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CN118398879A - Flattening method for ceramic solid electrolyte film - Google Patents

Flattening method for ceramic solid electrolyte film Download PDF

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Publication number
CN118398879A
CN118398879A CN202410674375.XA CN202410674375A CN118398879A CN 118398879 A CN118398879 A CN 118398879A CN 202410674375 A CN202410674375 A CN 202410674375A CN 118398879 A CN118398879 A CN 118398879A
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solid electrolyte
lithium
film
oxide
sintering
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陈霖
卢勇光
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Shenzhen Xinjie Energy Technology Co ltd
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Shenzhen Xinjie Energy Technology 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
    • 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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a ceramic solid electrolyte film and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Mixing a solid electrolyte blank with a fiberizable polymer, fibrillating said polymer and uniformly mixing with said solid electrolyte blank; (2) Carrying out hot pressing treatment on the mixture obtained in the step (1) to a preset thickness to obtain a solid electrolyte green film; (3) And (3) sintering the solid electrolyte green film obtained in the step (2) at a high temperature to obtain a solid electrolyte film. The preparation method of the solid electrolyte film simplifies the preparation process, and the prepared solid electrolyte film has high ceramic content, compact structure and high ionic conductivity.

Description

Flattening method for ceramic solid electrolyte film
Technical Field
The invention relates to a ceramic solid electrolyte film and a preparation method thereof, comprising a flattening treatment step of the electrolyte film. The invention also relates to application of the ceramic solid electrolyte film in a solid-state battery, and a solid-state lithium metal battery comprising the ceramic solid electrolyte film.
Background
With the rapid development of renewable energy sources (such as solar and wind), the storage demand for electrical energy is also increasing. However, the conventional liquid battery has problems such as limited energy density, insufficient safety, short life, and long charging time, which become particularly remarkable in response to the demands of modern society for high performance, sustainable and safe energy storage.
Lithium metal batteries are considered as one potential solution to the energy storage problem. Lithium metal has a higher theoretical energy density and lower voltage loss, and thus can achieve a higher energy storage density and longer endurance. However, conventional liquid lithium metal batteries have safety problems due to the growth of lithium dendrites and instability of the liquid electrolyte, which limits their wide application.
Solid-state lithium metal batteries are a new battery technology that uses solid-state electrolytes instead of conventional liquid electrolytes. The rise of ceramic solid electrolyte technology solves many of the problems caused by liquid electrolytes. The ceramic electrolyte material has the characteristics of high ion conductivity, high temperature resistance, chemical stability and the like, can prevent the growth of lithium dendrites, and improves the safety of the battery. In addition, the solid state electrolyte can achieve a higher operating temperature range, thereby improving the performance of the battery in extreme environments.
However, the ceramic electrolyte needs to be sintered at a high temperature of more than 1000 ℃ in the preparation process, and the ceramic film is easy to deform and bend in the process, so that the uneven solid electrolyte film cannot be assembled. Therefore, improving the flatness of the electrolyte film is a key element for commercialization of ceramic solid electrolyte.
Disclosure of Invention
The invention aims to solve the technical problems that the solid electrolyte film produced by the prior art has uneven condition and the uniformity of the product is to be improved.
In order to solve the technical problems, the invention provides a preparation method of a solid electrolyte film, which is characterized in that a flattening sintering step is added after a densification sintering step of the solid electrolyte film, and the flatness of the electrolyte film can be improved while the defects of the electrolyte film are reduced through flattening heat treatment. The solid electrolyte film prepared by the preparation method has the advantages of flat surface, compact structure and high ionic conductivity.
The first aspect of the present invention provides a method for preparing a solid electrolyte film, which is characterized in that the method comprises the following flattening sintering steps:
And sintering the sintered solid electrolyte film at a high temperature under the condition of applying mechanical pressure to obtain the flattened solid electrolyte film.
In some embodiments, the mechanical pressure in the flattening sintering step is in the range of 1 to 500Pa, preferably 10 to 400Pa, more preferably 20 to 250Pa, still more preferably 50 to 150Pa.
In some embodiments, the sintered solid electrolyte film has a thickness of 1 to 600 μm, preferably 5 to 300 μm, more preferably 10 to 200 μm. According to specific embodiments, the thickness of the sintered solid electrolyte thin film may be 1 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, or any thickness within the above range.
In some embodiments, the flattening sintering temperature is higher than the densification sintering temperature, i.e., the sintering temperature at which the sintered solid electrolyte thin film is prepared from the solid electrolyte green film. Specifically, the flattening sintering temperature may be 900 to 1400 ℃, preferably 1300 to 1350 ℃. The temperature of the planarizing sintering is related to the chemical composition of the solid electrolyte.
In some embodiments, the flattening sintering has a ramp rate of 5 to 20 ℃/min, preferably 10 ℃/min; the holding time after reaching the flattening sintering temperature is 5 to 30 minutes, preferably 10 minutes.
In some embodiments, the mechanical pressure is applied during the planarizing sintering step by placing a setter plate over the sintered solid electrolyte film.
In some embodiments, in the flattening sintering step, the flattening solid electrolyte thin film is obtained by performing high-temperature sintering in a state where the sintered solid electrolyte thin film is placed between two setter plates.
In some embodiments, in the flattening sintering step, the surface of the setter plate in contact with the solid electrolyte membrane is a flat surface.
In some embodiments, the setter plate comprises one or more materials selected from magnesium oxide, zirconium oxide, aluminum oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum titanium oxide, lithium germanium aluminum lithium phosphate, or lithium titanium aluminum lithium phosphate. In some embodiments, the material of the setter plate is magnesium oxide or a lithium-containing material, preferably the same material as the solid electrolyte membrane material.
In some embodiments, the solid state electrolyte is an oxide solid state electrolyte, such as an oxide solid state electrolyte selected from the group consisting of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum titanium oxide, lithium germanium aluminum lithium phosphate, or lithium titanium aluminum phosphate.
In some embodiments, the sintered solid electrolyte film is obtained by:
(1) Mixing a solid electrolyte blank with a fiberizable polymer, fibrillating said polymer and uniformly mixing with said solid electrolyte blank;
(2) Carrying out hot pressing treatment on the mixture obtained in the step (1) to a preset thickness to obtain a solid electrolyte green film;
(3) And (3) sintering the solid electrolyte green film obtained in the step (2) at a high temperature to obtain the sintered solid electrolyte film.
In some embodiments, the fiberizable polymer comprises at least one of Polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), and Polyimide (PI). In a most preferred embodiment, the fibrillatable polymer is polytetrafluoroethylene.
In some embodiments, in step (1), the solid electrolyte blank is present in an amount of 80 to 99.9wt%, preferably 90 to 99wt%, more preferably 95 to 99wt%.
In some embodiments, in step (1), the fibrillatable polymer is present in an amount of 0.1 to 20wt%, preferably 1 to 10wt%, more preferably 1 to 5wt%.
In some embodiments, the method of fibrillating the polymer in step (1) is selected from at least one of the following:
(1) Grinding the polymer with the solid electrolyte blank;
(2) Shearing the polymer with the solid electrolyte blank at high speed;
(3) Carrying out heating stretching treatment on the polymer;
(4) The polymer is jet milled with the solid electrolyte blank.
It should be understood that the method of fiberizing a polymer is not particularly limited in the present invention, as long as the method of fiberizing a fiberizable polymer is included in the scope of the present invention.
In some embodiments, the hot pressing treatment of step (2) is one or more hot rolls using a roll press.
In some embodiments, the predetermined thickness in step (2) is 1 to 1000 μm, preferably 5 to 500 μm, more preferably 20 to 300 μm, still more preferably 50 to 200 μm. According to specific embodiments, the predetermined thickness of the solid electrolyte green film may be 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, 800 μm, 1000 μm, or any thickness within the above range.
In some embodiments, the step (3) causes the polymer in the solid electrolyte green film to decompose, preferably completely.
In some embodiments, the sintering temperature in step (3) is 800 to 1200 ℃. The sintering temperature depends on the chemical composition of the solid electrolyte. For example, for LLZO, LLZTO, LLAZO and LLGZO, the sintering temperature is preferably 1050-1200 ℃; for LLTO, the sintering temperature is preferably 1100-1200 ℃; for LAGP, the sintering temperature is preferably 800-900 ℃; for LATP, the sintering temperature is preferably 900 to 1000 ℃.
In some embodiments, in step (3), the rate of temperature increase is from 5 to 20 ℃/min, preferably 10 ℃/min; the sintering time is 6 to 24 hours, preferably 12 hours.
In some embodiments, when mixing the solid electrolyte blank with the fiberizable polymer in step (1), an excess of a precursor of lithium element is additionally added, wherein the precursor of lithium element is selected from the group consisting of LiOH H-H 2 O and Li 3PO4.
In some embodiments, the molar excess ratio of the precursor of lithium element in step (1) is 1% to 50%, wherein
When the solid electrolyte is selected from lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide or lithium lanthanum titanium oxide, the precursor of the lithium element is LiOH H 2 O, and the molar excess ratio of the precursor is 20-50%, preferably 30-50%;
When the solid electrolyte is selected from lithium aluminum germanium phosphate or lithium aluminum titanium phosphate, the precursor of the lithium element is Li 3PO4, and the molar excess ratio thereof is 1-20%, preferably 5-15%.
In some embodiments, the method for preparing the solid electrolyte blank in the step (1) includes the following steps:
(a1) According to the chemical composition of the solid electrolyte, mixing precursors of each element and excessive precursors of lithium element with a solvent, performing ball milling treatment, and then drying, wherein the precursors of lithium element are selected from LiOH.H 2 O and Li 3PO4;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
In some embodiments, the molar excess ratio of the precursor of lithium element in step (a 1) is 1% to 50%, wherein
When the solid electrolyte is selected from lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide or lithium lanthanum titanium oxide, the precursor of the lithium element is LiOH H 2 O, and the molar excess ratio of the precursor is 20-50%, preferably 30-50%;
When the solid electrolyte is selected from lithium aluminum germanium phosphate or lithium aluminum titanium phosphate, the precursor of the lithium element is Li 3PO4, and the molar excess ratio thereof is 1-20%, preferably 5-15%.
In some embodiments, the method of preparing a solid electrolyte thin film includes adding an excess of a precursor of lithium element in step (a 1) and adding an excess of a precursor of lithium element in step (1), wherein the sum of the molar excess ratio of the precursor of lithium element in step (a 1) and the precursor of lithium element in step (1) is 1% to 50%, wherein
When the solid electrolyte is selected from lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide or lithium lanthanum titanium oxide, the precursor of the lithium element is LiOH H 2 O, and the total excessive proportion of the mole number is 20-50%, preferably 30-50%;
when the solid electrolyte is selected from lithium aluminum germanium phosphate or lithium aluminum titanium phosphate, the precursor of the lithium element is Li 3PO4, and the total excess ratio of the molar number thereof is 1% to 20%, preferably 5% to 15%.
In a second aspect, the present invention provides a solid electrolyte membrane prepared by the preparation method of the first aspect of the present invention.
A third aspect of the present invention provides the use of a solid electrolyte membrane according to the second aspect of the invention as described above in a solid state lithium metal battery.
A fourth aspect of the present invention provides a solid state lithium metal battery comprising a solid state electrolyte membrane according to the second aspect of the present invention described above.
The preparation method of the solid electrolyte film has simple process, and the planarization of the solid electrolyte film is spontaneously completed under the action of pressure to form the solid electrolyte film with flat surface, compact structure and high ion conductivity.
Drawings
Fig. 1 shows a schematic diagram of flattening sintering using a setter plate in the preparation method of the ceramic solid electrolyte film of the present invention.
Fig. 2 shows a flow chart of a method for preparing a ceramic solid electrolyte film according to the present invention.
Fig. 3 shows a physical diagram of a solid electrolyte thin film of example 1 of the present invention.
Fig. 4 shows a physical diagram of a solid electrolyte thin film of comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following detailed description. Unless otherwise defined, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The numerical limits or ranges stated herein include the endpoints, and specifically include all values and subranges within the numerical limits or ranges.
The first aspect of the present invention provides a method for preparing a solid electrolyte film, which is characterized in that the method comprises the following flattening sintering steps:
And sintering the sintered solid electrolyte film at a high temperature under the condition of applying mechanical pressure to obtain the flattened solid electrolyte film.
In some embodiments, the mechanical pressure in the flattening sintering step is in the range of 1 to 500Pa, preferably 10 to 400Pa, 20 to 250Pa, more preferably 50 to 150Pa. The mechanical pressure in the flattening sintering step may be about 1Pa、10Pa、20Pa、30Pa、40Pa、50Pa、60Pa、70Pa、80Pa、90Pa、100Pa、110Pa、120Pa、130Pa、140Pa、150Pa、160Pa、170Pa、180Pa、190Pa、200Pa、210Pa、220Pa、230Pa、240Pa、250Pa、260Pa、270Pa、280Pa、290Pa、300Pa、350Pa、400Pa、450Pa、500Pa, or any pressure within the above ranges, depending on the particular embodiment. In the present invention, it is not necessary to apply a great mechanical pressure to the sintered solid electrolyte membrane. Because the solid electrolyte film is brittle at normal temperature, the uneven solid electrolyte film is crushed if the pressure is too high. The solid electrolyte film is softened at high temperature, has certain deformability, and can be gradually flattened under external pressure without fragmentation.
In some embodiments, the sintered solid electrolyte film has a thickness of 1 to 600 μm, preferably 5 to 300 μm, more preferably 10 to 200 μm. According to particular embodiments, the thickness of the sintered solid electrolyte film may be about 1 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, or any thickness within the above ranges.
In some embodiments, the flattening sintering temperature is higher than the densification sintering temperature, i.e., the sintering temperature at which the sintered solid electrolyte thin film is prepared from the solid electrolyte green film. Specifically, the flattening sintering temperature is 900-1400 ℃, preferably 1300-1350 ℃. The temperature of the planarizing sintering is related to the chemical composition of the solid electrolyte. For example, for LLZO, LLZTO, LLAZO and LLGZO, the flattening sintering temperature is preferably 1200-1400 ℃; for LLTO, the flattening sintering temperature is preferably 1300-1400 ℃; for LAGP, the flattening sintering temperature is preferably 800-1000 ℃; for LATP, the flattening sintering temperature is preferably 900-1100 ℃. The inventors have found through research that, in order to achieve the purpose of flattening the solid electrolyte film, the temperature required for secondary flattening sintering is related to the heat preservation time, and in a certain temperature range, the higher the temperature, the shorter the heat preservation time is required. In order to improve the production efficiency and avoid the loss caused by the volatilization of lithium at a high temperature, in the solid electrolyte thin film manufacturing method of the present invention, the temperature of flattening sintering is set higher than the temperature of densification sintering.
In some embodiments, the flattening sintering has a ramp rate of 5 to 20 ℃/min, preferably 10 ℃/min; the holding time after reaching the flattening sintering temperature is 5 to 30 minutes, preferably 10 minutes.
In some embodiments, the mechanical pressure is applied during the planarizing sintering step by placing a setter plate over the sintered solid electrolyte film.
In some embodiments, the setter plates have a thickness of 0.2-10mm, preferably 0.5-5mm, more preferably 1-2mm, and the mechanical pressure is generated by the weight of the setter plates. The thickness of the setter plates may be about 0.2mm、0.5mm、0.8mm、1mm、1.1mm、1.2mm、1.3mm、1.4mm、1.5mm、1.6mm、1.8mm、2mm、2.2mm、2.5mm、3mm、3.5mm、4mm、5mm、6mm、7mm、8mm、9mm、10mm, a or any thickness within the above ranges, depending on the particular embodiment.
In some embodiments, in the flattening sintering step, the flattening solid electrolyte thin film is obtained by performing high-temperature sintering in a state where the sintered solid electrolyte thin film is placed between two setter plates. Fig. 1 is a schematic view showing a state in which a solid electrolyte film is sandwiched between two setter plates.
In some embodiments, in the flattening sintering step, the surface of the setter plate in contact with the solid electrolyte membrane is a flat surface.
In the invention, in the flattening sintering step, the solid electrolyte film is softened at a high temperature, has a certain deformability, is deformed under the action of mechanical pressure applied to the contacted flat surface, and is gradually flattened to form a flat surface structure.
In some embodiments, the setter plate comprises one or more materials selected from magnesium oxide, zirconium oxide, aluminum oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum titanium oxide, lithium germanium aluminum lithium phosphate, or lithium titanium aluminum lithium phosphate. In some embodiments, the material of the setter plate is a magnesium oxide or lithium-containing material, preferably the same material as the solid electrolyte membrane material. The material of the setter plate has a certain influence on the ion conductivity of the prepared solid electrolyte. Lithium (e.g., li 2 O) in a solid electrolyte may volatilize at high temperatures. If the material of the setter plate is capable of absorbing the volatilized lithium element (Li 2 O), the second phase of the solid electrolyte film, which does not conduct lithium ions, increases, resulting in a decrease in ion conductivity. In contrast, if the material of the setter plate itself contains a large amount of lithium element, a lithium-rich atmosphere can be formed on the surface of the film at a high temperature, and the formation of the second phase in the solid electrolyte film can be suppressed.
The flattening sintering step of the present invention is applicable to solid electrolyte thin films prepared by any known method, including casting sintering method, dry sintering method, and the like.
The method for producing the solid electrolyte thin film of the present invention is not particularly limited as long as it is a ceramic solid electrolyte that can be produced by high-temperature sintering.
In some embodiments, the solid state electrolyte is selected from the group consisting of Lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Zirconium Tantalum Oxide (LLZTO), lithium lanthanum zirconium aluminum oxide (LLAZO), lithium lanthanum zirconium gallium oxide (LLGZO), lithium Lanthanum Titanium Oxide (LLTO), lithium germanium aluminum phosphate (LAGP), or lithium titanium aluminum phosphate (LATP).
In certain embodiments, the Lithium Lanthanum Zirconium Oxide (LLZO) has the chemical formula Li 7La3Zr2O12;
lithium Lanthanum Zirconium Tantalum Oxide (LLZTO) has the chemical formula Li 7-xLa3Zr2-xTaxO12, for example, when x=0.5, it is Li 6.5La3Zr1.5Ta0.5O12, and when x=0.6, it is Li 6.4La3Zr1.4Ta0.6O12;
lithium lanthanum zirconium aluminum oxide (LLAZO) has the chemical formula Li 7-3xLa3AlxZr2O12, for example, when x=0.1, the chemical formula is Li 6.7La3Al0.1Zr2O12, and when x=0.2, the chemical formula is Li 6.4La3Al0.2Zr2O12;
Lithium lanthanum zirconium gallium oxide (LLGZO) has the chemical formula Li 7-3xLa3GaxZr2O12, for example, when x=0.2, it is Li 6.4La3Ga0.2Zr2O12, and when x=0.3, it is Li 6.1La3Ga0.3Zr2O12;
Lithium Lanthanum Titanium Oxide (LLTO) has a chemical formula of Li 2-3xLaxTiO3, for example, when x=0.4, li 0.8La0.4TiO3, and when x=0.5, li 0.5La0.5TiO3;
Lithium Aluminum Germanium Phosphate (LAGP) has the chemical formula Li 1.5Al0.5Ge1.5(PO4)3;
the chemical formula of Lithium Aluminum Titanium Phosphate (LATP) is Li 1.3Al0.3Ti1.7(PO4)3.
Those skilled in the art will appreciate that the solid state electrolytes listed above are for illustrative purposes only and the scope of the present invention is not limited thereto. For example, LLZTO, LLAZO, and the like electrolytes are element doped forms of garnet-type solid state electrolytes LLZO, having similar properties in some respects, and can be prepared into solid state electrolyte films by the methods of the present invention. Other element doped forms of the listed solid state electrolytes and other solid state electrolytes not listed can also be prepared into films by the method of the present invention.
In some embodiments, the sintered solid electrolyte film is obtained by the following dry sintering step:
(1) Mixing a solid electrolyte blank with a fiberizable polymer, fibrillating said polymer and uniformly mixing with said solid electrolyte blank;
(2) Carrying out hot pressing treatment on the mixture obtained in the step (1) to a preset thickness to obtain a solid electrolyte green film;
(3) And (3) sintering the solid electrolyte green film obtained in the step (2) at a high temperature to obtain a solid electrolyte film.
In some embodiments, the basic flow of the method of preparing a solid electrolyte film including dry preparation of a green film, primary densification sintering, and secondary planarization sintering is shown in fig. 2.
In some embodiments, the fiberizable polymer comprises at least one of Polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), and Polyimide (PI). In the present invention, the fiberizable polymer is not particularly limited as long as it is a polymer that can be fiberized and can be decomposed at high temperature. In a most preferred embodiment, the fibrillatable polymer is Polytetrafluoroethylene (PTFE). The advantage of using polytetrafluoroethylene is that the polymer has a larger molecular weight, can form longer fibrils in the fiberization process, is easy to form a polymer network in the hot pressing treatment, and is beneficial to aggregation of electrolyte powder and formation of a compact electrolyte membrane. Similarly, when other polymers are used, it is advantageous to use polymers of greater molecular weight.
In some embodiments, in step (1), the solid electrolyte blank is present in an amount of 80 to 99.9wt%, preferably 90 to 99wt%, more preferably 95 to 99wt%. For example, the solid electrolyte blank may be present in an amount of about 80wt％、85wt％、88wt％、90wt％、91wt％、92wt％、93wt％、94wt％、95wt％、95.5wt％、96wt％、96.5wt％、97wt％、97.5wt％、98wt％、98.5wt％、99wt％、99.5wt％、99.9wt％ a, etc. According to the preparation method of the invention, the higher the content of the solid electrolyte blank, the easier the solid electrolyte blank is sintered into a compact ceramic film.
In some embodiments, in step (1), the fibrillatable polymer is present in an amount of 0.1 to 20wt%, preferably 1 to 10wt%, more preferably 1 to 5wt%. For example, the fiberizable polymer content may be about 0.1wt％、0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％、4wt％、4.5wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、12wt％、15wt％、20wt％, etc. According to the preparation method of the invention, the content of the fiberizable polymer is small, and the dense solid electrolyte film can be obtained by sintering.
In some embodiments, in step (1), the solid electrolyte blank and the fiberizable polymer are present in an amount that adds up to 100 weight percent.
In some embodiments, the method of fibrillating the polymer in step (1) is selected from at least one of the following:
(1) Grinding the polymer with the solid electrolyte blank;
(2) Shearing the polymer with the solid electrolyte blank at high speed;
(3) Carrying out heating stretching treatment on the polymer;
(4) The polymer is jet milled with the solid electrolyte blank.
It should be understood that the method of fiberizing a polymer is not particularly limited in the present invention, as long as the method of fiberizing a fiberizable polymer is included in the scope of the present invention.
In some embodiments, the hot pressing treatment of step (2) is one or more hot rolls using a roll press. In some preferred embodiments, in step (2), the mixture obtained in step (1) is subjected to multiple rolling under heating using a roll press, and the green film thickness is gradually reduced, thereby obtaining a solid electrolyte green film having a preset thickness. The temperature of the hot rolling is not particularly limited as long as it is a temperature favorable for processing, for example, 50 to 150 ℃, 60 to 120 ℃, 70 to 100 ℃, 75 to 90 ℃, and the like.
In some embodiments, the predetermined thickness in step (2) is 1 to 1000 μm, preferably 5 to 500 μm, more preferably 20 to 300 μm, still more preferably 50 to 200 μm. According to specific embodiments, the predetermined thickness of the solid electrolyte green film may be about 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, 800 μm, 1000 μm, or any thickness within the above range.
In some embodiments, the step (3) causes the polymer in the solid electrolyte green film to decompose, preferably completely. By high temperature sintering in step (3), the polymer component in the solid electrolyte green film can be substantially completely decomposed to form a solid electrolyte thin film of nearly 100% ceramic. The preparation method ensures that the solid electrolyte film has compact structure and high ion conductivity.
In some embodiments, the sintering temperature in step (3) is 800 to 1200 ℃. The sintering temperature depends on the chemical composition of the solid electrolyte. For example, for LLZO, LLZTO, LLAZO and LLGZO, the sintering temperature is preferably 1050-1200 ℃; for LLTO, the sintering temperature is preferably 1100-1200 ℃; for LAGP, the sintering temperature is preferably 800-900 ℃; for LATP, the sintering temperature is preferably 900 to 1000 ℃.
In some embodiments, in step (3), the rate of temperature increase is from 5 to 20 ℃/min, preferably from 5 to 10 ℃/min; the sintering time is 6 to 24 hours, preferably 12 hours.
Since lithium in the solid electrolyte blank is volatilized at high temperatures, it is preferable to include a portion of the excess lithium in the mixture to be sintered in order to obtain a solid electrolyte film of the desired stoichiometric ratio. For example, excess lithium may be contained in the solid electrolyte blank. Alternatively, excess lithium may be additionally added when mixing the solid electrolyte blank with the fiberizable polymer in said step (1).
Thus, in some specific embodiments, when mixing the solid electrolyte blank with the fiberizable polymer in step (1), an excess of a precursor of lithium element is additionally added, wherein the precursor of lithium element is selected from the group consisting of lioh.h 2 O and Li 3PO4.
Furthermore, in some specific embodiments, the method for preparing a solid electrolyte blank in step (1) includes the steps of:
(a1) According to the chemical composition of the solid electrolyte, mixing precursors of each element and excessive precursors of lithium element with a solvent, performing ball milling treatment, and then drying, wherein the precursors of lithium element are selected from LiOH.H 2 O and Li 3PO4;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
In addition, in some embodiments, the method of preparing a solid electrolyte thin film includes adding an excess of a precursor of lithium element in step (a 1) and adding an excess of a precursor of lithium element in step (1). In this case, the excess ratio of the number of moles of the precursor of lithium element in the step (a 1) and the step (1) should be calculated in combination.
In the context of the present invention, "excess" means that the number of moles of lithium element precursor charged during the preparation is greater than the molar content of lithium element in the solid electrolyte calculated on the basis of the chemical composition of the solid electrolyte in terms of the number of moles of other element precursors (e.g., lanthanum source, zirconium source, tantalum source, etc.). For example, when preparing LLZTO solid electrolyte having a chemical formula of Li 7-xLa3Zr2-xTaxO12, if the mole ratio of lithium, lanthanum, zirconium, tantalum elements in the lithium source, lanthanum source, zirconium source, tantalum source, li: la: zr: ta=m: 3:2-x: x, the mole ratio of lithium elements in the lithium source, M, is greater than 7-x; the percentage excess was calculated as (M- (7-x))/(7-x).
In a specific embodiment of the present invention, the molar excess ratio (or total excess ratio) of the lithium element is 1% to 50% regardless of whether the precursor of the lithium element is added in step (a 1), in step (1), or in both step (a 1) and step (1). According to a specific embodiment, the excess ratio of the number of moles of the precursor of the lithium element may be about 1％、3％、5％、8％、10％、12％、14％、16％、18％、20％、22％、22％、24％、25％、26％、28％、30％、31％、32％、33％、34％、35％、36％、37％、38％、39％、40％、41％、42％、43％、44％、45％、46％、48％、50％, or any ratio within the above range. Specifically, when the solid electrolyte is selected from lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide or lithium lanthanum titanium oxide, the precursor of the lithium element is lioh·h 2 O, and the molar excess ratio (or total excess ratio) thereof is 20% to 50%, preferably 30% to 50%; when the solid electrolyte is selected from lithium aluminum germanium phosphate or lithium aluminum titanium phosphate, the precursor of the lithium element is Li 3PO4, and the molar excess ratio (or total excess ratio) thereof is 1% to 20%, preferably 5% to 15%. The inventor finds that excessive lithium can be added during the preparation of solid electrolyte blanks and the preparation of green films, and the adding time of excessive lithium sources basically has no influence on the technical effect when the total amount of excessive proportion is kept at a certain time.
Since Li in the crystal lattice volatilizes during high-temperature heating to cause the transformation of the crystal phase, a second phase containing no lithium ions is generated, so that the ion conductivity is reduced, and the excessive supply of the lithium source can prevent the transformation of the crystal phase and improve the ion conductivity of the prepared solid electrolyte membrane. The inventor confirms through experiments that the excessive lithium source does not influence the phase structure of the solid electrolyte through the preparation method of the solid electrolyte. On the one hand, the volatilization of lithium element is more due to the high temperature treatment process, and the added excessive lithium source can compensate the volatilization amount of lithium. On the other hand, a small amount of lithium residues can form a lithium-rich phase at the grain boundary, so that the solid electrolyte grains are better connected, and the compactness after sintering is improved.
In a second aspect, the present invention provides a solid electrolyte membrane prepared by the preparation method of the first aspect of the present invention.
A third aspect of the present invention provides the use of a solid electrolyte membrane according to the second aspect of the invention as described above in a solid state lithium metal battery.
A fourth aspect of the present invention provides a solid state lithium metal battery comprising a solid state electrolyte membrane according to the second aspect of the present invention described above.
Examples
The present invention is described in detail below by way of examples, which are not intended to limit the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified.
In the following examples, PTFE was purchased from Keratin, had a weight average molecular weight of 10 6 g/mol and a median particle diameter of 0.3. Mu.m.
Preparation example 1: preparation of LLZTO solid electrolyte blank
To prepare LLZTO solid electrolyte of the formula Li 6.4La3Zr1.4Ta0.6O12, the following raw materials are weighed according to the stoichiometric ratio and molar ratio of the lithium source excess to a certain ratio: lithium hydroxide monohydrate (LiOH H 2 O), lanthanum oxide (La 2O3), zirconium oxide (ZrO 2), and tantalum oxide (Ta 2O5).
And putting the weighed precursor powder of each element into a zirconia ball milling tank, adding zirconia ball milling beads with the weight of five times of the weight of the raw materials, adding isopropanol with the same mass, performing wet ball milling for 3 hours at 500rpm, and uniformly mixing to obtain mixed powder. And then the mixed powder is placed in an oven for drying, so that the solvent isopropanol is completely removed.
And (3) placing the dried powder into a muffle furnace, calcining for 12 hours at 900 ℃, heating and cooling at a speed of 5 ℃/min, and cooling to obtain LLZTO solid electrolyte powder blank.
Preparation example 2: preparation of LLZTO solid electrolyte green film
95 Parts by mass of the LLZTO powder blanks obtained in preparation example 1 (LiOH. H 2 O excess 40% in the preparation of the blanks) and 5 parts by mass of PTFE powder were weighed separately, mixed uniformly, and put into a grinder, and fully ground at 200rpm for 30 minutes to fibrillate PTFE and fully mix with LLZTO powder to obtain a mixed block of fibrillated PTFE and LLZTO.
The above mixed block was rolled at 80℃for a plurality of times using a roll press to gradually reduce the thickness of the green film, and finally an electrolyte green film having a thickness of 100 μm was obtained.
Example 1: preparation of LLZTO solid electrolyte film
And (3) primary densification sintering: the LLZTO solid electrolyte green film obtained in preparation example 2 is placed in a magnesium oxide crucible, put in a muffle furnace and sintered at high temperature in air, wherein the sintering conditions are as follows: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 1150 ℃ and the heat preservation time is 12 hours; the cooling rate is 5 ℃/min. After cooling, a sintered LLZTO solid electrolyte film was obtained.
Secondary flattening and sintering: a magnesium oxide setter plate 60mm long, 40mm wide and 1.5mm thick was used. The pressure generated by the setter plate is about 50-150Pa depending on the size of the solid electrolyte film. Placing the sintered LLZTO solid electrolyte film horizontally between two magnesium oxide burning plates, placing the magnesium oxide burning plates into a muffle furnace, and performing secondary high-temperature heat treatment in the air, wherein the heat treatment conditions are as follows: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 1320 ℃ and the heat preservation time is 10min; the cooling rate is 5 ℃/min. After cooling, a flattened LLZTO solid electrolyte film was obtained.
Example 2: preparation of LLZTO solid electrolyte film
In this example, a planarized LLZTO solid electrolyte film was obtained in the same steps and conditions as in example 1, except that the magnesium oxide setter plate was replaced with LLZTO setter plates (the setter plate size was unchanged, the same applies below). The pressure generated by the setter plate is about 75-220Pa depending on the size of the solid electrolyte membrane.
Example 3: preparation of LLZTO solid electrolyte film
In this example, a flattened LLZTO solid electrolyte film was obtained in the same procedure and conditions as in example 1, except that the magnesium oxide setter plate was replaced with an aluminum oxide setter plate. The pressure generated by the setter plate is about 50-150Pa depending on the size of the solid electrolyte film.
Example 4: preparation of LLZTO solid electrolyte film
In this example, a flattened LLZTO solid electrolyte film was obtained in the same procedure and conditions as in example 1, except that the magnesia setter plate was replaced with a zirconia setter plate. The pressure generated by the setter plate is about 80-250Pa depending on the size of the solid electrolyte film.
Example 5: preparation of LLZTO solid electrolyte film
In this example, a planarized LLZTO solid electrolyte thin film was obtained in the same steps and conditions as in example 1, except that the magnesium oxide setter plate was replaced with a LLGZO setter plate. The pressure generated by the setter plate is about 70-210Pa depending on the size of the solid electrolyte membrane.
Example 6: preparation of LLZTO solid electrolyte film
In this example, a planarized LLZTO solid electrolyte thin film was obtained in the same steps and conditions as in example 1, except that the magnesium oxide setter plate was replaced with a LLAZO setter plate. The pressure generated by the setter plate is about 65-200Pa depending on the size of the solid electrolyte membrane.
Example 7: preparation of LLZTO solid electrolyte film
In this example, a flattened LLZTO solid electrolyte film was obtained in the same procedure and conditions as in example 2, except that the final thickness of the electrolyte green film in preparation example 2 was changed to 60 μm.
Example 8: preparation of LLZTO solid electrolyte film
In this example, a flattened LLZTO solid electrolyte film was obtained in the same procedure and conditions as in example 2, except that the final thickness of the electrolyte green film in preparation example 2 was changed to 150 μm.
Example 9: preparation of LATP solid electrolyte film
In this example, a LATP electrolyte green film having a final thickness of 100 μm was obtained in the same steps and conditions as in preparation example 2, except that LLZTO powder blank in preparation example 2 was replaced with LATP powder blank.
And (3) primary densification sintering: placing the LATP electrolyte green film in a magnesium oxide crucible, placing the magnesium oxide crucible in a muffle furnace, and sintering at high temperature in air under the following sintering conditions: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 950 ℃ and the heat preservation time is 12 hours; the cooling rate is 5 ℃/min. After cooling, a sintered LATP solid electrolyte film was obtained.
Secondary flattening and sintering: a setter plate 60mm long, 40mm wide and 1.5mm thick was used. Placing the above sintered LATP solid electrolyte film horizontally between two magnesium oxide burning plates, placing into a muffle furnace, and performing secondary high-temperature heat treatment in air under the following heat treatment conditions: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 1100 ℃ and the heat preservation time is 10min; the cooling rate is 5 ℃/min. After cooling, a planarized LATP solid electrolyte film was obtained.
Example 10: preparation of LAGP solid electrolyte film
In this example, a LAGP electrolyte green film having a final thickness of 100 μm was obtained in the same procedure and conditions as in preparation example 2, except that LLZTO powder blank in preparation example 2 was replaced with LAGP powder blank.
And (3) primary densification sintering: placing the LAGP electrolyte green film in a magnesium oxide crucible, placing the magnesium oxide crucible in a muffle furnace, and sintering at high temperature in air under the following sintering conditions: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 800 ℃ and the heat preservation time is 6 hours; the cooling rate is 5 ℃/min. After cooling, a sintered LAGP solid electrolyte film was obtained.
Secondary flattening and sintering: a setter plate 60mm long, 40mm wide and 1.5mm thick was used. Horizontally placing the sintered LAGP solid electrolyte film between two magnesium oxide burning plates, putting the magnesium oxide burning plates into a muffle furnace, and performing secondary high-temperature heat treatment in the air, wherein the heat treatment conditions are as follows: heating rate is 10 ℃/min; heat preservation temperature: the temperature is 1000 ℃ and the heat preservation time is 10min; the cooling rate is 5 ℃/min. After cooling, a flattened LAGP solid electrolyte film was obtained.
Comparative example 1: preparation of LLZTO solid electrolyte film
In this comparative example, LLZTO solid-state electrolyte thin film, i.e., LLZTO solid-state electrolyte thin film subjected to densification sintering only once, was obtained in the same procedure and conditions as in example 1, except that secondary flattening sintering was not performed.
Comparative example 2: preparation of LATP solid electrolyte film
In this comparative example, a LATP solid electrolyte film, that is, a LATP solid electrolyte film subjected to densification sintering only once, was obtained in the same procedure and conditions as in example 9, except that the secondary flattening sintering was not performed.
Comparative example 3: preparation of LAGP solid electrolyte film
In this comparative example, a LAGP solid electrolyte film, i.e., a LAGP solid electrolyte film subjected to only primary densification sintering, was obtained in the same procedure and conditions as in example 10, except that secondary planarization sintering was not performed.
Characterization of solid state electrolytes
The solid electrolyte films prepared according to the above examples and comparative examples were visually inspected to evaluate the film formation condition. Physical diagrams of the solid electrolyte thin films of example 1 and comparative example 1 are shown in fig. 3 and 4, respectively.
The diameter and thickness of the solid electrolyte film were measured using a micrometer.
In order to test the ionic conductivity of the solid electrolyte film, ag conductive layers are plated on two sides of the electrolyte film by using a thermal evaporation coating instrument, button cells are used for packaging, and then an electrochemical workstation Metrohm Autolab is used for alternating current impedance test, wherein the alternating current voltage is 10mV, and the frequency is 10MHz-1Hz. After measuring the ac impedance of the solid electrolyte film, the ionic conductivity σ is calculated by the formula σ=l/RS, where L is the electrolyte film thickness, R is the electrolyte film ac impedance, and S is the electrolyte film single-sided area.
Characterization results of the solid electrolytes of examples 1 to 4 and comparative example 1 are summarized in table 1.
Table 1 characterization data for solid electrolyte films
Results and evaluation
As shown in fig. 3, the LLZTO solid electrolyte film prepared in example 1 has high flatness, and the solid-state battery can be assembled without mechanical treatment such as polishing. In contrast, as shown in fig. 4, the LLZTO solid electrolyte film of comparative example 1, which was not subjected to the planarization treatment, had a bending deformation, and thus it was impossible to directly assemble the battery.
The LLZTO electrolyte films of example 1 and comparative example 1 were each semitransparent, indicating that the electrolyte films were thin and highly dense, and the thicknesses were substantially the same, indicating that the secondary heat treatment did not have a significant effect on the thin density of the electrolyte films.
The same applies to the case of the LAGP and LATP electrolyte films, i.e., the electrolyte films subjected to planarization treatment in examples 9 to 10 had higher flatness and substantially the same density and ion conductivity as those of the electrolyte films not subjected to planarization treatment in comparative examples 2 to 3.
As can be seen from the ionic conductivity data in table 1, the material of the setter plate has a certain influence on the ionic conductivity of the electrolyte thin film, wherein when lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum zirconium aluminum oxide and the like are used as the setter plate, the setter plate is made of a lithium-rich material and has the same or similar composition as the solid electrolyte, and the ionic conductivity of the obtained flattened solid electrolyte thin film is the highest. When the magnesium oxide setter plate is used, the ionic conductivity of the electrolyte film remains substantially unchanged while planarizing because it does not react with the volatilized lithium element. In contrast, when alumina or zirconia capable of reacting with lithium is used as the setter plate, the ionic conductivity of the electrolyte film decreases to some extent after the planarization treatment, but is still higher than that of the solid electrolyte film commonly seen in the prior art.
The exemplary embodiments of the present invention have been described above by way of example, but the present invention is not limited thereto. It will be appreciated by those skilled in the art that the above examples are for illustrative purposes only and that the detailed description and examples should not be construed as limiting the scope of the invention. The embodiments can be changed and modified within the scope of the gist of the present invention, and such changes and modifications are intended to be within the scope of the present invention.

Claims (20)

1. A method for preparing a ceramic solid electrolyte film, comprising the steps of:
And sintering the sintered solid electrolyte film at a high temperature under the condition of applying mechanical pressure to obtain the flattened solid electrolyte film.
2. The method of preparation according to claim 1, wherein the mechanical pressure is in the range of 1 to 500Pa, preferably 10 to 400Pa, more preferably 20 to 250Pa, still more preferably 50 to 150Pa.
3. The method of preparation according to claim 1 or 2, characterized in that the sintered solid electrolyte film has a thickness of 1-600 μm, preferably 5-300 μm, more preferably 10-200 μm.
4. A production method according to any one of claims 1 to 3, wherein the high-temperature sintering temperature is higher than a sintering temperature at which a sintered solid electrolyte thin film is produced from a solid electrolyte green film.
5. The method of any one of claims 1 to 4, wherein the mechanical pressure is applied by placing a setter plate over the sintered solid electrolyte membrane.
6. The production method according to claim 5, wherein the flattened solid electrolyte film is obtained by performing high-temperature sintering in a state where the sintered solid electrolyte film is placed between two setter plates.
7. The method according to claim 5 or 6, wherein the surface of the setter plate in contact with the solid electrolyte film is a flat surface.
8. The method of claim 5 or 6, wherein the setter plate comprises one or more materials selected from the group consisting of magnesium oxide, zirconium oxide, aluminum oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum titanium oxide, lithium germanium aluminum phosphate, and lithium titanium aluminum phosphate.
9. The method of any one of claims 1 to 8, wherein the solid state electrolyte is selected from the group consisting of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide, lithium lanthanum titanium oxide, lithium germanium aluminum lithium phosphate, and lithium titanium aluminum phosphate.
10. The production method according to any one of claims 1 to 8, wherein the sintered solid electrolyte film is obtained by:
(1) Mixing a solid electrolyte blank with a fiberizable polymer, fibrillating said polymer and uniformly mixing with said solid electrolyte blank;
(2) Carrying out hot pressing treatment on the mixture obtained in the step (1) to a preset thickness to obtain a solid electrolyte green film;
(3) And (3) sintering the solid electrolyte green film obtained in the step (2) at a high temperature to obtain the sintered solid electrolyte film.
11. The method of preparing according to claim 10, wherein the fiberizable polymer comprises at least one of polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, styrene-butadiene rubber, polyacrylic acid, carboxymethyl cellulose, and polyimide.
12. The method of claim 10 or 11, wherein in step (1), the solid electrolyte blank content is 80-99.9wt%, preferably 90-99wt%, more preferably 95-99wt%; and/or the fibrillatable polymer is present in an amount of 0.1 to 20wt%, preferably 1 to 10wt%, more preferably 1 to 5wt%.
13. The method of preparation according to any one of claims 10 to 12, wherein the hot press treatment of step (2) is one or more hot rolls using a roll press and/or the preset thickness is 1-1000 μm, preferably 5-500 μm, more preferably 20-300 μm, still more preferably 50-200 μm.
14. The production method according to any one of claims 10 to 13, wherein the step (3) causes complete decomposition of the polymer in the solid electrolyte green film, and/or the sintering temperature in the step (3) is 800 to 1200 ℃.
15. The method of any one of claims 10 to 14, wherein an excess of a precursor of lithium element is additionally added when mixing the solid electrolyte blank with the fiberizable polymer in step (1), wherein the precursor of lithium element is selected from LiOH H 2 O and Li 3PO4.
16. The production method according to any one of claims 10 to 15, wherein the production method of the solid electrolyte blank in the step (1) comprises the steps of:
(a1) According to the chemical composition of the solid electrolyte, mixing precursors of each element and excessive precursors of lithium element with a solvent, performing ball milling treatment, and then drying, wherein the precursors of lithium element are selected from LiOH.H 2 O and Li 3PO4;
(a2) Presintering the mixture obtained in step (a 1) to obtain the solid electrolyte blank.
17. The production method according to claim 16, wherein an excess of the precursor of the lithium element is additionally added when the solid electrolyte blank is mixed with the fiberizable polymer in the step (1), wherein the total excess ratio of the molar numbers of the precursor of the lithium element in the step (a 1) and the step (1) is 1 to 50%, wherein
When the solid electrolyte is selected from lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum zirconium gallium oxide or lithium lanthanum titanium oxide, the precursor of the lithium element is LiOH H 2 O, and the total excessive proportion of the mole number is 20-50%, preferably 30-50%;
when the solid electrolyte is selected from lithium aluminum germanium phosphate or lithium aluminum titanium phosphate, the precursor of the lithium element is Li 3PO4, and the total excess ratio of the molar number thereof is 1% to 20%, preferably 5% to 15%.
18. A ceramic solid electrolyte membrane prepared by the preparation method of any one of claims 1 to 17.
19. Use of the ceramic solid electrolyte membrane of claim 18 in a solid state lithium metal battery.
20. A solid state lithium metal battery comprising the ceramic solid state electrolyte thin film of claim 18.
CN202410674375.XA 2024-05-27 2024-05-27 Flattening method for ceramic solid electrolyte film Pending CN118398879A (en)

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