CN111748096A - Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte - Google Patents
Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte Download PDFInfo
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 81
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 81
- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 238000005266 casting Methods 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910000103 lithium hydride Inorganic materials 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- 229920000578 graft copolymer Polymers 0.000 claims description 10
- 229920000831 ionic polymer Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 4
- GPKDGVXBXQTHRY-UHFFFAOYSA-N 3-chloropropane-1-sulfonyl chloride Chemical compound ClCCCS(Cl)(=O)=O GPKDGVXBXQTHRY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 claims description 3
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 20
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- -1 dibromo alkyl compound Chemical class 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 125000002883 imidazolyl group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009827 uniform distribution 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M2300/0085—Immobilising or gelification of 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
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- 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
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Abstract
The invention provides a preparation method and application of a polybenzimidazole based single-ion polymer gel electrolyte. Firstly, preparing modified polybenzimidazole, namely adding lithium hydride into a polybenzimidazole solution to obtain deprotonated polybenzimidazole or reacting the deprotonated polybenzimidazole with a dibromo alkyl compound to obtain a polybenzimidazole-grafted copolymer; and then reacting the modified polybenzimidazole with lithium salt to obtain the polybenzimidazole single ion polymer. The single ion polymers with different degrees of substitution and different segment lengths are obtained by adjusting the addition amount of lithium hydride and the molecular weight of the graft. And mixing the single-ion polymer with polyvinylidene fluoride-hexafluoropropylene, and then casting and soaking to obtain the gel electrolyte. The gel electrolyte prepared by the invention has higher mechanical strength, ionic conductivity and lithium ion transference number, can effectively inhibit the growth of lithium dendrite, improves the interface stability, and can be widely applied to the fields of lithium ion batteries, lithium metal batteries and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method and application of a polybenzimidazole based single-ion polymer gel electrolyte.
Background
With the development of society and the progress of science and technology, people have higher and higher requirements on energy. However, the non-renewable energy sources such as fossil fuels are increasingly exhausted, and people are urgently required to develop efficient energy storage technology to fully play the roles of clean energy sources such as solar energy, wind energy and water energy. The lithium ion battery is one of energy storage devices, has the advantages of high specific energy, long cycle life, low self-discharge rate, no memory effect and the like, and is widely applied to the fields of mobile phones, computers, digital cameras, new energy automobiles and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte, a diaphragm and the like. The separator plays an important role as one of the important components of the battery. It isolates the positive and negative electrodes to prevent short circuit of the battery, provides a channel for ions and prevents electrons from passing through, adsorbs the electrolyte and prevents leakage of the electrolyte. At present, polyolefin materials have the advantages of high mechanical strength, stable electrochemical performance, low cost and the like, and are the most widely commercialized lithium battery separators. However, the polyolefin separator has the disadvantages of poor thermal stability, low porosity, low liquid absorption rate and the like, and thus the requirement of people for high-performance batteries is not met.
In recent decades, due to frequent occurrence of safety accidents such as mobile phone explosion, new energy automobile spontaneous combustion and the like, people pay more and more attention to the safety performance of the battery. The development of novel separators and the research of solid polymer electrolytes are the hot topics of the current lithium ion battery technology. As is well known, polybenzimidazole materials have the advantages of excellent mechanical properties, high temperature resistance, chemical stability, flame retardance and the like. Many researchers make full use of the advantages of polybenzimidazole which is engineering plastic, and prepare the lithium ion battery diaphragm by taking polybenzimidazole as a diaphragm substrate and using different pore-forming technologies. In the chinese patent CN 105789521A, polybenzimidazole is used as a polymer matrix, and polyethylene glycol is used as a pore-forming agent to form pores, so as to obtain a polybenzimidazole microporous membrane. The tensile strength of the microporous membrane is as high as 30MPa, and the salt absorption rate of the microporous membrane is 3 times that of Celgard 2400. However, pore-forming agent is used to form pores, which makes it difficult to control the size of the pore diameter and the uniform distribution of the pores. The Chinese patent CN 107845761A adopts a non-solvent induced phase separation technology and takes polybenzimidazole as a polymer matrix to prepare the lithium ion battery diaphragm with high porosity, fast liquid absorption rate and excellent thermal stability. Although the porosity of the porous film is high, the mechanical properties of the film vary, and the long-term stability of the battery is adversely affected. Chinese patent CN 109904370 a also uses polybenzimidazole as raw material to prepare porous membrane with high porosity, high solvent absorption and high mechanical strength by non-solvent induced phase inversion (NIPS). Researches find that the imidazole ring in polybenzimidazole can generate coordination with lithium ions, so that the lithium salt can be dissociated, and the ionic conductivity can be improved. But we can see from the SEM picture that the pore size distribution of the prepared porous membrane is not uniform, which will affect the performance of the battery. Subsequently, chinese patent CN 107845761 a synthesized a graft copolymer with polybenzimidazole as the main chain and polyethylene glycol as the side chain. The graft copolymer is mixed with lithium salt and succinonitrile to prepare the all-solid-state polymer electrolyte. The electrolyte has good mechanical properties and high ionic conductivity, but even the ionic conductivity value still does not meet the commercialization requirement.
In summary, either polybenzimidazole is prepared as a porous membrane or a solid electrolyte, a small molecular lithium salt is used as a lithium source. During the charging and discharging process of the battery, the movement of anions cannot be avoided, which will generate concentration polarization, and then affect the migration of lithium ions, finally resulting in the degradation of the battery performance. Meanwhile, the transference number of lithium ions is low, which accelerates the growth of lithium dendrites, affects the performance of the battery and even causes safety accidents such as explosion.
Disclosure of Invention
In order to solve the technical problem, the invention provides the following technical scheme:
the polybenzimidazole based single-ion polymer gel electrolyte is prepared to improve the transference number of lithium ions and inhibit the growth of lithium dendrites. Through the grafting reaction of the lithium salt and the polybenzimidazole, the lithium salt is positioned on the side chain of the polybenzimidazole, and the anion of the polybenzimidazole is fixed, so that the polybenzimidazole is difficult to migrate.
In order to improve the ionic conductivity of the polymer gel electrolyte, the invention also provides the following technical scheme:
the coordination of imidazole rings and lithium ions in the polybenzimidazole structure is utilized to promote the dissociation of lithium salt and improve the concentration of free lithium ions; meanwhile, the comb polymer containing the flexible side chain is prepared, and the flexible side chain can play a role in internal plasticization, so that the movement of a molecular chain is facilitated, and the mobility of lithium ions is improved.
In order to improve the safety performance of the battery, the invention also provides the following technical scheme:
the invention utilizes the good mechanical property, high temperature resistance and flame retardant property of polybenzimidazole to prepare the polymer gel electrolyte with excellent thermal stability, high tensile strength and non-flammability.
The invention also provides a preparation method of the comb-shaped polybenzimidazole based single-ion polymer gel electrolyte with different side chain lengths.
The specific technical scheme of the invention is as follows:
the invention provides a polybenzimidazole based single ion polymer, which has the following chemical structure:
wherein:
the invention also provides a preparation method of the polybenzimidazole based single ion polymer, which comprises the following specific steps:
mixing and dissolving modified polybenzimidazole and a solvent, adding a lithium salt, reacting at 80-100 ℃ for 10-40 h, cooling to room temperature to obtain a mixed solution, pouring the mixed solution into deionized water for precipitation, filtering, washing and drying to obtain a polybenzimidazole single-ion polymer finally;
further, the molar ratio of the modified polybenzimidazole to the lithium salt is 1: 1-1: 3;
further, the solvent is dimethyl sulfoxide or N, N-dimethylacetamide;
further, the modified polybenzimidazole is deprotonated polybenzimidazole or polybenzimidazole-based graft copolymer;
the deprotonated polybenzimidazole is prepared by the following method: mixing polybenzimidazole and dimethyl sulfoxide, heating and dissolving at the temperature of 60-80 ℃, adding lithium hydride, and continuously reacting for 10-12 hours to obtain deprotonated polybenzimidazole;
the polybenzimidazole based graft copolymer is prepared by the following method: mixing polybenzimidazole and N, N-dimethylacetamide, adding lithium hydride, reacting at 80-100 ℃ for 8-10 h, adding a dibromoalkyl compound, reacting at 100-150 ℃ for 24-40 h, cooling to room temperature, pouring the mixed solution into ethanol to obtain a precipitate, and filtering, washing and drying to obtain a polybenzimidazole-based graft copolymer;
furthermore, the molar ratio of the polybenzimidazole to the dibromoalkyl compound is 1: 1-1: 3.
Further, the molecular formula of the dibromoalkyl compound is Br (CH)2CH2)mBr，m＝2～6。
Further, the lithium salt is 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium or 3-hydroxypropane sulfonyl trifluoromethyl sulfonyl imide lithium, and the chemical structure of the lithium salt is as follows:
The lithium 3-chloropropanesulfonyltrifluoromethanesulfonimide is prepared by the following steps: under the protection of inert gas, mixing lithium hydroxide and trifluoromethanesulfonamide, adding acetonitrile, magnetically stirring for 0.5-2 h in an ice-water bath, adding 3-chloropropane sulfonyl chloride, heating to room temperature, reacting for 12-24 h, filtering, drying to obtain viscous liquid, and recrystallizing to obtain 3-chloropropane sulfonyl trifluoromethanesulfonimide lithium;
the lithium 3-hydroxypropanesulfonyltrifluoromethanesulfonimide is prepared by the following steps: adding lithium hydroxide monohydrate into acetic acid aqueous solution, adding 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium, magnetically stirring, refluxing and heating for 48 hours, cooling to room temperature, adding lithium hydroxide monohydrate, stirring, concentrating, adding acetonitrile, stirring, separating, concentrating, washing, and drying in vacuum to obtain 3-hydroxypropane sulfonyl trifluoromethyl sulfonyl imide lithium;
according to the invention, polybenzimidazole and lithium salt are subjected to a grafting reaction, anions in the lithium salt are fixed on a side chain of a polymer to inhibit the migration of the anions, concentration polarization is avoided, the performance of the battery is improved, flexible chain segments with different molecular weights are grafted, the swing of the flexible chain segments is fully utilized, the migration of lithium ions is promoted, and the ionic conductivity is improved;
the invention also provides an application of the polybenzimidazole based single ion polymer in a polymer gel electrolyte, which comprises the following preparation methods: mixing polybenzimidazole based single-ion polymer and polyvinylidene fluoride-hexafluoropropylene, dissolving in an organic solvent to obtain a casting solution, casting the casting solution on a glass plate, heating and drying to obtain an electrolyte membrane, and soaking the electrolyte membrane in a plasticizer to obtain the single-ion polymer gel electrolyte.
Further, the mass ratio of the single ion polymer to the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in the steps is 1: 1-1: 3;
the organic solvent is any one of acetonitrile, ethyl acetate, N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethylacetamide;
the plasticizer is any combination of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether and sulfolane.
According to the invention, the single ion polymer and the polyvinylidene fluoride-hexafluoropropylene are blended, so that on one hand, the mechanical strength of the gel electrolyte can be further improved; on the other hand, the compatibility of the single ion polymer and polyvinylidene fluoride-hexafluoropropylene is utilized, so that microphase separation is caused to generate micropores, and the micropores can promote the absorption of the plasticizer and contribute to the improvement of the ionic conductivity.
The polybenzimidazole based single-ion polymer gel electrolyte provided by the invention has higher mechanical property, excellent thermal stability, ideal ionic conductivity and lithium ion transference number, can effectively inhibit the growth of lithium dendrite, improves the interface stability, and has potential application value in lithium ion batteries and lithium metal batteries.
The present invention will be further described with reference to the accompanying drawings to fully illustrate the objects, technical features and technical effects of the present invention.
Drawings
FIG. 1 is a scheme for the synthesis of polybenzimidazole based monoionomers of examples 1 and 4 of the present invention;
FIG. 2 is a hydrogen nuclear magnetic spectrum of lithium 3-chloropropanesulfonyl trifluoromethanesulfonimide in example 1 of the present invention;
FIG. 3 shows the hydrogen nuclear magnetic spectrum of the polybenzimidazole-based single-ion polymer in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
EXAMPLE 1 Synthesis of polybenzimidazolyl Mono-Ionic Polymer
(1) Synthesis of 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium
4.068g of lithium hydroxide and 12.627g of trifluoromethanesulfonamide were added under nitrogen to a 100mL round-bottomed flask, 85mL of acetonitrile were added, and magnetic stirring was carried out for 0.5h in an ice-water bath. 15g of 3-chloropropanesulfonyl chloride are then added dropwise to the flask. After the addition was complete, the temperature was raised to room temperature and reacted for 24 h. The mixture was then filtered to remove insoluble salts and dried under vacuum to give a viscous liquid. And recrystallizing the viscous liquid in dichloromethane to obtain a pure white solid, namely the 3-chloropropane sulfonyl trifluoromethyl sulfimide lithium. The chemical structure of the 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium is as follows:
the chemical structure marks active hydrogen of the 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium with different chemical shifts. The characteristic peak at 3.74ppm is methylene H bonded to chlorine atomaChemical shift of (4), the characteristic peak at 3.10ppm is methylene H attached to lithium trifluoromethanesulfonimidecChemical shift of (2.15 ppm) characteristic peak is methylene HbChemical shift of (d). Thus, the 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium is successfully prepared, and the details are shown in the attached figure 2 of the specification.
(2) Synthesis of polybenzimidazole based single ionic polymers
Under the protection of nitrogen, 0.4g of polybenzimidazole and dimethyl sulfoxide are sequentially added into a beaker, the mixture is magnetically stirred and is completely dissolved at the temperature of 80 ℃, and lithium hydride is added after the dissolution to react for 10 hours; 0.1184g of 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium obtained in the step (1) is added into the solution, the solution is cooled to room temperature after reacting for 36h at 100 ℃, then the reaction solution is poured into deionized water, the solution is filtered, a filter cake is washed for 3-5 times by the deionized water, and the polybenzimidazole based single ion polymer is obtained after drying. The chemical structure of the polybenzimidazole based single ion polymer is as follows:
the chemical structures mark the active hydrogen of different chemical shifts of the polybenzimidazole based single ion polymer. The characteristic peak at 7.25ppm was H on the benzene ring bonded to the imidazole ring1Chemical shift of (2), the characteristic peak at 7.43ppm is H on the benzene ring bonded to the imidazole ring4Chemical shift of (2), the characteristic peak at 7.90ppm is H on the benzene ring bonded to the imidazole ring3Chemical shift of (2), the characteristic peak at 7.99ppm is H on the benzene ring bonded to the imidazole ring5Chemical shift of (2), the characteristic peak at 8.30ppm is H on the benzene ring bonded to the imidazole ring2Chemical shift of (5), the characteristic peak at 4.64ppm is the side chain methylene H6Chemical shift of (5), the characteristic peak at 3.12ppm is the side chain methylene H8Chemical shift of (2.25 ppm) characteristic peak is side chain methylene H7The chemical shift of (A) is detailed in the attached figure 3 of the specification. This demonstrates the successful preparation of polybenzimidazolyl single ion polymers.
Example 2 Synthesis of a MonoIonic Polymer gel electrolyte (polybenzimidazolyl MonoIonic Polymer: PVDF-HFP ═ 1:1)
Mixing the polybenzimidazole based single ion polymer obtained in the step (2) of the example 1 and PVDF-HFP according to the mass ratio of 1:1 to obtain a mixture, dissolving the mixture in N-methylpyrrolidone to obtain a casting solution, then casting the casting solution on a clean glass plate, placing the glass plate on a vacuum oven, drying the glass plate for 12 hours at 80 ℃, vacuumizing the glass plate, drying the glass plate for 24 hours at 100 ℃ to obtain an electrolyte membrane, and then soaking the electrolyte membrane in ethylene carbonate/propylene carbonate (the volume ratio is 1:1) to obtain a single ion polymer gel electrolyte.
The single-ion polymer gel electrolyte obtained in example 2 is assembled into a button cell and a performance test is carried out, wherein the specific discharge capacity at room temperature and 0.2C reaches 150 mA.h/g, and the transference number of lithium ions is 0.91.
Example 3 Synthesis of a MonoIonic Polymer gel electrolyte (polybenzimidazolyl MonoIonic Polymer: PVDF-HFP ═ 1:2)
Mixing the polybenzimidazole based single ion polymer obtained in the step (2) of example 1 with PVDF-HFP according to the mass ratio of 1:2 to obtain a mixture, dissolving the mixture in N-methylpyrrolidone to obtain a casting solution, then casting the casting solution on a clean glass plate, placing the glass plate on a vacuum oven, drying the glass plate for 12 hours at 80 ℃, vacuumizing the glass plate, drying the glass plate for 24 hours at 100 ℃ to obtain an electrolyte membrane, and then soaking the electrolyte membrane in ethylene carbonate/propylene carbonate (the volume ratio is 1:1) to obtain a single ion polymer gel electrolyte.
The single-ion polymer gel electrolyte obtained in example 3 was assembled into a button cell and tested for performance, the specific capacity at 0.2C at room temperature reached 145mA · h/g, and the transference number of lithium ions was 0.89.
EXAMPLE 4 Synthesis of polybenzimidazolyl single ion Polymer
(1) Synthesis of 3-hydroxypropanesulfonyltrifluoromethylsulfonyl imide lithium
Adding 1.11g of lithium hydroxide monohydrate to 18mL of acetic acid aqueous solution, adding 5.18g of 3-chloropropanesulfonyltrifluoromethanesulfonimide lithium obtained in step (1) of example 1, magnetically stirring the above mixed solution, heating under reflux for 48h, cooling to room temperature, adding 0.924g of lithium hydroxide monohydrate, stirring the mixture at room temperature for 4h, concentrating, adding 30mL of acetonitrile, stirring the mixture for 30min, collecting the supernatant, concentrating, washing, and vacuum drying to obtain 3-hydroxypropanesulfonyltrifluoromethanesulfonimide lithium.
(2) Synthesis of polybenzimidazole based single ionic polymers
Under the protection of nitrogen, 0.4g of polybenzimidazole and N, N-dimethylacetamide are sequentially added into a beaker, the mixture is completely dissolved at the temperature of 80 ℃ by magnetic stirring, and then lithium hydride is added for reaction for 10 hours; adding 0.4879g of 1, 6-dibromohexane into the solution, then raising the temperature, reacting at 100 ℃ for 24h, cooling to room temperature, pouring the reaction solution into ethanol, filtering, washing the filter cake with ethanol for 3 times, and drying to obtain the polybenzimidazole-based graft copolymer; 0.5641g of polybenzimidazole-based graft copolymer is dissolved in N, N-dimethylacetamide, magnetic stirring is carried out, the mixture is completely dissolved at the temperature of 80 ℃, 0.110g of 3-hydroxypropanesulfonyltrifluoromethanesulfonimide lithium obtained in the step (1) is added, then the temperature is raised, the reaction is carried out at the temperature of 100 ℃ for 36 hours, then the cooling is carried out to the room temperature, the reaction solution is poured into deionized water, the filtration is carried out, the filter cake is washed for 3-5 times by the deionized water, and the polybenzimidazole-based mono-ionic polymer is obtained after drying.
Example 5 Synthesis of a Monoionic Polymer gel electrolyte (Monoionic Polymer: PVDF-HFP ═ 1:1)
The polybenzimidazole based single ion polymer obtained in the step (2) of example 4 and PVDF-HFP were mixed in a mass ratio of 1:1 to obtain a mixture, and the mixture was dissolved in N-methylpyrrolidone to obtain a uniform and transparent casting solution. And then casting the casting solution on a clean glass plate, placing the glass plate in a vacuum oven, drying for 12 hours at 80 ℃, vacuumizing again, and drying for 24 hours at 100 ℃ to obtain the electrolyte membrane. Then, the electrolyte membrane is soaked in ethylene carbonate/propylene carbonate (volume ratio is 1:1) to obtain the single-ion polymer gel electrolyte.
The single-ion polymer gel electrolyte obtained in example 5 was assembled into a button cell and tested for performance, the specific capacity at 0.2C at room temperature reached 155mA · h/g, and the transference number of lithium ions was 0.91.
Example 6 Synthesis of a Monoionic Polymer gel electrolyte (Monoionic Polymer: PVDF-HFP ═ 1:2)
The polybenzimidazole based single ion polymer obtained in the step (2) of example 4 and PVDF-HFP were mixed in a mass ratio of 1:2 to obtain a mixture, and the mixture was dissolved in N-methylpyrrolidone to obtain a uniform and transparent casting solution. And then casting the casting solution on a clean glass plate, placing the glass plate in a vacuum oven, drying for 12 hours at 80 ℃, vacuumizing again, and drying for 24 hours at 100 ℃ to obtain the electrolyte membrane. Then, the electrolyte membrane is soaked in ethylene carbonate/propylene carbonate (volume ratio is 1:1) to obtain the single-ion polymer gel electrolyte.
The single-ion polymer gel electrolyte obtained in example 6 was assembled into a button cell and tested for performance, the specific capacity at 0.2C at room temperature reached 145mA · h/g, and the transference number of lithium ions was 0.88.
Claims (10)
1. A polybenzimidazole based single ion polymer having the structure:
wherein:
2. a polybenzimidazole-based mono-ionic polymer according to claim 1, prepared by the following steps:
mixing and dissolving modified polybenzimidazole and a solvent, adding a lithium salt, reacting at 80-100 ℃ for 10-40 h, cooling to room temperature to obtain a mixed solution, pouring the mixed solution into deionized water for precipitation, filtering, washing and drying to obtain the polybenzimidazole single-ion polymer.
3. The polybenzimidazole-based polyion of claim 2, wherein the modified polybenzimidazole is a deprotonated polybenzimidazole or a polybenzimidazole-based graft copolymer.
4. A polybenzimidazole based mono-ionic polymer according to claim 3, characterized in that said deprotonated polybenzimidazole is prepared by: mixing polybenzimidazole and dimethyl sulfoxide, heating and dissolving at the temperature of 60-80 ℃, then adding lithium hydride, and continuing to react for 10-12 h to obtain deprotonated polybenzimidazole.
5. The polybenzimidazolyl single ion polymer of claim 3, wherein the polybenzimidazolyl graft copolymer is prepared by: mixing polybenzimidazole and N, N-dimethylacetamide, adding lithium hydride, reacting at 80-100 ℃ for 8-10 h, adding a dibromoalkyl compound, wherein the molar ratio of polybenzimidazole to the dibromoalkyl compound is 1: 1-1: 3, reacting at 100-150 ℃ for 24-40 h, cooling to room temperature to obtain a mixed solution, pouring the mixed solution into ethanol for precipitation, filtering, washing and drying to obtain the polybenzimidazole-based graft copolymer.
6. The polybenzimidazolyl polyion according to claim 5, wherein the dibromoalkyl compound has the formula of Br (CH)2CH2)mBr，m＝2～6。
7. The polybenzimidazolyl single ion polymer of claim 2, wherein the lithium salt is lithium 3-chloropropanesulfonyltrifluoromethanesulfonylimide or lithium 3-hydroxypropanesulfonyltrifluoromethanesulfonylimide.
8. The polybenzimidazole based mono-ionic polymer according to claim 7, wherein said lithium 3-chloropropanesulfonyltrifluoromethanesulfonimide is prepared by the following steps: mixing lithium hydroxide and trifluoromethanesulfonamide, adding acetonitrile, stirring for 0.5-2 h in an ice-water bath, adding 3-chloropropane sulfonyl chloride, heating the reaction temperature to room temperature, reacting for 10-24 h, filtering, drying and recrystallizing to obtain the 3-chloropropane sulfonyl trifluoromethanesulfonyl imide lithium.
9. The polybenzimidazolyl single ion polymer of claim 7, wherein the lithium 3-hydroxypropanesulfonyltrifluoromethylsulfonyl imide is prepared by the following steps: mixing lithium hydroxide monohydrate and acetic acid aqueous solution, adding 3-chloropropane sulfonyl trifluoromethyl sulfonyl imide lithium described in claim 7 to obtain a mixed solution, stirring the mixed solution, refluxing and heating for 40-48 h, cooling to room temperature, adding lithium hydroxide monohydrate, stirring and concentrating, adding 30mL acetonitrile, stirring, separating, concentrating, washing, and vacuum drying to obtain 3-hydroxypropane sulfonyl trifluoromethyl sulfonyl imide lithium.
10. The use of a polybenzimidazole-based mono-ionic polymer according to claim 1 in a lithium metal battery, comprising the following steps: dissolving the polybenzimidazole based single-ion polymer and polyvinylidene fluoride-hexafluoropropylene of claim 1 in an organic solvent to obtain a casting solution, casting the casting solution on a glass plate, heating and drying to obtain an electrolyte membrane, and soaking the electrolyte membrane in a plasticizer to obtain a single-ion polymer gel electrolyte.
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