CN112838265B - Thin layered composite solid electrolyte membrane and preparation method and application thereof - Google Patents

Thin layered composite solid electrolyte membrane and preparation method and application thereof Download PDF

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CN112838265B
CN112838265B CN202110025374.9A CN202110025374A CN112838265B CN 112838265 B CN112838265 B CN 112838265B CN 202110025374 A CN202110025374 A CN 202110025374A CN 112838265 B CN112838265 B CN 112838265B
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王景涛
李文鹏
武文佳
张婕
吕睿鑫
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Zhengzhou University
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Abstract

The invention belongs to the technical field of all-solid-state lithium batteries, and discloses a thin layered composite solid electrolyte membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) preparing a two-dimensional nanosheet layered film from two-dimensional nanosheets; 2) inserting an inorganic ceramic electrolyte between the layers of the two-dimensional nanosheet layered membrane; 3) coating polyethylene oxide on the surface of the layered membrane obtained in the step 2) to obtain the thin layered composite solid electrolyte membrane. The thin layered composite solid electrolyte membrane prepared according to the present invention exhibits superior lithium ion conductivity and mechanical properties compared to conventional electrolyte membranes.

Description

Thin layered composite solid electrolyte membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of all-solid-state lithium batteries, and particularly relates to a thin layered composite solid electrolyte membrane and a preparation method and application thereof.
Background
Lithium metal batteries are generally considered to be the most promising secondary energy storage devices due to their high energy density. However, the conventional lithium metal battery and the liquid electrolyte have serious safety hazards such as leakage of the electrolyte, combustion, and even explosion caused by growth of lithium dendrite. Solid electrolytes are receiving more and more attention because of being capable of effectively solving the safety problem of liquid electrolytes, but the solid electrolytes have low conductivity, poor mechanical stability and low energy density, and limit the practical application of all-solid-state metal lithium batteries. A qualified all solid-state lithium battery should have the following characteristics: first, the lithium ion conductivity of the solid electrolyte should be greater than 10- 5Scm-1(ii) a Secondly, the solid electrolyte with certain mechanical strength can inhibit the growth of lithium dendrites and buffer the volume change of the lithium metal negative electrode in the charging and discharging processes; third, it has high energy density to meet the needs of production and living applications.
Currently, thin electrolyte membrane materials commonly used include polyethylene oxide (PEO), garnet-type fast ion conductors, perovskite-type fast ion conductors, and polymer lithium single ion conductors. Inorganic ceramic electrolytes are the first and most studied due to their high conductivity, but they are difficult to make thin, brittle and fragile, and have too high areal density leading to too low energy density. The perovskite crystal structure has abundant defects to promote the rapid transmission of lithium ions, so that the perovskite crystal structure has higher conductivity, and the room-temperature ionic conductivity is generally higher than that of a PEO (polyethylene oxide) base, so that the perovskite crystal structure is a relatively potential thin solid electrolyte material. In addition to perovskites, inorganic electrolyte systems such as garnet type and Nasicon type, which have high transmissibility, have been drawing attention from researchers because of their high ionic conductivity.
However, the solid electrolyte membrane has low ion conductivity and is fragile due to inherent brittleness, discontinuous internal crystal grains and large grain boundary resistance; low ionic conductivity requires the membrane to be used at higher temperatures, making the cell incapable of operating at low temperatures. The assembled battery has strict operation and use requirements due to poor mechanical property. In addition, the poor mechanical properties inherent in ceramic electrolyte membranes also limit membrane processing and long cycle operation. Therefore, it is necessary to develop an electrolyte membrane having high energy density, good lithium ion transport properties, and mechanical properties, which can be applied to an all-solid lithium battery.
Disclosure of Invention
In view of the above circumstances, an object of the present invention is to provide a thin layered composite solid electrolyte membrane exhibiting higher energy density and continuous transfer channels than conventional ceramic solid electrolyte membranes, and a method for preparing the same and applications thereof.
The first aspect of the present invention provides a method for producing a thin layered composite solid electrolyte membrane, comprising the steps of:
1) preparing a two-dimensional nanosheet layered film from two-dimensional nanosheets;
2) inserting an inorganic ceramic electrolyte between the layers of the two-dimensional nanosheet layered membrane;
3) coating polyethylene oxide (PEO) on the surface of the layered membrane obtained in the step 2) to obtain the thin layered composite solid electrolyte membrane.
Preferably, step 1) comprises: preparing a two-dimensional nanosheet dispersion; and forming a film by using the two-dimensional nanosheet dispersion liquid through suction filtration, spin coating, deposition or electrostatic atomization, and drying to obtain the two-dimensional nanosheet layered film.
In the invention, the two-dimensional nanosheet dispersion can be obtained by dispersing directly purchased two-dimensional nanosheets, or can be obtained by dispersing two-dimensional nanosheets obtained by stripping corresponding layered materials by adopting a conventional method in the prior art. Preferably, the two-dimensional nanosheet dispersion is a two-dimensional nanosheet ethanol dispersion, and the concentration thereof is 0.5 to 10g/L, and more preferably 1 g/L. And (3) defoaming the two-dimensional nanosheet dispersion liquid by ultrasonic for 20-40min, preferably 30min, and then preparing the membrane.
In the step 1), the two-dimensional nanosheet dispersion is formed into a membrane by a suction filtration method.
According to the invention, the drying conditions in step 1) may be 150 ℃ at 250 ℃ for 10-24h, preferably 200 ℃ for 12 h. The thickness of the prepared two-dimensional nanosheet layered membrane can be 10-195 μm, which is determined according to the thickness of the required thin layered composite solid electrolyte membrane.
In the present invention, the two-dimensional nanoplatelets include, but are not limited to: graphene Oxide (GO), MXene, g-C3N4Vermiculite nanosheet and BN nanosheet. The two-dimensional nanosheets are preferably vermiculite nanosheets.
According to the invention, step 2) comprises: swelling the two-dimensional nanosheet layered film with absolute ethyl alcohol; the inorganic ceramic electrolyte is inserted between the layers of the two-dimensional nano-sheet layered membrane in the form of precursor liquid by suction filtration, and then is kept stand and calcined.
In the present invention, the inorganic ceramic electrolyte may be selected from at least one of Lanthanum Lithium Titanate (LLTO), Lithium Lanthanum Zirconium Oxide (LLZO), titanium aluminum lithium phosphate (LATP), and germanium aluminum lithium phosphate (LAGP), and preferably is lanthanum lithium titanate.
According to the present invention, the preparation of the inorganic ceramic electrolyte precursor liquid can be performed in a conventional manner in the art, for example, the preparation method of the precursor liquid of lanthanum lithium titanate includes: lithium nitrate, lanthanum nitrate hexahydrate, tetrabutyl titanate, absolute ethyl alcohol and acetic acid are stirred and mixed to prepare the precursor liquid of the lithium lanthanum titanate.
Preferably, the molar ratio of the lithium nitrate, the lanthanum nitrate hexahydrate and the tetrabutyl titanate is 1: 1-4: 2-5, more preferably 1: 1.5: 2.7, the dosage of the absolute ethyl alcohol is 500mL-2000mL per mol of the lithium nitrate, and the dosage of the acetic acid is 5% of the volume of the absolute ethyl alcohol.
According to one embodiment, the preparation of the precursor liquid of lanthanum lithium titanate comprises: 1.4709g of lithium nitrate, 14.1741g of lanthanum nitrate hexahydrate, 20g of tetrabutyl titanate, 4mL of acetic acid and 20mL of ethanol are mixed, and then the mixture is placed at room temperature and stirred magnetically for 30min to obtain LLTO precursor liquid.
The purity of lithium nitrate and lanthanum nitrate hexahydrate used in the invention is more than 99.99%, the purity of tetrabutyl titanate is more than 99.9%, the purity of acetic acid is more than 99.8%, and absolute ethyl alcohol is an analytical pure grade reagent.
In the step 2), the two-dimensional nanosheet layered membrane is kept stand in absolute ethyl alcohol for 2-4h to swell, and the specific operation can be as follows: and (3) placing the two-dimensional nanosheet layered membrane in a suction filtration device, adding 10-20mL of absolute ethyl alcohol under the normal pressure of the suction filtration device, and standing for 2-4 h.
According to the invention, in the step 2), the suction filtration pressure is 5-10MPa, and the precursor liquid of the inorganic ceramic electrolyte is pumped to the interlayer of the two-dimensional nanosheet layered membrane, preferably to the surface to form a thin liquid membrane. The standing time is 3-12h, preferably 6h, so that the interlayer precursor liquid of the two-dimensional nanosheet layered film forms gel. The calcination conditions include: calcining at 800-1200 ℃ for 2-3h under the air condition, preferably at 800 ℃ for 2 h.
In the present invention, the surface coating of polyethylene oxide may be carried out by a conventional method, preferably a blade coating method, and specifically, the step 3) comprises: and (3) carrying out blade coating on an acetonitrile solution of polyethylene oxide to the thickness of 1-10 mu m, soaking the front and back surfaces of the laminated membrane in the acetonitrile solution of polyethylene oxide, and then drying to obtain the thin laminated composite solid electrolyte membrane.
According to the invention, the concentration of the acetonitrile solution of polyethylene oxide may be 0.01 to 0.1g/L, preferably 0.02 g/L; the coating temperature is 30-40 ℃, preferably 30 ℃, the coating thickness is preferably 5 μm, and the drying conditions comprise: vacuum drying at 45-60 deg.C for 18-24h, wherein the temperature range is favorable for volatilizing solvent and not causing the polymer to melt and present fluid state, and preferably vacuum drying at 55 deg.C for 24 h.
The second aspect of the present invention provides a thin layered composite solid electrolyte membrane obtained by the above-described production method.
Preferably, the thin layered composite solid electrolyte membrane has a thickness of 15 to 200 μm, more preferably 15 to 100 μm.
The third aspect of the present invention provides the thin laminar composite solid electrolyte membrane obtained by the above-mentioned preparation method or the use of the above-mentioned thin laminar composite solid electrolyte membrane in an all-solid lithium battery.
The operating steps and parameters not defined in the present invention can be selected conventionally according to the prior art.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the thin layered composite solid electrolyte membrane, the inorganic ceramic electrolyte is introduced between the layered membrane layers, so that inorganic ceramic electrolyte crystals in the confined space tend to grow in the horizontal direction, and compared with inorganic ceramic electrolyte crystal particles which grow macroscopically freely, the thin layered composite solid electrolyte membrane has more regular and continuous arrangement orientation and can transmit lithium ions more effectively; the two-dimensional nanosheet layered membrane has the advantages of thinness and controllable membrane thickness, and can greatly reduce the area density so as to improve the energy density.
2. The invention takes the two-dimensional nano-sheet as the layered mechanical support, reduces the film thickness and improves the mechanical property of the electrolyte film to a certain extent, and simultaneously opens up a continuous fast ion conduction path due to the continuous growth of the inorganic ceramic electrolyte in a limited space. In addition, the two-dimensional nanosheets have regular sizes and thicknesses, so that the two-dimensional nanosheet layered film prepared by suction filtration also has good film forming property and regular interlayer channels; the two-dimensional nanosheets, such as the vermiculite nanosheets, are rigid sheets and are high-temperature-resistant materials, so that the two-dimensional nanosheets have high mechanical properties and cannot damage the structure of the vermiculite nanosheets in the subsequent high-temperature calcination process; in addition, the energy density of the all-solid-state lithium metal battery can be improved by controlling the film thickness to reduce the surface resistance, so that the energy density of the electrolyte film can meet the requirements of production and living. The thin layered composite solid electrolyte membrane prepared by the invention shows more excellent lithium ion transfer capability and high energy density.
3. The preparation method of the thin-type layered composite solid electrolyte membrane is simple in process and mild in condition, and the thin-type layered composite solid electrolyte membrane prepared by the preparation method is applied to the field of all-solid-state lithium batteries, so that the energy density can be effectively improved, and the conductivity and the mechanical property can be improved.
Drawings
FIG. 1 is a sectional scanning electron microscope image of a thin layered composite solid electrolyte membrane obtained in example 1.
Fig. 2 is a graph comparing lithium ion conductivities of electrolyte membranes manufactured in respective examples and comparative examples.
Fig. 3 is a graph showing the charge and discharge cycle characteristics of a battery obtained from the electrolyte membrane obtained in example 1.
Fig. 4 is a graph of efficiency-specific capacity performance of cells manufactured from the electrolyte membranes manufactured in each of examples and comparative examples.
Fig. 5 is a nano-indentation performance graph of the electrolyte membrane and the vermiculite nanosheet layered membrane prepared in example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
A preparation method of a thin layered composite solid electrolyte membrane comprises the following steps:
1) the vermiculite nanosheet is prepared by using thermally expanded vermiculite as a raw material and adopting a two-step ion exchange method. The specific experimental steps are as follows: adding 2g of thermal expansion vermiculite (particle size: 8-13mm) into saturated NaCl solution, magnetically stirring for 48 hours at 120 ℃, and then washing for 5 times by using deionized water to obtain sodium ion intercalated expansion vermiculite; then, the sodium ion-intercalated expanded vermiculite was continuously refluxed in 2M LiCl solution for 24 hours (oil bath temperature: 120 ℃ C.), then filtered and washed with deionized water 5 times, anhydrous ethanolWashing 3 times until no Cl is detected in the filtrate-So as to obtain expanded vermiculite with lithium ion intercalation; adding 0.5g of expanded vermiculite of lithium ion intercalation into 200mL of deionized water, magnetically stirring for 30 minutes, and continuing ultrasonic treatment for 30 minutes; then, centrifuging at 12000 rpm/separation time for 20 minutes to remove the non-peeled vermiculite sheets to obtain a nearly transparent vermiculite nano sheet dispersion liquid, and calibrating the concentration of the vermiculite nano sheet dispersion liquid to be about 1 g.L by a drying and weighing method-1And adding 25mL of vermiculite nanosheet dispersion liquid into a suction filtration device for suction filtration, and after the suction filtration is finished, putting the vermiculite nanosheet dispersion liquid into a 200 ℃ drying oven for drying for 12 hours to obtain the vermiculite nanosheet layered membrane for later use.
2) Adding absolute ethyl alcohol into the prepared vermiculite nanosheet layered membrane to swell for 1 hour so as to ensure that the interlayer spacing is enlarged. 14.1741g of lanthanum nitrate hexahydrate, 1.4709g of lithium nitrate and 20g of tetrabutyl titanate are weighed and placed in a 100mL beaker, 20mL of absolute ethyl alcohol and 4mL of acetic acid are added, and after a preservative film is sealed, the mixture is magnetically stirred for 1h, so that precursor salt is completely dissolved and dispersed to obtain inorganic ceramic electrolyte precursor liquid. And pumping and filtering the obtained inorganic ceramic electrolyte precursor liquid to the interlayer of a vermiculite two-dimensional layered membrane skeleton under the pressure of 0.1MPa, standing for 12h, and calcining the precursor liquid at the high temperature of 800 ℃ in a tubular furnace for 2h when the precursor liquid becomes gel between the layers.
3) A PEO solution (0.02 g/L) with a thickness of 5 μm in acetonitrile was applied by blade coating to a coater, and both sides of the calcined layered membrane were wetted and vacuum-dried at 60 ℃ for 24 hours to obtain a thin layered composite solid electrolyte membrane, the membrane thickness was 15 μm and was designated as membrane-1, and the Scanning Electron Microscope (SEM) cross-section thereof is shown in FIG. 1.
Example 2
In the step 1), 125mL of vermiculite nanosheet dispersion liquid is added into a suction filtration device for suction filtration, and the rest steps and parameters are the same as those in the example 1. A thin, layered, composite solid electrolyte membrane having a film thickness of 100 μm was obtained and was designated as membrane-2.
Comparative example 1
1) Lanthanum nitrate hexahydrate, lithium nitrate and tetrabutyl titanate which are the same in mass as those in the example 1 are weighed, dissolved in the same absolute ethyl alcohol and acetic acid solvent as those in the example 1, then are magnetically stirred, and are calcined at high temperature for the same temperature and time as those in the example 1 after gel is formed, so that LLTO particles are obtained. The resulting solid was ground into powder to obtain LLTO powder.
2) Taking out a certain amount of LLTO powder, pressing into tablets under 20MPa, and hot pressing to ensure the film forming property of the pure LLTO film. After hot pressing, PEO was coated in the same manner as in example 1, and finally the film thickness was measured to prepare a LLTO laminate film having a thickness of 100 μm according to the ratio and was designated as film-3.
The films obtained in examples 1-2 and comparative example 1 were subjected to a performance test:
1. solid electrolyte membrane ionic conductivity test
Membrane-1, membrane-2 and membrane-3 were cut into electrolyte membranes with a diameter of 19mm, respectively, and the membranes were assembled with two stainless steel gaskets with a diameter of 16mm and a thickness of 1mm in a glove box into a CR2032 type coin-cell battery. The cell is heat treated at 60 deg.C for 30min, cooled to room temperature, and the electrolyte membrane impedance is measured at 30 deg.C, 45 deg.C and 60 deg.C, respectively.
Lithium ion conductivity was calculated from the following formula:
Figure BDA0002890133720000091
wherein R is solid electrolyte membrane resistance (omega), L is solid electrolyte membrane thickness (cm), A is contact area (cm) of the solid electrolyte membrane and two stainless steel gaskets2)。
Membrane-1 lithium ion conductivity results: the impedance of the solid electrolyte membrane was measured to be 12.6 omega at 30 ℃, and the lithium ion conductivity of the solid electrolyte membrane was calculated to be 6.07 x 10-5S·cm-1(ii) a At 45 ℃, the impedance of the solid electrolyte membrane is measured to be 7 omega, and the lithium ion conductivity of the solid electrolyte membrane is calculated to be 1.09 multiplied by 10-4S·cm-1(ii) a The impedance of the solid electrolyte membrane is measured to be 4.08 omega under the condition of 60 ℃, and the lithium ion conductivity of the solid electrolyte membrane is calculated to be 1.87 multiplied by 10-4S·cm-1。
Membrane-2 lithium ion conductivity results: under the condition of 30 ℃, the impedance of the solid electrolyte membrane is measured to be 154.8 omega, and the solid is obtained by calculationThe lithium ion conductivity of the electrolyte membrane in the state of 3.29X 10-5S·cm-1(ii) a The impedance of the solid electrolyte membrane was measured to be 84.74 Ω at 45 ℃, and the lithium ion conductivity of the solid electrolyte membrane was calculated to be 6.02 × 10-5S·cm-1(ii) a At 60 ℃, the impedance of the solid electrolyte membrane is measured to be 39.69 omega, and the lithium ion conductivity of the solid electrolyte membrane is calculated to be 1.28 multiplied by 10-4S·cm-1。
Membrane-3 lithium ion conductivity results: the impedance of the solid electrolyte membrane was measured to be 296.9 Ω at 30 ℃, and the lithium ion conductivity of the solid electrolyte membrane was calculated to be 1.71 × 10-5S·cm-1(ii) a The impedance of the solid electrolyte membrane was measured to be 227.9 omega at 45 ℃, and the lithium ion conductivity of the solid electrolyte membrane was calculated to be 2.24 × 10-5S·cm-1(ii) a The impedance of the solid electrolyte membrane was measured to be 54.69 omega at 60 ℃, and the lithium ion conductivity of the solid electrolyte membrane was calculated to be 9.33X 10-5S·cm-1。
A graph comparing lithium ion conductivities of film-1, film-2 and film-3 is shown in FIG. 2.
2. Solid electrolyte membrane charge-discharge performance test
And cutting the membrane-1, the membrane-2 and the membrane-3 into electrolyte membranes with the diameter of 19mm, and assembling the electrolyte membranes, a lithium sheet and a lithium iron phosphate anode into the CR2032 type button cell in a glove box. The battery is subjected to heat treatment at 60 ℃ for 30min, and then the charge-discharge cycle performance of the battery is measured at 0.5 ℃ and 60 ℃. The charge and discharge performance of the battery prepared from the membrane-1 is shown in figure 3, after the charge and discharge cycle of the membrane-1 is measured to be 150 circles, the higher capacity retention performance is still obtained, the average attenuation per circle is 0.063%, and the efficiency-specific capacity performance of the battery prepared from the membrane-1, the membrane-2 and the membrane-3 is simultaneously measured, as shown in figure 4.
3. Testing of stability of vermiculite nanosheet dispersion
Preparing LLTO precursor liquid according to the method in the embodiment 1, standing the vermiculite nanosheet dispersion liquid and the LLTO precursor liquid, and recording the change conditions of the casting solution at different times. The result shows that the state of the dispersion liquid of the vermiculite nano-sheets is not changed after being placed for a long time, and the phenomena of flocculation, sedimentation and the like do not exist in the precursor liquid. The vermiculite nanosheet dispersion can generate the Tyndall phenomenon by irradiation of a laser pen. Therefore, the dispersion liquid and the precursor liquid of the vermiculite nanosheet are relatively stable, so that the prepared thin layered composite solid electrolyte membrane is more uniform and continuous.
4. Mechanical Property test
The film-1 prepared in example 1 and the vermiculite nano sheet layered film prepared in step 1) in example 1 are subjected to a nano indentation test, and as shown in fig. 5, the vermiculite nano sheets themselves have a young's modulus as high as 175GPa, so that the vermiculite nano sheet layered film prepared in example 1 still has good mechanical properties. Further, due to the higher modulus of the inorganic ceramic and the interaction force between the ceramic and the vermiculite nanosheet layered membrane, the membrane-1 has more excellent mechanical properties to inhibit the growth of lithium dendrites.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims (8)

1. A preparation method of a thin layered composite solid electrolyte membrane is characterized by comprising the following steps:
1) preparing a two-dimensional nanosheet layered film from two-dimensional nanosheets, wherein the two-dimensional nanosheet layered film is provided with regular interlayer channels, the two-dimensional nanosheets are vermiculite nanosheets, and the step 1) comprises:
preparing a two-dimensional nanosheet dispersion, including washing with absolute ethanol until no chloride ions are detected; the two-dimensional nanosheet dispersion is a two-dimensional nanosheet ethanol dispersion, and the concentration of the two-dimensional nanosheet ethanol dispersion is 0.5-10 g/L;
forming a film by using a two-dimensional nanosheet dispersion liquid through suction filtration, spin coating, deposition or electrostatic atomization, and then drying to obtain a two-dimensional nanosheet layered film, wherein the thickness of the two-dimensional nanosheet layered film is 10-195 micrometers;
2) interposing an inorganic ceramic electrolyte between the layers of the two-dimensional nanosheet layered membrane, comprising: swelling the two-dimensional nanosheet layered film with absolute ethyl alcohol; the inorganic ceramic electrolyte is inserted between the layers of the two-dimensional nano-sheet layered membrane in the form of precursor liquid by suction filtration, and then is kept stand and calcined;
3) coating polyethylene oxide on the surface of the layered membrane obtained in the step 2) to obtain the thin layered composite solid electrolyte membrane.
2. The method for preparing a thin layered composite solid electrolyte membrane according to claim 1, wherein the inorganic ceramic electrolyte in step 2) is selected from at least one of lanthanum lithium titanate, lithium lanthanum zirconium oxide, lithium titanium aluminum phosphate and lithium germanium aluminum phosphate.
3. The method for preparing a thin layered composite solid electrolyte membrane according to claim 2, wherein the inorganic ceramic electrolyte is lanthanum lithium titanate, and the method for preparing a precursor liquid of lanthanum lithium titanate comprises: lithium nitrate, lanthanum nitrate hexahydrate, tetrabutyl titanate, anhydrous ethanol and acetic acid are stirred and mixed to prepare a precursor liquid of the lanthanum lithium titanate.
4. The method for producing a thin layered composite solid electrolyte membrane according to claim 3, wherein the molar ratio of lithium nitrate, lanthanum nitrate hexahydrate and tetrabutyl titanate is 1: 1-4: 2-5, the amount of absolute ethyl alcohol is 500mL-2000mL per mol of lithium nitrate, and the amount of acetic acid is 5% by volume of absolute ethyl alcohol.
5. The method for preparing the thin-type layered composite solid electrolyte membrane according to claim 2, wherein in the step 2), the two-dimensional nanosheet layered membrane is left standing in absolute ethyl alcohol for 2-4h to swell; the pressure of the suction filtration is 5-10 MPa; standing for 3-12 h; the calcination conditions include: calcining for 2-3h at 800-1200 ℃ under the air condition.
6. The method for producing a thin layered composite solid electrolyte membrane according to claim 1, wherein step 3) comprises: coating acetonitrile solution of polyoxyethylene to the thickness of 1-10 μm, soaking the front and back surfaces of the laminated membrane in the acetonitrile solution of the polyoxyethylene, and drying to obtain the thin laminated composite solid electrolyte membrane;
the concentration of the polyoxyethylene in acetonitrile is 0.01-0.1g/mL, and the drying conditions include: vacuum drying at 45-60 deg.C for 18-24 hr.
7. The thin layered composite solid electrolyte membrane obtained by the production method according to any one of claims 1 to 6, characterized in that the thickness of the thin layered composite solid electrolyte membrane is 15 to 200 μm.
8. Use of the thin, layered composite solid electrolyte membrane obtained by the production method according to any one of claims 1 to 6 or the thin, layered composite solid electrolyte membrane according to claim 7 in an all-solid lithium battery.
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