CN110233287A - 一种尼龙基复合凝胶聚合物电解质及其制备方法 - Google Patents
一种尼龙基复合凝胶聚合物电解质及其制备方法 Download PDFInfo
- Publication number
- CN110233287A CN110233287A CN201910276572.5A CN201910276572A CN110233287A CN 110233287 A CN110233287 A CN 110233287A CN 201910276572 A CN201910276572 A CN 201910276572A CN 110233287 A CN110233287 A CN 110233287A
- Authority
- CN
- China
- Prior art keywords
- nylon
- electrolyte
- high molecular
- film
- gel polymer
- 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
- 239000004677 Nylon Substances 0.000 title claims abstract description 57
- 229920001778 nylon Polymers 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 4
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004642 Polyimide Substances 0.000 claims abstract description 3
- 229920002678 cellulose Polymers 0.000 claims abstract description 3
- 239000001913 cellulose Substances 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 3
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 3
- 239000004417 polycarbonate Substances 0.000 claims abstract description 3
- 229920001721 polyimide Polymers 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001523 electrospinning Methods 0.000 claims description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000005213 imbibition Methods 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003660 carbonate based solvent Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000011245 gel electrolyte Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 229920006284 nylon film Polymers 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 31
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 31
- 239000000499 gel Substances 0.000 description 26
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- 229910001290 LiPF6 Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 8
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- -1 PA6 compound Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/69—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with phosphorus; with halides or oxyhalides of phosphorus; with chlorophosphonic acid or its salts
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
Abstract
本发明属于高分子材料和电池领域，具体涉及一种尼龙基复合凝胶聚合物电解质及其制备方法，同时还包括此类凝胶电解质在电池中的应用。该聚合物电解质由尼龙基复合膜吸收液体电解质制得。尼龙复合膜由尼龙和其它高分子材料复合得到，涉及的其它高分子材料包括但限于聚醚、聚丙烯腈、聚丙烯酸酯、含氟聚烯烃、聚碳酸酯、聚酰亚胺、纤维素等的均聚物、共聚物或共混物。该凝胶电解质不但具有无纺布机械强度大、生产成本低的特点，而且电导率高，电化学窗口宽，循环性能好，安全性能高，可用于大容量、高功率、高能量密度的一次或二次电池系统中。
Description
技术领域
本发明属于电化学技术领域，具体涉及一种尼龙基复合凝胶聚合物电解质及其制备方法，本发明还涉及该聚合物电解质的应用。
背景技术
锂离子电池具有能量密度高、输出功率大、循环寿命长、无记忆效应、环境友好等特点，自上世纪90年代商品化以来被广泛应用于手机、平板电脑、移动电源等便携式电子产品中，作为动力电池其在电动汽车系统中也发挥了举足轻重作用，同时锂离子电池作为储能电池在智能电网系统应用潜力也十分巨大。然而，由于锂离子电池中广泛使用有机液体电解液(电解质盐和少量添加剂溶于易燃的有机溶剂)和聚烯烃微孔隔膜，电池在大倍率充放或滥用等情况极易发生起火、爆炸等安全事故。随着电池能量密度的大幅提升，锂离子电池的安全性问题成为全社会关注的焦点。
为提高锂离子电池的安全性，凝胶聚合物电解质(Gel polymer electrolytes，GPE)，兼具液体电解质和固体电解质的双重性质(安全性高、可塑性强、电导率高、电化学窗口宽、与电极材料相容性好等)，受到研究人员的广泛关注。目前对聚合物电解质的研究主要集中在以下几类：聚醚类(主要是PEO)、聚丙烯腈 (PAN)类、聚甲基丙烯酸酯(PMMA)类及聚偏氟乙烯(PVDF)类等。但这些材料制备工艺复杂，价格较高，大大限制了聚合物锂离子电池的广泛应用。开发价格低廉、性能优异、可与电解液凝胶化的高分子材料成为聚合物电解质研究的热点。
尼龙(nylon)，学名聚酰胺(polyamide，PA),是分子主链上含有重复酰胺基团(—[NHCO]—)的热塑性树脂总称。尼龙可由二元胺和二元酸制取，也可以用ω-氨基酸或环内酰胺来合成。根据二元胺和二元酸或氨基酸中含有碳原子数的不同，可制得多种不同的聚酰胺，聚酰胺品种多达几十种，如有PA6、 PA66、PAll、PAl2、PA46、PA610、PA612、PAl010等。尼龙力学性能、耐热性、耐磨损性、电绝缘性、化学稳定性、自润滑性和阻燃性等诸多方面表现优异，且易于加工，被广泛应用于服装、电子电气、汽车、建筑、办公设备、机械、航空航天等诸多行业。
静电纺丝纺法(电纺法)是将直流高压施加于聚合物溶液与收集装置之间，使聚合物溶液带上几千至上万伏高压静电，当电场力足够大时，带电的聚合物液滴克服表面张力形成喷射细流，细流在喷射过程中随溶剂蒸发固化，最终落在收集装置上，形成类似无纺布的纤维毡，纺丝纤维直径可从几纳米至数百微米，成膜厚度可控、孔径可控、孔径均一，在制备高分子膜材料方面优势明显。
发明内容
本发明的目的是要提供一种尼龙基复合凝胶聚合物电解质及其制备方法，它不但离子迁移数高、机械性能好，安全性能高，化学性能稳定，生产成本低高、电化学窗口宽，而且还能与常见电极材料匹配性，表现出优异的电化学性能(低的内阻、长的循环稳定性和优异的倍率性能)。这不仅可以拓展尼龙的应用，同时可以降低聚合物电解质的生产成本，降低锂离子电池的价格。
本发明的另一目的在于提供一种上述凝胶聚合物电解质的制备方法及其在锂离子电池或钠离子电池中的应用。
一种尼龙基复合凝胶聚合物电解质，其特征在于所述的电解质包括尼龙 (Nylon)与除尼龙之外的一种或多种其他高分子材料复合得到的聚合物膜；还包括液体电解质。
所述的尼龙(Nylon)亦称聚酰胺(Polyamide)、锦纶或耐纶，是分子主链重复单元中含有酰胺基团(—NHCO—)的高聚物的总称。
所述的其它高分子材料包括聚醚、聚丙烯腈、聚丙烯酸酯、含氟聚烯烃、聚碳酸酯、聚酰亚胺或纤维素中任意两种或者两种以上物质的均聚物、共聚物或共混物。
所述的复合膜包括但不仅限于尼龙/其它高分子材料共混电纺膜、尼龙 /其它高分子材料/尼龙三明治结构电纺膜、其它高分子材料/尼龙/其它高分子材料三明治结构电纺膜、外层为尼龙内层为其它高分子材料的尼龙/其它高分子材料同轴电纺膜、外层为其它高分子材料内层为尼龙的其它高分子材料/ 尼龙同轴电纺膜、尼龙/其它高分子材料并轴电纺膜、其它高分子嵌入尼龙电纺膜孔隙组成的复合物或尼龙嵌入其它高分子电纺膜孔隙组成的复合物。
一种尼龙基复合凝胶聚合物电解的制备方法，其特征在于以下步骤：
(1)将尼龙和其它高分子材料溶解于溶剂中，得到均一澄清溶液；
(2)通过静电纺丝法或结合其它方法：浸渍法、浇铸法或热压法制得复合膜，膜的厚度控制在15-65μm；
(3)将步骤(2)得到的复合膜置于真空干燥箱中，在室温至120℃条件下干燥，去除痕量溶剂；
(4)在无水无氧环境中将干燥后的步骤(3)得到的复合物浸泡在电解液中 1分钟至24小时，得到凝胶聚合物电解质。
所述步骤(1)所述的溶剂为为甲酸、乙酸、丙酮、N,N-二甲基甲酰胺、 N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的一种或多种的混合物。
所述步骤(1)所述的溶解过程，是在室温-80℃下搅拌溶解0.5小时-12 小时。
所述步骤(2)所述的制备过程，所有电纺丝膜均为电纺丝机上制得，电压范围-100KV至+100KV。
所述步骤(3)所述制备得复合聚合物在制备凝胶电解质前先置于真空干燥箱干燥至120℃条件下干燥去除痕量溶剂。
所述步骤(4)所述制备凝胶聚合物电解质在手套箱，氩气氛，水分含量小于1ppm中进行，且吸液时间在1min-24h之间；所述步骤(4)所述的电解液由电解质锂盐或钠盐溶解于碳酸酯类溶剂构成，浓度在0.5mol l-1-2 mol l-1之间。
所述步骤(4)所采用的电解液由电解质锂盐、钠盐，如LiClO4、LiBF4、LiAsF6、LiPF6、LiTFSI、LiFSI、LiBOB、LiODFB、LiTDI、NaClO4、NaBF4、 NaAsF6、NaPF6、NaTFSI、NaFSI、NaBOB、NaODFB、NaTDI等，溶解于碳酸酯类溶剂构成，浓度在0.5mol l-1-2mol l-1之间。
本发明还提供一种上述尼龙基复合凝胶聚合物电解质的制备方法及其在锂离子电池或钠离子电池中的应用。
本发明采用静电纺丝法制备得到尼龙基复合高分子膜，其与有机液体电解液凝胶化复合凝胶聚合物电解质，所得凝胶聚合物膜不但具有强度大、生产成本低的特点，而且电导率高，电化学窗口宽，循环性能好，安全性能高，可用于大容量、高功率、高能量密度的锂离子电池或钠离子电池。
电解质凝胶化制备复合无纺布凝胶聚合物电解质，所得凝胶聚合物膜不但具有无纺布机械强度大、生产成本低的特点，而且电导率高，电化学窗口宽，循环性能好，安全性能高，可用于大容量、高功率、高能量密度的锂离子电池。
附图说明
图1a是本发明实施例1所得PA6/PVDF/PA6复合膜的表面扫描电镜图；
图1b是本发明实施例1所得中间层PVDF电纺膜的表面扫描电镜图；
图1c是本发明实施例1所得PA6/PVDF/PA6复合膜的断面扫描电镜图；
图1d是本发明对比例中Celgard 2400表面扫描电镜图。
图2是本发明实施例1所得PA6/PVDF/PA6复合膜和对比例所用Celgard 2400 隔膜的拉力-应力曲线对比图。
图3是本发明实施例1所得PA6/PVDF/PA6复合膜和对比例所用Celgard 2400 隔膜的热重曲线对比图。
图4是本发明实施例1所得PA6/PVDF/PA6复合膜和对比例所用Celgard 2400 隔膜吸收等量1mol l-1LiPF6电解液后在氩气氛中的热重曲线对比图。
图5是本发明实施例1所得PA6/PVDF/PA6凝胶聚合物电解质和对比例所用1 moll-1LiPF6电解液饱和的Celgard 2400隔膜的阿累尼乌斯方程曲线对比图。
图6是本发明实施例1所得PA6/PVDF/PA6凝胶聚合物电解质和对比例所用1 moll-1LiPF6电解液饱和的Celgard 2400隔膜锂离子迁移数测试对比图。
图7是本发明实施例1所得PA6/PVDF/PA6凝胶聚合物电解质和对比例所用1 moll-1LiPF6电解液饱和的Celgard 2400电化学窗口测试对比图。
图8是本发明实施例1所得PA6/PVDF/PA6凝胶聚合物电解质和对比例所用1 moll-1LiPF6电解液饱和的Celgard 2400通过LiFePO4/凝胶膜或隔膜/Li电池体系的充放电曲线对比图。
图9是本发明实施例1所得PA6/PVDF/PA6凝胶聚合物电解质和对比例所用1 moll-1LiPF6电解液饱和的Celgard 2400通过LiFePO4/凝胶膜或隔膜/Li电池体系的倍率性能对比图。
具体实施方式
下面结合附图对表发明做进一步说明。
如图1至图9，实施例1
(1)将PA6按质量百分比为12％的比例溶解于甲酸/乙酸(1/1，V/V)混合溶液中中，在50℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。将PVDF 按质量百分比为15％的比例溶解于DMAc中，在40℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。
(2)在静电纺丝机上先纺一层PA6，纺丝条件：0.8mL h-1，20KV；接着在 PA6层上电纺一层PVDF，纺丝条件：1mL h-1，16KV；完成两层后，在PVDF 层上纺一层PA6膜，纺丝条件：：0.8mL h-1，20KV。将纺得的复合膜从铝箔上接下来，即得到厚度为60μm的PA6/PVDF/PA6复合膜。
(3)将PA6/PVDF/PA6复合电放膜剪裁成适当尺寸后，置于真空干燥箱80 ℃条件下24小时干燥去除痕量溶剂，真空冷至室温转移进手套箱。电纺复合膜浸泡在1.5mol l- 1LiPF6电解液中8小时即得PA6/PVDF/PA6凝胶电解质。(电解液直接购自张家港市国泰华荣化工新材料有限公司)
实施例2
(1)将PA6按质量百分比为12％的比例溶解于甲酸/乙酸(1/1，V/V)混合溶液中中，在50℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。将 PVDF-HFP按质量百分比为15％的比例溶解于DMAc中，在40℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。
(2)在静电纺丝机上先纺一层PA6，纺丝条件：0.8mL h-1，20KV；接着在PA6层上电纺一层PVDF-HFP，纺丝条件：1mL h-1，15KV；完成两层后，在PVDF层上纺一层PA6膜，纺丝条件：0.8mL h-1，20KV。将纺得的复合膜从铝箔上接下来，即得到厚度为50μm的PA6/PVDF-HFP/PA6复合膜。
(3)将PA6/PVDF-HFP/PA6复合电放膜剪裁成适当尺寸后，置于真空干燥箱80℃条件下24小时干燥去除痕量溶剂，真空冷至室温转移进手套箱。电纺复合膜浸泡在1.5mol l- 1LiPF6电解液中8小时即得PA6/PVDF-HFP/PA6凝胶电解质。(电解液直接购自张家港市国泰华荣化工新材料有限公司)
实施例3
(1)将PA6按质量百分比为12％的比例溶解于甲酸/乙酸(1/1，V/V)混合溶液中中，在50℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。将 PVDF-HFP按质量百分比为15％的比例溶解于DMAc中，在40℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。
(2)在静电纺丝机选用同轴针头进行喷丝，内管喷出PVDF丝，外管喷出 PA6丝，喷丝条件1mL h-1，15KV，喷丝距离30厘米，喷丝时间6h。将纺得的复合膜从铝箔上接下来，即得到厚度为40μm的PA6/PVDF复合膜。
(3)将PA6/PVDF复合电放膜剪裁成适当尺寸后，置于真空干燥箱80℃条件下24小时干燥去除痕量溶剂，真空冷至室温转移进手套箱。电纺复合膜浸泡在1.5mol l-1LiPF6电解液中8小时即得PA6/PVDF凝胶电解质。(电解液直接购自张家港市国泰华荣化工新材料有限公司)
实施例4
(1)将PA6按质量百分比为12％的比例溶解于甲酸/乙酸(1/1，V/V)混合溶液中中，在50℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。将 PVDF-HFP按质量百分比为15％的比例溶解于DMAc中，在40℃的水浴中加热搅拌2小时得澄清均一溶液，冷至室温。
(2)在静电纺丝机选用并轴针头进行喷丝，一根针头喷出PVDF丝，另一根针头喷出PA6丝，喷丝条件1mL h-1，15KV，喷丝距离30厘米，喷丝时间4 h。将纺得的复合膜从铝箔上接下来，即得到厚度为40μm的PA6/PVDF复合膜。
(3)将PA6/PVDF复合电放膜剪裁成适当尺寸后，置于真空干燥箱80℃条件下24小时干燥去除痕量溶剂，真空冷至室温转移进手套箱。电纺复合膜浸泡在1.5mol l-1LiPF6电解液中8小时即得PA6/PVDF凝胶电解质。(电解液直接购自张家港市国泰华荣化工新材料有限公司)
对比例1
将商用锂离子电池隔膜(Celgard 2400，PP)剪裁成适当尺寸后，置于真空干燥箱80℃条件下减压干燥24小时，真空冷至室温转移进手套箱。进行电化学测试前需将Celgard2400隔膜浸泡在1mol l-1LiPF6电解液中8小时。(电解液直接购自张家港市国泰华荣化工新材料有限公司)
对上述实施例1方法获得的PA6/PVDF/PA6复合膜及对比例中Celgard 2400 隔膜进行了扫描电镜、TG、吸液率、拉力应力表征；对凝胶聚合物电解质及1mol l-1LiPF6电解液饱和的Celgard 2400隔膜进行了TG、电导率、离子迁移数及充放电测试。测试结果如图1-9。
吸液率是将复合无纺布及Celgard 2400隔膜浸泡在电解液8小时后，根据公式(1)计算得到：
η＝(Wt–W0)/W0×100％ (1)
其中，W0和Wt分别代表干膜和吸饱电解液后的质量。对比例中Celgard 2400隔膜的吸液率为90.0％，实施例1方法获得的PA6/PVDF/PA6复合膜的吸液率为 273％。
电导率由公式(2)计算得到：
σ＝l/(RbA)(S cm-1) (2)
其中，σ是电导率，Rb是膜的阻抗,l是膜的厚度,A是极片面积。对比例中1mol l- 1LiPF6电解液饱和的Celgard 2400隔膜的的室温电导率为1.0mS cm-1，实施例 1方法获得的PA6/PVDF/PA6凝胶膜的室温电导率达4.2mS cm-1。
锂离子迁移数由公式(3)计算得到：
tLi +＝Iss/I0 (3)
其中，Iss是计时电量法所得到的稳态电流值，I0是计时电量法所得到的初始态电流值。1mol l-1LiPF6电解液饱和的Celgard 2400隔膜的的室温锂离子迁移数为 0.25，实施例1方法获得的PA6/PVDF/PA6凝胶膜的室温锂离子迁移数为0.32。
从对比例和实施例的对比来看，基于无纺布材料的锂离子电池凝胶聚合物电解质具有高安全性、高强度、低造价的特点，而且具有和商用锂离子电池隔膜相媲美的电导率和电化学性质，对锂离子电池特别是大功率、高效率、高能量密度锂离子电池极具吸引力。
Claims (10)
1.一种尼龙基复合凝胶聚合物电解质，其特征在于所述的电解质包括尼龙(Nylon)与除尼龙之外的一种或多种其他高分子材料复合得到的聚合物膜；还包括液体电解质。
2.如权利要求1所述的尼龙基复合凝胶聚合物电解质，其特征在于所述的尼龙(Nylon)亦称聚酰胺(Polyamide)、锦纶或耐纶，是分子主链重复单元中含有酰胺基团(—NHCO—)的高聚物的总称。
3.如权利要求1所述的尼龙基复合凝胶聚合物电解质，其特征在于所述的其它高分子材料包括聚醚、聚丙烯腈、聚丙烯酸酯、含氟聚烯烃、聚碳酸酯、聚酰亚胺或纤维素中任意两种或者两种以上物质的均聚物、共聚物或共混物。
4.如权利要求1所述的尼龙基复合凝胶聚合物电解质，其特征在于所述的复合膜包括但不仅限于尼龙/其它高分子材料共混电纺膜、尼龙/其它高分子材料/尼龙三明治结构电纺膜、其它高分子材料/尼龙/其它高分子材料三明治结构电纺膜、外层为尼龙内层为其它高分子材料的尼龙/其它高分子材料同轴电纺膜、外层为其它高分子材料内层为尼龙的其它高分子材料/尼龙同轴电纺膜、尼龙/其它高分子材料并轴电纺膜、其它高分子嵌入尼龙电纺膜孔隙组成的复合物或尼龙嵌入其它高分子电纺膜孔隙组成的复合物。
5.一种如权利要求1所述的尼龙基复合凝胶聚合物电解的制备方法，其特征在于以下步骤：
(1)将尼龙和其它高分子材料溶解于溶剂中，得到均一澄清溶液；
(2)通过静电纺丝法或结合其它方法：浸渍法、浇铸法或热压法制得复合膜，膜的厚度控制在15-65μm；
(3)将步骤(2)得到的复合膜置于真空干燥箱中，在室温至120℃条件下干燥，去除痕量溶剂；
(4)在无水无氧环境中将干燥后的步骤(3)得到的复合物浸泡在电解液中1分钟至24小时，得到凝胶聚合物电解质。
6.如权利要求5所述的方法，其特征在于所述步骤(1)所述的溶剂为为甲酸、乙酸、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的一种或多种的混合物。
7.如权利要求5所述的方法，其特征在于所述步骤(1)所述的溶解过程，是在室温-80℃下搅拌溶解0.5小时-12小时。
8.如权利要求5所述的方法，其特征在于所述步骤(2)所述的制备过程，所有电纺丝膜均为电纺丝机上制得，电压范围-100KV至+100KV。
9.如权利要求5所述的方法，其特征在于所述步骤(3)所述制备得复合聚合物在制备凝胶电解质前先置于真空干燥箱干燥至120℃条件下干燥去除痕量溶剂。
10.如权利要求5所述的方法，其特征在于所述步骤(4)所述制备凝胶聚合物电解质在手套箱，氩气氛，水分含量小于1ppm中进行，且吸液时间在1min-24h之间；所述步骤(4)所述的电解液由电解质锂盐或钠盐溶解于碳酸酯类溶剂构成，浓度在0.5mol l-1-2mol l-1之间。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310095248.XA CN116632333A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质的制备方法 |
| CN201910276572.5A CN110233287A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910276572.5A CN110233287A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质及其制备方法 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310095248.XA Division CN116632333A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110233287A true CN110233287A (zh) | 2019-09-13 |
Family
ID=67860715
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910276572.5A Pending CN110233287A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质及其制备方法 |
| CN202310095248.XA Pending CN116632333A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质的制备方法 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310095248.XA Pending CN116632333A (zh) | 2019-04-08 | 2019-04-08 | 一种尼龙基复合凝胶聚合物电解质的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN110233287A (zh) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707357A (zh) * | 2019-10-23 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | 一种核壳结构的凝胶聚合物电解质及其制备方法和应用 |
| CN111106391A (zh) * | 2019-12-11 | 2020-05-05 | 西安交通大学 | 一种高强度固态电解质膜的制备方法和应用 |
| CN111430792A (zh) * | 2020-04-01 | 2020-07-17 | 深圳市奥能动力科技有限公司 | 复合凝胶固态电解质、制备方法及全固态锂离子电池 |
| CN111554973A (zh) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | 基于树枝状聚酰胺-6纳米纤维膜的全固态聚合物电解质及其制备方法 |
| CN112466674A (zh) * | 2020-10-29 | 2021-03-09 | 电子科技大学 | 高温凝胶聚合物电解质锂离子电容器的制备方法 |
| CN113130987A (zh) * | 2021-04-21 | 2021-07-16 | 昆山宝创新能源科技有限公司 | 凝胶电解质膜及其制备方法和应用 |
| CN113506951A (zh) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | 用于金属二次电池的纤维素基复合隔膜及其制备方法 |
| CN114976233A (zh) * | 2022-06-21 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | 一种复合凝胶聚合物电解质及其制备方法和应用 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1689177A (zh) * | 2002-09-11 | 2005-10-26 | 可乐丽股份有限公司 | 碱性电池隔板和使用该隔板的电池 |
| CN101626097A (zh) * | 2009-06-05 | 2010-01-13 | 长沙高新开发区材盛新能源科技有限公司 | 高吸液率微纳结构聚合物电解质膜及其制备方法 |
| CN102074735A (zh) * | 2010-12-03 | 2011-05-25 | 浙江大学 | 基于双烯/醚共聚物的锂离子凝胶电解质膜及其制备方法 |
| CN103022557A (zh) * | 2012-12-25 | 2013-04-03 | 复旦大学 | 基于无纺布的锂离子电池凝胶聚合物电解质及其制备方法 |
| CN104393336A (zh) * | 2014-11-13 | 2015-03-04 | 湘潭大学 | 一种纳米复合纤维增强凝胶聚合物电解质及其制备方法 |
| US20150064602A1 (en) * | 2012-03-29 | 2015-03-05 | Kolon Industries, Inc. | Polymer electrolyte membrane, a method for fabricating the same, and a membrane-electrode assembly including the same |
| CN104746236A (zh) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | 一种聚酰亚胺/聚氧化乙烯电缆型复合纳米纤维膜及其制备方法 |
| CN105633326A (zh) * | 2015-06-03 | 2016-06-01 | 北京星和众工设备技术股份有限公司 | 芳香族聚酰胺复合隔膜 |
| CN106654365A (zh) * | 2013-01-23 | 2017-05-10 | 浙江地坤键新能源科技有限公司 | 基于固态聚合物电解质的复合凝胶聚合物电解质及其制备方法与应用 |
| CN107658500A (zh) * | 2017-08-07 | 2018-02-02 | 南昌大学 | 一种原位制备柔性锂离子电池聚合物电解质的方法及应用 |
| CN108365261A (zh) * | 2018-01-15 | 2018-08-03 | 浙江衡远新能源科技有限公司 | 一种锂离子电池凝胶聚合物电解质及其制备方法 |
-
2019
- 2019-04-08 CN CN201910276572.5A patent/CN110233287A/zh active Pending
- 2019-04-08 CN CN202310095248.XA patent/CN116632333A/zh active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1689177A (zh) * | 2002-09-11 | 2005-10-26 | 可乐丽股份有限公司 | 碱性电池隔板和使用该隔板的电池 |
| CN101626097A (zh) * | 2009-06-05 | 2010-01-13 | 长沙高新开发区材盛新能源科技有限公司 | 高吸液率微纳结构聚合物电解质膜及其制备方法 |
| CN102074735A (zh) * | 2010-12-03 | 2011-05-25 | 浙江大学 | 基于双烯/醚共聚物的锂离子凝胶电解质膜及其制备方法 |
| US20150064602A1 (en) * | 2012-03-29 | 2015-03-05 | Kolon Industries, Inc. | Polymer electrolyte membrane, a method for fabricating the same, and a membrane-electrode assembly including the same |
| CN103022557A (zh) * | 2012-12-25 | 2013-04-03 | 复旦大学 | 基于无纺布的锂离子电池凝胶聚合物电解质及其制备方法 |
| CN106654365A (zh) * | 2013-01-23 | 2017-05-10 | 浙江地坤键新能源科技有限公司 | 基于固态聚合物电解质的复合凝胶聚合物电解质及其制备方法与应用 |
| CN104746236A (zh) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | 一种聚酰亚胺/聚氧化乙烯电缆型复合纳米纤维膜及其制备方法 |
| CN104393336A (zh) * | 2014-11-13 | 2015-03-04 | 湘潭大学 | 一种纳米复合纤维增强凝胶聚合物电解质及其制备方法 |
| CN105633326A (zh) * | 2015-06-03 | 2016-06-01 | 北京星和众工设备技术股份有限公司 | 芳香族聚酰胺复合隔膜 |
| CN107658500A (zh) * | 2017-08-07 | 2018-02-02 | 南昌大学 | 一种原位制备柔性锂离子电池聚合物电解质的方法及应用 |
| CN108365261A (zh) * | 2018-01-15 | 2018-08-03 | 浙江衡远新能源科技有限公司 | 一种锂离子电池凝胶聚合物电解质及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| MELTEM YANILMAZ 等: "High-strength, thermally stable nylon 6,6 composite nanofiber separators for lithium-ion batteries", 《JOURNAL OF MATERIALS SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707357A (zh) * | 2019-10-23 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | 一种核壳结构的凝胶聚合物电解质及其制备方法和应用 |
| CN111106391A (zh) * | 2019-12-11 | 2020-05-05 | 西安交通大学 | 一种高强度固态电解质膜的制备方法和应用 |
| CN111430792A (zh) * | 2020-04-01 | 2020-07-17 | 深圳市奥能动力科技有限公司 | 复合凝胶固态电解质、制备方法及全固态锂离子电池 |
| CN111554973A (zh) * | 2020-04-09 | 2020-08-18 | 天津工业大学 | 基于树枝状聚酰胺-6纳米纤维膜的全固态聚合物电解质及其制备方法 |
| CN112466674A (zh) * | 2020-10-29 | 2021-03-09 | 电子科技大学 | 高温凝胶聚合物电解质锂离子电容器的制备方法 |
| CN112466674B (zh) * | 2020-10-29 | 2022-03-15 | 电子科技大学 | 高温凝胶聚合物电解质锂离子电容器的制备方法 |
| CN113130987A (zh) * | 2021-04-21 | 2021-07-16 | 昆山宝创新能源科技有限公司 | 凝胶电解质膜及其制备方法和应用 |
| CN113506951A (zh) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | 用于金属二次电池的纤维素基复合隔膜及其制备方法 |
| CN114976233A (zh) * | 2022-06-21 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | 一种复合凝胶聚合物电解质及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116632333A (zh) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110233287A (zh) | 一种尼龙基复合凝胶聚合物电解质及其制备方法 | |
| Li et al. | A review of electrospun nanofiber-based separators for rechargeable lithium-ion batteries | |
| Zhang et al. | A sandwich PVDF/HEC/PVDF gel polymer electrolyte for lithium ion battery | |
| CN103855361B (zh) | 掺氮多孔碳纳米纤维布的制备方法 | |
| US20160351876A1 (en) | Heat resisting separator having ultrafine fibrous layer and secondary battery having the same | |
| JP4803984B2 (ja) | リチウムイオン二次電池用セパレータおよびその製造方法とリチウムイオン二次電池 | |
| Kang et al. | A thermostability gel polymer electrolyte with electrospun nanofiber separator of organic F-doped poly-m-phenyleneisophthalamide for lithium-ion battery | |
| JP2013510389A (ja) | 耐熱性、高強度超極細繊維状分離膜およびその製造方法およびこれを利用した２次電池 | |
| CN103022557B (zh) | 基于无纺布的锂离子电池凝胶聚合物电解质及其制备方法 | |
| CN101626097A (zh) | 高吸液率微纳结构聚合物电解质膜及其制备方法 | |
| JP2010500717A (ja) | 耐熱性超極細繊維状分離膜及びそれを利用した二次電池 | |
| Guo et al. | Mussel stimulated modification of flexible Janus PAN/PVDF-HFP nanofiber hybrid membrane for advanced lithium-ion batteries separator | |
| CN104638294B (zh) | 一种纳米掺杂网格图案化凝胶聚合物电解质的制备方法 | |
| CN103085442B (zh) | 一种锂电池纳米纤维隔膜的制备方法 | |
| CN104269526A (zh) | 钠离子电池用聚丙烯腈/木质素碳纳米纤维电极的制备 | |
| CN1331935C (zh) | 复合微孔聚合物电解质及其制备方法 | |
| CN110400923A (zh) | 电池负极材料、负极材料浆料、负极极片和电化学电池 | |
| CN104362280A (zh) | 一种锂离子电池用共混超细纤维隔膜 | |
| CN107565161B (zh) | 一种共混纤维素的凝胶聚合物电解质及其制备方法与应用 | |
| CN103268955B (zh) | 一种复合凝胶聚合物电解质及其制备方法与应用 | |
| CN104577198A (zh) | 基于芯/壳结构纤维膜的凝胶聚合物电解质及制备方法 | |
| CN108493459B (zh) | 一种纤维状空气电池 | |
| CN114539554A (zh) | 一种木质素基单离子聚合物电解质、制备方法及其应用 | |
| CN111718482B (zh) | 一种磺化聚芳醚酮、制备方法及其应用 | |
| CN105552313A (zh) | 生化腐植酸基炭纳米纤维电极的制备方法 |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190913 |
|
| RJ01 | Rejection of invention patent application after publication |