention provides a water-soluble polyion liquid, which is prepared by introducing polar groups into the polyion liquid through molecular design and polymerizing to form the water-soluble polyion liquid, so that the polarity of the polyion liquid is increased, and the polyion liquid can be dissolved in aqueous solution with larger polarity and can not be dissolved in ether electrolyte with smaller polarity. The polyion liquid is coated on the negative plate, is insoluble in electrolyte, does not swell, and has excellent polysulfide isolation capability, so that the shuttle effect of polysulfide ions can be reduced through the water-soluble polyion liquid, and the long-cycle performance of the lithium-sulfur battery is improved.
The invention firstly provides a water-soluble polyionic liquid which has a structure shown in a formula I:
Wherein A is imidazolyl or pyridyl; b is a polar group containing nitrile, amino, carboxyl, hydroxyl or sulfo groups; c - is an organic anion; n is an integer greater than 1; both B and C - are attached to the same N atom on the imidazole or pyridine ring of A.
Further, B is a substituent having formula II, wherein M is M/2, M is a positive integer, preferably 2-6; r 1 is a nitrile group, amino group, carboxyl group, hydroxyl group, or sulfo group. The proper carbon chain length can reduce steric hindrance to promote polymerization reaction of polyionic liquid, can maintain stronger polarity of polar groups, and can improve electron-withdrawing effect of the polyionic liquid on imidazole rings or pyridine rings, so that ionization of N atoms is promoted, and water solubility is improved.
Further, the C is fluorine-containing sulfonyl imide root, fluorine-containing phosphate radical or double oxalic acid borate radical.
Further, on the imidazole ring or pyridine ring, the N atom attached to the B and C is located in a non-ortho position to the atom attached to the main chain.
The invention also provides a preparation method of the water-soluble polyionic liquid, which comprises the following steps:
s1: quaternizing vinyl imidazole or vinyl pyridine with alkane containing halogen and polar groups to obtain vinyl imidazole or vinyl pyridine with the same N atom on the imidazole ring or pyridine ring connected with substituent of formula II and halogen ion;
Wherein the alkane containing halogen and polar groups has a structure of formula III, M is M/2, M is a positive integer, preferably 2-6; r 1 is a nitrile group, amino group, carboxyl group, hydroxyl group, or sulfo group; x is halogen, specifically F, cl, br, I;
The reaction route of the step is as follows:
S1：
S2: carrying out anion exchange on the product obtained in the step S1 and lithium salt to obtain vinyl imidazole or vinyl pyridine with the same N atom on an imidazole ring or pyridine ring connected with a substituent of the formula II and lithium salt anions at the same time, namely the water-soluble polyion liquid monomer;
The reaction route of the step is as follows:
S2：
S3: carrying out an ethylenic addition polymerization reaction on the product obtained in the step S2 to obtain a target water-soluble polyion liquid;
The reaction route of the step is as follows:
S3：
In the above steps:
The step S1 is carried out at 40-80 ℃ for 24-48 hours, and the reaction solution is preferably ethyl acetate.
The specific operation method of the step S2 is that the product obtained in the step S1 is dissolved in chloroform, and aqueous solution of lithium salt is added dropwise to the chloroform to obtain water-soluble polyion liquid monomer; stirring was continued at 40-80 ℃ until the reaction was complete.
The specific operation method of the step S3 is that the product obtained in the step S2 is added with an initiator in the presence of lithium salt to obtain a uniform mixed solution, the uniform mixed solution is coated on a required substrate (such as a negative electrode plate), and polymerization reaction is carried out under the condition of heating or illumination to obtain the target water-soluble polyion liquid coated on the substrate, and the target water-soluble polyion liquid can be used as an electrolyte.
Further, in the step S1, the reaction further comprises a purification operation, specifically comprises a process of distilling for 40min at 80 ℃ and 10mbar, and washing with ethyl acetate after the distillation is finished; in the step S2, the purification operation is also included after the reaction is completed, specifically, deionized water is adopted to wash until no chloride ions are detected in the washing water, then vacuum distillation is performed for 40min at 70 ℃, and freeze drying is performed after the distillation is completed.
Further, in the step S3, the thermal polymerization temperature is 40-80 ℃ and the polymerization time is 6-12h; the photopolymerization adopts 365nm ultraviolet light, and the illumination time is 5s-10min; the initiator is one or more of thermal initiators such as azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, dialkyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like, or photoinitiators such as 2-hydroxy-methylphenyl propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and the like.
Further, in the step S3, the lithium salt accounts for 5-40% of the mass of the water-soluble polyion liquid monomer, and the initiator accounts for 0.1-5% of the mass of the water-soluble polyion liquid monomer.
Further, in the steps S2 and S3, the lithium salts may be the same or different, and each is independently selected from one or more of lithium salts of fluorine-containing sulfimide, fluorine-containing phosphate, or bisoxalato borate; the lithium salt in step S2 is used for ion exchange reaction, and the lithium salt in step S3 is used as an essential constituent of ion conduction in the electrolyte.
The invention also provides application of the water-soluble polyionic liquid in one of the following aspects:
(1) As an electrolyte;
(2) For lithium sulfur batteries;
(3) For reducing swelling;
(4) Shuttle for inhibiting polysulfide ions;
(5) Is used for improving the cycle stability of the lithium-sulfur battery.
The invention also provides a lithium sulfur battery, comprising:
And (3) a negative electrode: a lithium strip coated with the water-soluble polyionic liquid,
Current collector: the carbon-coated aluminum foil is coated on the surface of the aluminum foil,
A diaphragm: polypropylene
And (3) a positive electrode: a composite material of S8+ carbon nano tube + polyvinylidene fluoride + carbon black,
Electrolyte solution: lithium sulfur electrolyte containing polysulfide ions.
The invention has the beneficial effects that: 1. the polyionic liquid is soluble in water and has the advantage of environmental friendliness. 2. The polyionic liquid has the advantages of high temperature resistance and no combustion. 3. Is insoluble in electrolyte, does not swell, has excellent polysulfide isolation capability, and improves the long cycle performance of the lithium sulfur battery.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a synthetic route of example 3 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of an ionic liquid monomer containing polar groups of example 3.
Fig. 3 is a graph showing the cycle performance results of lithium sulfur batteries assembled in examples of the present invention and comparative examples.
FIG. 4 shows the results of a solubility test of the polyionic liquid prepared in example 9 of the present invention.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
1. Preparation of the water-soluble polyion liquid
Vinyl imidazole or vinyl pyridine is dissolved in ethyl acetate with halogen-and polar-group-containing alkane, and the halogen-and polar-group-containing alkane may be slightly excessive, for example, 1.05 to 1.5 times the molar amount of vinyl imidazole or vinyl pyridine, in stoichiometric ratio, and reacted at 40 to 80 ℃ for 24 to 48 hours. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. Washing with ethyl acetate three times (separating liquid) after the distillation is finished, and distilling for 40min at 80 ℃ and 10mbar to obtain vinyl imidazole or vinyl pyridine with polar group substituent and halogen ion simultaneously connected to the same N atom on the imidazole ring or pyridine ring;
Dissolving the product obtained in the previous step in chloroform; dissolving lithium salt in deionized water, slowly dripping at 40 ℃, and continuously stirring at 40-80 ℃ for more than 6 hours according to the stoichiometric ratio, wherein the molar quantity of the lithium salt is 1.05-1.5 times that of the reaction product in the last step. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested with AgNO 3 solution to prevent precipitation (silver halide precipitation color was different). And (3) carrying out reduced pressure distillation at 70 ℃ for 40min, and obtaining the water-soluble polyion liquid monomer after the distillation is finished.
Mixing the water-soluble polyion liquid monomer obtained in the previous step with lithium salt and an initiator to prepare a polymer electrolyte precursor solution, magnetically stirring for more than 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating or illuminating to initiate polymerization reaction to obtain the water-soluble polyion liquid electrolyte. In the polymer electrolyte precursor solution, the lithium salt accounts for 5-40% of the mass of the water-soluble polyion liquid monomer, and the initiator accounts for 0.1-5% of the mass of the water-soluble polyion liquid monomer.
Table 1 shows several polyionic liquid products prepared using the above method. As an example of the reaction scheme, fig. 1 shows a specific reaction scheme of example 3 in table 1. FIG. 2 shows the nuclear magnetic resonance spectrum of the polyionic liquid monomer obtained in example 3, confirming that the target product can be obtained by using the synthetic route of the present invention.
By changing the optimized reaction process conditions, the adjustment of the product yield can be realized. Examples of the ability to adjust the product yield by changing the reaction conditions are provided below by examples 9-21.
Example 9
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 40℃for 24 hours. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation was completed, the reaction mixture was washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40 minutes to give 7.6g of a product in 16% yield.
7G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. And (3) carrying out reduced pressure distillation at 70 ℃ for 40min, and freeze-drying after the distillation is finished, thus obtaining 8.5g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 30wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: azobisisobutyronitrile (1% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 60 ℃ for 9 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 10
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 5wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: azobisisobutyronitrile (0.1% of the monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 40 ℃ for 6 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 11
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 40wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: azobisisobutyronitrile (5% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 80 ℃ for 12 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 12
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 30wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: dibenzoyl peroxide (1% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 60 ℃ for 9 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 13
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 5wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: dibenzoyl peroxide (0.1% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 40 ℃ for 6 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 14
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 40wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: dibenzoyl peroxide (5% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a thermal initiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 80 ℃ for 12 hours to obtain the water-soluble polyionic liquid electrolyte.
Example 15
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 30wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-hydroxy-methylphenyl-propan-1-one (1% of the monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 5min to obtain the water-soluble polyionic liquid electrolyte.
Example 16
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 5wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-hydroxy-methylphenyl-propan-1-one (0.1% of the monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 2 minutes to obtain the water-soluble polyionic liquid electrolyte.
Example 17
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 40wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-hydroxy-methylphenyl-propan-1-one (5% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 10min to obtain the water-soluble polyionic liquid electrolyte.
Example 18
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 30wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholino-1-propanone (1% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 5min to obtain the water-soluble polyionic liquid electrolyte.
Example 19
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 5wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholino-1-propanone (0.1% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 2 minutes to obtain the water-soluble polyionic liquid electrolyte.
Example 20
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 1:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 4-chlorobutyronitrile and 53.0g of 1-vinylimidazole were dissolved in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation is completed, the mixture is washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40min to give 30.5g of the product in 64% yield.
14G of the product obtained in the previous step is taken and dissolved in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. Distilling at 70 ℃ under reduced pressure for 40min, and freeze-drying after the distillation is finished, thus obtaining 17g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 40wt% of lithium bis (trifluoromethanesulfonyl imide), and a photoinitiator: 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholino-1-propanone (5% of monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and irradiating with 365nm ultraviolet light for 10min to obtain the water-soluble polyionic liquid electrolyte.
Example 21
In the steps of this example, the preparation reaction of the reactive monomer and the polymer electrolyte is shown in fig. 2:
(1) Preparation of polar group-containing water-soluble ionic liquid monomer
25.0G of 3-chloropropionitrile and 53.0g of 4-vinylpyridine are taken up in 50ml of ethyl acetate and reacted at 80℃for 48h. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation was completed, the reaction mixture was washed three times with 20ml of ethyl acetate (liquid separation) and distilled at 80℃and 10mbar for 40 minutes to give 40.5g of a product in a yield of 74.3%.
Dissolving 10g of the product obtained in the previous step in 10ml of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10ml of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water, and the washing water was tested for chlorine ion-free with AgNO 3 solution. And (3) carrying out reduced pressure distillation at 70 ℃ for 40min, and freeze-drying after the distillation is finished, thus obtaining 15g of water-soluble ionic liquid monomer containing polar groups.
(2) Polymer electrolyte precursor solution composition: polar group-containing water-soluble ionic liquid monomer, lithium salt: 30wt% of lithium bis (trifluoromethanesulfonyl imide), and a thermal initiator: azobisisobutyronitrile (0.1% of the monomer mass).
(3) Water-soluble polyionic liquid electrolyte: uniformly mixing a water-soluble ionic liquid monomer containing polar groups and lithium salt, adding a photoinitiator, magnetically stirring for 2 hours to obtain a uniform solution, uniformly coating the solution on a negative electrode plate, and heating at 60 ℃ for 3 hours to obtain the water-soluble polyionic liquid electrolyte.
2. Performance detection of assembled battery
A lithium sulfur button cell was assembled using an electrolyte containing polysulfide ions (0.6M Li 2S8 +0.6M LiTFSI+DME/DOL (1:1)) as a lithium sulfur electrolyte, using the method of example 9, making a negative electrode on a 50 μm ultrathin lithium strip, using carbon-coated aluminum foil as a current collector, using polypropylene (PP) as a separator, using a composite of S8+ Carbon Nanotubes (CNTs) +polyvinylidene fluoride (HSV 900) +carbon black (SP) (mass ratio 60:20:10:10) as a positive electrode material.
Two sets of comparative examples are provided simultaneously:
Comparative example 1
The lithium sulfur button cell is assembled by taking electrolyte containing polysulfide ions (0.6M Li 2S8 +0.6M LiTFSI+DME/DOL (1:1)) as lithium sulfur electrolyte, taking polypropylene (PP) as a diaphragm and taking S8+ Carbon Nanotubes (CNTs) +polyvinylidene fluoride (HSV 900) +carbon black (SP) (the mass ratio is 60:20:10:10) composite material as a positive electrode material.
Comparative example 2
The electrolyte containing polysulfide ions (0.6M Li 2S8 +0.6M LiTFSI+DME/DOL (1:1)) is used as lithium sulfur electrolyte, and conventional ionic liquid monomer (1-vinyl-3-ethylimidazole bistrifluoromethane sulfonate imine salt) is selected) Adding 30wt% of LiTFSI and 0.1wt% of azodiisobutyl, uniformly mixing, coating on a 50 mu m ultrathin lithium belt, heating and polymerizing for 9 hours at 60 ℃, wherein polypropylene (PP) is a diaphragm, and S8+ Carbon Nanotubes (CNTs) +polyvinylidene fluoride (HSV 900) +carbon black (SP) (the mass ratio is 60:20:10:10) composite material is used as a positive electrode material to assemble the lithium sulfur button cell.
After the above battery was allowed to stand for 5 hours, its electrochemical performance was tested on a LAND battery test system at a rate of 0.1C and a test temperature of 25 ℃. The results of the electrochemical performance test are shown in FIG. 3. It can be seen that the capacity retention of the inventive examples after 23 cycles was 94%. The comparative example 1 had a capacity retention of 69.8% after 23 cycles, and the shuttle effect of polysulfide caused a rapid decrease in cell cycle capacity due to the absence of the polyionic liquid electrolyte material of the present invention. The comparative example 2 had a capacity retention of 81.5% after 23 cycles, and was also added with an ionic liquid, but the compound had a certain solubility in an ether electrolyte due to the lack of a polar group in the structure, and the effect was poor although the blocking effect against polysulfide ions was improved to some extent, and it was difficult to achieve the excellent cycle stability of the present invention.
Fig. 4 shows the solubility of the polyionic liquid prepared in example 9 of the present invention, and it can be seen that it has excellent water solubility.
TABLE 1
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. An application of a water-soluble polyion liquid in inhibiting polysulfide ion shuttle in a lithium-sulfur battery, which is characterized in that the water-soluble polyion liquid has a structure of a formula I:
；
Wherein A is imidazolyl; c - is an organic anion; n is an integer greater than 1; b and C - are both attached to the same N atom on the imidazole ring of A; b is a substituent having the formula II,
；
Wherein M is M/2, M is a positive integer of 2-6; r 1 is a nitrile group.
2. The use of a water-soluble polyionic liquid according to claim 1 for inhibiting shuttle of polysulfide ions in lithium-sulfur battery, wherein C - is fluorosulfonyl imide, fluorophosphate, or bisoxalato borate.
3. The use of a water-soluble polyionic liquid according to claim 1 for inhibiting shuttle of polysulfide ions in lithium-sulfur battery, wherein the N atoms attached to B and C - are located in non-ortho positions to the atoms attached to the backbone chain on the imidazole ring.
4. The use of the water-soluble polyionic liquid according to claim 1 for inhibiting the shuttling of polysulfide ions in lithium-sulfur batteries, wherein the preparation method of the water-soluble polyionic liquid comprises the following steps:
S1: quaternizing vinyl imidazole with alkane containing halogen and polar groups to obtain vinyl imidazole with the same N atom on an imidazole ring connected with substituent groups and halogen ions in the formula II at the same time;
S2: carrying out anion exchange on the product obtained in the step S1 and lithium salt to obtain vinyl imidazole in which the substituent group of the formula II and lithium salt anions are simultaneously connected to the same N atom on an imidazole ring, namely the water-soluble polyion liquid monomer;
S3: and (3) adding an initiator into the product obtained in the step (S2) in the presence of lithium salt to obtain a uniform mixed solution, coating the uniform mixed solution on a required substrate, and carrying out polymerization reaction under the condition of heating or illumination to obtain the target water-soluble polyion liquid coated on the substrate.
5. The use of the water-soluble polyionic liquid as claimed in claim 4 for inhibiting the shuttling of polysulfide ions in lithium-sulfur batteries,
In the step S1, the alkane containing halogen and polar groups has a structure of a formula III,
；
M is M/2, M is a positive integer of 2-6; r 1 is a nitrile group; x is halogen, specifically F, cl, br, I.
6. The use of the water-soluble polyionic liquid as claimed in claim 4 for inhibiting the shuttling of polysulfide ions in lithium-sulfur batteries,
The step S1 is carried out for 24-48 hours at the temperature of 40-80 ℃;
The specific operation method of the step S2 is that the product obtained in the step S1 is dissolved in chloroform, and aqueous solution of lithium salt is added dropwise to the chloroform to obtain water-soluble polyion liquid monomer; stirring was continued at 40-80 ℃ until the reaction was complete.
7. The use of the water-soluble polyionic liquid according to claim 4 for inhibiting polysulfide ion shuttling in lithium sulfur batteries, wherein the reaction solution of step S1 is ethyl acetate.
8. The use of the water-soluble polyionic liquid as claimed in claim 4 for inhibiting the shuttling of polysulfide ions in lithium-sulfur batteries,
In the step S1, the reaction further comprises a purification operation, specifically comprises a process of distilling 40min at 80 ℃ and 10 mbar, and washing with ethyl acetate after the distillation is finished; in the step S2, the reaction comprises a purification operation after completion, and concretely comprises a process of washing with deionized water until no chloride ions are detected in the washing water, performing reduced pressure distillation at 70 ℃ for 40min, and performing freeze drying after the distillation is completed;
In the step S3, the thermal polymerization temperature is 40-80 ℃ and the polymerization time is 6-12h; 365 nm ultraviolet light is adopted for photopolymerization, and the illumination time is 5 s-10 min;
In the step S3, the initiator is a thermal initiator or a photoinitiator; the thermal initiator comprises one or more of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, dialkyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide, and the photoinitiator comprises one or more of 2-hydroxy-methylphenyl propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide;
in the step S3, the lithium salt accounts for 5-40% of the mass of the water-soluble polyion liquid monomer, and the initiator accounts for 0.1-5% of the mass of the water-soluble polyion liquid monomer;
In the steps S2 and S3, the lithium salts are the same or different, and are independently selected from one or more of fluorine-containing sulfimide, fluorine-containing phosphate or bisoxalato borate.
9. A lithium sulfur battery comprising:
and (3) a negative electrode: a lithium strip coated with the water-soluble polyionic liquid according to any of claim 1 to 4,
Current collector: the carbon-coated aluminum foil is coated on the surface of the aluminum foil,
A diaphragm: polypropylene
And (3) a positive electrode: a composite material of S8+ carbon nano tube + polyvinylidene fluoride + carbon black,
Electrolyte solution: lithium sulfur electrolyte containing polysulfide ions.
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