CN113666642A - Electrolyte membrane for all-solid-state battery and preparation method and application thereof - Google Patents
Electrolyte membrane for all-solid-state battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an electrolyte membrane for an all-solid-state battery, and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing a lithium source, an aluminum source, a first titanium source and a phosphorus source to obtain a mixture, and then melting the mixture to obtain liquid glass; (2) carrying out crystallization reaction on the liquid glass in the step (1) and a nucleating agent to obtain an electrolyte block; (3) and (3) mechanically processing the electrolyte block in the step (2) to obtain the electrolyte membrane for the all-solid-state battery. According to the invention, the raw materials of the LATP electrolyte membrane are mixed and then subjected to melting and crystallization reaction, and mechanical treatment is carried out after cooling, so that a colloid/liquid pulping and forming mode is replaced, the LATP electrolyte membrane with high density and high room temperature conductivity is obtained, the preparation process is simple, no residual impurities exist, no repeated heat treatment process exists, the cycle and difficulty of turnover operation are reduced, and the LATP electrolyte membrane is green and environment-friendly and is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of all-solid-state batteries, and relates to an electrolyte membrane for an all-solid-state battery, and a preparation method and application thereof.
Background
The all-solid-state battery is a battery which is not soaked with electrolyte between the anode and the cathode and only comprises a separation film. The separator of the battery contains a solid electrolyte, and the separator of the battery is very different from the existing separator materials except for the polymer battery. A rocking chair type battery (also referred to as a feather ball type battery), which is a representative battery of Li ion secondary batteries, does not require an electrolyte in principle since it is not necessary to cause an oxidation-reduction reaction between the electrolyte and electrodes, as compared with conventional lead-acid, nickel-hydrogen, and nickel-cadmium batteries. The conventional lithium ion secondary battery uses an electrolyte (liquid state) only as a path for Li ions to pass back and forth between electrodes, while the all-solid-state battery directly realizes the back and forth passage of Li ions through a separator containing a solid electrolyte. The all-solid-state battery has the advantages of high safety (electrolyte leakage or volatilization and fire risk disappearance), capability of realizing ultra-fast charging of 80-90% of charging, increased design freedom of the battery, possibility of realizing multilayering, and capability of using raw materials and parts capable of realizing surface packaging on a substrate.
The most well known solid electrolytes include: polymer electrolytes, oxide solid electrolytes, sulfide solid electrolytes. In the oxide electrolyte, the room temperature ionic conductivity of LATP, LAGP, LLZO, LLTO reaches more than 10-4S.cm-1The grade (d) of (a), most closely to the level of conventional liquid electrolytes, is representative of practical electrolytes. Especially, LATP is the most commercialized electrolyte material due to its low raw material cost, light powder density and high air and water stabilityResearch is very necessary.
Although the preparation and synthesis of the LATP electrolyte material are quite mature at present, the preparation of the LATP electrolyte membrane, especially the preparation of the electrolyte membrane with the thickness of 100-200 μm, is difficult, and in order to ensure high ionic conductivity and high bending strength, the LATP powder must be prepared as much as possible and the porosity reduced, but conventional colloidal forming methods such as Tape casting (Tape casting), injection molding (injection molding) and Gel casting (Gel casting) are all used for preparing LATP powder and then preparing slurry with certain viscosity for molding (toxic organic matters such as solvent, dispersant and binder are added in the process, impurity residues are inevitable in the subsequent sintering process), and after molding, thermal treatment such as binder removal sintering and the like is carried out (the volatilization of the organic matters can hardly cause residual pores), and the most fundamental powder particles are prepared by a method of firstly synthesizing and then physically processing through powder engineering (the process is very complicated at first, such as solid phase method, coprecipitation method, sol-gel method, and then crushing and grinding the synthesized powder to cause irregular particle appearance and exponential increase of specific surface area). These all bring about an increase in grain boundaries and an increase in resistance, making it difficult to produce a high-density LATP film and making it impossible to develop the maximum potential of the LATP electrolyte material.
CN108615934A discloses a method for preparing solid electrolyte lithium titanium aluminum phosphate for lithium ion battery, which comprises the following steps: mixing Li2CO3、Al2O3、TiO2、NH3H2PO4Mixing with boron oxide, placing the mixture into a ball milling tank, adding absolute ethyl alcohol, ball milling the mixture for 3-4 h in a planetary ball mill at the speed of 250r/min, drying the powder obtained after ball milling at 65-75 ℃ for 11-13 h in a drying box, placing the dried powder into a quartz boat, calcining the powder for 2.5-3.5 h in a sintering furnace at the temperature of 370-390 ℃ under argon atmosphere, ball milling the obtained substance again, pressing the ball milled substance under the pressure of 27-29 MPa to form a wafer with the diameter of 15mm and the thickness of 2mm, sintering the wafer for 6h at the temperature of 850-870 ℃, and cooling to obtain the boron-doped silicon carbide material.
CN108428935A discloses a method for preparing a solid electrolyte membrane and a lithium battery, wherein the method for preparing the solid electrolyte membrane comprisesThe following steps: step 1, mixing polyoxyethylene and conductive lithium salt, adding the mixture into an acetonitrile solvent to form a mixed solution, and stirring the mixed solution at 15-25 ℃ for 4-16 hours until the conductive lithium salt is completely dissolved to form an electrolyte colloid. Step 2, adding an inorganic electrolyte into the electrolyte colloid, wherein the mass fraction of the inorganic electrolyte in the electrolyte colloid is 1-30%; the inorganic electrolyte comprises Li1+xAlxTi2–x(PO4)3(LATP), wherein x is more than or equal to 0.2 and less than or equal to 0.4. And 3, stirring for 6-24 hours at 15-25 ℃ until the inorganic electrolyte is completely dissolved to form the gel-state composite electrolyte. And 4, coating the gel-state composite electrolyte on a substrate, pressing and flattening, drying at 20-25 ℃ in vacuum, and removing the acetonitrile solvent to prepare the solid electrolyte membrane.
The preparation method in the above documents is nothing except that LATP powder is prepared, then the powder is processed, solvent, dispersant, binder and the like are added to prepare slurry, then the slurry is formed by a scraper or a mold, then the blank is subjected to glue discharging, sintering and heat treatment to obtain a sintered body, and finally the sintered body is subjected to fine machining to obtain the LATP sheet.
Therefore, how to improve various properties of LATP to facilitate its application in all-solid-state batteries is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide an electrolyte membrane for an all-solid-state battery, and a preparation method and application thereof. According to the invention, the raw materials of the LATP electrolyte membrane are mixed and then subjected to melting and crystallization reaction, and mechanical treatment is carried out after cooling, so that a colloid/liquid pulping and forming mode is replaced, the LATP electrolyte membrane with high density and high room temperature conductivity is obtained, the preparation process is simple, no residual impurities exist, no repeated heat treatment process exists, the cycle and difficulty of turnover operation are reduced, and the LATP electrolyte membrane is green and environment-friendly and is suitable for mass production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for producing an electrolyte membrane for an all-solid battery, the method comprising the steps of:
(1) mixing a lithium source, an aluminum source, a first titanium source and a phosphorus source to obtain a mixture, and then melting the mixture to obtain liquid glass;
(2) carrying out crystallization reaction on the liquid glass in the step (1) and a nucleating agent to obtain an electrolyte block;
(3) and (3) mechanically processing the electrolyte block in the step (2) to obtain the electrolyte membrane for the all-solid-state battery.
According to the invention, the raw materials are mixed and then subjected to melting and crystallization reaction, and mechanical treatment is carried out after cooling, so that a colloid/liquid pulping and forming mode is replaced, the LATP electrolyte membrane with high density and high room temperature conductivity is obtained, the preparation process is simple, no residual impurities exist, no repeated heat treatment process exists, the cycle and difficulty of turnover operation are reduced, and the preparation method is green, environment-friendly and suitable for mass production.
Preferably, the mixture in step (1) further comprises a doping source.
Preferably, the fineness of the particles of the doping source is less than or equal to 325 meshes, such as 325 meshes, 300 meshes, 275 meshes, 250 meshes, 225 meshes, 200 meshes, 175 meshes, 150 meshes, 125 meshes, 100 meshes and the like.
In the invention, the particle fineness of the doping source is too large, so that the doping source is not beneficial to stirring and full infiltration, and the system components are kept consistent.
Preferably, the dopant source comprises a silicon material and/or germanium dioxide.
In the present invention, the silicon material may be selected from various forms such as fine silicon powder and simple substance silicon.
Preferably, the lithium source of step (1) comprises lithium carbonate and/or lithium hydroxide.
Preferably, the aluminum source of step (1) comprises any one of alumina, aluminum hydroxide, boehmite or pseudo-boehmite, or a combination of at least two thereof.
Preferably, the first titanium source of step (1) comprises rutile titanium dioxide and/or anatase titanium dioxide.
Preferably, the phosphorus source of step (1) comprises any one of ammonium dihydrogen phosphate, phosphorus pentoxide or aluminum phosphate, or a combination of at least two thereof.
Preferably, the melting temperature in step (1) is 800-1400 ℃, such as 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, or 1400 ℃.
Preferably, the melting time in the step (1) is 4-6 h, such as 4h, 4.5h, 5h, 5.5h or 6 h.
Preferably, the nucleating agent of step (2) comprises a second titanium source.
In the invention, a titanium source is still selected as the nucleating agent, because the titanium element is the main element of the main final product, the influence on the whole variable is small, and the metering error caused by adding can be reduced.
Preferably, the second titanium source is present in an amount of 5% by mass or less, for example, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, preferably 1 to 5%, based on 100% of the sum of the first and second titanium sources in step (1).
In the invention, the mass ratio of the second titanium source is 1-5%, the effect is better, if the mass ratio is too small, the system is not favorable for quick crystallization, the reaction time is too long, the energy consumption is too large, and if the mass ratio is too large, the crystallization speed is too high, the uniform stirring is not achieved, and the uniform distribution starts crystallization and sedimentation.
Preferably, the second titanium source comprises rutile titanium dioxide and/or anatase titanium dioxide.
Preferably, the crystallization reaction of step (2) comprises:
and (2) carrying out primary stirring on the liquid glass in the step (1), then adding a nucleating agent, carrying out secondary stirring, and cooling to obtain an electrolyte block.
According to the invention, through stirring, air holes in the liquid glass can be eliminated, a more compact homogeneous body is formed, the liquid glass is stirred firstly, and then the nucleating agent is added, so that bubbles can float, break and eliminate more favorably, and if the liquid glass is not stirred for one time, the bubbles remain in crystals, the local crystal morphology becomes poor, and the crystal strength is influenced.
Preferably, the mechanical treatment of step (3) comprises sequentially mechanically cutting and grinding the electrolyte block of step (2).
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing a lithium source, an aluminum source, a first titanium source, a phosphorus source and a doping source with the particle fineness of less than or equal to 325 meshes to obtain a mixture, and then melting the mixture at 800-1400 ℃ for 4-6 h to obtain liquid glass;
(2) stirring the liquid glass in the step (1) for the first time, then adding a nucleating agent for stirring for the second time, and cooling to obtain an electrolyte block and obtain an electrolyte block;
(3) sequentially carrying out mechanical cutting and grinding on the electrolyte block in the step (2) to obtain the electrolyte membrane for the all-solid-state battery;
wherein the nucleating agent of step (2) comprises a second titanium source; and (2) taking the sum of the first titanium source and the second titanium source in the step (1) as 100%, wherein the mass ratio of the second titanium source is 1-5%.
In a second aspect, the present invention provides an electrolyte membrane for an all-solid battery, which is produced by the method for producing an electrolyte membrane for an all-solid battery according to the first aspect, the electrolyte membrane for an all-solid battery having a chemical formula of Li1+xAlxTi2-x(PO4)30 < x < 1, e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc.
Preferably, the electrolyte membrane further includes a silicon element and/or a germanium element.
In the present invention, when the electrolyte membrane is doped with other elements, the chemical formula may be Li1+m+3zAlm(Ti,Ge)2-mSi3zP3-zO12Including a main crystal phase Li1+mAlmGeyTi2-m-yP3O12And a secondary crystal phase Li1+m+3zAlm(Ge,Ti)2-m(SizPO4)3And AlPO4，0＜m≤0.7，0＜y≤0.1，0＜z≤0.1。
For example, m may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, etc., y may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, etc., and z may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, etc.
In a third aspect, the present invention also provides an all-solid battery including the electrolyte membrane for an all-solid battery according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the raw materials of the LATP electrolyte membrane are mixed, then subjected to melting and crystallization reaction, and subjected to mechanical treatment after cooling, so that a colloid/liquid pulping and forming mode is replaced, the LATP electrolyte membrane with high density and high room temperature conductivity is obtained, the preparation process is simple, no residual impurities exist, no repeated heat treatment process exists, the cycle and difficulty of turnover operation are reduced, the preparation method is green and environment-friendly, and is suitable for mass production, the density of the finally obtained LATP electrolyte membrane is more than 96.9%, the porosity is less than 3.1%, and the bending strength is 130N x mm-2Above, the ion conductivity at room temperature can reach 4.12 x 10-4S.cm-1The above.
Drawings
Fig. 1 is an SEM image of the electrolyte membrane for an all-solid battery provided in example 1.
Fig. 2 is a flow chart of the preparation method provided in example 2.
Fig. 3 is an SEM image of the electrolyte membrane for an all-solid battery provided in comparative example 1.
Fig. 4 is a flow chart of the preparation process provided in comparative example 1.
Fig. 5 is an SEM image of the electrolyte membrane for an all-solid battery provided in comparative example 2.
Fig. 6 is a flow chart of a preparation method provided in comparative example 2.
Fig. 7 is an SEM image of the electrolyte membrane for an all-solid battery provided in comparative example 3.
Fig. 8 is a flow chart of a manufacturing process provided in comparative example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a chemical formula of Li1.3Al0.3Ti1.7(PO4)3The electrolyte membrane for all-solid-state batteries of (1).
The preparation method of the electrolyte membrane comprises the following steps:
(1) according to Li1.3Al0.3Ti1.7(PO4)3Weighing lithium carbonate, boehmite, rutile titanium dioxide and ammonium dihydrogen phosphate according to the stoichiometric ratio, uniformly mixing in a mixer, and controlling the particle fineness of each raw material to be below 300 meshes to obtain a mixture;
(2) slowly pouring the mixture obtained in the step (1) into a refractory melting furnace, controlling the temperature in the furnace at 1350 ℃, melting at high temperature for 5 hours, and obtaining liquid glass after all the raw materials are melted;
(3) slowly stirring liquid glass by a corundum rod until bubbles in the liquid glass completely float out and no bubbles burst on the liquid surface, slowly pouring rutile titanium dioxide into the liquid glass to initiate crystal nucleation of the liquid glass, slowly pouring the liquid glass into a refractory mold, and cooling the liquid glass into blocks while nucleating to obtain the glass with the chemical general formula of Li1.3Al0.3Ti1.7(PO4)3The electrolyte block of (1), wherein the nucleating agent comprises 5% of the total mass of all rutile titanium dioxide;
(4) machining the cooled electrolyte block into a plate by using diamond wire cutting equipment, and then carrying out finish machining by using a grinding machine and a grinding machine to obtain the electrolyte blockTo Li of 150 μm thickness1.3Al0.3Ti1.7(PO4)3An electrolyte membrane.
Example 2
This example provides a chemical formula of Li1.3Al0.3Ge0.05Ti1.65(PO4)3The electrolyte membrane for all-solid-state batteries of (1).
The preparation method of the electrolyte membrane is as follows (the flow chart is shown in figure 2):
(1) according to Li1.3Al0.3Ge0.05Ti1.65(PO4)3Weighing lithium hydroxide, aluminum oxide, rutile titanium dioxide, aluminum phosphate and germanium dioxide according to the stoichiometric ratio, and uniformly mixing in a mixer, wherein the particle fineness of each raw material is controlled below 325 meshes to obtain a mixture;
(2) slowly pouring the mixture obtained in the step (1) into a refractory melting furnace, controlling the temperature in the furnace at 800 ℃, melting at high temperature for 6 hours, and obtaining liquid glass after all the raw materials are melted;
(3) slowly stirring liquid glass by a corundum rod until bubbles in the liquid glass completely float out and no bubbles burst on the liquid surface, slowly pouring rutile titanium dioxide (nucleating agent) into the liquid glass to initiate the crystal state nucleation reaction of the liquid glass, slowly pouring the liquid glass into a refractory mold, and cooling the liquid glass into blocks while nucleating to obtain the glass with the chemical general formula of Li1.3Al0.3Ge0.05Ti1.65(PO4)3The electrolyte block of (1), wherein the nucleating agent accounts for 3% of the total mass of all rutile titanium dioxide;
(4) machining the cooled electrolyte block into a plate by using diamond wire cutting equipment, and performing finish machining by using a grinding machine and a grinding machine to obtain Li with the thickness of 140 mu m1.3Al0.3Ge0.05Ti1.65(PO4)3An electrolyte membrane.
Example 3
This example provides a chemical formula of Li1.26Al0.2Ge0.05Ti1.75Si0.06(PO4)3The electrolyte membrane for all-solid-state batteries of (1).
The preparation method of the electrolyte membrane comprises the following steps:
(1) according to Li1.26Al0.2Ge0.05Ti1.75Si0.06(PO4)3Weighing lithium carbonate, pseudo-boehmite, anatase titanium dioxide, ammonium dihydrogen phosphate, germanium dioxide and silicon micropowder according to the stoichiometric ratio, and uniformly mixing in a mixer, wherein the particle fineness of each raw material is controlled below 280 meshes to obtain a mixture;
(2) slowly pouring the mixture obtained in the step (1) into a refractory melting furnace, controlling the temperature in the furnace at 1400 ℃, melting at high temperature for 4 hours, and obtaining liquid glass after the raw materials are completely melted;
(3) slowly stirring liquid glass by a corundum rod until bubbles in the liquid glass completely float out and no bubbles burst on the liquid surface, slowly pouring anatase titanium dioxide into the liquid glass to initiate the crystalline nucleation reaction of the liquid glass, slowly pouring the liquid glass into a refractory mold, and cooling the liquid glass into blocks while nucleating to obtain the glass with the chemical general formula of Li1.26Al0.2Ge0.05Ti1.75Si0.06(PO4)3The electrolyte block of (1), wherein the nucleating agent accounts for 1% of the total mass of all anatase titania;
(4) processing the cooled electrolyte block into a plate by using a diamond wire cutting device, and performing finish machining by using a grinding machine and a grinding machine to obtain Li with the thickness of 130 mu m1.26Al0.2Ge0.05Ti1.75Si0.06(PO4)3An electrolyte membrane.
Example 4
The difference between this example and example 1 is that in this example, the rutile titanium dioxide is directly poured slowly into the liquid glass for stirring in step (3), and the liquid glass is not stirred in advance.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The present example is different from example 1 in that the nucleating agent accounts for 6% by mass in step (3) of the present example.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this embodiment and embodiment 2 is that the fineness of the germanium dioxide particles in step (1) of this embodiment is 350 mesh.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The process is as shown in fig. 4, lithium carbonate, alumina, titanium dioxide and ammonium dihydrogen phosphate are mixed uniformly in advance, LATP solid electrolyte powder is synthesized by adopting a high-temperature solid phase method at 1400 ℃, after the powder is ground to the median particle size of 1-5 μm, organic solvent, dispersant, binder, plasticizer and the like are added to prepare slurry with certain viscosity, the slurry is dried to form a film at the temperature of 80 ℃ through a drying tunnel of a casting machine, and the film blank is peeled off to be subjected to glue discharging, sintering and finishing treatment to obtain the LATP electrolyte film.
Comparative example 2
The flow is shown in figure 6, lithium hydroxide, alumina, titanium dioxide and ammonium dihydrogen phosphate are mixed uniformly in advance, LATP solid electrolyte powder is synthesized by adopting a high-temperature solid phase method at 1350 ℃, paraffin, a dispersing agent, polypropylene and the like are added to prepare injection feed after the powder is ground to the median grain diameter of 3-5 mu m, the injection feed is injected into a die cavity by an injection machine at 115 ℃ to form a sheet-shaped film blank, and the film blank is peeled off to be subjected to glue discharging, sintering and finishing treatment to obtain the LATP electrolyte membrane.
Comparative example 3
The process is as shown in fig. 8, mixing lithium carbonate, pseudo-boehmite, titanium dioxide and ammonium dihydrogen phosphate uniformly in advance, synthesizing LATP solid electrolyte powder at 1380 ℃ by adopting a high-temperature solid phase method, grinding the powder to a median particle size of 2-5 μm, adding deionized water, a dispersant, a monomer, a cross-linking agent, an initiator, a catalyst and the like to prepare gel slurry, pouring the gel slurry into a grouting mold, drying at 70 ℃ to form a sheet membrane blank, stripping the membrane blank, and performing glue discharging, sintering and finishing treatment to obtain the LATP electrolyte membrane.
Fig. 1 is an SEM image of an electrolyte membrane for an all-solid battery provided in example 1, fig. 3 is an SEM image of an electrolyte membrane for an all-solid battery provided in comparative example 1, fig. 5 is an SEM image of an electrolyte membrane for an all-solid battery provided in comparative example 2, and fig. 7 is an SEM image of an electrolyte membrane for an all-solid battery provided in comparative example 3.
Through comparison, it can be seen that the electrolyte membranes in fig. 3, 5 and 7 have obvious pores, the electrolyte powder particles are not densely stacked, the number of defects is large, the barrier is brought to ion migration, and the electrolyte membranes are easy to break in practical application, while the electrolyte membrane in example 1 has fewer pores, the particles are stacked well, and a high-density high-conductivity assembly is easy to form.
Various properties of the electrolyte membranes for all-solid batteries provided in examples 1 to 6 and comparative examples 1 to 3 are listed in table 1.
TABLE 1
From the data results of examples 1 and 4, it is understood that when the liquid glass is not stirred at an early stage but stirred by directly adding the nucleating agent, the porosity is increased, the density is decreased, and the ionic conductivity is decreased.
From the data results of examples 1 and 5, it is understood that the nucleating agent is too much to facilitate the crystallization reaction at a proper rate, and the melt conductivity value is greatly different from the theoretical value.
From the data results of the embodiment 2 and the embodiment 6, it is known that the excessive grain fineness of the doping source can lead to incomplete crystallization, insufficient local density, more overall defects, and larger difference between the ion conductivity and the theoretical value.
From the data results of example 1 and comparative examples 1 to 3, it is understood that the LATP electrolyte membrane provided by the present invention has significantly reduced porosity, significantly improved room temperature ionic conductivity, bending strength, and the like, and more limited processability, compared to the LATP electrolyte membrane prepared by the conventional preparation method.
In conclusion, the raw materials of the LATP electrolyte membrane are mixed, then the mixture is subjected to melting and crystallization reaction, and mechanical treatment is carried out after cooling, so that the LATP electrolyte membrane with high density and high room temperature conductivity is obtained by replacing a colloidal state/liquid state pulping forming mode, the preparation process is simple, no residual impurities exist, no repeated heat treatment process exists, the period and difficulty of turnover operation are reduced, the method is green and environment-friendly, and suitable for mass production, the finally obtained LATP electrolyte membrane has the density of more than 96.9%, the porosity of less than 3.1%, and the bending strength of 130N mm-2Above, the ion conductivity at room temperature can reach 4.12 x 10- 4S.cm-1The above.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for producing an electrolyte membrane for an all-solid battery, characterized by comprising the steps of:
(1) mixing a lithium source, an aluminum source, a first titanium source and a phosphorus source to obtain a mixture, and then melting the mixture to obtain liquid glass;
(2) carrying out crystallization reaction on the liquid glass in the step (1) and a nucleating agent to obtain an electrolyte block;
(3) and (3) mechanically processing the electrolyte block in the step (2) to obtain the electrolyte membrane for the all-solid-state battery.
2. The production method of an electrolyte membrane for all-solid batteries according to claim 1, characterized in that the mixture of step (1) further comprises a doping source;
preferably, the grain fineness of the doping source is less than or equal to 325 meshes;
preferably, the dopant source comprises a silicon material and/or germanium dioxide.
3. The production method of an electrolyte membrane for all-solid batteries according to claim 1 or 2, characterized in that the lithium source of step (1) includes lithium carbonate and/or lithium hydroxide;
preferably, the aluminum source of step (1) comprises any one of alumina, aluminum hydroxide, boehmite or pseudo-boehmite, or a combination of at least two thereof;
preferably, the first titanium source of step (1) comprises rutile titanium dioxide and/or anatase titanium dioxide;
preferably, the phosphorus source of step (1) comprises any one of ammonium dihydrogen phosphate, phosphorus pentoxide or aluminum phosphate, or a combination of at least two thereof.
4. The method for producing an electrolyte membrane for an all-solid battery according to any one of claims 1 to 3, wherein the temperature of the melting in step (1) is 800 to 1400 ℃;
preferably, the melting time in the step (1) is 4-6 h.
5. The production method for an electrolyte membrane for an all-solid battery according to any one of claims 1 to 4, wherein the nucleating agent of step (2) comprises a second titanium source;
preferably, the mass ratio of the second titanium source is less than or equal to 5%, preferably 1-5%, calculated by taking the sum of the first titanium source and the second titanium source in the step (1) as 100%;
preferably, the second titanium source comprises rutile titanium dioxide and/or anatase titanium dioxide.
6. The production method of an electrolyte membrane for all-solid batteries according to any one of claims 1 to 5, wherein the crystallization reaction of step (2) comprises:
carrying out primary stirring on the liquid glass in the step (1), then adding a nucleating agent, carrying out secondary stirring, and cooling to obtain an electrolyte block;
preferably, the mechanical treatment of step (3) comprises sequentially mechanically cutting and grinding the electrolyte block of step (2).
7. The production method of an electrolyte membrane for an all-solid battery according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) mixing a lithium source, an aluminum source, a first titanium source, a phosphorus source and a doping source with the particle fineness of less than or equal to 325 meshes to obtain a mixture, and then melting the mixture at 800-1400 ℃ for 4-6 h to obtain liquid glass;
(2) stirring the liquid glass in the step (1) for the first time, then adding a nucleating agent for stirring for the second time, and cooling to obtain an electrolyte block and obtain an electrolyte block;
(3) sequentially carrying out mechanical cutting and grinding on the electrolyte block in the step (2) to obtain the electrolyte membrane for the all-solid-state battery;
wherein the nucleating agent of step (2) comprises a second titanium source; and (2) taking the sum of the first titanium source and the second titanium source in the step (1) as 100%, wherein the mass ratio of the second titanium source is 1-5%.
8. An electrolyte membrane for all-solid batteries, which is produced by the method for producing an electrolyte membrane for all-solid batteries according to any one of claims 1 to 7, and which has a chemical formula of Li1+xAlxTi2-x(PO4)3，0＜x＜1。
9. The electrolyte membrane for all-solid batteries according to claim 8, further comprising a silicon element and/or a germanium element.
10. An all-solid battery comprising the electrolyte membrane for an all-solid battery according to claim 8 or 9.
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