CN113964378A - Composite solid electrolyte and manufacturing method thereof - Google Patents
Composite solid electrolyte and manufacturing method thereof Download PDFInfo
- Publication number
- CN113964378A CN113964378A CN202111088647.0A CN202111088647A CN113964378A CN 113964378 A CN113964378 A CN 113964378A CN 202111088647 A CN202111088647 A CN 202111088647A CN 113964378 A CN113964378 A CN 113964378A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- composite solid
- lithium
- additive
- powder
- 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.)
- Granted
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- -1 polydimethylsiloxane Polymers 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 238000001962 electrophoresis Methods 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 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 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 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 claims 1
- 229920000307 polymer substrate Polymers 0.000 claims 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 18
- 229910007780 Li2W2O7 Inorganic materials 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 102000004310 Ion Channels Human genes 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 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
- H01M10/052—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
- H01M10/056—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a composite solid electrolyte, which comprises the following raw materials in percentage by mass: 5-90% of polymer base material, 5-50% of lithium salt and 5-90% of additive. The composite solid electrolyte is prepared by the steps of mixing, coating, drying, storing and the like. After the technical scheme of the invention is adopted, the solid electrolyte is prepared by using the polyvinylidene fluoride base, the preparation process is very simple and effective, and the composite solid electrolyte also has the ion conductivity, high ion migration number, good mechanical property, good cycle performance and good rate capability at room temperature.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a composite solid electrolyte and a manufacturing method thereof.
Background
With new energy electric automobile and portable electronic deviceThe lithium ion battery becomes the first choice of commercial batteries through continuous development, but the traditional liquid lithium ion battery has low energy density, and the energy density of the liquid lithium iron phosphate secondary battery is only about 150Wh/kg, so that the requirement of new energy electric automobiles and portable electronic equipment on the high energy density secondary battery is difficult to meet, and meanwhile, the safety of the liquid lithium ion battery is difficult to guarantee and is another important factor restricting the development of new energy industries. Therefore, the search for a secondary battery system with higher energy density and higher safety is the key for the development of new energy industry. In recent years, solid-state batteries based on lithium metal negative electrodes have become a focus of research. First, the lithium metal negative electrode has a very high theoretical lithium storage capacity (3860mAh g)-1). And secondly, the use of liquid organic electrolyte is avoided due to the presence of the solid electrolyte, so that the safety of the whole system is greatly improved while the energy density is improved. With the rapid development of novel all-solid-state batteries, it is imperative that the requirements of the development plan of "2025 of Chinese manufacture" be satisfied. Solid electrolytes are an extremely important part of all-solid batteries, but still face many problems to be solved. One of the reasons is that the ionic conductivity at room temperature needs to be improved, and the most mature PEO-based polymer solid electrolyte has poor ionic conductivity at room temperature because the PEO has high activation energy at room temperature and lithium ions are difficult to break bonds with functional groups in the PEO to form bonds, thereby weakening the lithium ion transmission. The inorganic compound solid electrolyte such as LLZO, LLZTO, LATP, etc. has large interface impedance with the anode and cathode, and the preparation and processing cost is high, which is the key to restrict the commercialization. Sulfur-based solid electrolytes, while possessing high ionic conductivity at room temperature, have limited their use in high energy density power cells due to their poor electrochemical stability, which makes them susceptible to water reaction to form H2S, reducing the useful life of the electrolyte. As the most commercially promising polymer solid electrolyte, how to improve the room-temperature ionic conductivity of the polymer solid electrolyte, and improve the energy density and battery performance of the battery becomes a major and difficult point of research.
The solid electrolyte between the positive and negative electrodes of the battery not only provides an ion transmission channel, but also influences the electrode/electrolyte interface properties, and is closely related to the overall performance of the battery. The adoption of effective polymer electrolyte materials and additives is an effective way for improving the ion conductivity of the polymer solid electrolyte at room temperature.
Disclosure of Invention
The invention provides a composite solid electrolyte and a manufacturing method thereof, and aims to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite solid electrolyte comprises the following raw materials in percentage by mass:
5 to 90 percent of polymer base material
5 to 50 percent of lithium salt
5 to 90 percent of additive.
Further, the composite solid electrolyte comprises the following raw materials in percentage by mass:
40% of additive.
Further, the polymer base material is polyvinylidene fluoride-based polymer, and comprises one or more of poly (vinylidene fluoride), polyvinylidene fluoride-hexafluoropropylene, polybutylacrylate and polyacrylonitrile, poly (ethylene oxide), polypropylene oxide, poly (acrylonitrile), poly (methyl methacrylate), poly (methoxy ethoxy ethoxide-phosphazene), polyvinyl chloride, polydimethylsiloxane and poly (perfluorosulfonic acid).
Further, the lithium salt comprises one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (difluoro) sulfonimide and lithium bis (trifluoromethyl) sulfonimide.
Further, the preparation method of the additive comprises the following steps:
(1) 13.8% by mass of Li2CO386.2% of WO3Stirring in isopropanolPouring the solution into a ball milling tank for ball milling at the speed of 800r/min for 30 circles after 12 hours, and fully mixing to obtain a mixed material;
2) drying the mixed material prepared in the step (1), grinding the dried block into powder, uniformly placing the powder in a crucible, and firing the powder in air at 750 ℃ for 6 hours at the temperature rising speed of 5 ℃ per hour;
3) and (3) after the powder is taken out, changing the light yellow of the powder into white, successfully firing, and carrying out ball milling on the powder sample subjected to paper firing in the step (2) at the speed of 800r/min for 30 circles, wherein the time of each circle is 5 min.
The invention also provides a manufacturing method of the composite solid electrolyte, which comprises the following steps:
(1) weighing a polymer base material, an additive and a lithium salt, selecting a solvent, wherein the solvent comprises one or more of NMP and DMF, the solvent is controlled to be 60-85% of the total mass of the slurry according to the mass ratio, and the solvent is prepared by mixing the components in percentage by mass according to the weight ratio of 2: 10, separation in proportion;
(2) adding a polymer base material into a solvent with a majority proportion in a closed container, and stirring for 1-2h at room temperature to form a stable and uniform transparent colloid;
(3) in a closed container, adding the additive into a small part of solvent in proportion for ultrasonic dispersion for 10-60 min;
(4) adding the additive subjected to the ultrasound treatment in the step (3) and lithium salt into the colloid prepared in the step (2) in a closed container, stirring for 12-24h, and uniformly mixing to form slurry for coating the solid electrolyte;
(5) coating the slurry prepared in the step (4) to prepare composite solid electrolyte slurry with uniform thickness;
(6) putting the composite solid electrolyte slurry with uniform thickness coated in the step (5) into a vacuum oven at 60 ℃ for baking for 12-24 h;
(7) and (4) packaging and storing the dried electrolyte in the step (6), taking two smooth and clean plastic films, clamping the electrolyte, removing bubbles, and storing to obtain the composite solid electrolyte.
Further, the film-forming substrate in the step (5) comprises a glass plate, a metal foil or a PET plastic.
Further, the film forming method in the step (5) includes one of coating, electrophoresis, and pulling.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the additive is Li2W2O7The solid electrolyte powder has the main functions of improving the ion conductivity of the solid electrolyte, inhibiting the growth of lithium dendrite and finally improving the cycle performance and rate performance of the battery, the lithium salt is LiTFSI and provides movable lithium ions for the solid electrolyte so that the battery can be normally charged and discharged, and in the invention, the additive is Li2W2O7A solid electrolyte powder. Additive Li2W2O7The preparation method of the solid electrolyte powder is relatively simple, the efficiency can be improved, and the mechanical property of the diaphragm and the cycle performance and rate performance of the full battery manufactured by the diaphragm can be obviously improved.
(2) After the technical scheme of the invention is adopted, the solid electrolyte is prepared by using the polyvinylidene fluoride base, the preparation process is very simple and effective, and the composite solid electrolyte also has the ion conductivity, high ion migration number, good mechanical property, good cycle performance and good rate capability at room temperature.
(3) The novel inorganic solid electrolyte used in the invention improves the ionic conductivity of the solid electrolyte, can inhibit the growth of lithium dendrites, improves the energy density of the battery, and finally improves the cycle and rate performance of the battery.
(4) By using the mixing method, the solid electrolyte slurry can be well mixed in a short time, the production efficiency is high, and the manufacturing cost is low.
(5) In the present invention, Li2W2O7Is prepared from WO6Octahedron and LiO4Layered structure of tetrahedrons by sharing edges, WO6Octahedron and (W)207)2-The anions are connected. Lithium ions occupy distorted tetrahedral interchain sites, and (W)207)2-Chain linkAnd (6) connecting. Layered Li of the invention2W2O7In the structure, W of larger radius+Acting as "pillars" to effectively strengthen the interlayer ion channels, can lead to multi-ion co-migration behavior, facilitating Li + diffusion. And contributes to the improvement of the ionic conductivity. China is the biggest tungsten reserve country and producing country in the world, producing Li2W2O7The raw materials are low in cost and easy to prepare, and a foundation is provided for large-scale use of the raw materials.
The lithium tungstate material has the characteristics of better chemical stability, higher melting temperature and the like, so that the prepared product can not generate decomposition reaction due to overhigh temperature, the capacity attenuation speed of the battery can be effectively slowed down, and the service life of the battery can be prolonged.
(6) The patent provides a positive electrode material for nonaqueous electrolyte secondary batteries, which contains Li2W2O7When the positive electrode material is used as a positive electrode material for a battery, gelation of the positive electrode composite paste can be suppressed without lowering charge/discharge capacity and output characteristics.
Li in the invention2W2O7The electrolyte is not used in electrodes, but is used in solid electrolyte (similar to a diaphragm of a traditional liquid battery, and is positioned between an anode and a cathode, and is mainly used for isolating the anode and the cathode and providing a lithium ion conduction channel). Li2W2O7As a solid electrolyte additive (filler), the role played by which lithium ion conduction is promoted is quite different from that played by lithium tungstate in the above prior art patents, and is not comparable. Li in the invention2W2O7Through the interaction of the lithium ion battery with the polymer matrix and the lithium salt, the crystallinity of the polymer matrix can be reduced, the dissociation of the lithium salt is promoted, the number of free Li < + > and a rapid transmission channel of the Li < + > are increased, and the ionic conductivity is improved.
Drawings
FIG. 1 is a graph of the PVDF polymer and Li obtained in example 12W2O7Composite solid stateTensile test plots with electrolytes;
FIG. 2 is a graph of the PVDF polymer and Li obtained in example 12W2O7Battery cycling test patterns by compounding solid electrolytes;
FIG. 3 is a graph of the PVDF polymer and Li obtained in example 12W2O7An ionic conductivity test pattern of the composite solid electrolyte;
FIG. 4 is a graph of the PVDF polymer and Li obtained in example 12W2O7Battery rate test chart of composite solid electrolyte.
Detailed Description
In order to make the objects, technical problems to be solved, and technical solutions of the present invention clearer, the present invention is further described below with reference to the accompanying drawings and specific embodiments.
A composite solid electrolyte comprises the following raw materials in percentage by mass:
5 to 90 percent of polymer base material
5 to 50 percent of lithium salt
5 to 90 percent of additive
The polymer base material is a polyvinylidene fluoride-based polymer and comprises one or more of poly (vinylidene fluoride) (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polybutyl acrylate (PBA), Polyacrylonitrile (PA), poly (ethylene oxide) (PEO), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl methacrylate) (PMMA), poly (methoxy ethoxy ethoxide-phosphazene), polyvinyl chloride, polydimethylsiloxane and poly (perfluorosulfonic acid).
Wherein the lithium salt is lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) And lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium bis (difluorosulfonimide) (LiFSI) and lithium bis (trifluoromethylsulfonimide) (LiTFSI).
Wherein the additive is Li serving as a novel solid electrolyte2W2O7The synthesis equation is as follows:
Li2CO3+2WO3 Li2W2O7+CO2↑
1) 13.8% by mass of Li2CO386.2% of WO3Stirring in isopropanol for 12h, pouring the solution into a ball milling tank for ball milling at the speed of 800r/min for 30 circles, and fully mixing to obtain a mixed material;
2) drying the mixed material prepared in the step (1), grinding the dried block into powder, uniformly placing the powder in a crucible, and firing the powder in air at 750 ℃ for 6 hours at the temperature rising speed of 5 ℃ per hour;
3) and (3) after the powder is taken out, changing the light yellow of the powder into white, successfully firing, and carrying out ball milling on the powder sample subjected to paper firing in the step (2) at the speed of 800r/min for 30 circles, wherein the time of each circle is 5 min.
The manufacturing method of the composite solid electrolyte comprises the following steps:
(1) weighing a polymer base material, an additive and a lithium salt, selecting a solvent, wherein the solvent comprises one or more of NMP and DMF, the solvent is controlled to be 60-85% of the total mass of slurry (the slurry comprises the polymer base material, the additive and the lithium salt) according to the mass ratio, and the solvent is mixed according to the weight ratio of 2: 10, separation in proportion;
(2) adding a polymer base material into a solvent with a majority proportion in a closed container, and stirring for 1-2h at room temperature to form a stable and uniform transparent colloid;
(3) in a closed container, adding the additive into a small part of solvent in proportion for ultrasonic dispersion for 10-60 min;
(4) adding the additive subjected to the ultrasound treatment in the step (3) and lithium salt into the colloid prepared in the step (2) in a closed container, stirring for 12-24h, and uniformly mixing to form slurry for coating the solid electrolyte;
(5) coating the slurry prepared in the step (4) to prepare composite solid electrolyte slurry with uniform thickness, wherein a film-forming substrate comprises a glass plate, a metal foil or PET (polyethylene terephthalate) plastic, and the film-forming method comprises one of coating, electrophoresis and lifting;
(6) putting the composite solid electrolyte slurry with uniform thickness coated in the step (5) into a vacuum oven at 60 ℃ for baking for 12-24h, wherein the vacuum degree is-0.08-0.1 MPa;
(7) and (4) packaging and storing the dried electrolyte in the step (6), taking two smooth and clean plastic films, clamping the electrolyte, removing bubbles, and storing to obtain the composite solid electrolyte.
The following is a more specific example.
Example 1
A method of manufacturing a composite solid electrolyte comprising the steps of:
(1) selecting 50 percent of PVDF polymer and 10 percent of Li in percentage by mass2W2O7Solid electrolyte powder, 40% of LiTFSI, and a certain mass of solvent solution, such as NMP, are selected, calculated according to mass ratio, the mass ratio is controlled to be 85% of the total mass of slurry (the slurry comprises a polymer base material, an additive and a lithium salt), and the solvent is mixed according to the ratio of 2: 10, separation in proportion;
said Li2W2O7The preparation method of the solid electrolyte powder comprises the following steps:
1) 13.8% by mass of Li2CO386.2% of WO3Stirring in isopropanol for 12h, pouring the solution into a ball milling tank for ball milling at the speed of 800r/min for 30 circles, and fully mixing to obtain a mixed material;
2) drying the mixed material prepared in the step (1), grinding the dried block into powder, uniformly placing the powder in a crucible, and firing the powder in air at 750 ℃ for 6 hours at the temperature rising speed of 5 ℃ per hour;
3) taking out the powder, changing the light yellow of the powder into white, successfully firing, and carrying out ball milling on the powder sample subjected to paper firing in the step (2) at the speed of 800r/min for 30 circles, wherein the time of each circle is 5min to prepare Li2W2O7Solid electrolyte powder;
(2) adding PVDF into NMP solution with the proportion accounting for most parts in a closed container, and stirring for 1h to form stable and uniform colloid;
(3) in a closed container, Li2W2O7Adding solid electrolyte powder into a small part of NMP solution, and performing ultrasonic dispersion for 20 min;
(4) in a closed container, Li after the ultrasonic dispersion in the step (3)2W2O7Adding solid electrolyte powder and LiTFSI into the colloid prepared in the step (2), stirring for 18h, and uniformly mixing to obtain slurry;
(5) coating the obtained slurry on a substrate by using a film coating machine, wherein the film coating substrate comprises a glass plate, a metal plate, metal foil or PET (polyethylene terephthalate) plastic, and keeping the substrate flat;
(6) putting the composite solid electrolyte slurry with uniform thickness coated in the step (5) into a vacuum oven at the temperature of 60 ℃ for baking for 12 hours, wherein the vacuum degree is-0.09-0.1 MPa, and obtaining Li2W2O7A polymer solid electrolyte having a thickness in the range of 10-100 μm;
(7) and (4) packaging and storing the dried electrolyte in the step (6), taking two smooth and clean plastic films to sandwich the electrolyte and remove redundant bubbles, and storing the plastic films in a drying tank in an argon environment to obtain the composite solid electrolyte.
Comparative example 1
A method of manufacturing a solid electrolyte comprising the steps of:
(1) 60% of PVDF polymer and 40% of LiTFSI are selected, a certain mass of solvent solution such as NMP is selected, calculated according to mass ratio, the mass ratio of the solvent solution to the total mass of slurry including polymer base material, additive and lithium salt) is controlled to be 85%, and the ratio of the solvent to the total mass of slurry including polymer base material, additive and lithium salt) is controlled to be 2: 10, separation in proportion;
(2) adding PVDF into NMP solution with the proportion accounting for most parts in a closed container, and stirring for 1h to form stable and uniform colloid;
(3) adding LiTFSI into the uniform colloid in the step (2) in a closed container, stirring for 18 hours, and uniformly mixing to obtain slurry;
(4) coating the obtained slurry on a substrate by using a coating machine, and keeping the substrate flat;
(5) putting the composite solid electrolyte slurry with uniform thickness coated in the step (4) into a vacuum oven at the temperature of 60 ℃ for baking for 12 hours, wherein the vacuum degree is-0.09-0.1 MPa, and obtaining Li2W2O7A polymer solid electrolyte having a thickness in the range of 50-100 μm;
(6) and (5) packaging and storing the dried electrolyte in the step (5), taking two smooth and clean plastic films to sandwich the electrolyte and remove redundant bubbles, and storing the electrolyte in a drying tank in an argon environment to obtain the solid electrolyte.
For PVDF Polymer and Li prepared in example 12W2O7The composite solid electrolyte was subjected to a tensile test to obtain fig. 1, and the tensile test was carried out using a tensile tester (GH-949C), and the experimental electrolyte was a square solid electrolyte having a length of 30mm and a width of 10 mm. From the analysis of FIG. 1, Li2W2O7The mechanical property of the composite solid electrolyte is obviously improved, the tensile rate of the diaphragm is improved by 67.8 percent compared with that of PVDF, the breaking strength is also improved by 63.1 percent, and the improvement is very obvious.
For PVDF Polymer and Li prepared in example 12W2O7The composite solid electrolyte was subjected to battery cycling tests to obtain fig. 2, and cycling was performed at room temperature (25 ℃) on a novice battery test system with a battery rate of 0.5C for the assembled LFP positive electrode-solid electrolyte-lithium plate button half cell. From the battery cycle of FIG. 2, Li2W2O7The composite solid electrolyte can achieve higher and more stable battery capacity than a PVDF solid electrolyte.
For PVDF Polymer and Li prepared in example 12W2O7The composite solid electrolyte is subjected to an ionic conductivity test to obtain a graph 3, the ionic conductivity of the button cell assembled by the steel sheet-solid electrolyte-steel sheet is measured at 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, and the impedance of the button cell is measured by a formula sigma L/RS, wherein sigma is the ionic conductivity, L is the thickness of the solid electrolyte, R is the impedance of the test, and S is the area of the steel sheet. Shown in FIG. 3, with Li2W2O composite solid electrolyteLi prepared by comparing with pure PVDF solid electrolyte2W2O7The composite solid electrolyte has high ion conductivity, and can reach 3.2 × 10 at room temperature-3S cm-1While pure PVDF is only 2.2X 10 at room temperature-3S cm-1。
For PVDF Polymer and Li prepared in example 12W2O7The composite solid electrolyte is subjected to battery multiplying power test to obtain a graph 4, the multiplying power is that under the condition that the LFP positive electrode-solid electrolyte-lithium sheet button half battery is at room temperature (25 ℃), the circulating test is carried out on a Xinwei battery test system by changing the magnitude of the surface current, namely, the circulating test is carried out under various multiplying powers of 0.1C,0.2C,0.5C,1C,2C and 0.1C respectively, namely, the circulating test is started to circulate 0.2C after the circulating test is carried out for 5 circles by 0.1C of the same battery, and the like. From the battery rate data plot shown in FIG. 4, Li can be seen2W2O7The composite solid electrolyte is more stable under high multiplying power, and the battery capacity is larger than that of a pure PVDF solid battery.
Experiments prove that:
the composite polymer solid electrolyte slurry prepared from the components and the proportion provided by the invention can keep good stability and uniformity, and the prepared composite polymer solid electrolyte has excellent ionic conductivity, ion migration number and high voltage stability at room temperature, and effectively inhibits the growth of lithium dendrite in a battery system. The LFP/Li battery prepared by the composite polymer solid electrolyte has excellent cycle performance and rate capability and higher capacity.
The preparation method of the lithium ion battery composite diaphragm and the slurry thereof provided by the invention has the advantages of simple process, easiness in implementation, contribution to improving the production efficiency and saving the production cost, and the comprehensive performance of the composite diaphragm is superior to that of a pure polymer solid electrolyte and other composite polymer solid electrolytes, so that the technology of the invention is remarkably improved.
The above embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the above embodiments, and modifications and changes thereof may be made by those skilled in the art within the scope of the claims of the present invention.
Claims (8)
1. The composite solid electrolyte is characterized by comprising the following raw materials in percentage by mass:
5 to 90 percent of polymer base material
5 to 50 percent of lithium salt
5 to 90 percent of additive.
2. The composite solid electrolyte according to claim 1, comprising the following raw materials in percentage by mass:
polymer base material 50%
Lithium salt 10%
40% of additive.
3. The composite solid electrolyte of claim 1 or 2, wherein the polymer substrate is a polyvinylidene fluoride based polymer comprising one or more of poly (vinylidene fluoride), polyvinylidene fluoride-hexafluoropropylene, polybutylacrylate and polyacrylonitrile, poly (ethylene oxide), polypropylene oxide, poly (acrylonitrile), poly (methyl methacrylate), poly (bismethoxyethoxyethoxyethanol-phosphazene), polyvinyl chloride, polydimethylsiloxane, poly (perfluorosulfonic acid).
4. The composite solid-state electrolyte according to claim 1 or 2, wherein the lithium salt comprises one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate and lithium hexafluorophosphate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (difluoro-sulfonyl) imide and lithium bis (trifluoromethyl-sulfonyl) imide.
5. The composite solid electrolyte according to claim 1 or 2, characterized in that the preparation method of the additive comprises the steps of:
(1) 13.8% by mass of Li2CO386.2% of WO3Stirring in isopropanol for 12h, pouring the solution into a ball milling tank for ball milling at the speed of 800r/min for 30 circles, and fully mixing to obtain a mixed material;
2) drying the mixed material prepared in the step (1), grinding the dried block into powder, uniformly placing the powder in a crucible, and firing the powder in air at 750 ℃ for 6 hours at the temperature rising speed of 5 ℃ per hour;
3) and (3) after the powder is taken out, changing the light yellow of the powder into white, successfully firing, and carrying out ball milling on the powder sample subjected to paper firing in the step (2) at the speed of 800r/min for 30 circles, wherein the time of each circle is 5 min.
6. A method of manufacturing a composite solid electrolyte according to any one of claims 1 to 5, comprising the steps of:
(1) weighing a polymer base material, an additive and a lithium salt, selecting a solvent, wherein the solvent comprises one or more of NMP and DMF, the solvent is controlled to be 60-85% of the total mass of the slurry according to the mass ratio, and the solvent is prepared by mixing the components in percentage by mass according to the weight ratio of 2: 10, separation in proportion;
(2) adding a polymer base material into a solvent with a majority proportion in a closed container, and stirring for 1-2h at room temperature to form a stable and uniform transparent colloid;
(3) in a closed container, adding the additive into a small part of solvent in proportion for ultrasonic dispersion for 10-60 min;
(4) adding the additive subjected to the ultrasound treatment in the step (3) and lithium salt into the colloid prepared in the step (2) in a closed container, stirring for 12-24h, and uniformly mixing to form slurry for coating the solid electrolyte;
(5) coating the slurry prepared in the step (4) to prepare composite solid electrolyte slurry with uniform thickness;
(6) putting the composite solid electrolyte slurry with uniform thickness coated in the step (5) into a vacuum oven at 60 ℃ for baking for 12-24 h;
(7) and (4) packaging and storing the dried electrolyte in the step (6), taking two smooth and clean plastic films, clamping the electrolyte, removing bubbles, and storing to obtain the composite solid electrolyte.
7. The method for producing a composite solid electrolyte according to claim 6, wherein the film-forming substrate in the step (5) comprises a glass plate, a metal foil, or a PET plastic.
8. The method for producing a composite solid electrolyte according to claim 6, wherein the film forming method in the step (5) includes one of coating, electrophoresis, and pulling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111088647.0A CN113964378B (en) | 2021-09-16 | 2021-09-16 | Composite solid electrolyte and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111088647.0A CN113964378B (en) | 2021-09-16 | 2021-09-16 | Composite solid electrolyte and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113964378A true CN113964378A (en) | 2022-01-21 |
| CN113964378B CN113964378B (en) | 2023-09-26 |
Family
ID=79461799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111088647.0A Active CN113964378B (en) | 2021-09-16 | 2021-09-16 | Composite solid electrolyte and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113964378B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130505A (en) * | 2013-03-25 | 2013-06-05 | 桂林理工大学 | Low-temperature sinterable lithium-based microwave dielectric ceramic Li2W2O7 and preparation method thereof |
| JP2016225277A (en) * | 2015-05-29 | 2016-12-28 | 住友金属鉱山株式会社 | Positive electrode material for nonaqueous electrolyte secondary battery and method of producing the same, and nonaqueous electrolyte secondary battery using the positive electrode material |
| CN106784614A (en) * | 2017-03-22 | 2017-05-31 | 江苏元景锂粉工业有限公司 | A kind of high security lithium ion battery and preparation method thereof |
| CN106887638A (en) * | 2015-12-15 | 2017-06-23 | 国联汽车动力电池研究院有限责任公司 | A kind of composite solid electrolyte material, its preparation method and all solid state lithium ion secondary cell comprising the electrolyte |
| CN107256947A (en) * | 2017-05-17 | 2017-10-17 | 中国东方电气集团有限公司 | A kind of preparation method of conducting polymer lithium-ion energy storage device |
| CN107452983A (en) * | 2016-05-31 | 2017-12-08 | 比亚迪股份有限公司 | A kind of lithium ion battery composite electrolyte and preparation method thereof and lithium ion battery |
| JP2019067756A (en) * | 2017-09-29 | 2019-04-25 | 住友金属鉱山株式会社 | Lithium tungstate and production method thereof, lithium ion secondary battery cathode active material and production method thereof, and lithium ion secondary battery and production method thereof |
| CN111009686A (en) * | 2019-12-24 | 2020-04-14 | 武汉理工大学 | All-solid-state polymer electrolyte containing high-concentration lithium salt and preparation method thereof |
| CN111725559A (en) * | 2020-07-06 | 2020-09-29 | 电子科技大学 | Solid electrolyte, method for preparing the same, and lithium secondary solid battery |
| CN112242506A (en) * | 2019-07-18 | 2021-01-19 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN112864452A (en) * | 2019-11-27 | 2021-05-28 | 恒大新能源技术(深圳)有限公司 | Lithium tungstate solid electrolyte, preparation method thereof and solid battery |
-
2021
- 2021-09-16 CN CN202111088647.0A patent/CN113964378B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130505A (en) * | 2013-03-25 | 2013-06-05 | 桂林理工大学 | Low-temperature sinterable lithium-based microwave dielectric ceramic Li2W2O7 and preparation method thereof |
| JP2016225277A (en) * | 2015-05-29 | 2016-12-28 | 住友金属鉱山株式会社 | Positive electrode material for nonaqueous electrolyte secondary battery and method of producing the same, and nonaqueous electrolyte secondary battery using the positive electrode material |
| CN106887638A (en) * | 2015-12-15 | 2017-06-23 | 国联汽车动力电池研究院有限责任公司 | A kind of composite solid electrolyte material, its preparation method and all solid state lithium ion secondary cell comprising the electrolyte |
| CN107452983A (en) * | 2016-05-31 | 2017-12-08 | 比亚迪股份有限公司 | A kind of lithium ion battery composite electrolyte and preparation method thereof and lithium ion battery |
| CN106784614A (en) * | 2017-03-22 | 2017-05-31 | 江苏元景锂粉工业有限公司 | A kind of high security lithium ion battery and preparation method thereof |
| CN107256947A (en) * | 2017-05-17 | 2017-10-17 | 中国东方电气集团有限公司 | A kind of preparation method of conducting polymer lithium-ion energy storage device |
| JP2019067756A (en) * | 2017-09-29 | 2019-04-25 | 住友金属鉱山株式会社 | Lithium tungstate and production method thereof, lithium ion secondary battery cathode active material and production method thereof, and lithium ion secondary battery and production method thereof |
| CN112242506A (en) * | 2019-07-18 | 2021-01-19 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN112864452A (en) * | 2019-11-27 | 2021-05-28 | 恒大新能源技术(深圳)有限公司 | Lithium tungstate solid electrolyte, preparation method thereof and solid battery |
| CN111009686A (en) * | 2019-12-24 | 2020-04-14 | 武汉理工大学 | All-solid-state polymer electrolyte containing high-concentration lithium salt and preparation method thereof |
| CN111725559A (en) * | 2020-07-06 | 2020-09-29 | 电子科技大学 | Solid electrolyte, method for preparing the same, and lithium secondary solid battery |
Non-Patent Citations (1)
| Title |
|---|
| 李朝晖,苏光耀,高德淑,王霞瑜,李小平: "硅钨酸锂在聚合物电解质中的应用", 《电源技术》, pages 743 - 747 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113964378B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110581314B (en) | Multilayer-structure composite solid electrolyte membrane, preparation method thereof and solid battery | |
| CN110581311B (en) | Composite solid electrolyte membrane, preparation method thereof and solid battery | |
| CN108493486B (en) | Preparation method of in-situ polymerization solid-state battery | |
| CN105958008B (en) | A kind of lithium ion battery anode composite piece, preparation method and lithium ion battery | |
| CN102522560B (en) | Lithium ion secondary battery and preparation method thereof | |
| CN106654365A (en) | Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof | |
| CN110581253A (en) | Electrode pole piece, preparation method thereof and solid-state battery | |
| CN111430788A (en) | Composite solid electrolyte membrane, preparation method and solid lithium battery | |
| CN108767263B (en) | Preparation method and application of modified metal lithium negative electrode copper foil current collector | |
| CN110534795A (en) | The preparation method and solid state battery of solid state battery | |
| CN113471408B (en) | Method for manufacturing all-solid-state battery composite positive electrode, composite positive electrode and all-solid-state battery | |
| CN114665065B (en) | Positive electrode plate and preparation method and application thereof | |
| CN111725559B (en) | Solid electrolyte, method for preparing the same, and lithium secondary solid battery | |
| CN110311130B (en) | Titanium niobate negative electrode material and preparation method thereof | |
| WO2021189161A1 (en) | All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same | |
| CN110676433B (en) | Composite lithium cathode, preparation method thereof and lithium battery | |
| CN114976263B (en) | Positive electrode and electrolyte integrated solid-state battery and preparation method thereof | |
| CN110931852A (en) | Composite solid electrolyte, method for preparing same, and lithium secondary solid battery comprising same | |
| CN113451580A (en) | Interface layer and lithium ion battery comprising same | |
| CN103427113A (en) | Gel polymer electrolyte, polymer battery, and preparation method thereof | |
| CN112366293A (en) | Solid metal lithium battery and preparation method thereof | |
| CN109873111B (en) | High-specific-surface-area lithium metal cathode and preparation and application thereof | |
| CN114512718A (en) | Composite solid electrolyte, preparation method thereof and high-performance all-solid-state battery | |
| CN112271324B (en) | High-voltage solid-state lithium battery and preparation method thereof | |
| CN115714200B (en) | Method for preparing solid-state battery by selective solidification |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |