CN113285118A - 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 - Google Patents
一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 Download PDFInfo
- Publication number
- CN113285118A CN113285118A CN202110397771.9A CN202110397771A CN113285118A CN 113285118 A CN113285118 A CN 113285118A CN 202110397771 A CN202110397771 A CN 202110397771A CN 113285118 A CN113285118 A CN 113285118A
- Authority
- CN
- China
- Prior art keywords
- mof
- lithium
- dimensional framework
- solid electrolyte
- composite solid
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000002121 nanofiber Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 59
- 239000013207 UiO-66 Substances 0.000 claims description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 31
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000002033 PVDF binder Substances 0.000 claims description 19
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 19
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 239000013118 MOF-74-type framework Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 229920002312 polyamide-imide Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 114
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000013148 Cu-BTC MOF Substances 0.000 description 4
- 229910013188 LiBOB Inorganic materials 0.000 description 4
- 239000013178 MIL-101(Cr) Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 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
- 238000000429 assembly Methods 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
本发明属于固态电解质的技术领域,具体涉及一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法,其制备包括如下步骤:将锂盐‑聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;所述锂盐‑聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中;所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到。所述复合物固态电解质的MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长,能够更好地应用于锂金属负极二次电池。
Description
技术领域
本发明属于固态电解质的技术领域,具体涉及一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法。
背景技术
锂离子电池因其能量密度高、自放电率低及循环寿命长等特点成为便携电子设备、电动汽车和无人机的主要储能装置。然而,锂离子电池的高性能与安全性仍然是一个棘手的问题。同时,对高能量密度锂电池不断增长的需求促使人们使用金属锂阳极,这使得安全性问题更加突出。锂离子电池在电化学锂电镀和剥离过程中形成的锂枝晶可穿透隔膜,内部短路导致强烈的热量释放,并具有潜在的爆炸危险。充放电过程中锂枝晶形成的固有问题以及锂金属低的库伦效率严重阻碍了其在锂金属电池中的应用。
固态电解质因其离子电导率高、机械强度大、非挥发性、不易燃和化学/电化学稳定性好而作为锂金属电池中易燃液体电解质的替代品,并引起了极大的关注。固态电解质可归纳为三类:无机(陶瓷/玻璃)固态电解质、聚合物固态电解质及复合物固体电解质。无机固态电解质离子电导率很高,但是仍然存在致命的缺点,比如质脆且硬,与电极接触存在的界面问题等。聚合物固态电解质的室温离子电导率不高,但聚合物具有较好的柔性和对电极界面稳定性。复合物固体电解质能充分发挥无机固态电解质与聚合物固态电解质两者优点,因此,本发明致力于提供一种性能优异的复合固态电解质。
发明内容
针对上述问题,本发明的目的在于提供一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法,通过静电纺丝,将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中制备出新型离子导电率高、机械性能好、界面阻抗低的复合固态电解质。
本发明的技术内容如下:
本发明提供了一种基于MOF三维骨架支撑的复合物固态电解质的制备方法,包括如下步骤:
将锂盐-聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;
所述锂盐-聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中,锂盐与聚合物的使用比例为(0.1~10):1;
所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到,MOF粉体材料与聚合物的使用比例为1:(0.2~5);
所述锂盐-聚合物溶液中的聚合物包括聚环氧乙烷(PEO)、聚丙烯腈(PAN)、聚碳酸酯(PC)、聚偏二氟乙烯(PVDF)的一种;
所述锂盐包括双氟磺酰亚胺锂盐(LiFSI)、双三氟甲磺酰亚胺锂盐(LiTFSI)、二氟草酸硼酸锂盐(LiODFB)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、三氟甲磺酸锂(LiOTF)、二草酸硼酸锂(LiBOB)、高氯酸锂(LiClO4)、六氟合砷酸锂(LiAsF6)的一种或以上;
所述MOF粉体材料包括UIO-66、UIO-66-NH2、ZIF-8、HKUST、MOF-74、MOF-100、MIL-101的一种;
所述纳米纤维材料的制备所采用的聚合物包括聚丙烯腈(PAN)、聚乙烯醇(PVA)、聚偏二氟乙烯(PVDF)、聚甲基丙烯酸甲酯(PMMA)、聚己内酯(PCL)、聚酰胺-酰亚胺(PAI)的一种。
本发明还提供了一种以上所述制备方法制得的基于MOF三维骨架支撑的复合物固态电解质,所述复合物固态电解质为通过MOF材料与聚合物构筑成三维骨架结构,并在三维骨架结构上填充锂盐-聚合物溶液制备得到;
以上所述基于MOF三维骨架支撑的复合物固态电解质应用于锂金属电池,主要应用于锂金属负极二次电池。
本发明的有益效果如下:
本发明的基于MOF三维骨架支撑的复合物固态电解质的制备方法,通过静电纺丝,将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中制备出新型离子导电率高、机械性能好、界面阻抗低的MOF-聚合物复合固态电解质薄膜;
本发明的基于MOF三维骨架支撑的复合物固态电解质,其MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长。同时,MOFs材料本身具有丰富的有序孔道结构能够促进锂盐的分离,促使锂离子能够沿着MOFs的有序孔道均匀地沉积到锂负极,从而抑制锂枝晶的生长,提高了电池的循环稳定性。
附图说明
图1为实施例1中MOF材料的扫描电镜图;
图2为实施例1中MOF材料的粉末衍射图;
图3为实施例1中纳米纤维材料的扫描电镜图;
图4为实施例1的复合物固态电解质的的扫描电镜图;
图5为本发明的复合物固态电解质的合成示意图;
图6为实施例1的三维骨架支撑的复合物固态电解质的Li|Li对称电池在电流密度为0.3 mA/cm2、60℃下长循环性能图;
图7为各种复合物固态电解质组装的LiFePO4|Li电池在电流密度为0.5 C、60℃下的循环性能对比图;
图8为各种复合物固态电解质组装的LiFePO4|Li电池在电流密度为0.1C-1C、60℃下的倍率性能对比图。
具体实施方式
以下通过具体的实施案例以及附图说明对本发明作进一步详细的描述,应理解这些实施例仅用于说明本发明而不用于限制本发明的保护范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
若无特殊说明,本发明的所有原料和试剂均为常规市场的原料、试剂。
实施例1
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆,对苯二甲酸在以1:1的摩尔比在N,N-二甲基甲酰胺(DMF)中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到白色粉末,将其依次用DMF、甲醇(MeOH)洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO-66粉末;
如图1所示,为合成的UIO-66材料的扫描电镜图,可见其呈现为均匀的八面体状;
图2为UIO-66材料的XRD粉末衍射图,可以发现合成的UIO-66粉末特征峰与UIO-66XRD模拟图谱十分吻合,表明UIO-66粉末成功合成;
2)纳米纤维材料:步骤1)合成的UIO-66材料超声溶解于DMF中,将PAN加入DMF中搅拌12 h,UIO-66、PAN与DMF质量比为1:0.5:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料(PAN/UIO-66),其扫描电镜图如图3所示,UIO-66材料均匀分布在PAN中;
3)锂盐-聚合物溶液:将PEO、LiTFSI以1:1的质量比溶解在乙腈中,得到PEO/LiTFSI混合溶液;
4)将PEO/LiTFSI浇筑在PAN/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质(PEO/LiTFSI/PAN/UIO-66),其扫描电镜图如图4所示,三维骨架结构的复合物固态电解质的横截面约为100 μm厚。
实施例2
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、2-氨基对苯二甲酸在以1:1的摩尔比在去离子水与乙酸混合溶液(体积比3:2)中超声溶解,然后在100℃油浴锅中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到淡黄色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO66-NH2粉末;
2)纳米纤维材料:将步骤1)合成的UIO66-NH2材料超声溶解于DMF中,将PAN加入DMF中搅拌12 h,UIO66-NH2、PAN与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiFSI以1:5的质量比溶解在乙腈中,得到PEO/LiFSI混合溶液;
4)将PEO/LiFSI浇筑在PAN/UIO66-NH2上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例3
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将Zn(NO3)2·6H2O、二甲基咪唑在以1:1的质量比分别溶解在体积比为3:2的甲醇溶液中,然后在55℃油浴锅中反应5分钟,室温静置48 h。反应停止后,在8000 rpm转速下离心8分钟,得到白色粉末,将其用MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到ZIF-8粉末;
2)纳米纤维材料:将步骤1)合成的ZIF-8材料超声溶解于DMF中,将PCL加入DMF中搅拌12小时,ZIF-8、PCL与DMF质量比为1:2:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiODFB以1.84:1的质量比溶解在乙腈中,得到PEO/LiODFB混合溶液;
4)将PEO/LiODFB浇筑在PCL/ZIF-8上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得三维骨架结构的复合物固态电解质。
实施例4
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:称取0.0495g 2,5-二羟基对苯二甲酸溶解于20 mL DMF、MeOH及H2O的混合溶液(体积比1:1:1),超声至配体完全溶解,再称取0.2403 g Co(NO3)2·6H2O完全溶解于上述溶液即得到红棕色合成液,将该合成液转移至含有聚四氟内衬的不锈钢反应釜中,置于100℃鼓风烘箱中晶化24 h。反应停止后,在8000 rpm转速下离心8分钟,得到黄色粉末将,其用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到MOF-74粉末;
2)纳米纤维材料:将步骤1合成的MOF-74材料超声溶解于DMF中,将PVA加入DMF中搅拌12 h,MOF-74、PVA与DMF质量比为1:3:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PAN、LiPF6以5.49:1的质量比溶解在乙腈中,得到PAN/LiPF6混合溶液;
4)将PAN/LiPF6浇筑在PVA/MOF-74上并晾干,100℃真空干燥24 h,放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得三维骨架结构的复合物固态电解质。
实施例5
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、对苯二甲酸在以1:1的摩尔比在DMF中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到白色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO-66粉末;
2)纳米纤维材料:将步骤1)合成的UIO-66材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,UIO-66、PVDF与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PC、LiBF4在以1:10的质量比溶解在乙腈中,得到PC/LiBF4混合溶液;
4)将PC/LiBF4浇筑在PVDF/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例6
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、对苯二甲酸在以1:1的摩尔比在DMF中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24小时。反应停止后,在9000 rpm转速下离心9分钟,得到白色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h,得到UIO-66粉末;
2)纳米纤维材料:将步骤1)合成的UIO-66材料超声溶解于DMF中,将聚酰胺-酰亚胺(PAI)加入DMF中搅拌12小时,UIO-66、PAI与DMF质量比为1:4:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝的到三维骨架结构的纳米纤维材料,然后在300℃下热处理得到聚酰亚胺(PI)三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiOTF、LiBOB以8.15:1:1的质量比溶解在乙腈中,得到PEO/LiOTF/LiBOB混合溶液;
4)将PEO/LiOTF/LiBOB浇筑在PAI/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例7
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将3.93 g Cu(NO3)2·3H2O和2.00 g聚乙烯吡咯烷酮(PVP,(K30))溶解于250 mL甲醇(溶液A)中,2.15 g 1,3,5-三苯甲酸(H3BTC)溶解于250 mL甲醇(溶液B)中。随后,将溶液B逐滴加入溶液A中,并将所得溶液在室温下保存24小时,将所得的HKUST-1蓝色产品离心收集,用甲醇洗涤三次,然后在60℃下干燥,然后将所得产品放入150℃下的真空烘箱中过夜活化以去除通道中的微量溶剂,从而得到HKUST-1粉末;
2)纳米纤维材料:将步骤1合成的HKUST-1材料超声溶解于DMF中,将PMMA加入DMF中搅拌12 h,HKUST-1、PMMA与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PVDF、LiAsF6以3:1的质量比溶于无水N,N-二甲基甲酰胺中,得到PVDF/LiAsF6混合溶液;
4)将PVDF/LiAsF6浇筑在PMMA/HKUST-1上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例8
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:称量0.807 g (0.2 mol)九水合硝酸铁(Fe(NO3)3·9H2O)溶解于10 mL超纯水中,将其搅拌均匀后,准确称量0.420 g(0.2 mol)均苯三甲酸(H3BTC)加入其中,使用电动搅拌器将混合物匀速搅拌30 min,此时悬浊液变得均匀,便得到MOF-100(Fe)材料的前驱体物质。将制得的前驱体悬浮液转移至100 mL容量的聚四氟乙烯内衬中,放置反应釜内拧合后将其放入鼓风烘箱中去,并打开鼓风开光,调节温度至200℃,加热反应8 h,得到MOF-100(Fe)粉末;
2)纳米纤维材料:将步骤1合成的MOF-100(Fe)材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,MOF-100(Fe)、PVDF与DMF质量比为1:2:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiFSI以1:3的质量比溶解在乙腈中,得到PEO/LiFSI混合溶液;
4)将PEO/LiFSI浇筑在PVDF/MOF-100(Fe)上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例9
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:取4.0 g Cr(NO3)3·9H2O和1.66 g对苯二甲酸溶于50 mL去离子水中,边搅拌边滴加1 mL 40%的浓盐酸,超声震荡30 min后转移至100 mL的聚四氟乙烯内衬中,置于不锈钢的密封反应釜中,然后200℃下反应12 h。冷却至室温后将产物离心分离,然后用热的DMF和无水乙醇交替洗涤多次,冷却,离心,洗涤。放入干燥箱中100℃下干燥过夜,即得到纯化后的MIL-101(Cr)样品;
2)纳米纤维材料:将步骤1)合成的MIL-101(Cr)材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,MIL-101(Cr)、PVDF与DMF质量比为1:5:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PAN、LiClO4在以10:1的质量比溶解在N,N-二甲基甲酰胺中,得到PAN/LiClO4混合溶液;
4)将PAN/LiClO4浇筑在PVDF/MIL-101(Cr)上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
如图5所示,为本发明的基于MOF的三维骨架结构的复合物固态电解质的制备流程示意图。可见,通过静电纺丝将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中,制备出离子导电率高、机械性能好、界面阻抗低的MOF-聚合物复合固态电解质薄膜。
将实施例1制得的复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|Li对称电池以及Li|LiFePO4电池,并测试其各项电池性能。
锂锂对称电池测试:在手套箱中,以锂片分别作为为正极和负极、PEO/LiTFSI/PAN/UIO-66作为固态电解质膜,组装成锂锂对称电池。运用电化学测试系统在60℃下测试数据。
本发明的复合固态电解质在60℃下的离子电导率达到2.89×10-4 S/m2 。图6为复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|Li对称电池,PEO/LiTFSI/PAN/UIO-66可以在0.3 mA/cm2的大电流密度下依然可以稳定的循环700 h,极化稳定在100 mV以下,说明PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质能够很大程度上提高界面兼容性,并很好地抑制锂枝晶,从而保护锂负极。
磷酸铁锂电池测试:将磷酸铁锂(LiFePO4)和Li400、PVDF粘结剂按照80:12:8的比例利用N-甲基吡咯烷酮(NMP)溶液分散制备成浆料,将其涂覆在铝箔上,在60℃的真空干燥箱中干燥24 h。利用切片机将其切成直径为12 mm的电极圆片,利用不同100 μm厚度的刮刀分制备成载量为2 mg/cm2的极片。在手套箱中,以所制备的极片为正极、锂片为负极、PEO/LiTFSI/PAN/UIO-66固态电解质组装成CR-2032扣式电池。运用电化学测试系统在60℃下测试数据。
图7为复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|LiFePO4电池。从图中可以看到本发明基于MOF三维骨架支撑的复合物固态电解质性能远高于纯PEO/LiTFSI、PEO/LiTFSI/PAN及简单混合的PEO/LiTFSI/UIO-66复合物固态电解质,表明利用PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质的电池具有非常好的循环稳定性,0.5 C电池密度下循环200圈后容量保持率超过90.3%。
图8为各种复合物固态电解质组装的磷酸铁锂电池在电流密度为0.1C-1C、60℃下的倍率性能对比图。表明PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质的电池具有优异地倍率性能,当速率反转回到0.2 C时,电池比容量几乎可以恢复。
本发明的MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,从而有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长。同时,MOFs材料本身具有丰富的有序孔道结构能够增强锂盐的解离,促使锂离子能够沿着MOFs的有序孔道均匀地沉积到锂负极,从而抑制锂枝晶的生长,提高了电池的循环稳定性。相比现有技术,简单混合的复合物固态电解质无法实现锂枝晶有效均匀的沉积,从而导致锂枝晶快速戳破电解质,导致电池短路,常规的对锂负极保护的措施往往只能在小的电流密度下,如0.1 mA/cm2的电流密度下进行诱导锂枝晶均匀沉积,无法实现大电流密度循环下对锂负极的有效保护。
Claims (9)
1.一种基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,包括如下步骤:
将锂盐-聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;
所述锂盐-聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中;
所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到。
2.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐-聚合物溶液的制备中,锂盐与聚合物的使用比例为(0.1~10):1。
3.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述纳米纤维材料的制备中,MOF粉体材料与聚合物的使用比例为1:(0.2~5)。
4.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐-聚合物溶液中的聚合物包括聚环氧乙烷、聚丙烯腈、聚碳酸酯、聚偏二氟乙烯的一种。
5.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐包括双氟磺酰亚胺锂盐、双三氟甲磺酰亚胺锂盐、二氟草酸硼酸锂盐、六氟磷酸锂、四氟硼酸锂、三氟甲磺酸锂、二草酸硼酸锂、高氯酸锂、六氟合砷酸锂的一种或以上。
6.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述MOF粉体材料包括UIO-66、UIO-66-NH2、ZIF-8、HKUST、MOF-74、MOF-100、MIL-101的一种。
7.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述纳米纤维材料的制备所采用的聚合物包括聚丙烯腈、聚乙烯醇、聚偏二氟乙烯、聚甲基丙烯酸甲酯、聚己内酯、聚酰胺-酰亚胺的一种。
8.一种权利要求1~7任一项所述制备方法制得的基于MOF三维骨架支撑的复合物固态电解质。
9.由权利要求8所述的基于MOF三维骨架支撑的复合物固态电解质,其特征在于,所述复合物固态电解质为通过MOF材料与聚合物构筑成三维骨架结构,并在三维骨架结构上填充锂盐-聚合物溶液制备得到。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110397771.9A CN113285118A (zh) | 2021-04-14 | 2021-04-14 | 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110397771.9A CN113285118A (zh) | 2021-04-14 | 2021-04-14 | 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113285118A true CN113285118A (zh) | 2021-08-20 |
Family
ID=77276693
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110397771.9A Pending CN113285118A (zh) | 2021-04-14 | 2021-04-14 | 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113285118A (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113903989A (zh) * | 2021-11-16 | 2022-01-07 | 河北工业大学 | 一种锂硫电池固态电解质的制备方法及其应用 |
CN113921901A (zh) * | 2021-11-18 | 2022-01-11 | 北京化工大学 | 一种金属有机框架基复合纳米纤维膜及其制备方法和应用 |
CN114031782A (zh) * | 2021-09-14 | 2022-02-11 | 温州大学新材料与产业技术研究院 | 一种双uio-66基mof材料的制备方法及其产品和在固态电池中的应用 |
CN114551981A (zh) * | 2021-09-23 | 2022-05-27 | 万向一二三股份公司 | 一种三维骨架材料混合液、三维复合固体电解质膜、正极片的制备方法及固体锂电池 |
CN115332624A (zh) * | 2022-10-13 | 2022-11-11 | 西北工业大学 | 热稳定、超薄轻质、阻燃peo基固态电解质的制备方法 |
CN115403081A (zh) * | 2022-11-02 | 2022-11-29 | 宜宾锂宝新材料有限公司 | 一种高镍三元正极材料及其制备方法与电池 |
CN116315076A (zh) * | 2023-05-22 | 2023-06-23 | 西北工业大学 | 一种具有连续离子传输通路的固态电解质及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109148944A (zh) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | 一种高离子电导率的复合固态电解质及其制备方法 |
CN110911742A (zh) * | 2019-12-27 | 2020-03-24 | 湖北大学 | 一种固态电池用聚合物电解质复合膜的制备方法 |
-
2021
- 2021-04-14 CN CN202110397771.9A patent/CN113285118A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109148944A (zh) * | 2018-09-30 | 2019-01-04 | 中国航发北京航空材料研究院 | 一种高离子电导率的复合固态电解质及其制备方法 |
CN110911742A (zh) * | 2019-12-27 | 2020-03-24 | 湖北大学 | 一种固态电池用聚合物电解质复合膜的制备方法 |
Non-Patent Citations (1)
Title |
---|
HUI YANG 等: "A Single-Ion Conducting UiO-66 Metal − Organic Framework Electrolyte for All-Solid-State Lithium Batteries", 《ACS APPL.ENERGY MATER》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114031782A (zh) * | 2021-09-14 | 2022-02-11 | 温州大学新材料与产业技术研究院 | 一种双uio-66基mof材料的制备方法及其产品和在固态电池中的应用 |
CN114551981A (zh) * | 2021-09-23 | 2022-05-27 | 万向一二三股份公司 | 一种三维骨架材料混合液、三维复合固体电解质膜、正极片的制备方法及固体锂电池 |
CN114551981B (zh) * | 2021-09-23 | 2023-06-09 | 万向一二三股份公司 | 一种三维骨架材料混合液、三维复合固体电解质膜、正极片的制备方法及固体锂电池 |
CN113903989A (zh) * | 2021-11-16 | 2022-01-07 | 河北工业大学 | 一种锂硫电池固态电解质的制备方法及其应用 |
CN113921901A (zh) * | 2021-11-18 | 2022-01-11 | 北京化工大学 | 一种金属有机框架基复合纳米纤维膜及其制备方法和应用 |
CN115332624A (zh) * | 2022-10-13 | 2022-11-11 | 西北工业大学 | 热稳定、超薄轻质、阻燃peo基固态电解质的制备方法 |
CN115403081A (zh) * | 2022-11-02 | 2022-11-29 | 宜宾锂宝新材料有限公司 | 一种高镍三元正极材料及其制备方法与电池 |
CN116315076A (zh) * | 2023-05-22 | 2023-06-23 | 西北工业大学 | 一种具有连续离子传输通路的固态电解质及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113285118A (zh) | 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 | |
CN110416597B (zh) | 一种醚类电解液以及锂硫二次电池 | |
CN113471442B (zh) | 负极活性材料和使用其的负极极片、电化学装置和电子装置 | |
CN112993389A (zh) | 一种富锂反钙钛矿氧化物复合电解质及其制备方法和应用 | |
KR20010067222A (ko) | 피복된 리튬 혼합 산화물 입자 및 그의 용도 | |
KR20070066453A (ko) | 정극 활물질. 그 제조방법 및 이를 구비한 리튬 이차 전지 | |
CN109786869B (zh) | 一种含有受阻胺结构的聚合物在二次锂电池中的应用 | |
CN112751081A (zh) | 电解液、电化学装置及电子装置 | |
KR100743982B1 (ko) | 활물질. 그 제조방법 및 이를 구비한 리튬 이차 전지 | |
CN103762350A (zh) | 一种用于锂电的钛系负极材料及其制备方法 | |
CN111799502B (zh) | 一种石榴石型固态化复合电解质、制备方法及应用 | |
CN101197436A (zh) | 一种锂离子二次电池的正极片及包括该正极片的电池 | |
TWI756875B (zh) | 用於電化學裝置之單離子導電性聚合物 | |
CN112421046B (zh) | 用于锂金属二次电池的单离子导电聚合物复合材料的制备方法 | |
EP4312297A1 (en) | Solid-state electrolyte (sse) with sandwich structure and preparation method and use thereof, and solid-state lithium ion battery | |
CN110661034A (zh) | 聚合物电解质组合物、聚合物电解质片及其制造方法、电化学装置用电极、聚合物二次电池 | |
CN112670673A (zh) | 一种离子传导有机-无机复合修饰隔膜及其制备方法和应用 | |
CN114566700B (zh) | 一种阻燃的聚合物电解质隔膜及其制备方法和应用 | |
CN112687954B (zh) | 电解液、电化学装置及电子装置 | |
CN111987351B (zh) | 一种聚合物凝胶电解质及其制备方法和应用 | |
CN111704723B (zh) | 组合物、锆基金属交联聚合网络、隔膜及其制备方法,以及电化学电池 | |
CN115677931A (zh) | 一种聚合物材料、电解质及电池 | |
CN113328144A (zh) | 一种锂离子电池电解液及使用该电解液的锂离子电池 | |
CN118063647B (zh) | 聚离子液体及制备方法、组合物、陶瓷电解质薄膜及应用 | |
CN110247111B (zh) | 一种含磺酸或磷酸衍生物结构的固态聚合物电解质及其在二次锂电池中的应用 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210820 |