CN110931848A - Preparation method of all-solid-state electrolyte battery and all-solid-state electrolyte battery - Google Patents

Preparation method of all-solid-state electrolyte battery and all-solid-state electrolyte battery Download PDF

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CN110931848A
CN110931848A CN201911397991.0A CN201911397991A CN110931848A CN 110931848 A CN110931848 A CN 110931848A CN 201911397991 A CN201911397991 A CN 201911397991A CN 110931848 A CN110931848 A CN 110931848A
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solid electrolyte
layer
solid
positive electrode
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赵瑞瑞
蓝威杰
范弘扬
韦福鑫
陈红雨
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South China Normal University
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention discloses a preparation method of an all-solid-state electrolyte battery, which comprises the steps of preparing a solid-state electrolyte layer, preparing anode slurry, compounding the anode layer and the solid-state electrolyte layer, compounding the cathode layer and the solid-state electrolyte layer and the like. The invention provides a simple interface modification method of an all-solid-state battery, which realizes good contact between a positive electrode material and a negative electrode material and a solid electrolyte by forming a three-dimensional porous structure on two surfaces of the solid electrolyte, reduces the interface impedance between the solid electrolyte and the positive electrode and the negative electrode, and improves the utilization rate of an active material, thereby further improving the capacity and the cycle life of the all-solid-state electrolyte battery. In addition, the method does not need to additionally drip electrolyte, does not need to additionally construct an interface modification layer and carry out low-temperature sintering, and has easy operation and good effect. Also discloses an all-solid-state electrolyte battery, which comprises a solid-state electrolyte base layer, and a positive electrode layer and a negative electrode layer which are arranged on two sides of the solid-state electrolyte base layer.

Description

Preparation method of all-solid-state electrolyte battery and all-solid-state electrolyte battery
Technical Field
The invention relates to the field of solid electrolyte batteries, in particular to a preparation method of an all-solid-state electrolyte battery and the all-solid-state electrolyte battery.
Background
At present, organic electrolyte is mainly adopted in commercial lithium ion batteries, but the organic electrolyte has safety problems of flammability, easy leakage and the like, so that the lithium ion batteries have great potential safety hazards. All-solid batteries in which an organic electrolytic solution is replaced by a nonflammable solid electrolyte are considered to have higher safety and higher specific energy, and are receiving wide attention.
Inorganic solid electrolytes are mainly classified into two main groups, namely oxides and sulfides, among which lanthanum lithium zirconate (Li) of garnet structure7La3Zr2O12LLZO) has high ion conductivity (10)-4～10-3S/cm), a wide electrochemical window, and stability to metallic lithium, are considered to be one of the most ideal electrolytes for all-solid batteries. Although the ion conductivity of the LLZO is high, the solid interface problem between the LLZO and the anode and cathode materials has always prevented the development and application of the LLZO-based all-solid-state battery.
The currently adopted cathode interface modification method is mainly a method of adding electrolyte dropwise and increasing an interface modification layer to increase the wettability between a cathode and a solid electrolyte. The modification method of the anode interface mainly focuses on firstly compounding the anode material and the solid electrolyte and then sintering at low temperature to reduce the interface impedance. However, the method of dropping the electrolyte reduces the safety of the battery, the poor interface modification layer is difficult to effectively reduce the interface impedance, the low-temperature sintering easily causes the metal ions to shuttle between the positive electrode and the solid electrolyte lattice, the harmful impurity phase is formed, and the re-sintering process brings extra energy loss.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an all-solid-state electrolyte battery, which is a simple and convenient all-solid-state battery interface modification method, and the preparation method is characterized in that a three-dimensional network structure is formed on two surfaces of a solid electrolyte, so that a positive electrode material and a negative electrode material are in good contact with the solid electrolyte, the interface impedance between the solid electrolyte and the positive electrode and the negative electrode is reduced, the utilization rate of an active material is improved, and the capacity and the cycle life of the all-solid-state battery are further improved. The invention does not need to add extra electrolyte, does not need to build extra interface modification layer and sinter at low temperature, has easy operation and good effect, and can at least solve one of the problems.
According to an aspect of the present invention, there is provided a method of manufacturing an all-solid electrolyte battery, including the steps of:
s1, preparing a solid electrolyte layer: respectively dripping acid solution on two surfaces of the LLZO solid electrolyte sheet to obtain solid electrolyte layers with three-dimensional porous structures on the two surfaces;
s2, preparing positive electrode slurry;
s3, compounding of the positive electrode layer and the solid electrolyte layer: coating the positive electrode slurry on one surface of the solid electrolyte layer prepared in the step S1, and drying to form a positive electrode layer;
s4, compounding of the negative electrode layer and the solid electrolyte layer: and (4) attaching the negative electrode material to the other surface of the solid electrolyte layer obtained in step S1 to form a negative electrode layer.
Therefore, the invention provides a simple interface modification method of an all-solid-state battery, and the method can realize good contact between the anode material and the solid electrolyte and between the cathode material and the solid electrolyte by forming three-dimensional porous structures on two surfaces of the solid electrolyte, reduce the interface impedance between the solid electrolyte and the anode and the cathode, and improve the utilization rate of the active material, thereby further improving the capacity and the cycle life of the all-solid-state electrolyte battery. In addition, the method does not need to additionally drip electrolyte, does not need to additionally construct an interface modification layer and carry out low-temperature sintering, and has easy operation and good effect.
In some embodiments, the cathode slurry in step S2 is a flowing slurry formed by dispersing a cathode material into a solution containing a dispersant and a binder. The resulting flowing slurry is thus homogeneous in composition.
In some embodiments, the positive electrode material is preferably a nanoscale positive electrode material. Therefore, the anode material of the nano-scale particles can be effectively attached to the inside of the porous structure, and the contact area of the anode material and the solid electrolyte is increased.
Thus, α -terpineol solution functions to dissolve the ethyl cellulose while uniformly dispersing the positive electrode material, enabling the positive electrode material and the binder to be uniformly coated on the surface of the solid electrolyte layer.
In some embodiments, the binder is ethyl cellulose.
In some embodiments, in step S3, after the cathode slurry is applied to the surface of the solid electrolyte layer obtained in step S1, the cathode slurry flows into the three-dimensional porous structure of the surface of the solid electrolyte layer to form a first composite layer.
In some embodiments, the positive electrode material is one of lithium iron phosphate, lithium cobaltate, lithium manganate, or a ternary material.
In some embodiments, the formation of the negative electrode layer in step S4 includes the steps of:
s401, attaching a negative electrode material to a solid electrolyte sheet, and heating to melt the negative electrode material;
and S402, pressurizing to enable the negative electrode material in the molten state to be tightly combined with the surface of the solid electrolyte layer.
In some embodiments, in step S401, the melted anode material flows into the three-dimensional porous structure on the surface of the solid electrolyte layer to form a second composite layer.
In some embodiments, after step S3, the method further includes:
s4, assembling the battery: and encapsulating the all-solid-state electrolyte battery in a battery case, adding a stainless steel gasket and an elastic sheet, and assembling to obtain the all-solid-state battery.
In some embodiments, the negative electrode material is a metallic lithium sheet.
In some embodiments, after the acid solution is respectively dropped on both surfaces of the LLZO solid electrolyte sheet in step S1, the LLZO solid electrolyte sheet needs to be washed first. Therefore, the acid solution is preferably an inorganic acid solution such as phosphoric acid, concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid or an organic acid solution such as citric acid or ascorbic acid, and the treatment time is preferably 1-10 min. The cleaning treatment can be carried out by cleaning the surface in absolute ethyl alcohol or isopropanol solvent, and then ultrasonic cleaning in an ultrasonic instrument. The purpose of cleaning is to remove acid solution remained on the surface and pores of the LLZO solid electrolyte sheet, and the treatment time is 1-3 minutes.
According to another aspect of the present invention, there is also provided an all-solid-state electrolyte battery, including a solid electrolyte base layer, and a positive electrode layer and a negative electrode layer disposed on both sides of the solid electrolyte layer, wherein holes are formed on both sides of the solid electrolyte layer, a positive electrode material constituting the positive electrode layer is filled in the holes on one side of the solid electrolyte layer to form a first composite layer with the solid electrolyte layer, a positive electrode material constituting the negative electrode layer is filled in the holes on the other side of the solid electrolyte layer to form a second composite layer with the solid electrolyte layer.
Therefore, the all-solid-state electrolyte battery has the advantages that the holes are formed in the two side faces of the solid electrolyte base layer to form the three-dimensional porous structure, so that the positive electrode materials and the negative electrode materials on the two sides can be in good contact with the solid electrolyte base layer, the interfacial impedance between the solid electrolyte and the positive and negative electrodes can be effectively reduced, the utilization rate of the active materials is improved, and the capacity and the cycle life of the all-solid-state electrolyte battery are further improved.
In some embodiments, the solid electrolyte layer is preferably a LLZO solid electrolyte sheet.
In some embodiments, the thickness of the positive electrode layer is preferably 5 to 10 μm.
In some embodiments, the thickness of the negative electrode layer is preferably 5 to 10 μm.
In some embodiments, the thickness of the solid electrolyte layer is preferably 500 to 700 μm.
In some embodiments, the thickness of the first composite layer is preferably 5 to 10 μm.
In some embodiments, the thickness of the second composite layer is preferably 5 to 10 μm.
The invention has the beneficial effects that:
the invention provides a simple and convenient interface modification method of an all-solid-state battery, which can simply and effectively form a three-dimensional porous structure on the surface of a solid electrolyte to form an ion transmission network, and simultaneously, can effectively attach positive and negative electrode materials of nano particles into the porous structure, improve the contact area of the positive and negative electrode materials and the solid electrolyte, and improve the performance of the all-solid-state battery. Meanwhile, the whole preparation process does not need to add organic electrolyte, an interface modification layer and low-temperature sintering treatment, and has great industrial application prospect. The capacity and the cycle life of the prepared all-solid-state electrolyte battery are greatly improved.
Drawings
Fig. 1 is a graph comparing the battery performance of the all-solid electrolyte battery obtained by the manufacturing method of the present invention of example 1 with that of a general all-solid electrolyte battery;
fig. 2 is a graph comparing the battery performance of the all-solid electrolyte battery obtained by the manufacturing method of the present invention of example 2 with that of a general all-solid electrolyte battery;
fig. 3 is a graph comparing the battery performance of the all-solid electrolyte battery obtained by the manufacturing method of the present invention of example 3 with that of a general all-solid electrolyte battery;
fig. 4 is a schematic structural view of an all-solid electrolyte battery according to an embodiment of the present invention.
Reference numerals in FIGS. 1 to 4: 2-all-solid-state electrolyte battery; 21-a solid electrolyte base layer; 22-positive electrode layer; 23-a negative electrode layer; 24-a first composite layer; 25-a second composite layer; 211-holes.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1
A method for preparing an all-solid-state electrolyte battery comprises the following steps:
s1, preparing a solid electrolyte layer: dropwise adding concentrated nitric acid to two surfaces of the well-fired and polished LLZO solid electrolyte sheet, respectively treating for 3min, then putting the LLZO solid electrolyte sheet into an absolute ethyl alcohol or isopropanol solvent, cleaning the surface with a brush, putting the LLZO solid electrolyte sheet into an ultrasonic instrument, and ultrasonically cleaning for 2min to finally obtain the LLZO solid electrolyte ceramic sheet with the three-dimensional porous structure on the two surfaces.
S2, preparing anode slurry, namely performing ball milling on the commercial ternary material (NMC532) to obtain the nanoscale NMC532 ternary material, and then dispersing the nanoscale NMC532 ternary material into a solution of α -terpineol and ethyl cellulose to form flowing slurry.
S3, compounding of the positive electrode layer and the solid electrolyte layer: coating the prepared positive electrode slurry on one surface of the solid electrolyte layer prepared in the step S1, and drying at 80 ℃ to remove the dispersing agent to form a positive electrode layer;
s4, compounding of the negative electrode layer and the solid electrolyte layer: transferring the dried NMC532/LLZO composite solid electrolyte to an inert atmosphere, attaching a metal lithium sheet with surface oxides scraped off to the other surface of the solid electrolyte layer obtained in step S1, heating on a heating table at 150 ℃ for 5min to melt the metal lithium sheet, and applying a certain force to tightly bond the molten lithium to the other surface of the solid electrolyte layer.
S5, assembling the battery: and packaging the all-solid-state electrolyte battery similar to the sandwich structure in a button battery case, adding a stainless steel gasket and an elastic sheet, and tightly packaging to obtain the all-solid-state battery.
As shown in fig. 1, in comparison, the all-solid-state electrolyte battery obtained by processing the above-mentioned preparation method has a greatly improved capacity and cycle life compared with the all-solid-state electrolyte battery obtained by assembling without processing (i.e., the conventional all-solid-state electrolyte battery).
Fig. 4 schematically shows an all-solid electrolyte battery according to an embodiment of the present invention. As shown in fig. 4, the all-solid electrolyte battery includes a solid electrolyte base layer, and a positive electrode layer and a negative electrode layer disposed on both sides of the solid electrolyte layer. And a plurality of holes are formed in two side surfaces of the solid electrolyte layer to form a three-dimensional porous structure, and the plurality of holes are formed by etching through an acid solution. The positive electrode material constituting the positive electrode layer is filled in the hole on one side surface of the solid electrolyte layer to form a first composite layer with the solid electrolyte layer. The positive electrode material constituting the negative electrode layer is filled in the hole on the other side surface of the solid electrolyte layer to form a second composite layer with the solid electrolyte layer.
The solid electrolyte layer of the present embodiment is preferably an LLZO solid electrolyte sheet. The positive electrode layer is preferably formed of a positive electrode material such as lithium iron phosphate, lithium cobaltate, lithium manganate, or a ternary material. The negative electrode layer is preferably lithium.
The thickness of the positive electrode layer is preferably 5-10 μm; the thickness of the negative electrode layer is preferably 5-10 μm; the thickness of the solid electrolyte layer is preferably 500-700 μm; the thickness of the first composite layer is preferably 5-10 μm; the thickness of the second composite layer is preferably 5 to 10 μm.
Example 2
A method for preparing an all-solid-state electrolyte battery comprises the following steps:
s1, preparing a solid electrolyte layer: and dripping 50% by mass of citric acid solution onto two surfaces of the well-fired and polished LLZO solid electrolyte sheet, respectively treating for 5min, then putting the LLZO solid electrolyte sheet into an absolute ethyl alcohol or isopropanol solvent, cleaning the surface with a brush, putting the LLZO solid electrolyte sheet into an ultrasonic instrument, and ultrasonically cleaning for 1min to finally obtain the LLZO solid electrolyte ceramic sheet with the three-dimensional porous structure on the two surfaces.
S2, preparing anode slurry, namely ball-milling commercial lithium iron phosphate (LFP) to obtain nano-scale LFP, and then dispersing the nano-scale LFP into a solution of α -terpineol and ethyl cellulose to form flowing slurry.
S3, compounding of the positive electrode layer and the solid electrolyte layer: coating the prepared positive electrode slurry on one surface of the solid electrolyte layer prepared in the step S1, and drying at 100 ℃ to remove the dispersing agent to form a positive electrode layer;
s4, compounding of the negative electrode layer and the solid electrolyte layer: transferring the dried LFP/LLZO composite solid electrolyte to an inert atmosphere, attaching a lithium metal sheet with surface oxides scraped off to the other surface of the solid electrolyte layer obtained in step S1, heating on a heating table at 150 ℃ for 5min to melt the lithium metal sheet, and applying a certain force to tightly bond the molten lithium to the other surface of the solid electrolyte layer.
S5, assembling the battery: and packaging the all-solid-state electrolyte battery similar to the sandwich structure in a button battery case, adding a stainless steel gasket and an elastic sheet, and tightly packaging to obtain the all-solid-state battery.
As shown in fig. 2, in comparison, the all-solid-state electrolyte battery obtained by processing the above-mentioned preparation method has a greatly improved capacity and cycle life compared with the all-solid-state electrolyte battery obtained by assembling without processing (i.e., the conventional all-solid-state electrolyte battery).
Example 3
A method for preparing an all-solid-state electrolyte battery comprises the following steps:
s1, preparing a solid electrolyte layer: and dripping 50% by mass of citric acid solution onto two surfaces of the well-fired and polished LLZO solid electrolyte sheet, respectively treating for 8min, then putting the LLZO solid electrolyte sheet into an absolute ethyl alcohol or isopropanol solvent, cleaning the surface with a brush, putting the LLZO solid electrolyte sheet into an ultrasonic instrument, and ultrasonically cleaning for 3min to finally obtain the LLZO solid electrolyte ceramic sheet with the three-dimensional porous structure on the two surfaces.
S2, preparing anode slurry, namely ball-milling commercial Lithium Cobaltate (LCO) to obtain nanoscale LCO, and then dispersing the LCO into a solution of α -terpineol and ethyl cellulose to form flowing slurry.
S3, compounding of the positive electrode layer and the solid electrolyte layer: coating the prepared positive electrode slurry on one surface of the solid electrolyte layer prepared in the step S1, and drying at 110 ℃ to remove the dispersing agent to form a positive electrode layer;
s4, compounding of the negative electrode layer and the solid electrolyte layer: transferring the dried LCO/LLZO composite solid electrolyte to an inert atmosphere, attaching a lithium metal sheet with surface oxides scraped off to the other surface of the solid electrolyte layer obtained in step S1, heating on a heating table at 150 ℃ for 5min to melt the lithium metal sheet, and applying a certain force to tightly bond the molten lithium to the other surface of the solid electrolyte layer.
S5, assembling the battery: and packaging the all-solid-state electrolyte battery similar to the sandwich structure in a button battery case, adding a stainless steel gasket and an elastic sheet, and tightly packaging to obtain the all-solid-state battery.
As shown in fig. 3, in comparison, the all-solid-state electrolyte battery obtained by processing the above-mentioned preparation method has a greatly improved capacity and cycle life compared with the all-solid-state electrolyte battery (i.e., the conventional all-solid-state electrolyte battery) assembled without processing.
The preparation method of the all-solid-state electrolyte battery can simply and effectively enable the surface of the solid electrolyte to form a three-dimensional porous structure to form an ion transmission network, and meanwhile, the anode and cathode materials of the nano particles are effectively attached to the porous structure, so that the contact area of the anode and cathode materials and the solid electrolyte is increased, and the performance of the all-solid-state battery is improved. Meanwhile, no organic electrolyte is added, no interface modification layer is additionally added, and low-temperature sintering treatment is not needed, so that the method has a great industrial application prospect.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the all-solid-state electrolyte battery is characterized by comprising the following steps of:
s1, preparing a solid electrolyte layer: respectively dripping acid solution on two surfaces of the LLZO solid electrolyte sheet to obtain solid electrolyte layers with three-dimensional porous structures on the two surfaces;
s2, preparing positive electrode slurry;
s3, compounding of the positive electrode layer and the solid electrolyte layer: coating the positive electrode slurry on one surface of the solid electrolyte layer prepared in the step S1, and drying to form a positive electrode layer;
s4, compounding of the negative electrode layer and the solid electrolyte layer: and (4) attaching the negative electrode material to the other surface of the solid electrolyte layer obtained in step S1 to form a negative electrode layer.
2. The method of manufacturing an all-solid electrolyte battery according to claim 1, wherein the positive electrode slurry in step S2 is a flowing slurry formed by dispersing a positive electrode material into a solution containing a dispersant and a binder.
3. The method of claim 2, wherein in step S3, after the positive electrode slurry is applied to the surface of the solid electrolyte layer obtained in step S1, the positive electrode slurry flows into the three-dimensional porous structure of the surface of the solid electrolyte layer to form the first composite layer.
4. The method of manufacturing an all-solid electrolyte battery according to claim 2, wherein the positive electrode material is one of lithium iron phosphate, lithium cobaltate, lithium manganate, or a ternary material.
5. The production method of an all-solid electrolyte battery according to claim 1, wherein the formation of the negative electrode layer in step S4 includes the steps of:
s401, attaching a negative electrode material to a solid electrolyte sheet, and heating to melt the negative electrode material;
and S402, pressurizing to enable the negative electrode material in the molten state to be tightly combined with the surface of the solid electrolyte layer.
6. The method of manufacturing an all-solid electrolyte battery according to claim 5, wherein in step S401, the melted anode material flows into the three-dimensional porous structure on the surface of the solid electrolyte layer to form a second composite layer.
7. The method for producing an all-solid electrolyte battery according to claim 1, further comprising, after the step S3:
s4, assembling the battery: and encapsulating the all-solid-state electrolyte battery in a battery case, adding a stainless steel gasket and an elastic sheet, and assembling to obtain the all-solid-state battery.
8. The all-solid electrolyte battery according to claim 1, wherein the negative electrode material is a metallic lithium sheet.
9. The method of manufacturing an all-solid electrolyte battery according to claim 1, wherein the LLZO solid electrolyte is washed after dropping the acid solution on both surfaces of the LLZO solid electrolyte sheet, respectively, in step S1.
10. The all-solid-state electrolyte battery comprises a solid electrolyte base layer (21), and a positive electrode layer (22) and a negative electrode layer (23) which are arranged on two sides of the solid electrolyte layer (21), and is characterized in that holes (211) are formed in two side faces of the solid electrolyte layer (21), a positive electrode material forming the positive electrode layer (22) is filled in the holes (211) in one side face of the solid electrolyte layer (21), a first composite layer (24) is formed by the positive electrode material forming the negative electrode layer (23) and is filled in the holes (211) in the other side face of the solid electrolyte layer (21), and a second composite layer (25) is formed by the positive electrode material and the solid electrolyte layer (21).
CN201911397991.0A 2019-12-30 2019-12-30 Preparation method of all-solid-state electrolyte battery and all-solid-state electrolyte battery Pending CN110931848A (en)

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CN112670543B (en) * 2020-09-08 2022-03-04 华中科技大学 Composite solid electrolyte membrane based on hollow MOF (metal organic framework) and preparation method and application thereof
CN112670561A (en) * 2020-12-09 2021-04-16 上海空间电源研究所 Method for improving surface defects of solid electrolyte and method for preparing composite solid electrolyte membrane
CN112652815A (en) * 2021-01-25 2021-04-13 郑州中科新兴产业技术研究院 Low-internal-resistance all-solid-state battery and preparation method thereof
CN112652815B (en) * 2021-01-25 2021-10-29 郑州中科新兴产业技术研究院 Low-internal-resistance all-solid-state battery and preparation method thereof
CN112952041A (en) * 2021-02-25 2021-06-11 横店集团东磁股份有限公司 Garnet type solid electrolyte composite positive electrode and preparation method and application thereof
CN113871703A (en) * 2021-09-24 2021-12-31 中汽创智科技有限公司 Garnet type solid electrolyte and preparation and application thereof
WO2023133587A3 (en) * 2022-01-10 2023-10-19 Battelle Energy Alliance, Llc Methods of improving an interface between an electrode and an electrolyte of an electrochemical cell

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