CN114361582A - Polymer electrolyte membrane, preparation method thereof and battery - Google Patents
Polymer electrolyte membrane, preparation method thereof and battery Download PDFInfo
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- CN114361582A CN114361582A CN202111494151.3A CN202111494151A CN114361582A CN 114361582 A CN114361582 A CN 114361582A CN 202111494151 A CN202111494151 A CN 202111494151A CN 114361582 A CN114361582 A CN 114361582A
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- 239000012528 membrane Substances 0.000 title claims abstract description 92
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- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 30
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- 238000000034 method Methods 0.000 claims abstract description 19
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- -1 polypropylene carbonate Polymers 0.000 claims description 7
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 7
- 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 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 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 claims description 3
- 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 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
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- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a polymer electrolyte membrane, which comprises the following steps: dissolving a first polymer and lithium salt in an organic solvent to obtain a first mixed solution; adding a first polymerization monomer and an initiator into the first mixed solution to obtain a second mixed solution; adding an inorganic oxide into the second mixed solution, and uniformly dispersing to obtain polymer electrolyte slurry; coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film; drying the wet membrane of the polymer electrolyte to obtain a finished product; the raw materials for preparing the polymer electrolyte membrane comprise the following components in parts by weight: 1-15 parts of first polymer, 30-70 parts of organic solvent, 0.5-5 parts of lithium salt, 0.1-5 parts of first polymerization monomer, 0.05-2 parts of initiator and 0.5-5 parts of inorganic oxide. Correspondingly, the invention also provides the polymer electrolyte membrane prepared by the method, which has good mechanical strength and good interface compatibility.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a polymer electrolyte membrane, a preparation method thereof and a battery.
Background
In order to meet the increasing demand for lithium batteries for consumer electronics and electric vehicles, all-solid-state lithium batteries have attracted considerable attention in recent years due to their superior safety and ultra-high energy density. Conventional lithium batteries containing organic liquid electrolytes exhibit serious safety problems of toxicity, flammability, corrosiveness and poor chemical stability. The use of solid electrolytes instead of electrolytes and separators can fundamentally eliminate the above safety problems. The all-solid-state lithium battery is divided into three types according to different types of solid electrolytes: polymers, oxides and sulfides. The all-solid-state battery assembled at this stage is difficult to operate at room temperature and low temperature due to low ionic conductivity and large interfacial resistance.
In the prior art, the polymer electrolyte is mainly prepared by dissolving polymers (PEO, PVDF-HFP, PPC, PMMA, etc.) in solvents (NMP, DMAC, DMF, ACN), and adding lithium salt (LiPF)6、LiCLO4LiTFSI, etc.), a plasticizer or an ionic liquid, and an inorganic oxide, etc. to prepare an electrolyte slurry. And forming the electrolyte slurry into a film by a solution casting method or a blade coating method, and then drying at high temperature to volatilize the solvent to prepare the polymer electrolyte film.
However, the polymer solid electrolytes all have poor compatibility with inorganic oxides, resulting in non-uniform dispersion of the inorganic oxides in the polymer, thereby deteriorating mechanical strength of the electrolyte membrane and having low ionic conductivity. The contact with the anode and the cathode is poor, so that the interface impedance of the battery is high, and the cycle performance of the battery at room temperature and low temperature is seriously influenced.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a polymer electrolyte membrane, which can improve the compatibility between an inorganic oxide and a polymer, improve the mechanical strength of the polymer electrolyte membrane, and improve the compatibility between the polymer electrolyte membrane and positive and negative electrode interfaces.
The technical problem to be solved by the present invention is to provide a polymer electrolyte membrane, wherein the polymer interface and the inorganic oxide interface are connected more tightly, and the mechanical strength is good. Accordingly, a battery containing the above polymer electrolyte membrane is provided.
In order to solve the above technical problems, the present invention provides a method for preparing a polymer electrolyte membrane, comprising the steps of:
dissolving a first polymer and lithium salt in an organic solvent to obtain a first mixed solution;
adding a first polymerization monomer and an initiator into the first mixed solution to obtain a second mixed solution;
adding an inorganic oxide into the second mixed solution, and uniformly dispersing to obtain polymer electrolyte slurry;
coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
drying the wet membrane of the polymer electrolyte to obtain a finished product;
the raw materials for preparing the polymer electrolyte membrane comprise the following components in parts by weight: 1-15 parts of first polymer, 30-70 parts of organic solvent, 0.5-5 parts of lithium salt, 0.1-5 parts of first polymerization monomer, 0.05-2 parts of initiator and 0.5-5 parts of inorganic oxide.
Preferably, the polymer electrolyte slurry comprises the following components in parts by weight: 2-8 parts of first polymer, 40-60 parts of organic solvent, 1-3 parts of lithium salt, 0.5-1.5 parts of first polymerization monomer, 0.08-1 part of initiator and 1-3 parts of inorganic oxide.
Preferably, the first polymeric monomer comprises one or a combination of maleic anhydride, dimethyl maleic anhydride, succinic anhydride;
the initiator comprises one or a combination of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and dimethyl azobisisobutyrate.
Preferably, the first polymeric monomer is maleic anhydride; the initiator is dicumyl peroxide.
Preferably, the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate and polymethyl methacrylate.
Preferably, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, acetonitrile;
the inorganic oxide comprises one or more of aluminum oxide, titanium dioxide and silicon dioxide.
Preferably, the polymer electrolyte slurry comprises the following components in parts by weight: 4-6 parts of polyvinylidene fluoride, 45-55 parts of N-methylpyrrolidone, 1.5-2.5 parts of lithium bis (trifluoromethanesulfonyl) imide, 0.8-1.2 parts of maleic anhydride, 0.09-0.5 part of dicumyl peroxide and 1.5-2.5 parts of alumina.
Preferably, the drying temperature of the wet polymer electrolyte membrane is 50-90 ℃, and the drying time is 20-28 h.
The invention also provides the polymer electrolyte membrane prepared by the preparation method. Accordingly, a battery comprising the above polymer electrolyte membrane is also provided.
The implementation of the invention has the following beneficial effects:
1. according to the preparation method of the polymer electrolyte membrane, provided by the invention, a specific raw material formula is adopted, and the first polymer and the first polymerization monomer are used for graft copolymerization, so that the dispersibility of the inorganic oxide in the polymer can be improved, and the contact of the interface between the polymer electrolyte membrane and the anode and the interface between the polymer electrolyte membrane and the cathode are improved. The prepared polymer electrolyte membrane has good mechanical strength and remarkably improved ionic conductivity.
2. The invention uses the existing solid electrolyte polymer and maleic anhydride and derivatives thereof to carry out graft copolymerization, on one hand, the invention improves the dispersion compatibility of the polymer and inorganic filler, and on the other hand, the invention improves the compatibility between the electrolyte membrane and the anode and the cathode.
Drawings
FIG. 1 is a graph showing a comparison of test performances of polymer electrolyte membranes obtained in examples 1 to 5 of the present invention and comparative examples 1 to 2;
FIG. 2 is a graph showing a comparison of the performances of the cells obtained from the polymer electrolyte membranes obtained in examples 1 to 5 of the present invention and comparative examples 1 to 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
In the prior art, the polymer electrolyte membrane has the defects that inorganic oxides are easy to agglomerate and are dispersed unevenly; poor contact between the electrolyte membrane and the positive and negative electrodes, and the like. The above problems result in poor mechanical strength of the resulting polymer electrolyte membrane, low ionic conductivity, and high impedance of the assembled cell.
The reason for the above problems is that the compatibility of inorganic oxide and polymer is poor, the dispersion is uneven, and the mechanical strength of the existing polymer system is low. The electrolyte membrane is in solid-solid contact with the positive electrode and the negative electrode, so that interface impedance is high.
In order to solve the above problems, the present invention provides a method for preparing a polymer electrolyte membrane, comprising the steps of:
s1, dissolving the first polymer and lithium salt in an organic solvent to obtain a first mixed solution;
s2, adding a first polymerization monomer and an initiator into the first mixed solution to obtain a second mixed solution;
s3, adding an inorganic oxide into the second mixed solution, and dispersing uniformly to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the wet membrane of the polymer electrolyte to obtain a finished product;
the raw materials for preparing the polymer electrolyte membrane comprise the following components in parts by weight: 1-15 parts of first polymer, 30-70 parts of organic solvent, 0.5-5 parts of lithium salt, 0.1-5 parts of first polymerization monomer, 0.05-2 parts of initiator and 0.5-5 parts of inorganic oxide.
According to the invention, a specific raw material formula is adopted, and the first polymer and the first polymerization monomer are used for graft copolymerization, so that the dispersibility of the inorganic oxide in the polymer can be improved, and the interfacial contact between the polymer electrolyte membrane and the anode and the cathode is improved. The prepared polymer electrolyte membrane has good mechanical strength and remarkably improved ionic conductivity.
Preferably, the first polymeric monomer comprises one or a combination of maleic anhydride, dimethyl maleic anhydride, succinic anhydride; the initiator comprises one or a combination of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and dimethyl azobisisobutyrate. More preferably, the first polymeric monomer is maleic anhydride; the initiator is dicumyl peroxide.
The maleic anhydride and the derivatives thereof have high polarity and reactivity by introducing strong polar reactive groups, and the monomers of the maleic anhydride and the derivatives thereof have stronger polarity compared with other monomers.
The maleic anhydride and the inorganic particles have good compatibility, the positive electrode and the negative electrode are composed of the inorganic active material particles, so that the compatibility of the polymer electrolyte membrane grafted by the maleic anhydride and the positive electrode and the negative electrode is improved, the melting point of the maleic anhydride is low, the material is soft, and the interface contact problem between the polymer electrolyte membrane and the positive electrode and the negative electrode can be improved after the battery is assembled.
Preferably, the first polymer comprises one or a combination of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polypropylene carbonate (PPC), polymethyl methacrylate (PMMA). Preferably, the first polymer is PVDF-HFP, the PVDF-HFP overcomes the defects of high crystallinity and high membrane brittleness of PVDF, and the polymer electrolyte membrane has good electrolyte absorption capacity and excellent electrochemical performance, so that the obtained polymer electrolyte membrane has better performance.
Preferably, the lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium difluorooxalatoborate (LiODFB), lithium perchlorate (LiClO)4) One or more of (a). More preferably, the lithium salt is LiTFSI, the LiTFSI has proper conductivity, high thermal stability and electrochemical stability and small probability of side reaction.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), Acetonitrile (ACN). More preferably, the organic solvent is N-methylpyrrolidone, NMP is miscible with water, PVDF, positive and negative electrode materials, and the like, and when manufacturing the electrode sheet, NMP is used as the solvent to fuse various electrode-required substances such as the binder, the positive electrode active material, the conductive agent, and the like together, so that the binder is in full contact with other substances and is uniformly distributed.
Preferably, the inorganic oxide comprises one or more of alumina, titania, silica. The inorganic oxide is aluminum oxide, and the inorganic oxide is aluminum oxide,
in summary, in the invention, a first polymer, an organic solvent, a lithium salt, a first polymeric monomer, an initiator, and an inorganic oxide are blended to obtain a polymer electrolyte slurry, wherein the first polymeric monomer in the polymer electrolyte slurry is grafted to the first polymer, so that the uniformity of the system of the polymer electrolyte slurry is improved, and the composition of the polymer electrolyte slurry has an important influence on the performance of the finally obtained polymer electrolyte membrane.
More preferably, the raw materials for preparing the polymer electrolyte membrane comprise, by weight: 2-8 parts of first polymer, 40-60 parts of organic solvent, 1-3 parts of lithium salt, 0.5-1.5 parts of first polymerization monomer, 0.08-1 part of initiator and 1-3 parts of inorganic oxide. Most preferably, the raw materials for preparing the polymer electrolyte membrane comprise, in parts by weight: 4-6 parts of polyvinylidene fluoride, 45-55 parts of N-methylpyrrolidone, 1.5-2.5 parts of lithium bis (trifluoromethanesulfonyl) imide, 0.8-1.2 parts of maleic anhydride, 0.09-0.5 part of dicumyl peroxide and 1.5-2.5 parts of alumina.
When the weight part of the first polymer is more than 8 parts, the viscosity of the system is too high to facilitate the grafting reaction. When the weight part size of the first polymer is less than 2 parts, lithium ion migration is limited and electrolyte membrane strength is affected. Too high a proportion by weight of the first polymeric monomer may affect the thermal and mechanical properties of the polymer electrolyte membrane. The initiator of more than 1 part by weight results in too large a residual rate of the initiator and an unstable polymer system. The initiator is less than 0.08 part by weight, the grafting ratio is too low, and the residual amount of the first polymerization monomer is too large. Too high a proportion by weight of the inorganic oxide may cause poor dispersion of the inorganic oxide in the polymer system. The weight ratio of the inorganic oxide is too low to improve the mechanical strength.
In addition, in the process of drying the wet polymer electrolyte membrane to obtain a finished product, the drying conditions influence the performance of the finally obtained polymer electrolyte membrane, and preferably, the drying temperature is 50-90 ℃ and the drying time is 20-28 h.
In summary, the invention provides a polymer electrolyte membrane obtained by the method, and correspondingly, a battery containing the polymer electrolyte membrane. The invention can improve the dispersibility of inorganic oxide in the polymer and improve the interface contact between the polymer electrolyte membrane and the anode and cathode by using the polymer, maleic anhydride and the derivative thereof for graft copolymerization. The prepared polymer electrolyte membrane has good mechanical strength and remarkably improved ionic conductivity. The impedance of a cell containing the polymer electrolyte membrane is low.
The invention is further illustrated by the following specific examples:
example 1
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 5g of PVDF and 2g of LiTFSI, and dissolving in 50g of NMP to obtain a first mixed solution;
s2, adding 1g of MAH and 0.1g of DCP into the first mixed solution to obtain a second mixed solution;
s3, adding 2gAl into the second mixed solution2O3Dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 60 ℃ for 24h to obtain a finished product.
Example 2
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 5g of PVDF-HFP and 2g of LiTFSI, and dissolving in 60g of NMP to obtain a first mixed solution;
s2, adding 1g of MAH and 0.1g of DCP into the first mixed solution to obtain a second mixed solution;
s3, adding 2gAl into the second mixed solution2O3Dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 60 ℃ for 24h to obtain a finished product.
Example 3
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 4g of PEO and 1.5g of LiPF6Dissolving in 50g ACN to obtain a first mixed solution;
s2, adding 1.5g of MAH and 0.15g of DCP into the first mixed solution to obtain a second mixed solution;
s3, adding 2gSiO into the second mixed solution2Dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 50 ℃ for 28h to obtain a finished product.
Example 4
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 5g PPC and 1.5g LiClO4Dissolving in 60g of NMP to obtain a first mixed solution;
s2, adding 1.2g of MAH and 0.12g of DCP into the first mixed solution to obtain a second mixed solution;
s3, adding 1.6gAl into the second mixed solution2O3Dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 60 ℃ for 24h to obtain a finished product.
Example 5
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 6g of PMMA and 3g of LiTFSI, and dissolving in 40g of NMP to obtain a first mixed solution;
s2, adding 2g of MAH and 0.2g of DCP into the first mixed solution to obtain a second mixed solution;
s3, adding 3gAl into the second mixed solution2O3Dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 70 ℃ for 24h to obtain a finished product.
Comparative example 1
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 4g of PEO and 1.5g of LiPF6Dissolving in 50g ACN to obtain a first mixed solution;
s2, adding 2gSiO into the first mixed solution2Dispersing to obtain polymer electrolyte slurry;
s3, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S4, drying the wet polymer electrolyte membrane at 50 ℃ for 28h to obtain a finished product.
Comparative example 2
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 5g PPC and 1.5g LiClO4Dissolving in 60g of NMP to obtain a first mixed solution;
s2, adding 1.6gAl into the first mixed solution2O3Dispersing to obtain polymer electrolyte slurry;
s3, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S4, drying the wet polymer electrolyte membrane at 60 ℃ for 24h to obtain a finished product.
The polymer electrolyte membranes prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to tensile strength and ionic conductivity tests, and the test results are shown in FIG. 1.
The tensile strength was measured by cutting the polymer electrolyte membranes obtained in examples 1 to 5 and comparative examples 1 to 2 into strips having a width of 15mm and testing the tensile strength of the electrolyte membranes using a universal tester.
The ionic conductivity and impedance test method comprises the steps of assembling the polymer electrolyte prepared in examples 1-5 and comparative examples 1-2 into a stainless steel sheet/electrolyte membrane/stainless steel sheet button cell, and measuring the electrochemical impedance spectrum of the electrolyte membrane by using an alternating current impedance method by using an electrochemical workstation. The results of the impedance test are shown in fig. 2, the thickness h and the diameter d of the polymer electrolyte sheet are measured by a thickness gauge, R is the impedance of the polymer electrolyte membrane, and the ionic conductivity is calculated by using formula 1.
Equation 1 calculation equation of ionic conductivity
The test results show that the tensile strength of examples 1-5 is higher than that of comparative examples 1-2. Also, the ion conductivities of the polymer electrolyte membranes obtained in the examples of the present invention were all higher than those of the comparative examples. Among them, example 2 has the highest ionic conductivity. Moreover, the impedance of the cells produced using the polymer electrolyte membranes obtained in the examples of the present invention was smaller than that of the comparative examples. Among them, the cell prepared using the polymer electrolyte membrane obtained in example 2 had the smallest impedance.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A method for producing a polymer electrolyte membrane, characterized by comprising the steps of:
dissolving a first polymer and lithium salt in an organic solvent to obtain a first mixed solution;
adding a first polymerization monomer and an initiator into the first mixed solution to obtain a second mixed solution;
adding an inorganic oxide into the second mixed solution, and uniformly dispersing to obtain polymer electrolyte slurry;
coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
drying the wet membrane of the polymer electrolyte to obtain a finished product;
the raw materials for preparing the polymer electrolyte membrane comprise the following components in parts by weight: 1-15 parts of first polymer, 30-70 parts of organic solvent, 0.5-5 parts of lithium salt, 0.1-5 parts of first polymerization monomer, 0.05-2 parts of initiator and 0.5-5 parts of inorganic oxide.
2. The method for producing a polymer electrolyte membrane according to claim 1, wherein the raw materials for producing the polymer electrolyte membrane comprise, in parts by weight: 2-8 parts of first polymer, 40-60 parts of organic solvent, 1-3 parts of lithium salt, 0.5-1.5 parts of first polymerization monomer, 0.08-1 part of initiator and 1-3 parts of inorganic oxide.
3. The method of claim 1, wherein the first polymeric monomer comprises one or a combination of maleic anhydride, dimethyl maleic anhydride, succinic anhydride;
the initiator comprises one or a combination of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and dimethyl azobisisobutyrate.
4. The method for preparing a polymer electrolyte membrane according to claim 3, wherein the first polymeric monomer is maleic anhydride; the initiator is dicumyl peroxide.
5. The method of manufacturing a polymer electrolyte membrane according to claim 1, wherein the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate, polymethyl methacrylate;
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide and lithium difluorooxalato borate.
6. The method for preparing a polymer electrolyte membrane according to claim 1, wherein the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, acetonitrile;
the inorganic oxide comprises one or more of aluminum oxide, titanium dioxide and silicon dioxide.
7. The method for producing a polymer electrolyte membrane according to any one of claims 4 to 6, wherein the raw materials for producing the polymer electrolyte membrane comprise, in parts by weight: 4-6 parts of polyvinylidene fluoride, 45-55 parts of N-methylpyrrolidone, 1.5-2.5 parts of lithium bis (trifluoromethanesulfonyl) imide, 0.8-1.2 parts of maleic anhydride, 0.09-0.5 part of dicumyl peroxide and 1.5-2.5 parts of alumina.
8. The method for preparing the polymer electrolyte membrane according to claim 1, wherein the drying temperature of the wet polymer electrolyte membrane is 50 ℃ to 90 ℃ and the drying time is 20 to 28 hours.
9. A polymer electrolyte membrane produced by the method for producing a polymer electrolyte membrane according to any one of claims 1 to 9.
10. A battery, comprising: a positive electrode, a negative electrode, and a polymer electrolyte membrane disposed between the positive electrode and the negative electrode, wherein the polymer electrolyte membrane is the polymer electrolyte membrane according to claim 9.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10324719A (en) * | 1997-05-15 | 1998-12-08 | Samsung General Chem Co Ltd | Vinyl acetate-based copolymer, gel polyelectrolyte composition containing the same and lithium-based polymeric secondary battery |
| KR19990025432A (en) * | 1997-09-12 | 1999-04-06 | 유현식 | Ethylene Vinyl Acetate Solid Polymer Electrolyte Composition |
| CN106531932A (en) * | 2016-12-10 | 2017-03-22 | 芜湖航达网业有限公司 | Polymer composite separator for lead acid storage battery and preparation method thereof |
| CN110957534A (en) * | 2019-12-18 | 2020-04-03 | 昆山宝创新能源科技有限公司 | Solid electrolyte membrane, method for producing same, and solid battery |
| CN110994015A (en) * | 2019-12-10 | 2020-04-10 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate cross-linked solid polymer electrolyte and application thereof |
| CN112054244A (en) * | 2020-08-21 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN112521616A (en) * | 2019-08-30 | 2021-03-19 | 比亚迪股份有限公司 | Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack |
| CN113113662A (en) * | 2020-08-06 | 2021-07-13 | 昆山宝创新能源科技有限公司 | Modified inorganic-organic composite solid electrolyte membrane and preparation method and application thereof |
-
2021
- 2021-12-08 CN CN202111494151.3A patent/CN114361582A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10324719A (en) * | 1997-05-15 | 1998-12-08 | Samsung General Chem Co Ltd | Vinyl acetate-based copolymer, gel polyelectrolyte composition containing the same and lithium-based polymeric secondary battery |
| KR19990025432A (en) * | 1997-09-12 | 1999-04-06 | 유현식 | Ethylene Vinyl Acetate Solid Polymer Electrolyte Composition |
| CN106531932A (en) * | 2016-12-10 | 2017-03-22 | 芜湖航达网业有限公司 | Polymer composite separator for lead acid storage battery and preparation method thereof |
| CN112521616A (en) * | 2019-08-30 | 2021-03-19 | 比亚迪股份有限公司 | Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack |
| CN110994015A (en) * | 2019-12-10 | 2020-04-10 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate cross-linked solid polymer electrolyte and application thereof |
| CN110957534A (en) * | 2019-12-18 | 2020-04-03 | 昆山宝创新能源科技有限公司 | Solid electrolyte membrane, method for producing same, and solid battery |
| CN113113662A (en) * | 2020-08-06 | 2021-07-13 | 昆山宝创新能源科技有限公司 | Modified inorganic-organic composite solid electrolyte membrane and preparation method and application thereof |
| CN112054244A (en) * | 2020-08-21 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Composite solid electrolyte and preparation method and application thereof |
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