CN111129560B - Oxide solid electrolyte sheet and preparation method and application thereof - Google Patents

Oxide solid electrolyte sheet and preparation method and application thereof Download PDF

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CN111129560B
CN111129560B CN201911382036.XA CN201911382036A CN111129560B CN 111129560 B CN111129560 B CN 111129560B CN 201911382036 A CN201911382036 A CN 201911382036A CN 111129560 B CN111129560 B CN 111129560B
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solid electrolyte
sheet
oxide solid
oxide
electrolyte sheet
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CN111129560A (en
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赵尚骞
张立
孙浩博
张刚宁
朱秀龙
杨容
赵春荣
武兆辉
王建涛
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China Automotive Battery Research Institute Co Ltd
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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Abstract

The invention belongs to the technical field of solid electrolytes, and particularly relates to an oxide solid electrolyte sheet and a preparation method and application thereof. The method comprises the following steps: and laminating two or more layers of oxide solid electrolyte green sheets into one layer by means of hot pressing. The invention adopts a double-layer or multi-layer hot-pressing compounding mode to obtain a compact oxide solid electrolyte sheet without through holes, and can effectively improve the gas-barrier sealing effect of the compact solid electrolyte sheet.

Description

Oxide solid electrolyte sheet and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to an oxide solid electrolyte sheet and a preparation method and application thereof.
Background
Common inorganic oxide ceramic-based solid electrolytes, such as Li of NASICON structure1.5Al0.5Ge1.5(PO4)3(LAGP) and Li1.4Al0.4Ti1.6(PO4)3(LATP), Garnet structured Li7La3Zr2O12(LLZO) and the like, and has a characteristic of supporting lithium ion conduction and electron insulation. Solid bodyThe thickness of the electrolyte sheet determines the internal resistance of a sample, the smaller the thickness is, the smaller the internal resistance is, in order to achieve the low internal resistance as far as possible, the thinner the oxide solid electrolyte sheet is, the better the oxide solid electrolyte sheet is, therefore, the development of the ultrathin solid electrolyte sheet (film) is the core development content of the all-solid battery, and the difficulty is high.
The preparation method of the oxide solid electrolyte sheet has three common modes:
(1) powder tabletting method. The powder sample which is dried or roasted, ground and uniformly mixed is put into a special die and is pressed into a sample piece under certain pressure by a press, namely powder tabletting. The powder is compacted into thin slices, the powder needs to be paved in a mould firstly in the powder tabletting process, and due to uneven paving, the thin slice sample is easy to distort and even crack in the sintering process. The prepared electrolyte sheet is thick, and in order to reduce the resistance, the surface of the electrolyte sheet needs to be polished before use, so that the electrolyte sheet is easy to damage.
(2) Cutting method: the slice is formed by directly sintering the powder into blocks and then cutting the blocks. The method requires special equipment, has higher requirements on the cutting process, is difficult to be made into a thin sheet, is usually to further polish the sheet after cutting to prepare the sheet, and also has electrolyte sheet damage caused by polishing. Related patents are: CN 105384801 a "a method for preparing oxide solid electrolyte membrane"; CN 106898821 a "preparation method of lithium lanthanum niobium oxygen solid electrolyte membrane"; CN 108408708A "method for preparing crystalline LAGP solid electrolyte sheet", but the above methods all have the above problems.
(3) A tape casting method. The Hulian research team at the university of Maryland reported a solution method for preparing Li7La3Zr2O12The (LLZO) sheet method, which is a liquid phase method requiring dispersion of solid electrolyte powder in toluene and isopropanol solvent, is to prepare an oxide solid electrolyte as a slurry, coat it on a polyester film, hot press it into a sheet, and sinter it into a solid electrolyte sheet.
Among the three methods, the casting coating method is more suitable for preparing the ultrathin solid electrolyte sheet, but due to factors such as impurities, bubbles, operation and the like, defects and even through holes are easily generated in the solid electrolyte sheet, the phenomenon is more easily generated in a large-size ultrathin solid electrolyte sheet, and the service performance of the ultrathin solid electrolyte is seriously influenced. Aiming at the problems in the prior art, the invention provides a compact oxide solid electrolyte sheet without through holes and a preparation method thereof.
Disclosure of Invention
The invention provides an oxide solid electrolyte sheet without a through hole and a preparation method thereof, wherein the preparation method comprises the following steps:
preparing an oxide solid electrolyte into an oxide solid electrolyte green sheet, and laminating two or more layers of the oxide solid electrolyte green sheets into one layer by means of hot pressing.
Aiming at the problems in the prior art in preparing the large-area oxide solid electrolyte thin sheet, the invention firstly proposes the operation of laminating two or more layers of green sheets into one sheet by adopting a hot-pressing mode, and through the operation, through holes generated in the preparation process of the green sheets can be effectively repaired to obtain the compact oxide solid electrolyte thin sheet without the through holes.
Preferably, in the hot pressing process, the pressure is controlled to be 100 kPa-3 MPa, the hot pressing time is 10 min-60 min, and the hot pressing temperature is 60-120 ℃.
Preferably, in the hot pressing process, the hot pressing device includes two pressing surfaces, a soft rubber pad and a release film are sequentially arranged from one pressing surface to the adjacent oxide solid electrolyte green sheet to be pressed, and a contact surface between the release film and the solid electrolyte sheet is easy to peel; the soft rubber pad is arranged, so that the uniformity of a hot pressing effect can be ensured, the release film ensures smooth demolding after hot pressing is completed, the adhesion of the solid electrolyte green sheet and a hot pressing mold is avoided, and the success rate of electrolyte thin sheet preparation can be effectively improved through the operation.
Further preferably, the soft rubber mat is one of silica gel, natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, ethylene propylene rubber, neoprene rubber, fluororubber, TPU, TPE, TPR, EVA, and POE.
More preferably, the peeling force range of the release film is 0.01-0.5N/25 mm.
The release film is one of a PE release film, a PET release film and an OPP release film.
The sizes of the soft rubber pad and the release film are larger than or equal to the solid electrolyte green sheet.
Preferably, a binder is added to the solid oxide electrolyte during the preparation of the solid oxide electrolyte green sheet; the binder can achieve good coating effect of the slurry, and can also ensure good composite effect during hot pressing, such as no binder, and two or more layers of solid electrolyte green sheets are easy to separate after hot pressing.
Further preferably, the binder comprises at least one of PVDF, PVB, PVA, PAA, SBR, CMC, PAN;
more preferably, the binder is present in an amount of 5 to 15 wt% after the solid oxide electrolyte and the binder are mixed.
Preferably, the pressure in the pressing process is controlled to be 300kPa to 500kPa for green sheets with adhesive being PVB or PVA and thickness being 100 to 300 μm, the hot pressing time is controlled to be 30min to 40min, and the hot pressing temperature is controlled to be 85 to 105 ℃. In the pressing process, in order to ensure an ideal pressing effect, the selection of the binder and the thickness of the green sheet have higher requirements on the pressing condition, and the green sheet with the binder of PVB or PVA and the thickness of 100-300 μm can obtain the ideal effect by adopting the method for pressing.
Preferably, the oxide solid electrolyte is prepared into an oxide solid electrolyte green sheet by a coating method.
More preferably, in the process of preparing the green sheet by coating, the slurry is dried at room temperature for 5 to 30 hours, still more preferably 15 to 18 hours after the coating is completed.
Preferably, the oxide solid electrolyte is one or more of an NASICON type solid electrolyte, a Garnet type solid electrolyte, a perovskite type solid electrolyte or a LISICON type solid electrolyte.
Preferably, the hot pressing method further comprises a sintering step after the hot pressing is finished, wherein the sintering temperature is 600-1500 ℃, and the sintering time is 30 min-12 h.
As a preferable scheme, the sintering temperature is 850-1000 ℃ for the NASICON type solid electrolyte;
as a preferable scheme, the sintering temperature is 900-1300 ℃ for the Garnet type solid electrolyte;
as a preferable scheme, the sintering temperature is 1100-1400 ℃ for the perovskite type solid electrolyte;
as a preferable scheme, the sintering temperature is 600-900 ℃ for the LISICON type solid electrolyte.
As a preferred mode of operation, the method of the invention comprises the steps of:
1) dispersing: adding a solvent, a dispersing agent and solid electrolyte powder into a ball milling tank, and fully dispersing by ball milling, wherein the ball-to-material ratio is 5: 1-10: 1;
2) pulping: taking a certain amount of solvent, adding a plasticizer, then adding a binder, and stirring to obtain a glue solution; adding the glue solution into the ball milling tank in the step 1, and continuing ball milling for 15-30 h to finish the preparation of the slurry;
3) coating: coating the slurry obtained in the step 2 on a substrate, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature, and drying to obtain a solid electrolyte green sheet, wherein the drying time is 5-30 hours, preferably 15-18 hours;
4) hot-pressing and compounding: and (3) cutting the solid electrolyte green sheet in the step (3), aligning and sticking two or more green films together, and applying uniform pressure to carry out hot-pressing compounding.
5) And (3) sintering: and (4) quickly transferring the hot-pressed solid electrolyte green sheet in the step (4) into a muffle furnace for sintering, wherein the sintering temperature is 600-1500 ℃, and the sintering time is 30 min-12 h.
Another object of the present invention is to protect the oxide solid electrolyte sheet prepared by the method of the present invention.
Preferably, the area of the oxide solid electrolyte sheet is 1cm2～400cm2And/or the thickness of the flake is 30 μm to 500 μm. The oxide solid electrolyte sheet prepared by the method of the invention can realize lower porosity and no through hole even under the condition of larger area.
Preferably, there are no through-holes perpendicular to the direction of the oxide solid electrolyte sheet, and/or the electrolyte sheet porosity is less than 10%. In the present invention, it should be noted that the porosity is the percentage of the volume of pores in the material to the total volume of the material in the natural state, and indicates that the pores in the material may be open or closed. Also in the present invention porosity is specifically referred to as not being through-holes.
It is a final object of the present invention to protect a battery comprising the oxide solid electrolyte sheet of the present invention.
Preferably, the battery is a lithium ion battery, a lithium air battery, a lithium water battery or a solid oxide fuel cell.
The invention has the following beneficial effects:
1) the invention provides a compact solid electrolyte sheet prepared by double-layer or multi-layer compounding and a preparation method thereof.
2) The method can be used for preparing solid electrolyte sheets with different materials on two sides, and the application range of the oxide solid electrolyte sheet is expanded.
3) In order to ensure good hot-pressing compounding effect, a novel hot-pressing compounding method is adopted, a mode of sharing a soft rubber cushion and a release film is adopted, hot pressing uniformity is ensured, the film can be smoothly stripped after hot pressing is finished, the area span of the film prepared by the method is large, and various sizes can be prepared.
Drawings
FIG. 1 is a solid electrolyte green sheet prepared by the casting coating method of comparative example 1;
FIG. 2 is a schematic view of a hot pressing step;
FIG. 3 is an electron micrograph of the surface of a single-layer LAGP solid electrolyte sheet prepared in comparative example 1 by a curtain coating method (hole defects can be seen on the surface);
FIG. 4 is a cross-sectional electron micrograph of a two-layer composited LAGP dense solid electrolyte sheet of example 1;
FIG. 5 is a photograph of a LLZO dense solid electrolyte sheet after two-layer compounding in example 3;
FIG. 6 is a photograph of a lithium electrode prepared from the resulting oxide solid electrolyte thin film prepared in example 3;
fig. 7 is a graph showing the change in mass of the oxide solid electrolyte thin film prepared in example 3 after being prepared into a lithium electrode.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The embodiment is carried out by adopting a hydraulic press or a pneumatic press in the pressing process, or adopting a pressurizing mould and placing the pressurizing mould in an oven for heating treatment.
Example 1
The present example relates to a NASICON type oxide solid electrolyte LAGP (Li)1.5Al0.5Ge1.5(PO4)3) A method of making a sheet comprising the steps of:
1) dispersing: the NASICON type oxide solid electrolyte LAGP of 10g D50 nm is taken and placed in a ball milling tank, then a certain amount of solvent (ethanol and xylene with the volume ratio of 1:1 in the embodiment) is added, dispersant is added, 80g of zirconium balls are added, and ball milling is carried out for 5 hours.
2) Pulping: pouring a certain amount of ethanol and xylene in a volume ratio of 1:1 into a rubber making cup, adding a plasticizer, adding 1g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. Opening the ball milling tank in the step 1), adding the prepared glue solution, and continuing ball milling for 20 hours.
3) Coating: coating the slurry in the ball milling tank on a substrate, wherein the coating thickness is 100 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 16h to obtain a solid oxide electrolyte membrane green sheet;
4) and (3) laminating: cutting the solid oxide electrolyte film green sheets into the size of 10cm multiplied by 10cm, aligning and bonding the two green sheets together, applying uniform pressure to carry out hot-pressing compounding, and sequentially arranging a silica gel soft rubber pad and a PET release film between the pressing surface on one side of a hot-pressing device and the surface of the adjacent oxide solid electrolyte green sheet to be pressed. The hot pressing pressure is 300kPa, the hot pressing time is 30min, and the hot pressing temperature is 90 ℃; the step schematic diagram is shown in FIG. 2;
5) and (3) sintering: and quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 900 ℃, the sintering time is 9 hours, and after natural cooling, the preparation of a compact solid electrolyte sheet is finished, and the thickness of the compact solid electrolyte sheet is 100 micrometers, and the size of the compact solid electrolyte sheet is 7cm multiplied by 7 cm.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that no sulfur element exists in the water, and proves that Na2SO4There is no diffusion through the dense oxide solid electrolyte sheet into the water, i.e., there are no through holes in the dense solid electrolyte sheet.
The LAGP described in this example was used as a raw material, and an oxide solid electrolyte sheet was prepared by a powder tableting method and sintered under the same conditions. The prepared LAGP solid electrolyte sheet has the room temperature ionic conductivity of 3.3 multiplied by 10-4S/cm～3.6×10-4S/cm；
The room temperature ionic conductivity of the LAGP solid electrolyte sheet prepared in the manner described in example 1 was 3.4X 10-4S/cm～3.6×10-4S/cm。
From the above data, it can be seen that the conductivity of the electrolyte sheet prepared by the method of the present invention is close to that of the sheet prepared by the method commonly used in the art, and the method of the present invention does not affect the conductivity of the sheet.
The cross-sectional electron microscope image of the electrolyte sheet prepared in this example is shown in fig. 4, and as can be seen from fig. 4, the prepared material has no pores.
Example 2
The present example relates to a NASICON type oxide solid electrolyte LATP (Li)1.4Al0.4Ti1.6(PO4)3) A method of making a sheet comprising the steps of:
1) dispersing: the NASICON type oxide solid electrolyte LATP with the particle size of 10g D50 being 300nm is put into a ball milling tank, and then a certain amount of solvent and dispersant are added, and 60g of zirconium balls are added for ball milling for 5 hours.
2) Pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1g of polyvinyl alcohol (PVA), and making rubber by using a homogenizer. Opening the ball milling tank in the step 1), adding the prepared glue solution, and continuing ball milling for 16 hours;
3) coating: coating the slurry in the ball milling tank on a substrate, wherein the coating thickness is 300 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 10h to obtain a solid oxide electrolyte membrane green sheet;
4) and (3) laminating: cutting the solid oxide electrolyte film green sheets into the size of 15cm multiplied by 15cm, aligning and bonding the three green sheets together, applying uniform pressure to carry out hot-pressing compounding, and sequentially arranging a fluorine rubber soft rubber pad and a PET release film between the pressing surface on one side of a hot-pressing device and the surface of the adjacent oxide solid electrolyte green sheet to be pressed. The hot pressing pressure is 500kPa, the hot pressing time is 40min, and the hot pressing temperature is 100 ℃;
5) and (3) sintering: and quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 950 ℃, the sintering time is 8 hours, and after natural cooling, the preparation of a compact solid electrolyte sheet is completed, and the thickness of the compact solid electrolyte sheet is 450 micrometers, and the size of the compact solid electrolyte sheet is 10.5cm multiplied by 10.5 cm.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that no sulfur element exists in the water, and proves that Na2SO4There is no diffusion through the dense oxide solid electrolyte sheet into the water, i.e., there are no through holes in the dense solid electrolyte sheet.
Using LATP described in this example as a raw material, an oxide solid electrolyte sheet was prepared by a powder tablet method, and sintered under the same conditions. The prepared LATP solid electrolyte sheet has the room-temperature ionic conductivity of 2.5 multiplied by 10-4S/cm～2.8×10-4S/cm；
The room temperature ionic conductivity of the LATP solid electrolyte sheet prepared as described in example 2 was 2.4 x 10-4S/cm～2.9×10-4S/cm。
From the above data, it can be seen that the conductivity of the electrolyte sheet prepared by the method of the present invention is close to that of the sheet prepared by the method commonly used in the art, and the method of the present invention does not affect the conductivity of the sheet.
Example 3
The present example relates to a Garnet-type oxide solid electrolyte LLZO (Li)7La3Zr2O12) A method of making a sheet comprising the steps of:
1) dispersing: taking a Garnet type oxide solid electrolyte LLZO (Li) with 10g D50 being 500nm7La3Zr2O12) Putting the mixture into a ball milling tank, then adding a certain amount of solvent, adding a dispersant, adding 90g of zirconium balls, and carrying out ball millingFor 4 hours.
2) Pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1.0g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. Opening the ball milling tank in the step 1), adding the prepared glue solution, and continuing ball milling for 30 hours.
3) Coating: coating the slurry in the ball milling tank on a substrate, wherein the coating thickness is 200 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 12h to obtain a solid oxide electrolyte membrane green sheet;
4) and (3) laminating: cutting the solid oxide electrolyte film green sheets into 7cm multiplied by 7cm, aligning and bonding the two green sheets together, applying uniform pressure to carry out hot-pressing compounding, and sequentially arranging a silica gel soft rubber pad and a PET release film from a pressing surface on one side of a hot-pressing device to the surface of the adjacent oxide solid electrolyte green sheet to be pressed. The hot pressing pressure is 200kPa, the hot pressing time is 30min, and the hot pressing temperature is 90 ℃;
5) and (3) sintering: and quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 10 hours, and after natural cooling, the preparation of a compact solid electrolyte sheet is completed, and the thickness of the compact solid electrolyte sheet is 180 micrometers, and the size of the compact solid electrolyte sheet is 5cm multiplied by 5 cm.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that no sulfur element exists in the water, and proves that Na2SO4Does not diffuse into water through the dense oxide solid electrolyte sheet, i.e., does not haveAnd a through hole.
The LLZO described in this example was used as a raw material to prepare an oxide solid electrolyte sheet by a powder tablet method, and sintered under the same conditions. The prepared LLZO solid electrolyte sheet has the room temperature ionic conductivity of 4.5 multiplied by 10-4S/cm～4.6×10-4S/cm；
The room temperature ionic conductivity of the LLZO solid electrolyte sheet prepared by the method described in example 3 was 4.6X 10-4S/cm～4.7×10-4S/cm。
From the above data, it can be seen that the conductivity of the electrolyte sheet prepared by the method of the present invention is close to that of the sheet prepared by the method commonly used in the art, and the method of the present invention does not affect the conductivity of the sheet.
The LLZO solid electrolyte sheet prepared in the embodiment is used for packaging metal lithium, the structure is 'LLZO solid electrolyte sheet-metal lithium foil-LLZO solid electrolyte sheet', the edge is bonded and sealed by waterproof glue, a lithium electrode protected by solid electrolyte is prepared, after the lithium electrode is placed in deionized water for 3 hours, fire and smoke do not occur (as shown in figure 6), the mass is reduced by only 0.114% before and after the lithium electrode is placed, and then the lithium electrode is placed in the air for 48 hours, and no obvious mass change occurs. (as shown in fig. 7).
Fig. 5 is a photograph of a LLZO dense solid electrolyte sheet after two-layer compounding in example 3.
Example 4
The present embodiment relates to a perovskite-type oxide solid electrolyte LLTO (Li)0.33La0.57TiO3) A method of making a sheet comprising the steps of:
1) dispersing: taking 10g D50 as 600nm perovskite type oxide solid electrolyte LLTO (Li)0.33La0.57TiO3) Putting the mixture into a ball milling tank, then adding a certain amount of solvent, adding a dispersant, adding 70g of zirconium balls, and carrying out ball milling for 6 hours;
2) pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1.5g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. Opening the ball milling tank in the step 1), adding the prepared glue solution, and continuing ball milling for 25 hours;
3) coating: coating the slurry in the ball milling tank on a substrate, wherein the coating thickness is 200 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 15h to obtain a solid oxide electrolyte membrane green sheet;
4) and (3) laminating: cutting the solid oxide electrolyte film green sheets into the size of 20cm multiplied by 20cm, aligning and bonding the two green sheets together, applying uniform pressure to carry out hot-pressing compounding, and sequentially arranging a fluorine rubber soft rubber pad and a PET release film between a pressing surface on one side of a hot-pressing device and the surface of the adjacent oxide solid electrolyte green sheet to be pressed. The hot pressing pressure is 400kPa, the hot pressing time is 20min, and the hot pressing temperature is 95 ℃;
5) and (3) sintering: and quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 1300 ℃, the sintering time is 12 hours, and after natural cooling, the preparation of a compact solid electrolyte sheet is finished, and the thickness of the compact solid electrolyte sheet is 200 mu m, and the size of the compact solid electrolyte sheet is 14cm multiplied by 14 cm.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that no sulfur element exists in the water, and proves that Na2SO4There is no diffusion through the dense oxide solid electrolyte sheet into the water, i.e., there are no through holes in the dense solid electrolyte sheet.
The LLTO material of this example was used to prepare oxide solid electrolyte sheet by powder pressing method and sintered under the same conditions. The prepared LLTO solid electrolyte sheet has the room temperature ionic conductivity of 2.1 multiplied by 10-5S/cm～2.3×10-5S/cm；
The room temperature ionic conductivity of the LLTO solid electrolyte sheet prepared by the method described in example 4 was 2.2X 10-5S/cm。
From the above data, it can be seen that the conductivity of the electrolyte sheet prepared by the method of the present invention is close to that of the sheet prepared by the method commonly used in the art, and the method of the present invention does not affect the conductivity of the sheet.
Example 5
The present example relates to a NASICON type oxide solid electrolyte LAGP (Li)1.5Al0.5Ge1.5(PO4)3) And Garnet type oxide solid electrolyte LLZO (Li)7La3Zr2O12) The preparation method of the composite sheet comprises the following steps:
1) dispersing: taking NASICON type oxide solid electrolyte LAGP (Li) with 10g D50 being 500nm1.5Al0.5Ge1.5(PO4)3) Putting the mixture into a ball milling tank 1, then adding a certain amount of solvent, adding a dispersing agent, adding 80g of zirconium balls, and carrying out ball milling for 5 hours.
2) Pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1.0g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. Opening the ball milling tank 1 in the step 1), adding the prepared glue solution, and continuing ball milling for 16 hours.
3) Coating: coating the slurry in the ball milling tank 1 on a substrate, wherein the coating thickness is 200 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 12h to obtain a LAGP solid oxide electrolyte membrane green sheet;
4) dispersing: taking a Garnet type oxide solid electrolyte LLZO (Li) with 10g D50 being 500nm7La3Zr2O12) Putting the mixture into a ball milling tank 2, then adding a certain amount of solvent, adding a dispersing agent, adding 80g of zirconium balls, and carrying out ball milling for 5 hours.
5) Pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1.0g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. Opening the ball milling tank 2 in the step 1), adding the prepared glue solution, and continuing ball milling for 18 h.
6) Coating: coating the slurry in the ball milling tank 2 on a substrate with the coating thickness of 200 μm, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 12h to obtain a LLZO solid oxide electrolyte membrane green sheet;
6) and (3) laminating: cutting the LAGP solid oxide electrolyte membrane green sheet obtained in the step 3 and the LLZO solid oxide electrolyte membrane green sheet obtained in the step 5 into the size of 7cm multiplied by 7cm respectively, aligning and bonding the LAGP green sheets and the LLZO green sheets together, applying uniform pressure to carry out hot-pressing compounding, and arranging a rubber soft rubber pad and a PET release film between the pressing surface on one side of a hot-pressing device and the surface of the adjacent oxide solid electrolyte membrane green sheet to be pressed in sequence. The hot pressing pressure is 300kPa, the hot pressing time is 25min, and the hot pressing temperature is 100 ℃.
7) And (3) sintering: and quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 10 hours, and after natural cooling, the preparation of a compact solid electrolyte sheet is completed, and the thickness of the compact solid electrolyte sheet is 190 micrometers, and the size of the compact solid electrolyte sheet is 5cm multiplied by 5 cm.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that no sulfur element exists in the water, and proves that Na2SO4There is no diffusion through the dense oxide solid electrolyte sheet into the water, i.e., there are no through holes in the dense solid electrolyte sheet.
The room temperature ionic conductivity of the LAGP/LLZO composite solid electrolyte sheet prepared by the method of the embodiment is 3X 10-4S/cm。
Comparative example 1
This comparative example relates to a method for producing an oxide solid electrolyte sheet, which is different from example 1 in that the operation of pressing is not performed, and only the operation of coating is performed.
1) Dispersing: and (3) putting 10g of NASICON oxide solid electrolyte LAGP into a ball milling tank, then adding a certain amount of solvent, adding a dispersing agent, adding 80g of zirconium balls, and carrying out ball milling for 5 hours.
2) Pulping: pouring a certain amount of solvent into a rubber making cup, adding a plasticizer, adding 1g of polyvinyl butyral (PVB), and making rubber by using a homogenizer. And opening the ball milling tank, adding the prepared glue solution, and continuing ball milling for 20 hours.
3) Coating: and coating the slurry in the ball milling tank on a substrate with the coating thickness of 100 mu m, placing the coated solid electrolyte membrane and the substrate in a solvent environment, drying at normal temperature to obtain a solid electrolyte green sheet, and drying for 16 h.
4) And (3) sintering: cutting the solid electrolyte green sheet into the size of 10cm multiplied by 10cm, transferring the solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 9h, and after natural cooling, finishing the preparation of a compact solid electrolyte sheet, wherein the thickness of the compact solid electrolyte sheet is 50 mu m.
To verify whether the above solid electrolyte sheet has good sealing properties:
cutting the aluminum-plastic film into a square shape, sticking the compact oxide solid electrolyte sheet to the square inner opening of the aluminum-plastic film by using hot melt adhesive, and sealing the four sides. Another aluminum-plastic film is taken and thermally sealed with the aluminum-plastic film stuck with the compact solid electrolyte sheet to form a bag, and Na is injected into the bag2SO4The saturated solution of (a) is then heat sealed. Cleaning the surface with deionized water, soaking in deionized water, standing for 3 days, taking a water sample, and testing the content of the S element in the water by using ICP (inductively coupled plasma). The test result shows that sulfur element appears in water, and proves that Na2SO4By diffusion through a sheet of solid electrolyte into the water, i.e. solid electricityDefects or through holes in the electrolyte sheet. FIG. 1 is a solid electrolyte green sheet prepared in this comparative example; FIG. 3 is an electron micrograph of the surface of a single-layer LAGP solid electrolyte sheet prepared in comparative example 1 by a casting coating method (hole defects can be seen on the surface).
Comparative example 2
This example is different from example 1 only in the process of thermocompression bonding.
The step 4) is specifically as follows:
cutting the solid electrolyte green sheets into 10cm × 10cm, aligning and bonding the two green sheets together, applying uniform pressure to perform hot pressing compounding, wherein the hot pressing pressure is 1kPa, the hot pressing time is 5min, and the hot pressing temperature is 50 ℃. And quickly transferring the hot-pressed composite solid electrolyte green sheet into a muffle furnace for sintering, wherein the sintering temperature is 900 ℃, the sintering time is 9 hours, and after natural cooling, the two layers of solid electrolyte sheets are split and are not compounded together.
Comparative example 3
This comparative example is different from example 1 only in that no soft rubber mat was added during the thermal compression bonding. After the release, it was found that the two green sheets were unevenly combined, and a part of the two green sheets were broken even by an excessive pressure, and further, the composite solid electrolyte green sheet subjected to the hot pressing was rapidly transferred to a muffle furnace to be sintered at a sintering temperature of 900 ℃ for a sintering time of 9 hours, and due to the uneven combination of the green sheets, a part of the composite solid electrolyte green sheet was cracked and curled after the sintering.
Comparative example 4
The comparative example is different from example 1 only in that a release film is not added during the thermal compression bonding. In the course of releasing, the solid electrolyte green sheet was found to have a sticky soft rubber mat, and the solid electrolyte green sheet was broken after releasing.
Comparative example 5
Compared with example 1, the comparative example is different only in that the soft rubber pad and the release film are not added in the hot pressing process. In the course of releasing, the solid electrolyte green sheet was found to be stuck to the contact surface of the thermocompression bonding apparatus, and the solid electrolyte green sheet was broken after releasing.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (8)

1. A method for preparing an oxide solid electrolyte sheet is characterized by comprising the following steps: preparing an oxide solid electrolyte into an oxide solid electrolyte green sheet by a coating method, and laminating two or more layers of the oxide solid electrolyte green sheets into one layer by a hot-pressing mode;
in the hot-pressing process, the hot-pressing device comprises two pressing surfaces, a soft rubber pad and a release film are sequentially arranged from one pressing surface to the adjacent oxide solid electrolyte green sheet to be pressed, and the contact surface of the release film and the oxide solid electrolyte green sheet is easy to peel;
the soft rubber cushion is made of one of silica gel, natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, ethylene propylene rubber, chloroprene rubber, fluororubber, TPU, TPE, TPR, EVA and POE, and/or the peeling force range of the release film is 0.01-0.5N/25 mm;
adding a binder into the oxide solid electrolyte in the process of preparing the oxide solid electrolyte green sheet, wherein the weight percentage of the binder is 5-15%, and for green sheets with the binder of PVB or PVA and the thickness of 100-300 μm, the pressure in the pressing process is controlled to be 300-500 kPa, the hot pressing time is 30-40 min, and the hot pressing temperature is 85-105 ℃;
the oxide solid electrolyte comprises one or more of NASICON type solid electrolyte, Garnet type solid electrolyte, perovskite type solid electrolyte and LISICON type solid electrolyte.
2. The method for preparing the composite material according to claim 1, wherein the release film is one of a PE release film, a PET release film or an OPP release film.
3. The production method according to claim 1 or 2, wherein the oxide solid electrolytes used in two or more of the oxide solid electrolyte green sheets are the same or different.
4. An oxide solid electrolyte sheet produced by the production method according to any one of claims 1 to 3.
5. The oxide solid electrolyte sheet according to claim 4, characterized in that the area of the oxide solid electrolyte sheet is 1cm2~400cm2And/or the thickness of the oxide solid electrolyte sheet is 30 μm to 500 μm.
6. The oxide solid electrolyte sheet according to claim 4 or 5, wherein a direction perpendicular to the oxide solid electrolyte sheet has no through-holes and/or an electrolyte sheet porosity of less than 10%.
7. A battery comprising the oxide solid electrolyte sheet according to any one of claims 4 to 6.
8. The battery of claim 7, wherein the battery is a lithium ion battery, a lithium air battery, a lithium water battery, or a solid oxide fuel cell.
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