CN116162200A - Polymer electrolyte with stable lithium ion deposition function and preparation method and application thereof - Google Patents
Polymer electrolyte with stable lithium ion deposition function and preparation method and application thereof Download PDFInfo
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- CN116162200A CN116162200A CN202310210445.1A CN202310210445A CN116162200A CN 116162200 A CN116162200 A CN 116162200A CN 202310210445 A CN202310210445 A CN 202310210445A CN 116162200 A CN116162200 A CN 116162200A
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- polymer electrolyte
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- electrolyte
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- lithium ion
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 81
- 230000008021 deposition Effects 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 49
- DFVPUWGVOPDJTC-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)C(F)(F)F DFVPUWGVOPDJTC-UHFFFAOYSA-N 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 229920001577 copolymer Polymers 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 239000012528 membrane Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 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 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
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- 150000002500 ions Chemical class 0.000 abstract description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
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- 230000000694 effects Effects 0.000 abstract description 2
- -1 hexafluoro butyl Chemical group 0.000 abstract description 2
- 125000001425 triazolyl group Chemical group 0.000 abstract description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 238000000151 deposition Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- 239000012265 solid product Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000004809 Teflon Substances 0.000 description 12
- 229920006362 Teflon® Polymers 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000013557 residual solvent Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- 238000007710 freezing Methods 0.000 description 9
- 229910013684 LiClO 4 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000008859 change Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 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 3
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- 238000013461 design Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
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- 239000007773 negative electrode material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000010405 anode material Substances 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of lithium metal battery electrolyte materials, and provides a polymer electrolyte with a stable lithium ion deposition function, and a preparation method and application thereof. The hexafluoro butyl methacrylate HFBMA monomer in the polymer electrolyte can promote the formation of a fluorinated interface in the deposition process, and the triazolyl methacrylate TBMA monomer can induce the formation of a nitriding interface in the deposition process, and meanwhile, the advantages of the fluorinated interface and the nitriding interface are exerted, so that the effects of stabilizing lithium ion deposition and improving the interface stability between the electrolyte and lithium metal are achieved. Compared with the traditional polymer electrolyte, the method can effectively overcome the defect that a loose solid electrolyte interface film is formed in the traditional electrolyte lithium deposition process, and the formed solid electrolyte interface film can inhibit side reaction, promote ion transmission between electrolyte and lithium metal, enhance interface stability and realize uniform lithium deposition and long-time cycling stability of a lithium metal battery.
Description
Technical Field
The invention relates to the technical field of lithium metal battery electrolyte materials, in particular to a polymer electrolyte with a stable lithium ion deposition function, and a preparation method and application thereof.
Background
Graphite has relatively low specific capacity (372 mAh g) as a negative electrode material of a lithium ion battery -1 ) This limits the energy density of lithium ion batteries, which makes it difficult to meet the high energy density requirements of lithium ion batteries. Lithium metal has the highest theoretical capacity and the lowest electrochemical potential (3.04V compared to standard hydrogen electrodes), which make it an ideal negative electrode material for preparing high energy density lithium batteries. However, the formation of side reactions of lithium metal with liquid electrolytes can form unstable Solid Electrolyte Interfaces (SEI) and lead to growth of lithium dendrites, "dead lithium" and loss of battery capacity. In addition, carbonate-type and ether-type electrolytes of common liquid electrolytes also have the problems of formation of a porous brittle SEI film and narrow electrochemical stability window (the oxidation voltage of most ether-type electrolytes is lower than 4.0V) respectively. These problems can affect the cycling performance of lithium metal batteries, limiting high voltage positiveThe utilization of the electrode material reduces the energy density and application range of the lithium metal battery. Therefore, the preparation of a novel electrolyte system capable of stabilizing lithium metal deposition and having a wide electrochemical window through reasonable design is of great significance to the development of high-performance lithium metal technology.
The construction of fluorine-containing SEI on the surface of lithium metal has proven to be an effective strategy for inhibiting lithium dendrite growth and stabilizing lithium metal. LiF has a high band gap (13.6 eV) and excellent electrochemical stability, and these characteristics enable LiF to construct a stable SEI passivation film on a lithium metal surface, while an ultrathin LiF layer can suppress electron tunneling effects. The fluorinated electrolyte may provide a fluorinated component that forms a LiF-containing SEI on the lithium metal surface during lithium deposition to stabilize the deposition behavior of the lithium metal battery. For example, the university of Qinghua Zhang Jiang group reports that fluoroethylene carbonate as an electrolyte additive induces the formation of a LiF-containing SEI layer on the surface of lithium metal, improving the stability of lithium ion deposition (Advanced Functional Materials 2017,27,1605989). However, liF has a low ionic conductivity (10 -9 ～10 -14 S cm -1 ) Preventing conduction of lithium ions between the SEI film and lithium metal and affecting cycle performance of the lithium metal battery. In addition, the fluoroelectrolyte additive still takes liquid electrolyte as a carrier, and the safety problems such as electrolyte leakage and the like are not improved. Therefore, it is important to develop polymer electrolyte systems with good electrochemical properties to optimize SEI structures, components.
Disclosure of Invention
In order to meet the above defects or improvement demands of the prior art, the invention provides a polymer electrolyte with a stable lithium ion deposition function, and a preparation method and application thereof. By improving the key structure, related composition (especially the key monomer structure design of the polymer electrolyte and the like) of the polymer electrolyte and the reaction conditions of each step in the corresponding preparation method, the polymer electrolyte with the stable lithium ion deposition function is formed. The invention is realized based on the following technical scheme:
in a first aspect, the present invention provides a polymer electrolyte with a stable lithium ion deposition function, comprising a poly (TBMA-co-HFBMA) copolymer composed of hexafluorobutyl methacrylate HFBMA and nitrogen-rich monomer triazolyl methacrylate TBMA, wherein the poly (TBMA-co-HFBMA) copolymer has the chemical structural formula:
the molecular structure of the HFBMA is as follows:
the molecular structure of the TBMA is as follows:
preferably, m/n=10 to 1.
Preferably, the polymer electrolyte further includes a polymer matrix including any one of polyvinylidene fluoride (PVDF), polycarbonate (PC), polyacrylonitrile (PAN), and polyethylene oxide (PEO).
Preferably, the poly (TBMA-co-HFBMA) copolymer is 20 to 60 parts by weight based on 100 parts by weight of the total polymer electrolyte.
Preferably, the polymer electrolyte further comprises a lithium salt including one or both of lithium perchlorate and lithium bistrifluoromethylsulfonylimide.
The second aspect of the object of the present invention provides a method for preparing a polymer electrolyte having a stable lithium ion deposition function, comprising the steps of:
1) 3-amino-1, 2, 4-triazole and ethyl 2-methacrylate are dissolved in a first solvent; after the obtained solution reacts under the stirring condition, washing a reaction product by using a first solvent, filtering to remove soluble impurities, and drying to obtain a nitrogen-rich monomer TBMA;
2) Uniformly mixing the obtained nitrogen-rich monomer TBMA, HFBMA, an initiator and a second solvent, and heating to react after deoxidizing and water to obtain a poly (TBMA-co-HFBMA) copolymer;
3) Mixing a poly (TBMA-co-HFBMA) copolymer and a polymer matrix in a third solvent, stirring to form a uniform solution, pouring the obtained solution on a mould, and vacuum drying to obtain a mNNF-x electrolyte membrane; wherein m and n are respectively the mole ratio of TBMA and HFBMA, and x is the part of copolymer poly (TBMA-co-HFBMA) accounting for the total mass (100 parts) of the polymer electrolyte;
4) And soaking the obtained mNNF-x electrolyte membrane in electrolyte, wherein the electrolyte consists of lithium salt and an organic solvent, and fully absorbing the electrolyte to obtain the polymer electrolyte with the function of stabilizing lithium ion deposition.
Preferably, the reaction temperature in the step 1) is 30-60 ℃ and the reaction time is 3-8 hours; the first solvent comprises any one or more of methanol, ethanol, N-dimethylformamide, acetonitrile and dimethyl sulfoxide.
Preferably, the initiator in step 2) comprises one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate; the amount of the initiator is 0.5-1% mol of the total monomer molar amount; the reaction temperature is 65-80 ℃ and the reaction time is 10-24 hours; the second solvent comprises any one or more of tetrahydrofuran, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the reaction temperature in the step 3) is 50-80 ℃, and the reaction time is 10-24 hours; the third solvent comprises any one or more of tetrahydrofuran, N-dimethylformamide and N-methylpyrrolidone.
Preferably, m/n=10 to 1 and x=20 to 60 in step 3).
Preferably, the organic solvent in step 4) includes any one or more, more preferably two, of ethylene carbonate and dimethyl carbonate, 1, 3-dioxolane and ethylene glycol dimethyl ether.
In a third aspect, the present invention provides a use of a polymer electrolyte with a stable lithium ion deposition function in a lithium metal battery.
Compared with the prior art, on the one hand, the invention provides a preparation method of the polymer electrolyte with the function of stabilizing lithium ion deposition, and the HFBMA monomer in the electrolyte structure can promote the formation of a fluorinated interface in the deposition process, and the TBMA monomer can induce the formation of a nitriding interface in the deposition process, and simultaneously plays the advantages of the fluorinated interface and the nitriding interface, thereby playing roles in stabilizing lithium ion deposition and improving the interface stability between the electrolyte and lithium metal. On the other hand, by controlling the content of both HFBMA and TBMA in the polymer electrolyte, the porous morphology of the polymer electrolyte can be regulated, thereby improving the porosity, the liquid absorption and the ionic conductivity of the polymer electrolyte. In addition, the addition of the copolymer can also obviously reduce the crystallinity of the polymer matrix and improve the electrochemical performance of the electrolyte membrane. The polymer electrolyte is applied to a lithium metal battery, can realize long-time stable circulation, and solves the technical problems of low ionic conductivity and poor interface stability with a lithium metal negative electrode of the existing polymer electrolyte.
Compared with the traditional polymer electrolyte, the polymer electrolyte with the stable lithium ion deposition function provided by the invention can effectively overcome the defect that a loose solid electrolyte interface film is formed in the traditional electrolyte lithium deposition process, and the formed Solid Electrolyte Interface (SEI) film can inhibit side reaction, promote ion transmission between electrolyte and lithium metal, enhance interface stability and realize uniform lithium deposition and long-time cycling stability of a lithium metal battery. In addition, the polymer electrolyte provided by the invention also has a very wide electrochemical window and higher lithium ion conductivity.
In general, the following beneficial effects can be achieved by the above technical scheme designed by the invention:
(1) Firstly, synthesizing a nitrogen-rich monomer TBMA through the reaction of 3-amino-1, 2, 4-triazole and 2-methyl ethyl acrylate, then obtaining a copolymer composed of monomers HFBMA and TBMA by adopting a copolymerization method, and finally blending the copolymer with a polymer matrix to prepare the polymer electrolyte with a stable lithium ion deposition function.
The HFBMA monomer in the polymer electrolyte can promote the formation of LiF interface during the deposition process, and the TBMA monomer can induce the formation of Li during the deposition process 3 And N interface. Due to Li 3 N has a high ionic conductivity (up to 10 -3 S cm -1 ) Can overcome the defect of low ionic conductivity of LiF interface (10 -9 ～10 -14 S cm -1 ) The advantages of the fluorinated interface and the nitrided interface are simultaneously exerted, so that the interface stability between the electrolyte and the lithium metal is improved. At present, a method for preparing a polymer electrolyte by using a polyfluoro group monomer HFBMA and a nitrogen-rich monomer TBMA to realize a stable lithium ion deposition function has not been reported yet.
(2) The porous morphology of the polymer electrolyte can be regulated and controlled by controlling the contents of the HFBMA and the TBMA in the polymer electrolyte, a porous structure with uniform void distribution and moderate size is formed, and the porosity, the liquid absorption and the ionic conductivity of the polymer electrolyte can be remarkably improved.
(3) The addition of the copolymer can obviously reduce the crystallinity of a polymer matrix, solve the problem that the current polymer electrolyte limits the rapid conduction of lithium ions due to higher crystallinity, and simultaneously, because fluorine atoms in the HFBMA have wider energy band gaps (energy difference between the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LUMO), the prepared polymer electrolyte has a very wide electrochemical window (higher than 5.2V), is suitable for lithium metal batteries assembled by high-voltage anode materials, and improves the energy density of the batteries.
(4) The polymer electrolyte membrane can be obtained by blending the synthesized copolymer with the polymer matrix, has simple preparation process and easily obtained raw materials, and is suitable for mass production of high-performance polymer electrolyte materials.
(5) The polymer electrolyte with the stable lithium ion deposition function can be used as an electrolyte material to be assembled into a lithium metal battery, and the excellent performance of the polymer electrolyte can realize long-time circulation of the lithium metal battery.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a nitrogen-enriched monomer TBMA prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a poly (TBMA-co-HFBMA) copolymer prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of an electrolyte membrane prepared in example 1 of the present invention;
FIG. 4 is a graph showing the change in conductivity with temperature of the polymer electrolytes prepared in examples 1 to 4 according to the present invention;
FIG. 5 is a graph of electrochemical window of the polymer electrolyte prepared in example 1 of the present invention;
FIG. 6 is a graph of polarization of a polymer electrolyte assembled symmetrical cell prepared in example 1 of the present invention;
FIG. 7 is an XPS fluorine spectrum of the surface of lithium metal after cycling in example 1 of the present invention;
FIG. 8 is an XPS profile of the surface of a lithium metal after cycling in example 1 of the present invention;
FIG. 9 is an electron microscopic image of the polymer film prepared in comparative example 1 of the present invention.
FIG. 10 is an electron microscopic image of the polymer film prepared in comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following preferred examples provided by the present invention, m and n are the molar ratios of TBMA and HFBMA, respectively, and x is the fraction of the copolymer poly (TBMA-co-HFBMA) to the total mass of the polymer electrolyte, based on 100 parts of the total mass of the polymer electrolyte.
Example 1
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA. The structure of the nitrogen-rich monomer TBMA synthesized in the embodiment is confirmed by nuclear magnetic resonance spectrum, and the spectrum is shown in figure 1.
1.912g of TBMA, 4.0g of HFBMA and 19.7mg of azobisisobutyronitrile were dissolved in 40mL of N, N-dimethylformamide, and water and oxygen in the system were removed by 3 times of freeze-vacuum-argon-filling cycles, and the mixture was heated to 65℃and reacted under argon atmosphere for 24 hours. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer. FIG. 2 is an infrared spectrum of a poly (TBMA-co-HFBMA) copolymer synthesized in this example, and the structure of the copolymer can be confirmed.
50mg of poly (TBMA-co-HFBMA) and 50mg of PVDF were mixed and stirred magnetically at 50℃for 24 hours, and dissolved in 1.5mL of N, N-dimethylformamide. The resulting dispersion was poured onto a teflon mold, and the solvent was removed by vacuum drying at 50 ℃ for 12 hours to obtain a 2N1F-50 electrolyte membrane. Fig. 3 is a scanning electron microscope image of the electrolyte membrane prepared in this example. As can be seen from the figure, the electrolyte membrane has a uniform porous structure, which is mainly formed by phase separation between TBMA and PVDF. The uniform porous structure is beneficial to improving the porosity, the liquid absorption rate and the ion conductivity of the electrolyte.
Soaking the obtained 2N1F-50 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained. The lithium ion conductivity and electrochemical properties of the polymer electrolyte were measured. FIG. 4 is a graph showing the change in the conductivity with temperature of the polymer electrolytes prepared in examples 1 to 4, in which the ionic conductivity at 25℃of 2N1F-50 was 1.164X 10 -3 S cm -1 Exhibiting higher ionic conductivity. Fig. 5 is a graph of electrochemical window of the polymer electrolyte prepared in this example, which electrochemical window exceeds 5.2V. The electrolyte membrane was assembled into a Li/2N1F-50/Li symmetric cell for cyclic testing, and fig. 6 is a polarization graph of the symmetric cell. At 0.5mA cm -2 Cycling at current density for 1200 hours stillExhibiting a stable polarization curve. XPS testing was then performed on the cycled lithium metal surface. Fig. 7 is a fluorine spectrum of the lithium metal surface after the polymer electrolyte prepared in this example is assembled into a Li/Li symmetric battery cycle, confirming that the SEI interface contains abundant LiF. FIG. 8 is a nitrogen spectrum of the surface of lithium metal after the polymer electrolyte prepared in this example is assembled into a Li/Li symmetric battery cycle, confirming that the SEI interface contains abundant Li 3 N and LiN x O y . XPS test results show that the prepared polymer electrolyte can form fluorinated and nitrided interfaces on the SEI surface, and the interface stability of lithium metal is improved.
Comparative example 1
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.0g of HFBMA and 6.56mg of azodiisobutyronitrile are dissolved in 40mL of N, N-dimethylformamide, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the mixture is heated to 65 ℃ and reacted for 24 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (HFBMA) polymer.
40mg of poly (HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 50℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain an electrolyte membrane 0N1F-40 containing no TBMA monomer. Fig. 9 is a scanning electron microscope image of the polymer electrolyte prepared in this comparative example, in which the polymer electrolyte surface is dense and has no porous structure without adding TBMA monomer, mainly because HFBMA has good compatibility with PVDF, indicating that TBMA plays an important role in forming a porous structure.
Comparative example 2
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
0.9g of TBMA and 3.71mg of azodiisobutyronitrile are dissolved in 40mL of N, N-dimethylformamide, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 65 ℃, and the reaction is carried out for 24 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) polymer.
40mg of poly (TBMA) were mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide and magnetically stirred at 65℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 1N0F-40 electrolyte membrane. Fig. 10 is a scanning electron microscope image of the polymer film prepared in this comparative example, in which the size of the pores of the polymer electrolyte surface was largest and non-uniform compared to the polymer electrolyte containing the TBMA monomer without adding the HFBMA monomer, due to the phase separation between the TBMA and PVDF polymer matrix, again demonstrating that TBMA plays an important role in forming a porous structure.
Example 2
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.912g of TBMA, 4.0g of HFBMA and 19.7mg of azobisisobutyronitrile were dissolved in 40mL of N, N-dimethylformamide, and water and oxygen in the system were removed by 3 times of freeze-vacuum-argon-filling cycles, and the mixture was heated to 65℃and reacted under argon atmosphere for 24 hours. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 50℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 2N1F-40 electrolyte membrane.
Soaking the obtained 2N1F-40 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained. The change of the conductivity of the polymer electrolyte prepared by the embodiment of the invention along with the temperature is shown in FIG. 4, and the ionic conductivity of 2N1F-40 at 25 ℃ is 0.4262 multiplied by 10 -3 S cm -1 Conductivity with 2N1F-50 (1.164X 10) -3 S cm -1 ) In contrast, higher poly (TBMA-co-HFBMA) content may prove to decrease the crystallinity of the polymer matrix and increase the more amorphous phase in the polymer matrix.
Example 3
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
0.9g of TBMA, 0.188g of HFBMA and 3.71mg of azodiisobutyronitrile are dissolved in 40mL of N, N-dimethylformamide, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 65 ℃, and the reaction is carried out for 24 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 50℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 5N1F-40 electrolyte membrane.
Will getImmersing the 5N1F-40 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained. The change of the conductivity of the polymer electrolyte prepared by the method is shown in a graph in FIG. 4, and the ionic conductivity of 5N1F-40 at 25 ℃ is 0.373 multiplied by 10 -3 S cm -1 . Conductivity with 2N1F-40 (0.426×10) -3 S cm -1 ) In contrast, the enhancement of ionic conductivity of 2N1F-40 is mainly due to-CF in HFBMA monomer 2 The chain segment can promote the combination of fluorine atoms and positively charged lithium ions, thereby facilitating the conduction of lithium ions. Thus, 2N1F-40 has a higher ionic conductivity than 5N 1F-40.
Example 4
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.0g TBMA, 0.0956g HFBMA and 7.49mg azodiisobutyronitrile are dissolved in 40mL N, N-dimethylformamide, and water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, and the mixture is heated to 65 ℃ and reacted for 24 hours under argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 50℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 10N1F-40 electrolyte membrane.
Soaking the obtained 10N1F-40 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained. The change of the conductivity of the polymer electrolyte prepared by the method is shown in a graph in FIG. 4, and the ionic conductivity of 10N1F-40 at 25 ℃ is 0.224×10 -3 S cm -1 . With 5N1F-40 (0.373X 10) -3 S cm -1 ) And 2N1F-40 (0.426×10) -3 S cm -1 ) In contrast, it can be seen that as the HFBMA content in poly (TBMA-co-HFBMA) decreases, the conductivity also decreases accordingly, which again confirms that fluorine atoms play an important role in regulating the conductivity.
Example 5
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of ethanol, and reacted at 30℃with stirring for 8 hours to give a primary product. The product was washed three times with ethanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.912g of TBMA, 4.0g of HFBMA and 19.7mg of azodiisoheptonitrile are dissolved in 40mL of N, N-dimethylformamide, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 65 ℃, and the reaction is carried out for 24 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 50℃for 24 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 2N1F-40 electrolyte membrane.
The resulting 2N1F-40 film was immersed in a 1M LiTFSI (DOL: dme=v: v=1:1) electrolyte to obtain a polymer electrolyte having a uniform lithium deposition function.
Example 6
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of N, N-dimethylformamide, and reacted at 40℃with stirring for 6 hours to give a primary product. The product was washed three times with N, N-dimethylformamide and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.0g of TBMA, 0.523g of HFBMA and 5.15mg of azodiisoheptonitrile are dissolved in 40mL of tetrahydrofuran, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 70 ℃, and the reaction is carried out for 18 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PC, dissolved in 1.5mL of tetrahydrofuran, and magnetically stirred at 70℃for 18 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 2N1F-40 electrolyte membrane.
Soaking the obtained 2N1F-40 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained.
Example 7
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of acetonitrile, and reacted at 50℃for 5 hours with stirring to give a primary product. The product was washed three times with acetonitrile and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
0.9g of TBMA, 0.188g of HFBMA and 3.71mg of dimethyl azodiisobutyrate are dissolved in 40mL of N-methylpyrrolidone, and water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, and the mixture is heated to 70 ℃ and reacted for 14 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
30mg of poly (TBMA-co-HFBMA) was mixed with 70mg of PAN, dissolved in 1.5mL of N-methylpyrrolidone, and magnetically stirred at 70℃for 14 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 60 ℃ for 24 hours, and the solvent was removed to obtain a 5N1F-30 electrolyte membrane.
Soaking the obtained 5N1F-30 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, the result hasA polymer electrolyte with uniform lithium deposition function.
Example 8
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of dimethyl sulfoxide, and reacted at 60℃with stirring for 3 hours to give a primary product. The product was washed three times with dimethyl sulfoxide and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.0g of TBMA, 0.095g of HFBMA and 7.49mg of dimethyl azodiisobutyrate are dissolved in 40mL of N-methylpyrrolidone, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 80 ℃, and the reaction is carried out for 10 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
30mg of poly (TBMA-co-HFBMA) was mixed with 70mg of PEO, dissolved in 1.5mL of N-methylpyrrolidone, and magnetically stirred at 80℃for 10 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 60 ℃ for 24 hours, and the solvent was removed to obtain a 10N1F-30 electrolyte membrane.
Soaking the obtained 10N1F-30 film in 1M LiClO 4 (EC: dmc=v: v=1:1) in the electrolyte, a polymer electrolyte having a uniform lithium deposition function is obtained.
Example 9
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 60℃with stirring for 3 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.0g TBMA, 0.0956g HFBMA and 7.49mg azodiisoheptonitrile were dissolved in 40mL N-methylpyrrolidone, and the system was subjected to freeze-vacuum-argon-filling cycle for 3 times to remove water and oxygen, heated to 80℃and reacted under argon atmosphere for 10 hours. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
30mg of poly (TBMA-co-HFBMA) was mixed with 70mg of PEO, dissolved in 1.5mL of N-methylpyrrolidone, and magnetically stirred at 80℃for 10 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 60 ℃ for 24 hours, and the solvent was removed to obtain a 10N1F-30 electrolyte membrane.
The resulting 10N1F-30 film was immersed in a 1M LiTFSI (DOL: dme=v: v=1:1) electrolyte to obtain a polymer electrolyte having a uniform lithium deposition function.
Example 10
1.0g of 3-amino-1, 2, 4-triazole and 1.86g of ethyl 2-methacrylate were dissolved in 20mL of methanol, and reacted at 60℃with stirring for 3 hours to give a primary product. The product was washed three times with methanol and the soluble impurities were filtered. And (3) drying in vacuum at 50 ℃ for 24 hours, and removing residual solvent to obtain white solid, namely the nitrogen-rich monomer TBMA.
1.912g of TBMA, 4.0g of HFBMA and 19.7mg of azodiisoheptonitrile are dissolved in 40mL of N, N-dimethylformamide, water and oxygen in the system are removed by freezing, vacuumizing and argon filling circulation for 3 times, the temperature is raised to 65 ℃, and the reaction is carried out for 24 hours under the argon atmosphere. The reaction solution was dropped into acetonitrile to precipitate for removing unreacted monomers, while obtaining a solid product. The solid product was dried under vacuum at 60℃for 24 hours to give a poly (TBMA-co-HFBMA) copolymer.
40mg of poly (TBMA-co-HFBMA) was mixed with 60mg of PVDF, dissolved in 1.5mL of N, N-dimethylformamide, and magnetically stirred at 60℃for 18 hours. The resulting dispersion was poured onto a teflon mold, dried in vacuo at 50 ℃ for 12 hours, and the solvent was removed to obtain a 2N1F-40 electrolyte membrane.
The resulting 2N1F-40 film was immersed in a 1M LiTFSI (DOL: dme=v: v=1:1) electrolyte to obtain a polymer electrolyte having a uniform lithium deposition function.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (10)
1. A polymer electrolyte having a stable lithium ion deposition function, wherein the polymer electrolyte comprises a poly (TBMA-co-HFBMA) copolymer consisting of hexafluorobutyl methacrylate HFBMA and triazolylmethacrylate TBMA, the poly (TBMA-co-HFBMA) copolymer having the chemical structural formula:
the molecular structure of the HFBMA is as follows:
the molecular structure of the TBMA is as follows:
2. the polymer electrolyte with a stable lithium ion deposition function according to claim 1, wherein m/n=10 to 1.
3. The polymer electrolyte with stable lithium ion deposition function according to claim 1, further comprising a polymer matrix comprising any one or more of polyvinylidene fluoride, polycarbonate, polyacrylonitrile, and polyethylene oxide.
4. A polymer electrolyte having a stable lithium ion deposition function according to claim 3, wherein the poly (TBMA-co-HFBMA) copolymer is 20 to 60 parts by weight based on 100 parts by weight of the total polymer electrolyte.
5. The polymer electrolyte with stable lithium ion deposition function according to claim 1, further comprising a lithium salt comprising one or both of lithium perchlorate and lithium bistrifluoromethylsulfonylimide.
6. A method for preparing a polymer electrolyte with a stable lithium ion deposition function, which is characterized by comprising the following steps:
1) Dissolving 3-amino-1, 2, 4-triazole and ethyl 2-methacrylate in a first solvent, reacting the obtained solution under the stirring condition, flushing a reaction product with the first solvent, filtering to remove soluble impurities, and drying to obtain a monomer TBMA;
2) Uniformly mixing the obtained monomer TBMA, HFBMA, an initiator and a second solvent, and heating to react after deoxidizing and water to obtain a poly (TBMA-co-HFBMA) copolymer;
3) Mixing a poly (TBMA-co-HFBMA) copolymer and a polymer matrix in a third solvent, stirring to form a uniform solution, pouring the obtained solution on a mold, and vacuum drying to obtain an electrolyte membrane;
4) And soaking the obtained electrolyte membrane in electrolyte, wherein the electrolyte consists of lithium salt and an organic solvent, and fully absorbing the electrolyte to obtain the polymer electrolyte with the function of stabilizing lithium ion deposition.
7. The method for preparing a polymer electrolyte with a stable lithium ion deposition function according to claim 6, wherein the reaction temperature in the step 1) is 30-60 ℃ and the reaction time is 3-8 hours; the first solvent comprises any one or more of methanol, ethanol, N-dimethylformamide, acetonitrile and dimethyl sulfoxide.
8. The method for preparing a polymer electrolyte with stable lithium ion deposition function according to claim 6, wherein the initiator in the step 2) comprises one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate; the amount of the initiator is 0.5-1% mol of the total monomer molar amount; the reaction temperature is 65-80 ℃ and the reaction time is 10-24 hours; the second solvent comprises any one or more of tetrahydrofuran, N-dimethylformamide and N-methylpyrrolidone.
9. The method for preparing a polymer electrolyte with a stable lithium ion deposition function according to claim 6, wherein the reaction temperature in the step 3) is 50-80 ℃, and the reaction time is 10-24 hours; the third solvent comprises any one or more of tetrahydrofuran, N-dimethylformamide and N-methylpyrrolidone; and/or
The organic solvent in the step 4) comprises any one or more of ethylene carbonate and dimethyl carbonate, 1, 3-dioxolane and ethylene glycol dimethyl ether.
10. Use of a polymer electrolyte with a stable lithium ion deposition function according to any one of claims 1 to 9 in lithium metal batteries.
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| CN107359309A (en) * | 2016-05-09 | 2017-11-17 | 三星电子株式会社 | Negative pole for lithium metal battery and the lithium metal battery including it |
| US20190097232A1 (en) * | 2017-09-28 | 2019-03-28 | Samsung Electronics Co., Ltd. | Composite membrane for lithium battery, cathode for lithium battery, and lithium battery comprising the composite membrane |
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| CN107359309A (en) * | 2016-05-09 | 2017-11-17 | 三星电子株式会社 | Negative pole for lithium metal battery and the lithium metal battery including it |
| US20190097232A1 (en) * | 2017-09-28 | 2019-03-28 | Samsung Electronics Co., Ltd. | Composite membrane for lithium battery, cathode for lithium battery, and lithium battery comprising the composite membrane |
| CN115353837A (en) * | 2022-08-24 | 2022-11-18 | 南开大学 | Single-component polyion liquid adhesive and preparation method and application thereof |
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