CN114725616A - Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery - Google Patents
Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery Download PDFInfo
- Publication number
- CN114725616A CN114725616A CN202210393452.5A CN202210393452A CN114725616A CN 114725616 A CN114725616 A CN 114725616A CN 202210393452 A CN202210393452 A CN 202210393452A CN 114725616 A CN114725616 A CN 114725616A
- Authority
- CN
- China
- Prior art keywords
- aramid
- nano
- fiber
- prepared
- inorganic filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 121
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 118
- 239000004760 aramid Substances 0.000 title claims abstract description 113
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011256 inorganic filler Substances 0.000 claims abstract description 39
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 44
- 239000000725 suspension Substances 0.000 claims description 42
- 239000002270 dispersing agent Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 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
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 abstract description 94
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 46
- 239000002131 composite material Substances 0.000 abstract description 31
- 230000001351 cycling effect Effects 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 38
- 239000004743 Polypropylene Substances 0.000 description 29
- 229920001155 polypropylene Polymers 0.000 description 29
- 238000000498 ball milling Methods 0.000 description 20
- 239000010408 film Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000004832 voltammetry Methods 0.000 description 13
- -1 polyethylene Polymers 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- MCIURFJELJKSNV-UHFFFAOYSA-N benzene-1,4-diamine;hydron;chloride Chemical compound Cl.NC1=CC=C(N)C=C1 MCIURFJELJKSNV-UHFFFAOYSA-N 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an inorganic hybrid aramid nanofiber membrane which is prepared from aramid nanofiber and an inorganic filler in a mass ratio of 1: 10-99: 1 through a water dispersion system. The inorganic hybrid aramid nanofiber membrane provided by the invention directly adopts water as a solvent, is nontoxic and environment-friendly, and does not generate pollutants in the preparation process. The battery diaphragm provided by the invention has fine and uniform pore diameter and good functions of passing ions and blocking electrons. The nano aramid fiber is intertwined and coiled, the silicon dioxide interacts with the aramid fiber nano fiber through intermolecular hydrogen bonds to form a continuous porous network structure, the electrolyte wettability is good, the interface impedance of lithium ion diffusion is small, and the ionic conductivity is good. The aramid nanofiber and inorganic filler composite diaphragm prepared by the invention has good heat resistance and stability. The battery diaphragm prepared by the invention has higher specific discharge capacity, excellent cycling stability, and longer cycle life, and can inhibit lithium dendrite.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an inorganic hybrid aramid nanofiber membrane, a preparation method and application thereof in a lithium battery.
Background
The aramid fiber is called aromatic polyamide fiber, and is long-chain synthetic polyamide fiber with over 85% of amido bond directly connected to benzene ring, and the amido bond is connected with aromatic ring or aromatic ring derivative, so that the aramid fiber has outstanding performances of flame retardance, high temperature resistance, high strength, high modulus, insulation and the like, and is a novel special high polymer material.
The aramid nano-fiber has the advantages of excellent bulk property of the aramid fiber and the nano effect of the high-performance polymer nano-fiber, becomes a novel nano-construction element, can effectively solve the problems of high chemical inertness, low reaction activity and unsatisfactory interface composite effect of the aramid fiber, and has wide application prospect in the fields of composite reinforcement, battery diaphragm, adsorption filtration, electrical insulation, flexible electrode and the like.
The lithium ion battery has the characteristics of high energy density, long cycle life, quick charging and the like, and becomes a research hotspot in the field of new energy automobiles in recent years. In the structure of the lithium battery, the diaphragm is the key for determining the performance of the lithium battery, determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, long cycle, puncture resistance, safety performance and other characteristics of the battery, and has the main functions of separating the positive electrode and the negative electrode of the battery, preventing the two electrodes from being short-circuited due to contact and also having the function of passing ions and electrons. The separator material is generally insulating, and its physical and chemical properties have a great influence on the performance of the battery. In the lithium battery system, since the electrolyte is an organic solvent system, a separator material is required to be resistant to an organic solvent, and a polyolefin porous film having a high strength and a thin film is generally used. The power battery has higher requirements on the diaphragm, and a composite membrane is generally adopted.
Polyolefin materials have the characteristics of excellent mechanical property, chemical stability and relative low price, so polyolefin microporous membranes such as polyethylene, polypropylene and the like are used as lithium battery diaphragms in the early stage of lithium battery research and development. At present, the commercial lithium ion battery diaphragm is mainly polyethylene or polypropylene diaphragm prepared by dry single-drawing, double-drawing, wet bidirectional asynchronous stretching process and bidirectional synchronous stretching process. However, the major bottlenecks that currently limit the development of lithium ion battery separators are that the traditional commercialized battery separators have low strength and poor thermal stability and shape stability, so that safety accidents such as battery short circuit and explosion are easily caused. The aramid fiber nanofiber membrane has the performance advantages of high strength, corrosion resistance, high temperature resistance and high dielectric strength, and can completely meet the requirements of the lithium ion battery on various aspects of membrane performance such as ion conduction, electron resistance, good chemical and thermal stability, excellent mechanical property and the like. Above all, the aramid nanofiber film can effectively solve the safety problem caused by poor thermal stability of the traditional battery diaphragm. Therefore, if the aramid nano-fiber can be applied to a lithium ion battery, the field of new energy automobiles can be developed for a long time.
Chinese patent publication No. CN104403119A, entitled "method for preparing poly (p-phenylene terephthalamide) thin film", is prepared by adding polymerization assistant and surfactant into solvent N-methyl pyrrolidone under inert gas protection and stirring, then adding poly (p-phenylene diamine) and terephthaloyl chloride under the condition of controlling temperature and the like to prepare colloid, then adding dispersant to obtain film-forming suspension, and preparing thin film finished product by controlling temperature and pressure.
The invention discloses a preparation method of a p-aramid nano-fiber lithium ion battery diaphragm with a pyrolysis pore-forming function, and the method is used for carrying out high-temperature ablation on the prepared p-aramid nano-fiber film in a gas atmosphere or a vacuum condition to obtain the p-aramid nano-fiber diaphragm with a controllable pore diameter. The method is post-processing treatment and has high energy consumption.
Chinese patent publication No. CN107452921A, the invention name of which is "a preparation method of a para-aramid nano-fiber composite lithium ion battery separator", the method is that under the condition of nitrogen, dissolving-assisting salt and raw materials are added into N-methyl-2-pyrrolidone to prepare para-aramid polymer slurry, a coating film is prepared by a coating method, and then the coating film is solidified in a specific solidification bath to form a film. The film prepared by the method avoids the problem that aramid fiber and resin are difficult to dissolve and the generation of dense skin layers, but has higher production cost and difficult control of the process, and is not suitable for industrial application.
Chinese patent publication No. CN113471624A, the invention name of which is "a composite diaphragm for lithium-sulfur battery, a preparation method thereof and a lithium-sulfur battery", the method is that long-fiber aramid is dissolved in dimethyl sulfoxide to prepare an aramid nano-fiber solution, the aramid nano-fiber solution is subjected to phase conversion to form a film, and then the film is immersed in a silane solution to grow silicon dioxide in situ to obtain the aramid-silicon dioxide composite material. The method still cannot avoid the use of organic solvents, and the phase inversion method is still difficult to implement industrially in the prior art.
The existing aramid fiber nanofiber membrane preparation technology has the problems of complicated preparation mode, adoption of organic solvents, environmental friendliness and the like. Therefore, how to realize green preparation and further improve the heat resistance and stability of the aramid nanofiber-based diaphragm is a main problem to be solved in large-scale production.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an inorganic hybrid aramid nanofiber membrane, a preparation method thereof, and an application thereof in a lithium battery.
The invention provides an inorganic hybrid aramid nanofiber membrane which is prepared from aramid nanofiber and an inorganic filler in a mass ratio of 1: 10-99: 1 through a water dispersion system.
Preferably, the aramid nanofiber and the inorganic filler are surface-modified aramid nanofiber and inorganic filler which are subjected to dispersing agent surface modification.
Preferably, the dispersant is one or more selected from silane coupling agents, surfactants, polymeric dispersants, and dopamine.
Preferably, the diameter of the aramid nanofiber is 50-80 nm, and the length-diameter ratio is 2000-5000;
the aramid nano-fiber is 1414 para-aramid nano-fiber synthesized by using paraphthaloyl chloride and p-phenylenediamine as monomers and/or 1313 meta-aramid nano-fiber synthesized by using isophthaloyl chloride and p-phenylenediamine as monomers.
Preferably, the inorganic filler is one or more selected from fumed silica, precipitated silica, polysilsesquioxane, in-situ generated silica, alumina, zirconia, lithium lanthanum zirconium oxide or ceramic micropowder.
The invention also provides a preparation method of the inorganic hybrid aramid nanofiber membrane, which comprises the following steps:
A) mixing aramid nano-fibers with water to obtain a suspension;
B) mixing an inorganic filler with a dispersant, adding a solvent, and performing ultrasonic dispersion to obtain an inorganic filler dispersion liquid;
C) adding the inorganic filler dispersion liquid into the aramid nano-fiber suspension liquid, and stirring to obtain a mixed dispersion liquid;
D) and dehydrating and drying the mixed dispersion liquid to obtain the inorganic hybrid aramid nanofiber membrane.
Preferably, the concentration of the aramid nano-fibers in the suspension is 0.1-0.6 wt%.
Preferably, the stirring speed of the mixing is 300rpm to 500 rpm; the temperature is 0-120 ℃; the time is 5-120 min;
the drying is one or more of room temperature drying, drying in a drying oven, vacuum freeze drying, mold pressing drying or paper making method forming drying.
The invention also provides a lithium battery which comprises the inorganic hybrid aramid nanofiber membrane or the inorganic hybrid aramid nanofiber membrane prepared by the preparation method.
Compared with the prior art, the invention provides an inorganic hybrid aramid nanofiber membrane which is prepared from aramid nanofibers and an inorganic filler in a mass ratio of 1: 10-99: 1 through a water dispersion system. The inorganic hybrid aramid nanofiber membrane provided by the invention directly adopts water as a solvent, avoids the use of an organic solvent, is non-toxic and environment-friendly, and does not generate pollutants in the preparation process. The battery diaphragm provided by the invention has fine and uniform pore diameter and has good effects of ion conduction and electron resistance. The nano aramid fiber is intertwined and coiled, the silicon dioxide interacts with the aramid fiber nano fiber through intermolecular hydrogen bonds to form a continuous porous network structure, the electrolyte wettability is good, the interface impedance of lithium ion diffusion is small, and the ionic conductivity is good. The aramid nanofiber and inorganic filler composite diaphragm prepared by the invention has good heat resistance and stability. The battery diaphragm prepared by the invention has higher specific discharge capacity, excellent cycling stability, longer cycle life and better performance when being used as a lithium battery diaphragm, and can inhibit lithium dendrite.
Drawings
FIG. 1 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation process of the present invention2) Prepared nano aramid fiber based composite lithium ionCell membranes and commercial PP membranes (USA)
) Comparison of thermal stability of (c);
FIG. 2 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation process of the present invention2) Prepared nano aramid fiber-based composite lithium ion battery diaphragm and commercial PP diaphragm (American Polypropylene (PP) diaphragm)
) Electrical cycling performance of;
FIG. 3 shows a nano-aramid fiber-based composite lithium ion battery separator and a commercial PP separator (American Polypropylene) prepared in example 3 of the preparation method of the present invention
) A graph of stability to lithium ions of (1);
fig. 4 is a stereomicroscope photograph of the white carbon black dispersion in the nano aramid fiber-based composite membrane prepared in example 2 (unmodified white carbon black) and example 3 (modified white carbon black) according to the preparation method of the present invention.
Detailed Description
The invention provides an inorganic hybrid aramid nanofiber membrane which is prepared from aramid nanofiber and an inorganic filler in a mass ratio of 1: 10-99: 1 through a water dispersion system.
In the invention, the diameter of the aramid nano-fiber is 50-80 nm, and the length-diameter ratio is 2000-5000; the aramid nano-fiber exists in the form of water-containing nano-aramid fiber, wherein the specific gravity of the aramid nano-fiber and water is 1.5-4.0: 96-98.5.
The aramid nano-fiber is 1414 para-aramid nano-fiber synthesized by using paraphthaloyl chloride and p-phenylenediamine as monomers and/or 1313 meta-aramid nano-fiber synthesized by using isophthaloyl chloride and p-phenylenediamine as monomers.
The inorganic filler is selected from one or more of fumed silica, precipitated silica, polysilsesquioxane, in-situ generated silica, alumina, zirconia, lithium lanthanum zirconium oxide or ceramic micro powder.The specific surface area of the inorganic filler is 100-400 m2Preferably 100, 200, 300, 400, or 100 to 400 m/g2Any value between/g.
The mass ratio of the aramid nanofibers to the inorganic filler is 1: 10-99: 1, preferably 1:10, 1:5, 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 99:1, or any value between 1: 10-99: 1.
In some embodiments of the present invention, the aramid nanofibers and the inorganic filler are surface-modified aramid nanofibers and inorganic filler with a dispersant.
Wherein the dispersing agent is selected from one or more of silane coupling agent, surfactant, high molecular polymer or dopamine. Preferably, the silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, methacryloxy silane, mercapto silane or ureido silane; the surfactant is one or more of cationic surfactant and anionic surfactant; the macromolecular dispersant is selected from one or more of polyacrylic acid, polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol.
In the invention, the thickness of the inorganic hybrid aramid nanofiber membrane is 10-60 μm, preferably 10, 20, 30, 40, 45, 50 or any value between 10-60 μm, and the pore diameter of the membrane is 10-20 nm.
The invention also provides a preparation method of the inorganic hybrid aramid nanofiber membrane, which comprises the following steps:
A) mixing aramid nano-fiber with water to obtain a suspension;
B) mixing an inorganic filler with a dispersant, adding a solvent, and performing ultrasonic dispersion to obtain an inorganic filler dispersion liquid;
C) adding the inorganic filler dispersion liquid into the aramid nano-fiber suspension liquid, and stirring to obtain a mixed dispersion liquid;
D) and dehydrating and drying the mixed dispersion liquid to obtain the inorganic hybrid aramid nanofiber membrane.
Firstly, aramid nano-fiber is mixed with water to obtain a suspension. In the suspension, the concentration of the aramid nanofibers is 0.1-0.6 wt%, preferably any value between 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, or 0.1-0.6 wt%.
And then, uniformly mixing the inorganic filler and the dispersing agent according to the mass ratio of 100: 1-100: 20. Preferably 100:5, 100:10, 100:15, 100:20, or any value between 100:1 and 100: 20.
The addition mode of the dispersing agent is direct addition or/and addition of a solution prepared into a concentration of 1 wt% -50 wt%. The solution concentration is preferably 10 wt%, 15 wt%, 20 wt%, or any value between 1 wt% and 50 wt%.
The mixing mode is one or more of ball mill mixing, high-speed mixer mixing, a pulverizer and grinding mixing.
And after mixing is finished, adding a solvent, and performing ultrasonic treatment for 30min to obtain an inorganic filler dispersion liquid. The solvent is preferably one or more of deionized water, ethanol and dimethyl sulfoxide.
The inorganic filler dispersion liquid and the aramid nano-fiber suspension liquid are mixed in a stirring manner, wherein the stirring manner is one or more of mechanical stirring and magnetic stirring. The stirring speed of the mixing is 300-500 rpm, preferably 300, 350, 400, 450, 500, or any value between 300-500 rpm; a temperature of 0 ℃ to 120 ℃, preferably 0, 10, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 120, or any value between 0 ℃ to 120 ℃; the time is 5-120 min. When the mixing needs heating, the heating mode is oil bath heating.
And dehydrating and drying the mixed dispersion liquid to obtain the inorganic hybrid aramid nanofiber membrane. The drying is one or more of room temperature drying, drying in an air drying oven at 40-60 ℃, mold pressing drying, vacuum freeze drying or papermaking forming drying. Drying to constant weight to obtain the inorganic hybrid aramid nanofiber composite lithium ion battery diaphragm.
The preparation method of the inorganic filler modified aramid nanofiber composite lithium ion battery diaphragm provided by the invention has the following advantages:
1. the preparation method can directly adopt water as the solvent, avoids the use of organic solvents, is non-toxic and environment-friendly, and does not produce pollutants in the preparation process.
2. The composite diaphragm of the aramid nano-fiber and the inorganic filler prepared by the invention has good heat resistance and stability.
3. The battery diaphragm prepared by the invention has fine and uniform aperture and good functions of ion conduction and electron resistance. The nano aramid fiber is intertwined and coiled, the inorganic particles interact with the aramid fiber nano fiber through intermolecular hydrogen bonds to form a continuous porous network structure, the electrolyte has good wettability, the interface impedance of lithium ion diffusion is small, and the ionic conductivity is good.
4. The battery diaphragm prepared by the invention has higher specific discharge capacity, excellent cycling stability, longer cycle life and better performance when being used as a lithium battery diaphragm, and can inhibit lithium dendrite.
In order to further understand the present invention, the following examples are given to illustrate the inorganic hybrid aramid nanofiber membrane, the preparation method and the application thereof in the lithium battery, and the scope of the present invention is not limited by the following examples.
Example 1
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 240ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.2 wt%.
2. And (3) transferring the aramid nano-fiber dispersion liquid prepared in the step (1) into a culture dish, and drying to obtain a pure nano-aramid fiber lithium ion battery diaphragm finished product. Placing the aramid nano-fiber dispersion liquid in a culture dish with the diameter of 20cm, drying the aramid nano-fiber dispersion liquid for 2 hours in a hot air oven at the temperature of 80 ℃, standing the aramid nano-fiber dispersion liquid for 2 hours at room temperature, and then carrying out vacuum freeze drying for 4 hours to obtain the pure nano-aramid fiber lithium ion battery diaphragm.
The thickness of the finished battery diaphragm prepared by the method is 40 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The method for preparing the diaphragm into the lithium ion battery comprises the following specific steps:
(1) preparation of the positive electrode: the cycle performance is lithium iron phosphate (LiFePO)4Theoretical specific capacity of 170mAh/g) as a positive electrode active material. Weighing lithium iron phosphate powder with the mass ratio of 8:1: conductive carbon black (super): and (3) preparing a positive electrode by using PVDF as a binder. Grinding lithium iron phosphate and conductive carbon black for 20-30min, adding prepared NMP solution of PVDF (6% by mass), continuously adding N-methylpyrrolidone (NMP) to adjust viscosity during the period, finally mixing uniform slurry with moderate viscosity, selecting an aluminum foil as a current collector, and hanging the slurry on the aluminum foil (200um scraper). Drying in 80 deg.C air blast for 12h, punching with 14mm punch, drying in 80 deg.C air blast box for 12h, weighing, drying in 80 deg.C vacuum oven for 12h, and transferring to glove box.
The electrolyte adopts 1M LiPF6in EC/DEC/EMC 1/1/1, Vol% with 1% VC, added 60ul dropwise.
The negative electrode adopts a lithium sheet with the diameter of 15.8 mm.
(2) Rate/cycle performance: assembled into Li// LiFePO4And the button cell tests the charge and discharge performance of the battery through the LAND battery test system. The rate performance is tested at different charging and discharging rates (0.1C, 0.2C, 0.5C, 1C, 2C and 0.2C), the test voltage is 2.5-4.0V, and the test temperature is 25 ℃. The cycle performance was charged and discharged at 0.5C.
(3) Polarization performance: the lithium/lithium button cell is assembled, and the interface stability of the electrolyte/diaphragm of the cell to lithium metal is tested in a LAND cell test system. The charging and discharging current is 0.5mA cm-2。
The lithium ion battery prepared by the diaphragm has excellent cycle stabilityIn addition, no attenuation is seen after 250 times of circulation under 0.5C discharge, and the charging and discharging specific capacity is higher than that of a commercial PP diaphragm (American PP diaphragm)
) About 5-10mAh/g higher. The specific discharge capacity tests under different multiplying powers show that the specific discharge capacity is kept unchanged after the charge-discharge cycles of 0.1C, 0.2C, 0.5C, 1C and 2C multiplying powers and the cycles of 0.2C. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved. Referring to FIGS. 1-2, FIG. 1 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation method of the present invention2) Prepared nano aramid fiber-based composite lithium ion battery diaphragm and commercial PP diaphragm (American Polypropylene (PP) diaphragm)
) Thermal stability of (c) was compared. FIG. 2 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation process of the present invention2) Prepared nano aramid fiber-based composite lithium ion battery diaphragm and commercial PP diaphragm (American Polypropylene (PP) diaphragm)
) Electrical cycling performance of.
Example 2
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 240ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.2 wt%.
2. Adding the nano aramid fiber suspension prepared in the step 10.56g of fumed silica (specific surface area 200. + -. 25 m) was added2/g), heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
3. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (2) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 48 +/-5 mu m. But the unmodified white carbon black has poor dispersibility in the aramid nano-fiber matrix and obvious agglomeration. Referring to fig. 4, fig. 4 is a stereomicroscope photograph of the white carbon black dispersion in the nano aramid fiber-based composite membrane prepared in example 2(a unmodified white carbon black) and example 3(b modified white carbon black) according to the preparation method of the present invention.
Example 3
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Taking appropriate amount of fumed silica (specific surface area is 200 +/-25 m)2And/g) and a dispersing agent are placed in a ball milling tank according to the mass ratio of 10: 1.
Wherein the dispersing agent is gamma-aminopropyl triethoxysilane, and the ball milling is carried out for 2h under the condition of 300 r/min.
And after the ball milling is finished, 0.56g of white carbon black dispersoid is taken out to be placed in 40ml of deionized water, and the ultrasonic treatment is carried out for 30min to obtain the nano silicon dioxide dispersion liquid.
3. And (3) adding the nano silicon dioxide dispersion liquid prepared in the step (2) into the nano aramid fiber suspension liquid prepared in the step (1), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 48 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the lithium ion battery prepared by preparing the separator according to the method of example 1 has excellent cycle stability, does not decay after 250 cycles under 0.5C discharge, and has a specific charge-discharge capacity ratio to that of a commercial PP separator (American PP separator)
) About 10-15mAh/g higher. The specific discharge capacity tests under different multiplying powers show that the specific discharge capacity is kept unchanged after the charge-discharge cycles of 0.1C, 0.2C, 0.5C, 1C and 2C multiplying powers and the cycles of 0.2C. The dynamic stability of the lithium negative interface is instructive for the cycling process of the cell by comparison with a commercial PP separator (US)
) The voltage curve of the aramid nano-fiber hybrid composite membrane is stable in the circulating process, and the short circuit phenomenon does not occur in the cycle of 1000 hours (the PP membrane begins to generate short circuit in the cycle of more than 600 hours). The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammogram before 5.0V, the electrochemical stability is higher, and the electrochemical stability can be matched with a conventional cathode material for use, so that the electrochemical stability is improvedThe utility model relates to the practicability of a lithium ion battery. Referring to FIGS. 1 to 3, FIG. 1 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation method of the present invention2) Prepared nano aramid fiber-based composite lithium ion battery diaphragm and commercial PP diaphragm (American Polypropylene (PP) diaphragm)
) Thermal stability of (c) was compared. FIG. 2 shows examples 1(ANFs) and 3 (ANFs/SiO) of the preparation process of the present invention2) Prepared nano aramid fiber-based composite lithium ion battery diaphragm and commercial PP diaphragm (American Polypropylene (PP) diaphragm)
) Electrical cycling performance of. FIG. 3 shows a nano-aramid fiber-based composite lithium ion battery separator and a commercial PP separator (American Polypropylene) prepared in example 3 of the preparation method of the present invention
) Graph of stability to lithium ions.
Example 4
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Taking appropriate amount of fumed silica (specific surface area is 200 + -25 m)2And/g) and a dispersing agent are placed in a ball milling tank according to the mass ratio of 10: 1.
Wherein the dispersing agent is gamma-aminopropyl triethoxysilane, and the ball milling is carried out for 2h under the condition of 300 r/min.
And after the ball milling is finished, 0.28g of white carbon black dispersoid is taken out to be placed in 40ml of deionized water, and the ultrasonic treatment is carried out for 30min to obtain the nano silicon dioxide dispersion liquid.
3. And (3) adding the nano silicon dioxide dispersion liquid prepared in the step (2) into the nano aramid fiber suspension liquid prepared in the step (1), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 48 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the separator prepared by the method of example 1 has excellent cycle stability. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved.
Example 5
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Taking appropriate amount of fumed silica (specific surface area is 200 +/-25 m)2And/g) and a dispersing agent are placed in a ball milling tank according to the mass ratio of 10: 1.
Wherein the dispersing agent is gamma-aminopropyl triethoxysilane, and the ball milling is carried out for 2h under the condition of 300 r/min.
And after the ball milling is finished, taking 0.168g of white carbon black dispersoid in 40ml of deionized water, and carrying out ultrasonic treatment for 30min to obtain the nano silicon dioxide dispersion liquid.
3. And (3) adding the nano silicon dioxide dispersion liquid prepared in the step (2) into the nano aramid fiber suspension liquid prepared in the step (1), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 38 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the separator prepared by the method of example 1 has excellent cycle stability. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved.
Example 6
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Taking a proper amount of lithium lanthanum zirconium oxide and a dispersing agent according to the mass ratio of 10:1, and placing the mixture into a ball milling tank.
Wherein the dispersing agent comprises polyacrylic acid, sodium dodecyl benzene sulfonate and polyvinyl alcohol which are added according to the mass ratio of 0.5:0.5: 1. The sequence of adding the dispersing agent is as follows: firstly, adding polyacrylic acid and sodium dodecyl benzene sulfonate into a ball mill, and carrying out ball milling for 2 hours under the condition of 300 r/min; then adding 10% polyvinyl alcohol water solution and ball milling for 2h again.
And after the ball milling is finished, 0.868g of the lithium lanthanum zirconium oxygen dispersion is taken to be placed in 40ml of deionized water, and the ultrasonic treatment is carried out for 30min to obtain the lithium lanthanum zirconium oxygen dispersion liquid.
3. And (3) adding the nano aramid fiber suspension prepared in the step (1) into the lithium lanthanum zirconium oxygen dispersion liquid prepared in the step (2), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 45 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the separator prepared by the method of example 1 has excellent cycle stability. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved.
Example 7
1. 40g of aramid nano fiber (1.4 wt%, 1414 para-position aramid fiber synthesized by taking paraphthaloyl chloride-p-phenylenediamine as a monomer, the diameter of the aramid nano fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the aramid nano fiber exists in the form of water-containing aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Taking a proper amount of nano alumina and a dispersing agent according to the mass ratio of 10:1, and placing the nano alumina and the dispersing agent into a ball milling tank.
Wherein the dispersing agent comprises polyacrylic acid, sodium dodecyl benzene sulfonate and polyvinyl alcohol which are added according to the mass ratio of 0.5:0.5: 1. The sequence of adding the dispersing agent is as follows: firstly, adding polyacrylic acid and sodium dodecyl benzene sulfonate into a ball mill, and carrying out ball milling for 2 hours under the condition of 300 r/min; then adding 10% polyvinyl alcohol water solution and ball milling for 2h again.
And after the ball milling is finished, 0.868g of lithium lanthanum zirconium oxygen dispersion is placed in 40ml of deionized water, and the ultrasonic treatment is carried out for 30min to obtain the nano aluminum oxide dispersion liquid.
3. And (3) adding the nano aramid fiber suspension prepared in the step (1) into the nano alumina dispersion prepared in the step (2), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (3) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying the nano aramid fiber dispersion liquid according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 46 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the separator prepared by the method of example 1 has excellent cycle stability. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved.
Example 8
1. 40g of aramid nano-fiber (1.4 wt%, 1414 para-position nano-aramid fiber synthesized by using paraphthaloyl p-phenylenediamine as a monomer, the diameter of the nano-aramid fiber is 50-80 nm, the length-diameter ratio is 2000-5000, the nano-aramid fiber exists in the form of water-containing nano-aramid fiber, and the specific gravity of ANFs and water is 1.5-4.0: 96-98.5). Adding 200ml of deionized water into a container, taking water as a dispersing agent, stirring and mixing at the stirring speed of 300-500 rpm for 30min to obtain uniform and stable nano aramid fiber suspension. The concentration of the nano aramid fiber suspension is 0.28 wt%.
2. Placing a proper amount of carboxyl polysilsesquioxane in a ball milling tank, and carrying out ball milling for 2 hours under the condition of 300 r/min; and after the ball milling is finished, 0.56g of polysilsesquioxane dispersion is taken and put into 40ml of dimethyl sulfoxide, and the mixture is subjected to ultrasonic treatment for 30min to obtain polysilsesquioxane dispersion liquid.
3. And (3) dropwise adding the polysilsesquioxane dispersion liquid obtained in the step (2) into the nano aramid fiber suspension liquid prepared in the step (1), and heating and stirring.
Wherein the heating mode is oil bath heating, the heating temperature is 120 ℃, the stirring speed is 300-500 rpm, and the heating and stirring time is 1 h. And preparing a dispersion liquid of the nano aramid fiber and the inorganic filler.
4. And (4) transferring the nano aramid fiber dispersion liquid prepared in the step (3) into a culture dish, and drying according to the method in the embodiment 1 to obtain the inorganic hybrid nano aramid fiber composite lithium ion battery diaphragm finished product.
The thickness of the finished battery diaphragm prepared by the method is 46 +/-5 mu m, and can be adjusted according to the content of the aramid nano-fiber suspension. The diameter of the film aperture is about 10-20nm by SEM electron microscope test analysis.
The lithium ion battery prepared by using the separator prepared by the method of example 1 has excellent cycle stability. The electrochemical stability is tested by a linear scanning voltammetry method, obvious current change is not monitored in a linear scanning voltammetry before 5.0V, the electrochemical stability is high, and the electrochemical stability can be matched with a conventional cathode material for use, so that the practicability of the lithium ion battery is improved.
The prepared diaphragm is not attenuated after being circularly measured for 250 times; the aramid nano-fiber hybrid composite membrane prepared by the method can inhibit the formation of lithium dendrites, and the polarization voltage curve does not generate short circuit within 1000-hour cycle, so that the aramid nano-fiber hybrid composite membrane is commercially available
The PP separator began to short circuit around 600 hours of cycling.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The inorganic hybrid aramid nanofiber membrane is characterized by being prepared from aramid nanofibers and an inorganic filler in a mass ratio of 1: 10-99: 1 through a water dispersion system.
2. The separator according to claim 1, wherein the aramid nanofibers and the inorganic filler are aramid nanofibers and inorganic filler surface-modified with a dispersant.
3. The separator according to claim 2, wherein the dispersant is selected from one or more of a silane coupling agent, a surfactant, a polymeric dispersant, or dopamine.
4. The membrane according to claim 1, wherein the aramid nanofibers have a diameter of 50 to 80nm and an aspect ratio of 2000 to 5000;
the aramid nano-fiber is 1414 para-aramid nano-fiber synthesized by using paraphthaloyl chloride and p-phenylenediamine as monomers and/or 1313 meta-aramid nano-fiber synthesized by using isophthaloyl chloride and p-phenylenediamine as monomers.
5. The separator according to claim 1, wherein the inorganic filler is one or more selected from fumed silica, precipitated silica, polysilsesquioxane, in situ silica, alumina, zirconia, lithium lanthanum zirconium oxide, or ceramic micropowder.
6. The preparation method of the inorganic hybrid aramid nanofiber membrane as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
A) mixing aramid nano-fiber with water to obtain a suspension;
B) mixing an inorganic filler with a dispersant, and then adding a solvent for ultrasonic dispersion to obtain an inorganic filler dispersion liquid;
C) adding the inorganic filler dispersion liquid into the aramid nano-fiber suspension liquid, and stirring to obtain a mixed dispersion liquid;
D) and dehydrating and drying the mixed dispersion liquid to obtain the inorganic hybrid aramid nanofiber membrane.
7. The preparation method of claim 6, wherein the concentration of the aramid nanofibers in the suspension is 0.1-0.6 wt%.
8. The production method according to claim 6, wherein the stirring speed of the mixing is 300 to 500 rpm; the temperature is 0-120 ℃; the time is 5-120 min;
the drying is one or more of room temperature drying, drying in a drying oven, vacuum freeze drying, mould pressing drying or paper making method forming drying.
9. A lithium battery is characterized by comprising the inorganic hybrid aramid nanofiber membrane as claimed in any one of claims 1 to 5 or the inorganic hybrid aramid nanofiber membrane prepared by the preparation method as claimed in any one of claims 6 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210393452.5A CN114725616A (en) | 2022-04-15 | 2022-04-15 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210393452.5A CN114725616A (en) | 2022-04-15 | 2022-04-15 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114725616A true CN114725616A (en) | 2022-07-08 |
Family
ID=82244446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210393452.5A Pending CN114725616A (en) | 2022-04-15 | 2022-04-15 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114725616A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115224438A (en) * | 2022-07-28 | 2022-10-21 | 哈尔滨工业大学无锡新材料研究院 | Preparation method of composite coating lithium ion battery polyethylene diaphragm |
| CN115434184A (en) * | 2022-07-20 | 2022-12-06 | 南京玻璃纤维研究设计院有限公司 | Nano composite coated paper and preparation method thereof |
| CN116023115A (en) * | 2022-12-01 | 2023-04-28 | 武汉中科先进材料科技有限公司 | Silicon aerogel-nanofiber composite membrane and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702900A (en) * | 2016-03-24 | 2016-06-22 | 武汉纺织大学 | Preparation for para-aramid nanofiber lithium ion battery diaphragm based on pyrolysis-caused-holes |
| CN108666501A (en) * | 2018-04-26 | 2018-10-16 | 烟台泰和新材料股份有限公司 | A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning |
| CN109411680A (en) * | 2018-10-29 | 2019-03-01 | 东莞理工学院 | A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof |
| CN109546056A (en) * | 2018-11-27 | 2019-03-29 | 河北金力新能源科技股份有限公司 | Diaphragm coating liquid and water system nanometer p-aramid fiber apply diaphragm |
| CN110845957A (en) * | 2019-11-22 | 2020-02-28 | 上海大学 | Aqueous aramid fiber coating liquid and preparation method thereof, lithium ion battery and diaphragm thereof |
| CN112216928A (en) * | 2020-10-10 | 2021-01-12 | 广东中显自动化设备有限公司 | Modified composite heat-resistant lithium ion battery diaphragm and preparation method thereof |
| CN113506949A (en) * | 2021-07-09 | 2021-10-15 | 陕西科技大学 | Preparation method of aramid nanofiber-based battery diaphragm with micro-nano porous structure |
-
2022
- 2022-04-15 CN CN202210393452.5A patent/CN114725616A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702900A (en) * | 2016-03-24 | 2016-06-22 | 武汉纺织大学 | Preparation for para-aramid nanofiber lithium ion battery diaphragm based on pyrolysis-caused-holes |
| CN108666501A (en) * | 2018-04-26 | 2018-10-16 | 烟台泰和新材料股份有限公司 | A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning |
| CN109411680A (en) * | 2018-10-29 | 2019-03-01 | 东莞理工学院 | A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof |
| CN109546056A (en) * | 2018-11-27 | 2019-03-29 | 河北金力新能源科技股份有限公司 | Diaphragm coating liquid and water system nanometer p-aramid fiber apply diaphragm |
| CN110845957A (en) * | 2019-11-22 | 2020-02-28 | 上海大学 | Aqueous aramid fiber coating liquid and preparation method thereof, lithium ion battery and diaphragm thereof |
| CN112216928A (en) * | 2020-10-10 | 2021-01-12 | 广东中显自动化设备有限公司 | Modified composite heat-resistant lithium ion battery diaphragm and preparation method thereof |
| CN113506949A (en) * | 2021-07-09 | 2021-10-15 | 陕西科技大学 | Preparation method of aramid nanofiber-based battery diaphragm with micro-nano porous structure |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115434184A (en) * | 2022-07-20 | 2022-12-06 | 南京玻璃纤维研究设计院有限公司 | Nano composite coated paper and preparation method thereof |
| CN115434184B (en) * | 2022-07-20 | 2024-01-05 | 南京玻璃纤维研究设计院有限公司 | Nano composite coated board paper and preparation method thereof |
| CN115224438A (en) * | 2022-07-28 | 2022-10-21 | 哈尔滨工业大学无锡新材料研究院 | Preparation method of composite coating lithium ion battery polyethylene diaphragm |
| CN116023115A (en) * | 2022-12-01 | 2023-04-28 | 武汉中科先进材料科技有限公司 | Silicon aerogel-nanofiber composite membrane and preparation method thereof |
| CN116023115B (en) * | 2022-12-01 | 2024-01-05 | 武汉中科先进材料科技有限公司 | Silicon aerogel-nanofiber composite membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Aramid nanofibers/polyphenylene sulfide nonwoven composite separator fabricated through a facile papermaking method for lithium ion battery | |
| Zhao et al. | Effect of OctaphenylPolyhedral oligomeric silsesquioxane on the electrospun Poly-m-phenylene isophthalamid separators for lithium-ion batteries with high safety and excellent electrochemical performance | |
| WO2016165559A1 (en) | Composite separator and preparation method therefor, and lithium-ion battery | |
| CN114725616A (en) | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery | |
| Xiao et al. | Preparation of core–shell structural single ionic conductor SiO2@ Li+ and its application in PVDF–HFP-based composite polymer electrolyte | |
| Arifeen et al. | A nano-silica/polyacrylonitrile/polyimide composite separator for advanced fast charging lithium-ion batteries | |
| CN111525184B (en) | Composite solid electrolyte film and preparation and application thereof | |
| Chen et al. | Investigation on high-safety lithium ion battery using polyethylene supported poly (methyl methacrylate-acrylonitrile-butyl acrylate) copolymer based gel electrolyte | |
| Wang et al. | Effect of different contents of organic-inorganic hybrid particles poly (methyl methacrylate) ZrO2 on the properties of poly (vinylidene fluoride-hexafluoroprolene)-based composite gel polymer electrolytes | |
| He et al. | Effectively suppressing lithium dendrite growth via an es-LiSPCE single-ion conducting nano fiber membrane | |
| Zhang et al. | Surface-modified boron nitride as a filler to achieve high thermal stability of polymer solid-state lithium-metal batteries | |
| WO2016161920A1 (en) | Composite separator and preparation method therefor, and lithium-ion battery | |
| WO2017167195A1 (en) | Non-porous separator and use thereof | |
| CN112521616B (en) | Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack | |
| TW202224243A (en) | Electrode mixture for secondary batteries, electrode mixture sheet for secondary batteries, method of production for same, and secondary battery | |
| Zhao et al. | Preparation and performance of the polyethylene-supported polyvinylidene fluoride/cellulose acetate butyrate/nano-SiO 2 particles blended gel polymer electrolyte | |
| CN112201905A (en) | Cellulose-based lithium battery flame-retardant diaphragm and preparation method thereof | |
| Li et al. | Evaporation and in-situ gelation induced porous hybrid film without template enhancing the performance of lithium ion battery separator | |
| CN110400923A (en) | Cell negative electrode material, negative electrode material slurry, cathode pole piece and electrochemical cell | |
| CN115064764A (en) | Ceramic filler modified high-conductivity wide-voltage-window composite electrolyte material, and preparation method and application thereof | |
| CN114649560A (en) | Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof | |
| Guo et al. | Microporous bayberry-like nano-silica fillers enabling superior performance gel polymer electrolyte for lithium metal batteries | |
| WO2023179550A1 (en) | Composite oil-based separator and preparation method therefor, and secondary battery | |
| Zhai et al. | Electrospun nanofibers for lithium-ion batteries | |
| JP2011086558A (en) | Scale-like inorganic solid electrolyte filler, solid electrolyte membrane containing the same, nonaqueous electrolyte secondary battery, and capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |