CN117551244A - Block polymer, preparation method and application thereof, solid electrolyte and application thereof - Google Patents
Block polymer, preparation method and application thereof, solid electrolyte and application thereof Download PDFInfo
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- CN117551244A CN117551244A CN202310119837.7A CN202310119837A CN117551244A CN 117551244 A CN117551244 A CN 117551244A CN 202310119837 A CN202310119837 A CN 202310119837A CN 117551244 A CN117551244 A CN 117551244A
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- block polymer
- salt
- solid electrolyte
- ionic liquid
- lithium
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- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 38
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 38
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 32
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 19
- 159000000002 lithium salts Chemical class 0.000 claims description 19
- -1 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 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 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- AFSJUFFXOPXIOH-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound CC[NH+]1CN(C)C=C1.[O-]S(=O)(=O)C(F)(F)F AFSJUFFXOPXIOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- XOZHIVUWCICHSQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1,2-dimethyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1C.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XOZHIVUWCICHSQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 125000003827 glycol group Chemical group 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 239000012528 membrane Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of electrolytes, in particular to a block polymer, a preparation method and application thereof, a solid electrolyte and application thereof. The block polymer provided by the invention disturbs the regular arrangement of polyethylene glycol chain segments, reduces the crystallinity of polyethylene glycol, enhances the lithium guiding function, and simultaneously introduces ionic liquid, so that the conduction of lithium ions can be enhanced, the ionic conductivity is improved, and the electrochemical performance of a lithium ion battery is further improved.
Description
Technical Field
The invention relates to the technical field of electrolytes, in particular to a block polymer, a preparation method and application thereof, a solid electrolyte and application thereof.
Background
With the continuous development of the emerging field, the demand for lithium ion batteries with high energy density is increasing, and in order to overcome potential safety hazards of easy leakage, easy combustion and the like of liquid electrolyte, it is imperative to replace the liquid electrolyte with solid electrolyte.
The polymer electrolyte has the excellent characteristics of high temperature resistance, long service life and the like, can inhibit the growth of lithium dendrites, and solves a series of problems caused by the lithium dendrites. Ether oxygen in the polyethylene glycol chain segment can interact with lithium ions to dissolve various lithium salts, so that the polymer is a common polymer of the polymer electrolyte at present, but the ionic conductivity is low at room temperature, so that the application is limited.
Disclosure of Invention
The invention aims to provide a block polymer, a preparation method and application thereof, a solid electrolyte and application thereof, wherein the block polymer has higher ionic conductivity at room temperature.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a block polymer, which has a structure shown in a formula I:
wherein, m=60 to 160, n=68 to 455.
The invention also provides a preparation method of the block polymer in the technical scheme, which comprises the following steps:
mixing polyethylene glycol, bromoisobutyryl bromide, 4-dimethylaminopyridine, triethylamine and a first solvent, and performing esterification reaction to obtain a PEG initiator;
mixing the PEG initiator, styrene, N, N, N' -pentamethyl divinyl triamine and copper salt, and carrying out polymerization reaction to obtain the block polymer.
Preferably, the molar ratio of the polyethylene glycol, the 4-dimethylaminopyridine, the triethylamine and the bromoisobutyryl bromide is (1-1.5): (3-5): (2-4): (4-7);
the molar ratio of the PEG initiator, N, N, N' -pentamethyldivinyl triamine and copper salt is (1-1.5): (4-6): (2-4).
Preferably, the temperature of the polymerization reaction is 50-160 ℃ and the time is 0.5-3 h.
The invention also provides application of the block polymer prepared by the technical scheme or the preparation method of the technical scheme in the field of electrolytes.
The invention also provides a solid electrolyte, which comprises a block polymer, lithium salt and ionic liquid;
the block polymer is prepared by the block polymer according to the technical scheme or the preparation method according to the technical scheme.
Preferably, the mass ratio of the block polymer to the lithium salt to the ionic liquid is (1-30): (0.5-1.5): 1.
Preferably, the lithium salt comprises LiAsF 6 、LiBF 4 、LiCH 3 SO 3 、LiClO 4 、LiCF 3 SO 3 、LiPF 6 And LiTFSI;
the ionic liquid comprises one or more of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazole tetrafluoroboric acid, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid salt, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt.
The invention also provides application of the solid electrolyte in the polymer lithium battery.
The invention provides a block polymer, which has a structure shown in a formula I:
wherein, m=60 to 160, n=68 to 455.
The block polymer provided by the invention disturbs the regular arrangement of polyethylene glycol chain segments, reduces the crystallinity of polyethylene glycol, enhances the lithium guiding function, and simultaneously introduces ionic liquid, so that the conduction of lithium ions can be enhanced, the ionic conductivity is improved, and the electrochemical performance of a lithium ion battery is further improved.
Drawings
FIG. 1 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the block polymer of example 1;
FIG. 2 is a graph showing the impedance of a solid electrolyte membrane as an electrolyte assembly steel versus steel button cell according to example 1;
FIG. 3 is a graph showing the impedance of a solid electrolyte membrane as an electrolyte assembled steel-to-steel button cell according to example 2;
FIG. 4 is a physical view of the solid electrolyte membrane according to example 2;
FIG. 5 is a graph showing the change in conductivity with temperature of the solid electrolyte membrane according to example 2;
fig. 6 is a specific capacity efficiency curve of the solid electrolyte membrane described in example 2.
Detailed Description
The invention provides a block polymer, which has a structure shown in a formula I:
wherein, m=60 to 160, n=68 to 455.
In the present invention, the m is preferably 90 to 120; the n is preferably 100 to 300.
The invention also provides a preparation method of the block polymer in the technical scheme, which comprises the following steps:
mixing polyethylene glycol, bromoisobutyryl bromide, 4-dimethylaminopyridine, triethylamine and a first solvent, and performing esterification reaction to obtain a PEG initiator;
mixing the PEG initiator, styrene, N, N, N' -pentamethyl divinyl triamine and copper salt, and carrying out polymerization reaction to obtain the block polymer.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
According to the invention, polyethylene glycol, bromoisobutyryl bromide, 4-dimethylaminopyridine, triethylamine and a first solvent are mixed for esterification reaction, so that a PEG initiator is obtained.
In the present invention, the molar ratio of the polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is preferably (1 to 1.5): (3-5): (2-4): (4 to 7), more preferably (1.1 to 1.4): (3.5-4.5): (2.5-3.5): (5-6), most preferably (1.2-1.3): (3.8-4.2): (2.8-3): (5.3-5.8). In the present invention, the esterification reaction can be more sufficiently performed by controlling the molar ratio of the polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide within the above range.
In the present invention, the first solvent preferably includes dichloromethane, chloroform or acetonitrile, more preferably dichloromethane. The amount of the first solvent used in the present invention is not particularly limited, and may be any amount known to those skilled in the art and sufficient to dissolve the respective components.
In the present invention, the mixing preferably includes mixing bromoisobutyryl bromide and a portion of the first solvent to obtain a bromoisobutyryl bromide solution; mixing polyethylene glycol, 4-dimethylaminopyridine, triethylamine and the rest of the first solvent, discharging air, and adding the bromo isobutyryl bromide solution. In the invention, the adding mode of the bromoisobutyryl bromide solution is preferably dropwise adding; the process of the dropping is not particularly limited, and may be performed by a process well known to those skilled in the art. In the invention, the dripping can avoid violent heat release in the reaction process and aggravate the progress of side reaction. In the present invention, the means for exhausting air is preferably by exhausting air in the device by introducing inert gas. In the invention, the purpose of the air discharge is to discharge water vapor in the air at the same time, so as to avoid hydrolysis of bromoisobutyryl bromide.
In the present invention, the 4-dimethylaminopyridine and triethylamine are used as a base for neutralizing an acid generated during the esterification reaction to promote the progress of the esterification reaction.
In the present invention, the temperature of the esterification reaction is preferably 25℃and the time is preferably 12 to 36 hours, more preferably 24 hours. The temperature and time of the esterification reaction can enable the esterification reaction to fully proceed. In the present invention, the esterification reaction is preferably carried out under stirring, preferably mechanical stirring; the process of the mechanical stirring is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the completion of the esterification reaction, the present invention also preferably includes a post-treatment, which preferably includes washing, drying, precipitation, and separation, which are sequentially performed. In the invention, the washing is preferably carried out by adopting saturated saline water and deionized water in sequence; the number of times of washing with saturated saline is preferably 2 times, and the number of times of washing with deionized water is preferably 1 time. In the present invention, the drying is preferably performed using anhydrous magnesium sulfate, and the drying process is not particularly limited and may be performed using a process well known to those skilled in the art. In the present invention, the precipitation is preferably performed in glacial diethyl ether. The separation mode is preferably filtration; the filtering process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the molecular weight of the PEG initiator is preferably 1000 to 50000g/mol, more preferably 3000 to 30000g/mol, and most preferably 8000 to 15000g/mol. In the invention, the PEG initiator with the molecular weight range can lead the finally prepared block polymer to have better mechanical property, thereby being more beneficial to the application of the block polymer in electrolytes and lithium batteries.
After the PEG initiator is obtained, the PEG initiator, styrene, N, N, N' -pentamethyl divinyl triamine and copper salt are mixed for polymerization reaction to obtain the block polymer.
In the present invention, the copper salt preferably comprises cuprous bromide and/or cuprous chloride.
In the present invention, the N, N, N' -pentamethyldivinyl triamine and copper salt as catalysts can promote the progress of the polymerization reaction.
In the invention, the styrene is both a reactant and a solvent, so that the polymerization reaction is more sufficient, the structure of the block polymer and the content of the styrene are regulated, and the performance of the block polymer is further improved.
In the present invention, the molar ratio of the PEG initiator, N, N, N' -pentamethyldivinyl triamine and copper salt is preferably (1 to 1.5): (4-6): (2 to 4), more preferably (1.1 to 1.4): (4.5-5.5): (2.5 to 3.5), most preferably (1.2 to 1.3): 5:3.
In the present invention, the molar ratio of styrene to PEG initiator is preferably (100 to 550): 1, more preferably (150 to 250): 1, more preferably (190 to 230): 1, most preferably 220:1
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the temperature of the polymerization reaction is preferably 50 to 160 ℃, more preferably 80 to 120 ℃, and most preferably 110 ℃; the time is preferably 0.5 to 3 hours, more preferably 1 to 2 hours. In the present invention, the polymerization reaction is preferably carried out under stirring, and the stirring process is not particularly limited, and may be carried out by a process known to those skilled in the art. In the invention, the PEG initiator and the styrene are subjected to polymerization reaction, and the reaction is ensured to be more sufficient in the temperature and time range, and the block polymer is obtained.
After the polymerization reaction is completed, the invention also preferably comprises post-treatment, wherein the post-treatment preferably comprises column passing, precipitation and separation which are sequentially carried out; the process of passing through the column, precipitating and separating is not particularly limited, and may be carried out by using a process well known to those skilled in the art. In an embodiment of the invention, the passing column is specifically a passing neutral alumina column; the precipitation is specifically carried out in ice-n-hexane; the separation is in particular filtration.
In the present invention, the block polymer has higher ionic conductivity and thermal stability.
The invention also provides application of the block polymer prepared by the technical scheme or the preparation method of the technical scheme in the field of electrolytes.
The invention also provides a solid electrolyte, which comprises a block polymer, lithium salt and ionic liquid;
the block polymer is prepared by the block polymer according to the technical scheme or the preparation method according to the technical scheme.
In the present invention, the lithium salt preferably includes LiAsF 6 、LiBF 4 、LiCH 3 SO 3 、LiClO 4 、LiCF 3 SO 3 、LiPF 6 And LiTFSI, when the lithium salt is two or more of the above specific choices, the invention does not limit the ratio of the above specific substances in any particular way, and the lithium salt is mixed according to any ratio.
In the present invention, the ionic liquid includes one or more of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazole tetrafluoroboric acid, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid salt, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, and when the ionic liquid is two or more of the above specific choices, the ratio of the above specific substances is not particularly limited, and the ionic liquid may be mixed according to any ratio.
In the present invention, the mass ratio of the block polymer, lithium salt and ionic liquid is preferably (1 to 30): (0.5-1.5): 1; the mass ratio of the block polymer to the lithium salt is preferably (2 to 20): 1, more preferably (4 to 10): 1, most preferably (5 to 8): 1, a step of; the mass ratio of the block polymer to the ionic liquid is preferably (1-20): 1, more preferably (2 to 10): 1, most preferably (3 to 6): 1. in the invention, the types and the proportions of the block polymer, the lithium salt and the ionic liquid are controlled within the above range, so that the migration number of lithium ions can be further improved, the agglomeration of the lithium salt can be avoided, and the electrolyte performance can be further improved.
In the present invention, the preparation method of the solid electrolyte preferably includes the steps of:
mixing the block polymer, lithium salt, ionic liquid and a second solvent to obtain a mixture;
and coating the mixture on a substrate, and drying to obtain the solid electrolyte.
The block polymer, the lithium salt, the ionic liquid and the second solvent are mixed to obtain a mixture.
In the present invention, the second solvent preferably includes one or more of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and when the second solvent is two or more of the above specific choices, the present invention is not limited in any particular way, and the above specific materials may be mixed in any ratio.
The amount of the second solvent is not particularly limited in the present invention, and the block polymer, the lithium salt and the ionic liquid may be sufficiently dissolved.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the mixture is obtained, the mixture is coated on a substrate and dried to obtain the solid electrolyte.
In the present invention, the substrate is preferably a polytetrafluoroethylene plate, a glass plate, a polypropylene plate, or an aluminum foil. The size of the substrate is not limited in any particular way, and the size can be adjusted according to actual needs.
In the present invention, the coating method is preferably blade coating, and the process of blade coating is not particularly limited, and may be performed by a process well known to those skilled in the art. The coating amount of the coating according to the present invention is not particularly limited, and may be any coating amount known to those skilled in the art.
In the present invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 60 to 120 ℃, more preferably 80 to 100 ℃; the time is preferably 8 to 48 hours, more preferably 15 to 30 hours.
After the drying is completed, the method also preferably comprises film uncovering, and the film uncovering process is not limited in any way and can be performed by adopting a process well known to a person skilled in the art.
In the present invention, the thickness of the solid electrolyte is preferably 20 to 150. Mu.m, more preferably 40 to 80. Mu.m, and most preferably 50 to 60. Mu.m.
In the invention, the preparation method can enable the lithium salt to be more uniformly dispersed into the block polymer, and further improve the performance of the block polymer electrolyte.
The invention also provides application of the solid electrolyte in the polymer lithium battery. The positive electrode, the negative electrode, the preparation method and the like of the polymer lithium battery are not limited in any way, and the polymer lithium battery is well known to those skilled in the art.
The block polymers, methods and applications for preparing the same, solid state electrolytes and applications thereof, provided by the present invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 0.927mL of bromoisobutyryl bromide in 20mL of dichloromethane to obtain bromoisobutyryl bromide solution, dissolving 15g of polyethylene glycol with molecular weight of 10000g/mol, 0.5499g of 4-dimethylaminopyridine and 0.489mL of triethylamine in 100mL of dichloromethane, introducing air in a nitrogen removal device, then dropwise adding the bromoisobutyryl bromide solution, stirring and reacting for 24 hours at 25 ℃, washing for 2 times with saturated saline water and 1 time with deionized water, drying with anhydrous magnesium sulfate, precipitating in glacial diethyl ether, filtering to obtain PEO initiator (the ratio of the amounts of polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is 1:3:2:5, and the molecular weight of PEO initiator is 10299 g/mol);
2.0598g of PEO initiator, 0.0574g of cuprous bromide, 0.167mLN, N' -pentamethyldivinyl triamine and 10.0mL of styrene (the molar ratio of the styrene to the PEO initiator is 532:1) are stirred and reacted for 2 hours at 110 ℃, then the mixture is precipitated in ice-N-hexane through a neutral alumina column and filtered to obtain a block polymer (the structural formula of the block polymer is shown as a formula 1, the value of m is 152, and the value of N is 227);
the block polymer is subjected to nuclear magnetic resonance hydrogen spectrum test, the test result is shown in figure 1, and as can be seen from figure 1, the invention successfully synthesizes the BAB type block polymer with the structure shown in the formula 1;
dissolving 0.2g of the block polymer, 0.0667g of LiTFSI (the mass ratio of the block polymer to the LiTFSI is 3:1) and 0.05g of ionic liquid (the mass ratio of the block polymer to the ionic liquid is 4:1) in 0.8mLN, N-dimethylformamide, stirring for 12 hours at 45 ℃, then scraping and coating the mixture on a 10 multiplied by 20cm rectangular polypropylene plate, drying the mixture for 12 hours at 60 ℃ in a vacuum oven, and uncovering a film to obtain a solid electrolyte membrane;
and the solid electrolyte membrane is used as electrolyte to assemble a steel-to-steel button cell (the assembling sequence is small button, steel sheet, solid electrolyte membrane, steel sheet, elastic sheet and large button). The resulting button cell was subjected to impedance test, and FIG. 2 is a graph showing impedance test of the button cell at room temperature, and as can be seen from FIG. 2, the ionic conductivity thereof at room temperature was 3.2X10 -5 S/cm。
Example 2
Dissolving 0.927mL of bromoisobutyryl bromide in 20mL of dichloromethane to obtain bromoisobutyryl bromide solution, dissolving 15g of polyethylene glycol with molecular weight of 10000g/mol, 0.5499g of 4-dimethylaminopyridine and 0.489mL of triethylamine in 100mL of dichloromethane, introducing air in a nitrogen removal device, then dropwise adding the bromoisobutyryl bromide solution, stirring and reacting for 24 hours at 25 ℃, washing for 2 times with saturated saline water and 1 time with deionized water, drying with anhydrous magnesium sulfate, precipitating in glacial diethyl ether, filtering to obtain PEO initiator (the ratio of the amounts of polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is 1:3:2:5, and the molecular weight of PEO initiator is 10299 g/mol);
2.0598g of PEO initiator, 0.0574g of cuprous bromide, 0.167mLN, N' -pentamethyldivinyl triamine and 10.0mL of styrene (the molar ratio of the styrene to the PEO initiator is 532:1) are stirred and reacted for 1h at 110 ℃, then the mixture is precipitated in ice-N-hexane through a neutral alumina column and filtered to obtain a block polymer (the structural formula of the block polymer is shown as a formula 1, the value of m is 83, and the value of N is 227);
dissolving 0.2g of the block polymer, 0.0667g of LiTFSI (the mass ratio of the block polymer to the LiTFSI is 3:1) and 0.05g of ionic liquid (the mass ratio of the block polymer to the ionic liquid is 4:1) in 0.8mLN, N-dimethylformamide, stirring for 12 hours at 45 ℃, then scraping and coating the mixture on a 10 multiplied by 20cm rectangular polypropylene plate, drying the mixture for 12 hours at 60 ℃ in a vacuum oven, and uncovering a film to obtain a solid electrolyte membrane;
and the solid electrolyte membrane is used as electrolyte to assemble a steel-to-steel button cell (the assembling sequence is small button, steel sheet, solid electrolyte membrane, steel sheet, elastic sheet and large button). The resulting button cell was subjected to impedance test, and FIG. 3 is a graph showing the impedance test of the button cell at room temperature, and as can be seen from FIG. 3, the ionic conductivity thereof was 1.22×10 -4 S/cm；
The solid electrolyte membrane is tiled, the physical diagram of which is shown in fig. 4, and the surface morphology is smooth and has no holes or air gaps as can be seen from fig. 4;
as shown in FIG. 5, the solid electrolyte membrane has a temperature-dependent curve of the conductivity, and as is clear from FIG. 5, the ionic conductivity is 1.21×10 at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, respectively -4 S/cm、1.44×10 -4 S/cm、2.14×10 - 4 S/cm、3.41×10 -4 S/cm、4.82×10 -4 S/cm、6.94×10 -4 S/cm；
The specific capacity efficiency curve of the solid electrolyte membrane is shown in fig. 6, and as can be seen from fig. 6, the specific discharge capacity is still kept at 152mAh/g after 100 cycles at a multiplying power of 0.1C, which indicates that the solid electrolyte membrane has good cycle performance.
Comparative example 1
Dissolving 0.927mL of bromoisobutyryl bromide in 20mL of dichloromethane to obtain bromoisobutyryl bromide solution, dissolving 15g of polyethylene glycol with molecular weight of 10000g/mol, 0.5499g of 4-dimethylaminopyridine and 0.489mL of triethylamine in 100mL of dichloromethane, introducing air in a nitrogen removal device, then dropwise adding the bromoisobutyryl bromide solution, stirring and reacting for 24 hours at 25 ℃, washing for 2 times with saturated saline water and 1 time with deionized water, drying with anhydrous magnesium sulfate, precipitating in glacial diethyl ether, filtering to obtain PEO initiator (the ratio of the amounts of polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is 1:3:2:5, and the molecular weight of the PEO initiator is 10299 g/mol);
2.0598g of PEO initiator, 0.0574g of cuprous bromide, 0.167mLN, N' -pentamethyldivinyl triamine and 10.0mL of styrene (the molar ratio of the styrene to the PEO initiator is 532:1) are stirred and reacted for 3 hours at 110 ℃, then the mixture is precipitated in ice-N-hexane through a neutral alumina column and filtered to obtain a block polymer (the structural formula of the block polymer is shown as a formula 1, the value of m is 235, and the value of N is 227);
0.2g of the block polymer, 0.0667g of LiTFSI (the mass ratio of the block polymer to the LiTFSI is 3:1) and 0.05g of an ionic liquid (the mass ratio of the block polymer to the LiTFSI is 4:1) are dissolved in 0.8mL of N, N-dimethylformamide, stirred for 12 hours at 45 ℃, then coated on a 10X 20cm rectangular polypropylene plate, dried for 12 hours at 60 ℃ in a vacuum oven, and the film is uncovered, thus obtaining a solid electrolyte membrane (the thickness is 126 μm).
The polymer electrolyte obtained was deformed during drying to return it to a flat morphology to fracture.
Comparative example 2
Dissolving 0.927mL of bromoisobutyryl bromide in 20mL of dichloromethane to obtain bromoisobutyryl bromide solution, dissolving 15g of polyethylene glycol with molecular weight of 10000g/mol, 0.5499g of 4-dimethylaminopyridine and 0.489mL of triethylamine in 100mL of dichloromethane, introducing air in a nitrogen removal device, then dropwise adding the bromoisobutyryl bromide solution, stirring and reacting for 24 hours at 25 ℃, washing for 2 times with saturated saline water and 1 time with deionized water, drying with anhydrous magnesium sulfate, precipitating in glacial diethyl ether, filtering to obtain PEO initiator (the ratio of the amounts of polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is 1:3:2:5, and the molecular weight of PEO initiator is 10299 g/mol);
2.0598g of PEO initiator, 0.0574g of cuprous bromide, 0.167mLN, N' -pentamethyldivinyl triamine and 10.0mL of styrene (the molar ratio of the styrene to the PEO initiator is 532:1) are stirred and reacted for 0.5h at 110 ℃, then the mixture is precipitated in ice-N-hexane through a neutral alumina column and filtered to obtain a block polymer (the structural formula of the block polymer is shown as a formula 1, the value of m is 47, and the value of N is 227);
0.2g of the block polymer, 0.0667g of LiTFSI (the mass ratio of the block polymer to the LiTFSI is 3:1) and 0.05g of the ionic liquid (the mass ratio of the block polymer to the LiTFSI is 4:1) are dissolved in 0.8mL of N, N-dimethylformamide, stirred for 12 hours at 45 ℃, then coated on a 10X 20cm rectangular polypropylene plate, and dried for 12 hours at 60 ℃ in a vacuum oven, so that the obtained block polymer electrolyte cannot be removed from the polypropylene plate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A block polymer, wherein the block polymer has a structure of formula i:
wherein, m=60 to 160, n=68 to 455.
2. The method for preparing a block polymer according to claim 1, comprising the steps of:
mixing polyethylene glycol, bromoisobutyryl bromide, 4-dimethylaminopyridine, triethylamine and a first solvent, and performing esterification reaction to obtain a PEG initiator;
mixing the PEG initiator, styrene, N, N, N' -pentamethyl divinyl triamine and copper salt, and carrying out polymerization reaction to obtain the block polymer.
3. The method of claim 1, wherein the molar ratio of polyethylene glycol, 4-dimethylaminopyridine, triethylamine and bromoisobutyryl bromide is (1 to 1.5): (3-5): (2-4): (4-7);
the molar ratio of the PEG initiator, N, N, N' -pentamethyldivinyl triamine and copper salt is (1-1.5): (4-6): (2-4).
4. A process according to claim 2 or 3, wherein the polymerization is carried out at a temperature of 50 to 160 ℃ for a time of 0.5 to 3 hours.
5. Use of a block polymer according to claim 1 or a block polymer prepared by a method according to any one of claims 2 to 4 in the field of electrolytes.
6. A solid electrolyte comprising a block polymer, a lithium salt, and an ionic liquid;
the block polymer is the block polymer of claim 1 or the block polymer prepared by the preparation method of any one of claims 2 to 4.
7. The solid electrolyte according to claim 6, wherein the mass ratio of the block polymer, the lithium salt and the ionic liquid is (1 to 30): (0.5-1.5): 1.
8. The solid state electrolyte of claim 6 or 7 wherein the lithium salt comprises LiAsF 6 、LiBF 4 、LiCH 3 SO 3 、LiClO 4 、LiCF 3 SO 3 、LiPF 6 And LiTFSI;
the ionic liquid comprises one or more of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazole tetrafluoroboric acid, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid salt, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt.
9. Use of a solid state electrolyte as claimed in any one of claims 6 to 8 in a polymer lithium battery.
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