CN113270634A - Composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and preparation method thereof - Google Patents
Composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and preparation method thereof Download PDFInfo
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- CN113270634A CN113270634A CN202110397752.6A CN202110397752A CN113270634A CN 113270634 A CN113270634 A CN 113270634A CN 202110397752 A CN202110397752 A CN 202110397752A CN 113270634 A CN113270634 A CN 113270634A
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- 239000004964 aerogel Substances 0.000 title claims abstract description 90
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 238000007710 freezing Methods 0.000 claims abstract description 21
- 230000008014 freezing Effects 0.000 claims abstract description 21
- 238000004108 freeze drying Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 10
- 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 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- -1 germanium aluminum lithium Chemical compound 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910013872 LiPF Inorganic materials 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910013075 LiBF Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims 3
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 229910003480 inorganic solid Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 229910052802 copper Inorganic materials 0.000 description 28
- 239000010949 copper Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 12
- 239000005518 polymer electrolyte Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000000306 component Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009396 hybridization Methods 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
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
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-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of solid electrolytes, and particularly relates to a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and a preparation method thereof, wherein the preparation method comprises the following steps: freezing the ceramic powder suspension, transferring after freezing, freeze-drying and calcining to obtain a three-dimensional aerogel skeleton material of the ceramic powder, dropwise adding a lithium salt-polymer solution into the three-dimensional aerogel skeleton material, and performing negative pressure filling operation to obtain a composite solid electrolyte supported by a three-dimensional aerogel skeleton; the solid electrolyte for the high-specific-energy and high-safety lithium battery, which has high ionic conductivity, good mechanical property, low interface impedance, low cost and large-scale production and can be produced in a large scale, is developed by constructing a three-dimensional ordered vertically-arranged framework supporting structure by using an inorganic solid electrolyte material to provide a channel for rapidly transmitting lithium ions and filling a polymer into a three-dimensional ordered vertical aerogel framework support by using a negative pressure method, and has good electrochemical cycling stability.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and a preparation method thereof.
Background
In recent decades, the performance of lithium ion batteries has been continuously improved, but the performance has not been met, for example, the energy density is insufficient and the potential safety hazard exists, the current commercialized lithium ion batteries are built with transition metal oxide positive electrode materials, graphite negative electrode materials, diaphragms and organic electrolytes, the specific energy of the battery is 250Wh/kg close to the theoretical limit, and the battery cannot meet the increasing energy requirement of electric vehicles and smart grids, so that other chemical methods capable of realizing higher energy density are urgently needed, and secondly, the flash point and the ignition point of the commercialized organic electrolytes are low, and if the battery is out of control due to heat, the electrolytes are easily ignited, so that the danger of battery combustion and even explosion is caused, and the potential safety hazard exists seriously. Therefore, other methods for achieving higher security are also urgently required.
Lithium metal has ultrahigh theoretical specific capacity (3860mAh/g) and lowest electrochemical potential (-3.040V vs. SHE), and is an excellent choice for the negative electrode of the next generation lithium battery. Lithium metal is used as a negative electrode instead of graphite (with the theoretical specific capacity of 372mAh/g), so that the energy density of the battery can be improved to a great extent. However, during the charge and discharge cycle, the commercial electrolyte is easily decomposed on the surface of lithium metal to form an unstable SEI film, which leads to severe capacity degradation and shortened cycle life of the battery; meanwhile, the uneven deposition of the lithium metal easily forms dendritic or moss-shaped dendritic crystals, the battery is short-circuited by puncturing the diaphragm, the danger of battery combustion and even explosion is further caused, the safety is greatly reduced, and the application of the lithium metal is limited.
To solve the above-mentioned problems and to realize a battery with high energy density and high safety performance, an effective approach is to develop an all-solid-state lithium metal battery by replacing an organic electrolyte with a solid electrolyte. Compared with organic electrolyte, the incombustibility of the solid electrolyte can fundamentally solve the safety problem of the lithium metal battery. The solid electrolyte is a key material for preparing the all-solid-state lithium metal battery with high energy density, high cycling stability and high safety performance as a core component of the all-solid-state lithium metal battery, so that the development of the solid electrolyte with excellent performance is a focus of attention of researchers.
Over the past decades, a great many researchers have been working on single-component solid electrolytes, but the single-component solid electrolytes have been difficult to meet the practical application requirements of lithium batteries. Therefore, the composite solid electrolyte is designed and prepared, the advantages of the inorganic ceramic solid electrolyte and the polymer electrolyte are combined, the functional hybridization of each component is realized, and the method becomes an effective way for improving the performance of the solid electrolyte. However, the inorganic filler is easy to aggregate, the inorganic filler is difficult to obtain good dispersibility in the polymer by common blending, a large amount of the inorganic filler (> 40%) is usually required to obtain more ideal conductivity, the flexibility of the solid electrolyte is poor, and the content and the structure of the inorganic filler can significantly influence the performance of the composite solid electrolyte.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a composite solid electrolyte based on an inorganic ceramic three-dimensional aerogel framework support and a preparation method thereof, wherein an inorganic solid electrolyte material is used to construct a three-dimensional ordered vertically arranged framework support structure to provide a channel for rapid transmission of lithium ions, and then a negative pressure method is used to fill a polymer into the three-dimensional ordered vertical aerogel framework support, so as to develop a solid electrolyte for a lithium battery with high ionic conductivity, good mechanical properties, low interface impedance, high specific energy and high safety.
The technical content of the invention is as follows:
the invention provides a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support, which comprises the following steps:
freezing the ceramic powder suspension, transferring after freezing, freeze-drying and calcining to obtain a three-dimensional aerogel skeleton material of the ceramic powder, dropwise adding a lithium salt-polymer solution into the three-dimensional aerogel skeleton material, and performing negative pressure filling operation to obtain a composite solid electrolyte supported by a three-dimensional aerogel skeleton;
the ceramic powder suspension is a mixed suspension of inorganic ceramic powder and a binder, wherein the inorganic ceramic powder accounts for 5-40 wt%, the binder accounts for 1-20 wt%, and the continuous through hole structure supported by the three-dimensional framework can provide a quick channel for the conduction of lithium ions to improve the ionic conductivity under the condition of low filler content (5% -20%), and greatly improve the mechanical property and the antioxidant stability of the polymer electrolyte;
the inorganic ceramic powder comprises one or more of Lithium Lanthanum Zirconium Oxide (LLZO), tantalum-doped lithium lanthanum zirconium oxide (LLZTO), aluminum-doped lithium lanthanum zirconium oxide (LLZAO), Lithium Aluminum Germanium Phosphate (LAGP) and Lithium Lanthanum Titanium Oxide (LLTO);
the binder comprises one of polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), Chitosan (CTS), polyethylene glycol (PEG) and polyethylene oxide (PEO);
the freeze-drying is to sublimate ice, and the calcining condition is to treat the ice at a high temperature of 600-1300 ℃ in a muffle furnace for 0.5-6 hours;
the lithium salt-polymer mixed solution is prepared by dissolving lithium salt in an organic solvent and adding a polymer, wherein the organic solvent comprises anhydrous acetonitrile or N, N-dimethylformamide;
the lithium salt includes lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluoro (oxalato) borate (LiODFB), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiOTF), lithium dioxalate borate (LiBOB), and lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) One or more of (a);
the polymer comprises one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), Polycarbonate (PC), polyvinylidene fluoride (PVDF).
The invention also provides a composite solid electrolyte with a three-dimensional framework supported continuous through hole structure, which is prepared by the preparation method;
the pore structure size of the composite solid electrolyte is 0.5-100 mu m.
The invention has the following beneficial effects:
according to the preparation method of the composite solid electrolyte based on the inorganic ceramic three-dimensional aerogel framework support, the inorganic solid electrolyte material is utilized to construct the three-dimensional ordered vertically-arranged framework support structure to provide a channel for rapid transmission of lithium ions, and then the polymer is filled into the three-dimensional ordered vertical aerogel framework support by utilizing a negative pressure method, so that the solid electrolyte for the lithium battery with high specific energy and high safety, which has high ionic conductivity, good mechanical property, low interface impedance, low cost and large-scale production, is developed;
the composite solid electrolyte has a continuous through hole structure supported by a three-dimensional framework, and can provide a quick channel for the conduction of lithium ions to improve the ionic conductivity and greatly improve the mechanical property and the antioxidant stability of the polymer electrolyte under the condition of low filler content; the seepage structure in the composite electrolyte can be directly regulated and controlled by accurately regulating and controlling the components and the structure in the composite electrolyte, so that the lithium ion conductivity is improved, the content of inorganic filler in the composite electrolyte is increased, the electrochemical circulation stability of the composite solid electrolyte can be effectively improved, the composite solid electrolyte has a good application prospect, and the popularization and application of the lithium metal battery in large-scale electronic equipment such as an electric vehicle and the like are expected to be promoted.
Drawings
FIG. 1 is a flow chart of the preparation of the composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support according to the present invention;
FIG. 2 is a scanning electron microscope image of various products in the preparation process of the composite solid electrolyte of the present invention;
FIG. 3 is a graph comparing LSV curves of a three-dimensional aerogel framework-supported composite solid electrolyte of the present invention with other electrolytes;
fig. 4 is a cycle performance test chart of an assembled battery of the three-dimensional aerogel framework-supported composite solid electrolyte and other electrolytes of the present invention.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving polyvinyl alcohol (PVA) in deionized water at 80 ℃, dispersing LLZO powder in the polyvinyl alcohol solution, and ultrasonically stirring overnight to obtain LLZO suspension, wherein the PVA accounts for 2.4 wt%, and the LLZO accounts for 21.6 wt%;
2) freeze-drying: pouring the LLZO suspension on a copper plate, freezing the bottom of the copper plate by adopting liquid nitrogen, completely freezing the copper plate, transferring the frozen copper plate to a BIOCOOL-FD-1C-80+ freeze dryer for freeze drying, and subliming ice to obtain a vertically-arranged LLZO/PVA three-dimensional aerogel skeleton material, wherein the size of a pore channel is 20-40 mu m;
3) and (3) calcining: placing the LLZO/PVA three-dimensional aerogel skeleton material in a muffle furnace for processing at 800 ℃ for 1h to obtain a vertically-arranged three-dimensional aerogel skeleton LLZO material;
4) preparing a composite solid electrolyte: dissolving the LiTFSI in anhydrous acetonitrile, and adding PEO to prepare a LiTFSI-PEO solution, wherein the mass ratio of the PEO to the LiTFSI is 2.45: 1;
subsequently, dripping a LiTFSI-PEO solution into the three-dimensional aerogel skeleton LLZO material obtained in the step 3), placing the material in a vacuum drier, vacuumizing (1MPa) for 5 minutes, repeatedly filling the material under negative pressure for many times until a vertically-arranged three-dimensional aerogel skeleton LLZO-supported composite solid electrolyte is obtained, and drying the material under vacuum at the temperature of 60 ℃ for 12 hours to completely remove residual solvent and water;
as shown in fig. 2, wherein (a) and (d) are a top view and a side view, respectively, of a three-dimensional aerogel of vertically aligned inorganic ceramic/binder; FIGS. 2(b) and (e) are top and side views, respectively, of a vertically aligned three-dimensional aerogel framework LLZO material; fig. 2(c) and (f) are top and side views, respectively, of a vertically aligned three-dimensional aerogel framework LLZO supported composite solid electrolyte; as can be seen from the three sets of figures, the vertically arranged three-dimensional aerogel of inorganic ceramic/binder is a vertical structure, and the vertically arranged three-dimensional aerogel framework LLZO material is also a vertical structure, and the vertically arranged three-dimensional aerogel framework LLZO supported composite solid electrolyte has been completely filled with PEO polymer electrolyte. ,
the PEO polymer electrolyte, the simple mixed (PEO/LLZO) composite solid electrolyte, and the LLZO supported composite solid electrolyte of the three-dimensional aerogel framework of example 1 were subjected to conductivity tests at 25 ℃ and 60 ℃, respectively, and the results are as follows:
TABLE 1 electrolyte conductivity (S/cm)
It can be seen that the conductivity of the composite solid electrolyte supported by the three-dimensional aerogel framework of example 1 of the present invention is significantly higher than that of the PEO polymer electrolyte and the simply mixed composite solid electrolyte.
As shown in fig. 3, which is a LSV curve chart of the above three different electrolytes, it can be seen that the composite solid electrolyte supported by the three-dimensional aerogel framework in example 1 of the present invention has high oxidation stability at room temperature
The above three different electrolytes were assembled into a lithium metal battery: lithium iron phosphate LiFePO4The acetylene black and the PVDF binder are dispersed by an N-methyl pyrrolidone (NMP) solution according to the proportion of 80:12:8 to prepare slurry, the slurry is coated on an aluminum foil, and the aluminum foil is dried in a vacuum drying oven at 60 ℃ for 24 hours. It was cut into electrode disks 12mm in diameter using a microtome. In a glove box, the prepared lithium iron phosphate pole piece is taken as a positive pole, the lithium piece is taken as a negative pole, PEO polymer electrolyte or simply mixed composite solid electrolyte or solidThe three-dimensional aerogel framework supported composite solid electrolyte of example 1 is an electrolyte, a CR-2302 button cell is assembled, and the cycling performance of the cell is tested, and as can be seen from fig. 4, the cycling stability and the coulombic efficiency of the three-dimensional ordered aerogel framework supported composite solid electrolyte of the present invention are significantly better than those of a composite solid electrolyte using a PEO polymer electrolyte and a simple mixture. The lithium metal battery assembled by the composite solid electrolyte supported by the three-dimensional ordered aerogel framework has better cycle stability even under the current density of 0.5C. The composite solid electrolyte supported by the three-dimensional ordered aerogel framework has good application prospect, and is expected to promote the popularization and application of lithium metal batteries in large-scale electronic equipment such as electric vehicles and the like.
Example 2
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving sodium carboxymethylcellulose (CMC) in deionized water at 80 ℃, dispersing LLTO powder in CMC solution, and ultrasonically stirring overnight to obtain LLTO suspension, wherein the CMC accounts for 3.6 wt%, and the LLTO accounts for 20.9 wt%;
2) freeze-drying: pouring the LLTO turbid liquid on a copper plate, freezing the copper plate at the bottom by adopting liquid nitrogen, transferring the frozen copper plate to a Labconco-80 freeze dryer for freeze drying after the copper plate is completely frozen, and subliming ice to obtain a three-dimensional aerogel skeleton material with the LLTO/CMC vertically arranged, wherein the size of a pore channel is 20-30 mu m;
3) and (3) calcining: placing the LLTO/CMC three-dimensional aerogel skeleton material in a muffle furnace for 850 ℃ treatment for 2h to obtain a vertically arranged three-dimensional aerogel skeleton LLTO material;
4) preparing a composite solid electrolyte: dissolving the LiTFSI in anhydrous acetonitrile, and adding PEO to prepare a LiTFSI-PEO solution, wherein the mass ratio of the PEO to the LiTFSI is 2.45: 1;
subsequently, the LiTFSI-PEO solution is dripped into the three-dimensional aerogel framework LLTO material obtained in the step 3), and the three-dimensional aerogel framework LLTO material is placed in a vacuum drier, vacuumized (0.05MPa) is carried out for 5 minutes, repeated negative pressure filling is carried out for multiple times until a composite solid electrolyte supported by the vertically arranged three-dimensional aerogel framework LLTO is obtained, and the composite solid electrolyte is dried in vacuum at the temperature of 60 ℃ for 12 hours, so that residual solvent and water are completely removed.
Example 3
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving chitosan CTS in deionized water at 80 ℃, dispersing LAGP and LLTO powder in the CTS solution, and ultrasonically stirring overnight to obtain LAGP-LLTO suspension, wherein the CTS accounts for 4.8 wt%, the LAGP accounts for 15.6 wt%, and the LLTO accounts for 15 wt%;
2) freeze-drying: pouring the LAGP-LLTO turbid liquid on a copper plate, freezing the bottom of the copper plate by adopting liquid nitrogen, freezing the copper plate completely, transferring the frozen copper plate to a Labconco-80 freeze dryer for freeze drying, and subliming ice to obtain a three-dimensional aerogel skeleton material with the LAGP-LLTO/CTS vertically arranged, wherein the size of a pore channel is 40-60 mu m;
3) and (3) calcining: placing the three-dimensional aerogel framework material of LAGP-LLTO/CTS in a muffle furnace for processing for 2h at 850 ℃ to obtain a vertically arranged three-dimensional aerogel framework LAGP-LLTO material;
4) preparing a composite solid electrolyte: dissolving LiODFB and LiOTF 1:1 in N, N-dimethylformamide, and adding PEO to prepare a LiODFB-LiOTF-PEO solution, wherein the mass ratio of the PEO to the LiODFB-LiOTF is 1.53: 1;
subsequently, the LiODFB-LiOTF-PEO solution is dropwise added into the three-dimensional aerogel framework LAGP-LLTO material obtained in the step 3), and the three-dimensional aerogel framework LAGP-LLTO material is placed in a vacuum drier, vacuumized (0.006MPa) for 5 minutes, repeated negative pressure filling is carried out for multiple times until a vertically arranged three-dimensional aerogel framework LAGP-LLTO-supported composite solid electrolyte is obtained, and the three-dimensional aerogel framework LAGP-LLTO-supported composite solid electrolyte is dried in vacuum at the temperature of 60 ℃ for 12 hours, so that residual solvent and water are completely removed.
Example 4
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving polyvinyl alcohol (PVA) in deionized water at 80 ℃, dispersing LLZO powder in the PVA solution, and ultrasonically stirring overnight to obtain LLZO suspension, wherein the PVA accounts for 1 wt%, and the LLZO accounts for 5 wt%;
2) freeze-drying: pouring the LLZO suspension on a copper plate, freezing the bottom of the copper plate by adopting liquid nitrogen, completely freezing the copper plate, transferring the frozen copper plate to a BIOCOOL-FD-1C-80+ freeze dryer for freeze drying, and subliming ice to obtain a vertically-arranged LLZO/PVA three-dimensional aerogel skeleton material, wherein the size of a pore channel is 50-80 mu m;
3) and (3) calcining: placing the LLZO/PVA three-dimensional aerogel skeleton material in a muffle furnace for processing at 600 ℃ for 0.5h to obtain a vertically-arranged three-dimensional aerogel skeleton LLZO material;
4) preparing a composite solid electrolyte: dissolving the LiTFSI in anhydrous acetonitrile, and adding PAN to prepare a LiTFSI-PEO solution, wherein the mass ratio of the PAN to the LiTFSI is 1.53: 1;
subsequently, the LiTFSI-PAN solution is dripped into the three-dimensional aerogel framework LLZO material obtained in the step 3), and the three-dimensional aerogel framework LLZO material is placed in a vacuum drier, vacuumized (1MPa) for 4 minutes, repeatedly filled under negative pressure for multiple times until a vertically arranged three-dimensional aerogel framework LLZO supported composite solid electrolyte is obtained, and is dried under vacuum at 60 ℃ for 12 hours, so that residual solvent and water are completely removed.
Example 5
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving polyvinyl alcohol (PVA) in deionized water at 80 ℃, dispersing LLZTO and LLTO powder in the PVA solution, and ultrasonically stirring overnight to obtain LLZTO-LLTO suspension, wherein the PVA accounts for 8.4 wt%, the LLZTO accounts for 15.6 wt%, and the LLTO accounts for 10 wt%;
2) freeze-drying: pouring the LLZTO-LLTO turbid liquid on a copper plate, freezing the bottom of the copper plate by adopting liquid nitrogen, freezing the copper plate completely, transferring the frozen copper plate to a BIOCOOL-FD-1C-80+ freezing dryer for freezing, and subliming ice to obtain a three-dimensional aerogel skeleton material of the vertically arranged LLZTO-LLTO/PVA, wherein the size of a pore channel is 70-100 mu m;
3) and (3) calcining: placing the LLZTO/PVA three-dimensional aerogel skeleton material in a muffle furnace for 850 ℃ treatment for 2h to obtain a vertically arranged three-dimensional aerogel skeleton LLZTO-LLTO material;
4) preparing a composite solid electrolyte: LiClO is added4Dissolving in N, N-dimethylformamide and adding PVDF to prepare LiClO4PVDF solution, PVDF and LiClO4The mass ratio of (A) to (B) is 3: 1;
subsequently, LiClO was added4-dripping a PVDF solution into the three-dimensional aerogel framework LLZTO-LLTO material obtained in the step 3), placing the material in a vacuum drier, vacuumizing (2MPa) for 3.5 minutes, repeatedly carrying out negative pressure filling for many times until a vertically arranged three-dimensional aerogel framework LLZTO-LLTO supported composite solid electrolyte is obtained, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to completely remove residual solvent and water.
Example 6
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving polyethylene glycol (PEG) in deionized water at 80 ℃, dispersing LAGP powder in the PEG solution, and ultrasonically stirring overnight to obtain LAGP suspension, wherein the PEG accounts for 15 wt% and the LAGP accounts for 35 wt%;
2) freeze-drying: pouring the LAGP suspension on a copper plate, freezing the copper plate at the bottom by adopting liquid nitrogen, freezing the copper plate completely, transferring the frozen copper plate to a Labconco-80 freeze dryer for freeze drying, and subliming ice to obtain a three-dimensional aerogel skeleton material with vertically arranged LAGP/PEG, wherein the size of a pore channel is 50-80 mu m;
3) and (3) calcining: placing the three-dimensional aerogel framework material of LAGP/PEG in a muffle furnace for processing for 4h at 1000 ℃ to obtain a vertically arranged three-dimensional aerogel framework LAGP material;
4) preparing a composite solid electrolyte: mixing LiBF4Dissolving LiBOB 1:1 in N, N-dimethylformamide, and adding PC to prepare a LiODFB-LiOTF-PC solution, wherein the mass ratio of the PC to the LiODFB-LiOTF is 1.53: 1;
subsequently, the solution of LiODFB-LiOTF-PC is dropwise added into the three-dimensional aerogel framework LAGP material obtained in the step 3), and the three-dimensional aerogel framework LAGP material is placed in a vacuum drier, vacuumized (2.5MPa) is carried out for 3.5 minutes, repeated negative pressure filling is carried out for multiple times until a composite solid electrolyte supported by the three-dimensional aerogel framework LAGP in a vertical arrangement is obtained, and the composite solid electrolyte is dried in vacuum at the temperature of 60 ℃ for 12 hours, so that residual solvent and water are completely removed.
Example 7
A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support comprises the following steps:
1) preparing a ceramic powder suspension: dissolving polyethylene oxide (PEO) in deionized water at 80 ℃, dispersing LLZAO and LLZO powder in a PEO solution, and ultrasonically stirring overnight to obtain a LLZAO-LLZO suspension, wherein the PEO accounts for 20 wt%, the LAGP accounts for 25 wt%, and the LLZO accounts for 15%;
2) freeze-drying: pouring the LLZAO-LLZO suspension on a copper plate, freezing the bottom of the copper plate by adopting liquid nitrogen, completely freezing the copper plate, transferring the frozen copper plate to a Labconco-80 freeze dryer for freeze drying, and subliming ice to obtain a three-dimensional aerogel skeleton material with the vertically arranged LLZAO-LLZO/PEO, wherein the size of a pore channel is 80-100 mu m;
3) and (3) calcining: placing the LLZAO-LLZO/PEO three-dimensional aerogel skeleton material in a muffle furnace to be treated for 6h at 1300 ℃ to obtain a vertically arranged three-dimensional aerogel skeleton LLZAO-LLZO material;
4) preparing a composite solid electrolyte: mixing LiPF6、LiAsF61:1 is dissolved in anhydrous acetonitrile, and PVDF is added to prepare LiPF6-LiAsF6PEO solution, PVDF and LiPF6-LiAsF6Is 1.53: 1;
subsequently, LiPF is added6-LiAsF6-dropwise adding a PVDF solution into the three-dimensional aerogel framework LLZAO-LLZO material obtained in the step 3), placing the material in a vacuum drier, vacuumizing (3MPa) for 3 minutes, repeatedly carrying out negative pressure filling for multiple times until a vertically arranged three-dimensional aerogel framework LLZAO-LLZO supported composite solid electrolyte is obtained, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to completely remove residual solvent and water.
The composite solid electrolyte prepared in the embodiments 2 to 7 is applied to a conductivity test, and the test results are shown in the following table, which shows that the composite solid electrolyte prepared in the invention has excellent conductivity.
TABLE 2 electrolyte conductivity (S/cm)
Claims (9)
1. A preparation method of a composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support is characterized by comprising the following steps:
freezing the ceramic powder turbid liquid, transferring after freezing, freeze-drying and calcining to obtain the three-dimensional aerogel skeleton material of the ceramic powder, dropwise adding the lithium salt-polymer solution into the three-dimensional aerogel skeleton material, and carrying out negative pressure filling operation to obtain the composite solid electrolyte supported by the three-dimensional aerogel skeleton.
2. The preparation method of the inorganic ceramic three-dimensional aerogel framework-based supported composite solid electrolyte as claimed in claim 1, wherein the ceramic powder suspension is a mixed suspension of inorganic ceramic powder and a binder, wherein the inorganic ceramic powder accounts for 5-40 wt%, and the binder accounts for 1-20 wt%.
3. The method of preparing the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel framework according to claim 2, wherein the inorganic ceramic powder comprises one or more of lithium lanthanum zirconium oxygen LLZO, tantalum-doped lithium lanthanum zirconium oxygen LLZTO, aluminum-doped lithium lanthanum zirconium oxygen LLZAO, germanium aluminum lithium lag phosphate, and lithium lanthanum titanium oxygen LLTO.
4. The method for preparing the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel skeleton according to claim 2, wherein the binder comprises one of polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), Chitosan (CTS), polyethylene glycol (PEG), and polyethylene oxide (PEO).
5. The preparation method of the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel framework, according to claim 1, is characterized in that the freeze-drying is performed to make ice biochemical, and the calcining is performed in a muffle furnace at 600-1300 ℃ for 0.5-6 hours.
6. The method for preparing the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel framework according to claim 1, wherein the lithium salt-polymer mixed solution is prepared by dissolving lithium salt in an organic solvent and adding a polymer, and the organic solvent comprises anhydrous acetonitrile or N, N-dimethylformamide.
7. The method of preparing the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel-based framework of claim 6, wherein the lithium salt comprises LiFSI, LiTFSI, LiODDB, LiPF, LiTFSI, LiODDB, LiPF, or LiTFI6Lithium tetrafluoroborate (LiBF)4Lithium triflate LiOTF, lithium dioxalate LiBOB, lithium perchlorate LiClO4Lithium hexafluoroarsenate LiAsF6One or more of (a).
8. The method for preparing the composite solid electrolyte supported by the inorganic ceramic three-dimensional aerogel skeleton according to claim 6, wherein the polymer comprises one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), Polycarbonate (PC), and polyvinylidene fluoride (PVDF).
9. A composite solid electrolyte with a three-dimensional framework-supported continuous through hole structure prepared by the preparation method of any one of claims 1 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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