CN118380637A - Solid electrolyte membrane, preparation method thereof and solid lithium metal battery - Google Patents
Solid electrolyte membrane, preparation method thereof and solid lithium metal battery Download PDFInfo
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- CN118380637A CN118380637A CN202410356971.3A CN202410356971A CN118380637A CN 118380637 A CN118380637 A CN 118380637A CN 202410356971 A CN202410356971 A CN 202410356971A CN 118380637 A CN118380637 A CN 118380637A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002023 wood Substances 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000011247 coating layer Substances 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
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- 238000001802 infusion Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
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- 229920002488 Hemicellulose Polymers 0.000 claims description 7
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 7
- 239000011245 gel electrolyte Substances 0.000 claims description 7
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 7
- 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 7
- 239000011259 mixed solution Substances 0.000 claims description 7
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
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- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
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- 239000002002 slurry Substances 0.000 claims description 5
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 5
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- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
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- PAHNBNDPQWLRQX-UHFFFAOYSA-N [N].[O].[P].[Li] Chemical compound [N].[O].[P].[Li] PAHNBNDPQWLRQX-UHFFFAOYSA-N 0.000 claims description 3
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
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- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
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- DGQGEJIVIMHONW-UHFFFAOYSA-N [O-2].[Ta+5].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[Zr+4].[La+3].[Li+] DGQGEJIVIMHONW-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Conductive Materials (AREA)
Abstract
The invention discloses a solid electrolyte membrane, a preparation method thereof and a solid lithium metal battery, wherein the solid electrolyte membrane comprises a wood layer and a coating layer arranged on at least one surface of the wood layer, and the wood layer comprises flexible wood which is treated by resin infusion; the coating layer includes a binding polymer, an ion-conducting ceramic powder, and a lithium salt. According to the solid electrolyte membrane, the traditional polyolefin diaphragm is replaced by the wood layer, and the flexible wood in the wood layer has a multi-scale hierarchical pore structure, so that the transmission of lithium ions is facilitated, the good mechanical property of the solid electrolyte membrane can be achieved, the mechanical strength of a coating layer can be enhanced, the lithium dendrite penetration resistance is improved, the safety of a lithium metal battery is further improved, and the solid electrolyte membrane has high commercial value and application prospect.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a solid electrolyte membrane, a preparation method thereof and a solid lithium metal battery.
Background
The secondary ion battery has the advantages of high energy density, long cycle life, no memory effect, low self-discharge rate and the like, and gradually takes the dominant role in the aspects of energy storage and supply. In recent years, lithium ion batteries among secondary batteries have been developed. The rapid development of portable electronic devices, electric automobiles and energy storage device markets presents an increasing challenge to current commercial lithium ion batteries, and lithium metal cathodes have entered the line of sight of researchers due to their extremely high theoretical capacity and low redox potential, and lithium metal batteries featuring lithium metal cathodes are receiving increasing attention as the most promising next generation alternatives to mature lithium ion batteries. However, the severe problem of lithium dendrite growth in lithium metal batteries, the potential short-circuit risk and the flammable liquid electrolyte leave considerable safety hazards.
It is well known that all-solid-state batteries are receiving attention because of their good safety and stability. For the liquid electrolyte of the traditional lithium battery, leakage and uncontrollable side reactions of the electrolyte exist, so that the battery is extremely easy to generate short circuit, and the safety accident of burning and even explosion is caused. Therefore, it is imperative to develop safer battery systems having excellent thermal stability and high mechanical strength. The solid electrolyte is adopted to replace the liquid electrolyte and the diaphragm, so that the potential safety hazard problem existing in the lithium metal battery can be effectively improved, but the common solid electrolyte has the problems of higher cost, lower room-temperature ion conductivity, lower mechanical property and the like, and the traditional polyolefin diaphragm also has the inherent defects of poor wettability to polymers, poor thermal stability, difficult degradation and the like, so that the commercialized application of the diaphragm is limited.
In view of the above-mentioned drawbacks of the current solid electrolyte membranes, it is necessary to provide a solution to the above-mentioned problems.
Disclosure of Invention
The invention aims at: the invention provides a solid electrolyte membrane, which comprises a wooden layer and a coating layer arranged on at least one surface of the wooden layer, wherein the wooden layer is adopted to replace a traditional polyolefin diaphragm, has good mechanical property, can improve the mechanical strength of the coating layer and the lithium dendrite penetration resistance, thereby improving the safety and the cycle life of a lithium metal battery.
A solid electrolyte membrane comprising a wooden layer and a coating layer provided on at least one surface of the wooden layer, wherein the wooden layer comprises flexible wood treated by resin infusion; the coating layer includes a binding polymer, an ion-conducting ceramic powder, and a lithium salt.
Preferably, the thickness of the solid electrolyte membrane is 13 to 90 μm, wherein the thickness of the wooden layer is 10 to 80 μm, and the thickness of the coating layer is 3 to 10 μm.
Preferably, the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium bisoxalato borate, lithium tetrafluorooxalato phosphate, and lithium difluorodioxaato phosphate.
Preferably, the binding polymer is one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, vinylidene fluoride-trifluoroethylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyethylene glycol methyl ether acrylate and polyethylene glycol diacrylate.
Preferably, the ion-conducting ceramic powder is at least one of lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, lithium phosphorus oxygen nitrogen and doped oxide solid electrolyte materials thereof.
Preferably, the mass ratio of the binding polymer, the ion-conducting ceramic powder and the lithium salt is 10-15: 5-10: 2 to 10.
The invention also provides a preparation method of the solid electrolyte membrane, which comprises the following steps:
Step one: delignification and hemicellulose treatment are carried out on the wood to obtain flexible wood, resin infusion is carried out on the flexible wood, and slicing is carried out to obtain a wood layer;
Step two: mixing the binding polymer and the organic solvent to obtain a mixed solution, adding lithium salt, stirring to obtain a uniform and transparent solution, adding ion-conducting ceramic powder, and stirring uniformly to obtain coating slurry;
step three: and uniformly coating the coating layer slurry on at least one surface of the wood layer, and drying to obtain the solid electrolyte membrane.
Preferably, in the second step, the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, anhydrous acetonitrile and N-methylpyrrolidone.
Preferably, in the first step, the solution used for the delignification and hemicellulose treatment is at least one of sodium hydroxide solution, sodium chlorite solution, sodium sulfite solution and hydrogen peroxide solution. The specific processing operation is as follows: the pH of a 1wt% aqueous sodium chlorite solution was adjusted to about 5 with glacial acetic acid, then wood was added, heated to 60℃and maintained for 8 hours. After cooling to room temperature, the wood was taken out, washed three times with deionized water, and slowly dried at room temperature.
Preferably, in the first step, the resin in the resin infusion is epoxy resin and polyethylene glycol. The specific processing operation is as follows: the wood was immersed in a mixed solution of 3wt% epoxy resin and polyethylene glycol, and vacuum infiltrated for 30 minutes at room temperature, and the infiltration process was repeated three times to ensure complete infiltration. The infiltrated sample was then sandwiched between two glass slides, wrapped with aluminum foil, and polymerized in an oven at 60 ℃ for 12h. After curing, the composite material was peeled off from the slide glass, and was freeze-dried in a freeze-dryer for 12 hours to obtain a flexible wood.
Preferably, in the third step, the coating method is one of a slurry coating method, a spray coating method and a spin coating method.
Preferably, in the third step, the temperature of the drying is 40 ℃ to 100 ℃.
The invention also provides a solid lithium metal battery, which comprises the solid electrolyte membrane.
Preferably, the solid lithium metal battery further comprises a gel electrolyte comprising a lithium salt, an organic solvent, an additive, and an initiator. The mass ratio of the lithium salt, the organic solvent, the additive and the initiator is 5-15: 80-98: 2-20: 0.1 to 0.3.
Preferably, the lithium salt includes at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium bisoxalato borate, lithium tetrafluorooxalato phosphate, and lithium difluorodioxaato phosphate.
Preferably, the organic solvent includes at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propyl propionate, fluoroethylene carbonate, and methyltrifluoroethyl carbonate.
Preferably, the additive is an unsaturated bond-containing monomer, and the unsaturated bond-containing monomer comprises at least one of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate and vinyl sulfite.
Preferably, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and dibenzoyl peroxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the traditional polyolefin diaphragm is replaced by the wood layer, and the flexible wood in the wood layer has a multi-scale hierarchical pore structure, so that the transmission of lithium ions is facilitated, the good mechanical property is realized, the mechanical strength of a coating layer can be improved, the lithium dendrite penetration resistance is improved, and the safety of a lithium metal battery is further improved.
(2) On the other hand, the wooden layer and the coating layer both contain a large number of oxygen-containing functional groups, which is beneficial to the rapid conduction of lithium ions, and the ionic conductivity of the solid electrolyte membrane is ensured by compounding the polymer solid electrolyte and the ion conducting ceramic powder.
Drawings
Fig. 1 is a schematic structural view of a solid electrolyte membrane according to embodiment 1 of the present invention.
In the figure: 1-a wood layer; 2-coating layer.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. 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 accordance with a first aspect of the present invention, there is provided a solid electrolyte membrane comprising a wooden layer 1 and a coating layer 2 provided on at least one surface of the wooden layer 1, wherein the wooden layer 1 comprises flexible wood treated by resin infusion; the coating layer 2 includes a binding polymer, ion-conducting ceramic powder and lithium salt.
In an embodiment according to the present invention, the thickness of the solid electrolyte membrane is 13 to 90 μm, and may be, for example, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm; wherein the thickness of the wooden layer 1 is 10 to 80 μm, and may be, for example, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm; the thickness of the coating layer 2 is 3 to 10. Mu.m, for example, 4. Mu.m, 5. Mu.m, 6. Mu.m, 7. Mu.m, 8. Mu.m, 9. Mu.m. Too thick of the wooden layer 1 can cause the problems of energy density reduction, ion conductivity reduction and the like of the battery, while too small of the wooden layer 1 has poor mechanical properties, so that the mechanical strength of the wooden layer 1 cannot be improved for the coating layer 2, the mechanical properties of the solid electrolyte membrane are poor, and the battery is easy to crack to cause short circuit.
In an embodiment according to the present invention, the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium bisoxalato borate, lithium tetrafluorooxalato phosphate, and lithium difluorodioxaato phosphate. The lithium salt is added into the solid electrolyte membrane to provide lithium ions for forming the SEI film, so that lithium ions lost by a positive electrode are reduced, and the initial efficiency of the battery is improved.
In one embodiment according to the present invention, the binding polymer is one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, vinylidene fluoride-trifluoroethylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyethylene glycol methyl ether acrylate, and polyethylene glycol diacrylate.
In one embodiment according to the present invention, the ion-conducting ceramic powder is at least one of lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, and lithium phosphorus oxygen nitrogen and doped oxide solid electrolyte materials thereof. The ion-conducting ceramic powder has high chemical stability and low reactivity with lithium metal anode, and has high ion conductivity to lithium, so that the ion-conducting ceramic powder can provide stable and efficient transmission medium for ion flow between anode and cathode in the battery, promote the development of the energy storage field and have great potential in paving roads for safer, more efficient and more environment-friendly batteries.
In one embodiment according to the invention, the mass ratio of the binding polymer, the ion-conducting ceramic powder and the lithium salt is 10 to 15: 5-10: 2 to 10.
In a second aspect of the present invention, there is also provided a method of preparing a solid electrolyte membrane, comprising the steps of:
Step one: delignification and hemicellulose treatment are carried out on the wood to obtain flexible wood, resin infusion and slicing are carried out to obtain a wood layer 1;
step two: mixing the binding polymer and an organic solvent to obtain a mixed solution, adding lithium salt, stirring to obtain a uniform and transparent solution, adding ion-conducting ceramic powder, and stirring uniformly to obtain coating layer 2 slurry;
Step three: and uniformly coating the slurry of the coating layer 2 on at least one surface of the wood layer 1, and drying to obtain the solid electrolyte membrane.
In an embodiment according to the invention, in step one, the solution used for the delignification and hemicellulose treatment is at least one of sodium hydroxide solution, sodium chlorite solution, sodium sulfite solution and hydrogen peroxide solution. The specific processing operation is as follows: the pH of a 1wt% aqueous sodium chlorite solution was adjusted to about 5 with glacial acetic acid, then wood was added, heated to 60℃and maintained for 8 hours. After cooling to room temperature, the wood was taken out, washed three times with deionized water, and slowly dried at room temperature.
In an embodiment of the present invention, in the step one, the resin in the resin infusion is epoxy resin and polyethylene glycol. The specific processing operation is as follows: the wood was immersed in a mixed solution of 3wt% epoxy resin and polyethylene glycol, and vacuum infiltrated for 30 minutes at room temperature, and the infiltration process was repeated three times to ensure complete infiltration. The infiltrated sample was then sandwiched between two glass slides, wrapped with aluminum foil, and polymerized in an oven at 60 ℃ for 12h. After curing, the composite material was peeled off from the slide glass, and was freeze-dried in a freeze-dryer for 12 hours to obtain a flexible wood.
In an embodiment according to the present invention, in step three, the coating is one of a slurry coating method, a spray coating method, and a spin coating method.
In an embodiment according to the invention, in step three, the temperature of the drying is 40-100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃.
In a third aspect of the present invention, there is also provided a solid lithium metal battery comprising a positive electrode sheet, a metal lithium negative electrode, a gel electrolyte and the solid electrolyte membrane; wherein the active material of the positive electrode is lithium cobaltate. The positive electrode plate, the metal lithium negative electrode and the solid electrolyte membrane are laminated to obtain a bare cell; and packaging the bare cell, injecting a trace amount of gel electrolyte, standing, performing high-temperature formation, performing hot and cold pressing, degassing, and vacuum packaging to obtain the solid-state lithium metal battery.
In one embodiment according to the present invention, both the positive electrode sheet and the solid electrolyte membrane are baked before lamination or winding, the baking temperature is 40-120 ℃, and the process before formation is performed in a drying room with a dew point of less than-35 ℃.
In an embodiment according to the invention, the solid state lithium metal battery further comprises a gel electrolyte comprising a lithium salt, an organic solvent, an additive and an initiator. The mass ratio of the lithium salt, the organic solvent, the additive and the initiator is 5-15: 80-98: 2-20: 0.1 to 0.3.
In an embodiment according to the present invention, the lithium salt includes at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium bisoxalato borate, lithium tetrafluorooxalato phosphate, and lithium difluorodioxaato phosphate.
In an embodiment according to the present invention, the organic solvent includes at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, propyl propionate, fluoroethylene carbonate, and methyltrifluoroethyl carbonate.
In one embodiment according to the present invention, the additive is an unsaturated bond-containing monomer including at least one of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate, and vinyl sulfite. The above additive can specifically and efficiently initiate polymerization reaction between initiators in the gel electrolyte.
In an embodiment according to the present invention, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and dibenzoyl peroxide. The initiator can purposefully and efficiently initiate polymerization reaction among the additives.
The invention is further illustrated by the following examples.
Example 1
Preparation of solid electrolyte membrane:
Step one: delignification and hemicellulose treatment are carried out on the wood to obtain flexible wood, resin infusion and slicing are carried out to obtain a wood layer 1;
Step two: mixing polyvinylidene fluoride-hexafluoropropylene and N, N-dimethylformamide to obtain a mixed solution, adding lithium bis (trifluoromethylsulfonyl) imide, stirring to obtain a uniform and transparent solution, adding lithium lanthanum zirconium tantalum oxide powder, and stirring uniformly to obtain a coating slurry; in the coating slurry, the mass fractions of the lithium bis (trifluoromethylsulfonyl) imide, polyvinylidene fluoride-hexafluoropropylene and lithium lanthanum zirconium tantalum oxide powder in the solution are respectively 1.2%,2.4% and 0.8%;
Step three: the slurry of the coating layer 2 was uniformly coated on one surface of the wooden layer 1, and dried at 50 c to obtain a solid electrolyte membrane having a thickness of 55 μm.
Preparation of solid-state lithium metal batteries:
the positive electrode plate, the metal lithium negative electrode and the solid electrolyte membrane are laminated to obtain a bare cell; and packaging the bare cell, injecting a trace amount of gel electrolyte, standing, performing high-temperature formation, performing hot and cold pressing, degassing, and vacuum packaging to obtain the solid-state lithium metal battery.
Example 2
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium aluminum titanium phosphate and the binding polymer used was polyacrylonitrile;
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium lanthanum zirconium oxide, and the binding polymer used was polyethylene glycol methacrylate;
The remainder is the same as embodiment 1 and will not be described here again.
Example 4
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium aluminum titanium phosphate, and the binding polymer used was polymethyl methacrylate;
The remainder is the same as embodiment 1 and will not be described here again.
Example 5
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium phosphorus oxynitride and the binding polymer used was polyacrylonitrile;
The remainder is the same as embodiment 1 and will not be described here again.
Example 6
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium aluminum titanium phosphate, and the binding polymer used was polyethylene glycol diacrylate;
The remainder is the same as embodiment 1 and will not be described here again.
Example 7
Unlike example 1, the ion-conducting ceramic powder used in step two of this example was lithium aluminum titanium phosphate, and the binding polymer used was polymethyl methacrylate;
The remainder is the same as embodiment 1 and will not be described here again.
Comparative example 1
Unlike example 1, a PE/PP separator was used in this example instead of the wood layer 1 of example 1;
The remainder is the same as embodiment 1 and will not be described here again.
Performance test:
the solid lithium metal batteries of examples 1 to 7 and comparative example 1 were subjected to battery tests, and the test results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, compared with the solid lithium metal battery prepared in comparative example 1, the solid lithium metal batteries prepared in examples 1 to 7 of the present application have the advantages of excellent initial efficiency, capacity exertion and cycle stability, and less occurrence of short circuit phenomenon, indicating that the solid electrolyte membrane of the present application has good electrochemical stability and ionic conductivity.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A solid electrolyte membrane comprising a wooden layer and a coating layer provided on at least one surface of the wooden layer, wherein the wooden layer comprises flexible wood treated by resin infusion; the coating layer includes a binding polymer, an ion-conducting ceramic powder, and a lithium salt.
2. The solid electrolyte membrane according to claim 1, wherein the thickness of the solid electrolyte membrane is 13 to 90 μm, wherein the thickness of the wooden layer is 10 to 80 μm, and the thickness of the coating layer is 3 to 10 μm.
3. The solid electrolyte membrane according to claim 1, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium bisoxalato borate, lithium tetrafluorooxalato phosphate, and lithium difluorodioxaato phosphate;
The bonding polymer is one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, vinylidene fluoride-trifluoroethylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyethylene glycol methyl ether acrylate and polyethylene glycol diacrylate;
The ion-conducting ceramic powder is at least one of lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, lithium phosphorus oxygen nitrogen and doped oxide solid electrolyte materials.
4. The solid electrolyte membrane according to claim 1, wherein a mass ratio of the binding polymer, the ion-conducting ceramic powder, and the lithium salt is 10 to 15: 5-10: 2 to 10.
5. A method for producing the solid electrolyte membrane according to any one of claims 1 to 4, comprising the steps of:
Step one: delignification and hemicellulose treatment are carried out on the wood to obtain flexible wood, resin infusion is carried out on the flexible wood, and slicing is carried out to obtain a wood layer;
Step two: mixing the binding polymer and the organic solvent to obtain a mixed solution, adding lithium salt, stirring to obtain a uniform and transparent solution, adding ion-conducting ceramic powder, and stirring uniformly to obtain coating slurry;
step three: and uniformly coating the coating layer slurry on at least one surface of the wood layer, and drying to obtain the solid electrolyte membrane.
6. The method for producing a solid electrolyte membrane according to claim 5, wherein in the second step, the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, anhydrous acetonitrile and N-methylpyrrolidone.
7. The method for producing a solid electrolyte membrane according to claim 5, wherein in the first step, the solution used for the delignification and hemicellulose treatment is at least one of a sodium hydroxide solution, a sodium chlorite solution, a sodium sulfite solution, and a hydrogen peroxide solution.
8. The method for producing a solid electrolyte membrane according to claim 5, wherein in the first step, the resin in the resin infusion is a mixed solution of an epoxy resin and polyethylene glycol.
9. A solid lithium metal battery comprising the solid electrolyte membrane according to any one of claims 1 to 4.
10. The solid state lithium metal battery of claim 9, further comprising a gel electrolyte comprising a lithium salt, an organic solvent, an additive, and an initiator.
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