A solid-state lithium battery ceramic composite electrolyte, its preparation method and application

Abstract

This invention discloses a solid-state lithium battery ceramic composite electrolyte, its preparation method, and its application. The composite electrolyte includes a support and a barrier layer; wherein the support is made of solid-state electrolyte; and the barrier layer is also made of solid-state electrolyte and is bonded to the smooth surface of the support electrode. The solid-state lithium battery ceramic composite electrolyte provided by this invention effectively solves the contact problem between the two materials by sintering the barrier layer on the surface of the support. Furthermore, it addresses the issue of reaction between the support electrode material and lithium metal.

Description

Technical Field

[0001] This invention relates to the field of solid electrolyte technology, and in particular to a solid lithium battery ceramic composite electrolyte, its preparation method, and its application. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Solid-state lithium-ion battery technology is a key technology for solving lithium battery safety issues, especially solid-state lithium batteries based on ceramic-based electrolytes. These batteries can fundamentally solve the safety problems caused by internal short circuits due to branched growth piercing the separator, leading to thermal runaway. A stable ceramic structure is also crucial for ensuring the safe and stable operation of the battery and is an important direction for future lithium battery development. Currently, most easily sinterable lithium-ion ceramic electrolytes cannot directly contact lithium metal, while those that can directly contact lithium metal are difficult to sinter, limiting the practical application of ceramic-based electrolytes. Summary of the Invention

[0004] This invention proposes a solid-state lithium battery ceramic composite electrolyte, its preparation method, and its application. This electrolyte can solve the problem of battery failure caused by reaction between the electrolyte and the negative electrode lithium metal due to contact between the two. To achieve the above objective, the technical solution of this invention is as follows:

[0005] In a first aspect of the present invention, a solid-state lithium battery ceramic composite electrolyte is disclosed, comprising a support and a barrier layer. The support is made of a solid electrolyte, wherein an electrolyte material that is easily sintered serves as the support, and an electrolyte material that does not react with lithium metal serves as the barrier layer.

[0006] Furthermore, the thickness of the support is 100-2000 μm, and the thickness of the barrier layer is 10-50 μm. The barrier layer can effectively prevent dendrites generated at the negative electrode of the battery from contacting the electrolyte in the support, thus preventing electrolyte reaction failure.

[0007] Furthermore, the positive electrode material is prepared on the support side.

[0008] Furthermore, the cathode material includes any one of the following: LiMO2 (M = at least one of Co, Ni, Mn, and Al), LiM2O4 (M = at least one of Ni and Mn), and LiMPO4 (M = at least one of Fe, Mn, Co, and Ni).

[0009] Furthermore, the surface of the barrier layer is also covered with a layer of battery negative electrode material. Preferably, the negative electrode material includes any one of carbon, lithium metal, lithium-titanium composite oxide, etc. By setting the barrier layer, the problem of electrolyte support reaction that easily occurs after the support and lithium metal come into contact can be effectively solved.

[0010] Furthermore, the material of the support includes Li. 0.34 La 0.51 TiO3, Li 0.06 La 0.66 Ti 0.93 Al 0.03 O3, LiSr2Ti2NbO9, LiTi2(PO4)3, LiGe2(PO4)3, Li 1.3 Al 0.3 Ti 1.7 Any one of (PO4)3, etc.

[0011] Furthermore, the barrier layer material includes: Li7La3Zr2O 12 Li5La3Nb2O 12 Li5La3Ta2O 12 Li 6.75 La3Zr 1.75 Ta 0.25 O 12 Li 6.55 La3Zr2Ga 0.15 O 12 Any of these materials can have their barrier layers in direct contact with the lithium anode without reacting.

[0012] In a second aspect of the present invention, a method for preparing the solid-state lithium battery ceramic composite electrolyte is disclosed, comprising the following steps:

[0013] I. Preparation of Electrode Support Electrode by Compression Method

[0014] (1) Dissolve polyvinyl alcohol (pva) or polyvinyl butyral (pvb) fully in water.

[0015] (2) Weigh a certain amount of electrolyte powder, add a small amount of PVA or PVB solution to the powder, mix evenly, and ensure that the powder is just moistened.

[0016] (3) Pressing the tablets in a mold.

[0017] (4) The support body from step (3) is co-sintered to obtain the support electrode.

[0018] II. Preparation of Support Electrodes by Phase Transformation Method

[0019] (1) After mixing solid electrolyte powder, phase inversion solution and dispersant evenly, exhaust treatment is performed to obtain premixed slurry.

[0020] (2) Cast the premixed slurry onto a flat plate or pour it into a mold, then add water to carry out phase inversion. After the phase inversion is completed, take out the preform and dry it.

[0021] (3) Sinter the dried electrolyte blank obtained in step (2).

[0022] III. Preparation of the Barrier Layer

[0023] (1) Disperse the powder mixture for the barrier layer in ethanol.

[0024] (2) The powder slurry is uniformly sprayed onto the surface of the supporting electrode using a spraying method.

[0025] (3) The electrodes from step (2) are co-sintered to obtain the microchannel structure solid ceramic composite electrolyte.

[0026] Furthermore, in step (2) of method two, the drying temperature is 40~80℃ and the time is 6~24h.

[0027] Further, in steps (3) of method one and step (3) of method two, the sintering process is as follows: first, the electrolyte preform is heated to 300~600℃ and held for 0.5~1.5h; then, it is heated to 1100~1200℃ and held for 5~20h, and then cooled to room temperature. The sample position is adjusted to prevent sticking to the wall, and then the temperature is raised to 500~800℃ and held for 0.5~2h; then, it is raised to 1200~1350℃ and held for 3~20h, thus obtaining the product.

[0028] Further, in step (3) of method three, the co-sintering process is as follows: first, the electrolyte blank is heated to 500~800℃ and held for 0.5~2h; then, it is heated to 900~1200℃ and held for 3~20h to obtain the desired result.

[0029] In a third aspect of the invention, the application of the solid-state lithium battery ceramic composite electrolyte in energy storage batteries is disclosed.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The supporting electrode material provided by the present invention is suitable for sintering and molding of film preforms prepared by different processes. After molding, it has good mechanical properties and high ionic conductivity.

[0032] (2) The present invention prepares a dense barrier layer on the surface of the supporting electrolyte through a sintering process, which can effectively prevent dendrite growth from piercing the electrolyte and contacting the positive electrode material, thus preventing battery short circuit. In addition, after preparing the barrier layer by co-sintering on the surface of the supporting electrode, the present invention can make the support directly contact the lithium negative electrode, avoid side reactions, and improve battery stability.

[0033] (3) The barrier layer prepared by the present invention is suitable for support electrodes prepared by different preparation methods. The material and the support electrode material do not undergo side reactions, and can be sintered on the support, thereby improving structural stability and performance. Attached Figure Description

[0034] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0035] Figure 1 This is a cross-sectional SEM image of the microchannel structure solid ceramic composite electrolyte prepared in Example 1 of the present invention.

[0036] Figure 2 This is a cross-sectional SEM image of the microchannel structure solid ceramic composite electrolyte prepared in Example 1 of the present invention after filling with positive electrode material (lithium iron phosphate).

[0037] Figure 3 The images show the charge-discharge curves of a solid-state lithium battery made with the microchannel structure solid-state ceramic composite electrolyte prepared in Example 1 and a solid-state lithium battery made with a single-phase electrolyte.

[0038] Figure 4 The charge-discharge cycle capacity diagrams are shown for solid-state lithium batteries made with the microchannel structure solid-state ceramic composite electrolyte prepared in Example 1 and solid-state lithium batteries made with single-phase electrolytes. Detailed Implementation

[0039] The following description further sets forth specific details of the invention to provide a thorough understanding of it. The terminology used in this specification is for illustrative purposes only and is not intended to limit the scope of the invention.

[0040] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as understood by one of ordinary skill in the art. Unless otherwise specified, the pharmaceuticals or reagents used in this invention are used in accordance with the product instructions or conventional methods in the relevant field. The process of this invention is now further described with reference to the accompanying drawings and specific embodiments.

[0041] Example 1

[0042] A method for preparing a microchannel structured solid ceramic composite electrolyte includes the following steps:

[0043] (1) Take 20.0012g of Li 0.34 La 0.51 TiO3 powder, 4.6829 g polysulfone, 78.0487 g N-methylpyrrolidone and 0.5854 g polyvinylpyrrolidone were weighed and placed in a ball mill jar, and ball milled for 10 hours using a planetary ball mill to form a premixed material.

[0044] (2) The premixed slurry is placed in a vacuum-assisted device for degassing. The vacuum degree is set at 0.1 MPa. After degassing for 20 minutes, a uniformly mixed electrolyte slurry is obtained.

[0045] (3) Pour the slurry into the lower mold, where the slurry height is 2mm. Then, place a stainless steel screen with a mesh size of 150μm on the surface of the slurry, allowing the slurry to pass through the screen. The purpose of the stainless steel screen is to cut off the vertically continuous holes, ensuring that the cross-section of the lower preform is perforated after cutting. Then, press the upper mold with openings at both ends onto the screen and inject the slurry, where the slurry height in the upper mold is 0.5mm.

[0046] (4) Water was used as a flocculant and poured from the top of the slurry to initiate the phase inversion process. After 5 hours of phase inversion, the membrane was demolded, the screen was removed, and the membrane preform was cut off at the interface where the screen was located. The resulting electrolyte preform was soaked in water for 6 hours to displace the remaining solvent N-methylpyrrolidone. Then, the electrolyte preform was dried in an oven at 60°C for 12 hours to obtain an electrolyte preform with vertically distributed channels inside.

[0047] (5) High-temperature sintering of the electrolyte blank: First, heat the temperature to 500℃ at 3℃ / min and hold for 90min to remove volatile substances; then heat the temperature to 800℃ at 3℃ / min and hold for 2h; then heat the temperature to 1150℃ at 3℃ / min and hold for 3h; after completion, cool the temperature to 500℃ at 5℃ / min and then let it cool naturally to obtain a support with vertically distributed channels inside and a dense layer on the upper surface.

[0048] (6) Add 3g Li 6.75 La3Zr 1.75 Ta 0.25 O 12Powder, 0.1g PVP40000, and 30ml ethanol were ball-milled in a ball mill jar for 10 hours to obtain a baffle layer slurry. The baffle layer slurry was sprayed onto the upper surface of the support in step (5) using a spray gun, and then co-sintered: first, the temperature was raised to 800℃ at 3℃ / min and held for 120 minutes to remove volatile substances; then, the temperature was raised to 1280℃ at 3℃ / min and held for 6 hours; finally, the temperature was lowered to 500℃ at 5℃ / min and allowed to cool naturally to obtain a composite ceramic electrolyte with a baffle layer on the upper surface. (Reference) Figure 1 .

[0049] (7) Take 0.67g LiFePO4 powder, 0.15g polyethylene oxide, 0.08g conductive carbon black, and 0.1g lithium bis(trifluoromethanesulfonyl)imide. Dissolve the above raw materials in 7g dimethyl sulfoxide and then heat and stir for 10h to obtain a positive electrode material slurry.

[0050] (8) Invert the composite ceramic electrolyte from step (6) so that the lower end of the channel in the support faces upward. Then, drop the positive electrode material slurry onto the lower end. Then, use a vacuum device to draw negative pressure downward to fill the channel in the support with the positive electrode material slurry. After drying, repeat the filling process three times to ensure the filling amount. The resulting microchannel structure solid ceramic composite electrolyte is as follows: Figure 2 As shown.

[0051] Example 2

[0052] A method for preparing a microchannel structured solid ceramic composite electrolyte includes the following steps:

[0053] (1) 20.0017g Li 0.34 La 0.51 TiO3 powder, 7.9997g polysulfone, 100.0015g N-methylpyrrolidone and 0.5854g polyvinylpyrrolidone were weighed and placed in a ball mill jar, and ball milled for 10 hours using a planetary ball mill to form a premixed material.

[0054] (2) The premixed slurry is placed in a vacuum-assisted device for degassing. The vacuum degree is set at 0.1 MPa. After degassing for 20 minutes, a uniformly mixed electrolyte slurry is obtained.

[0055] (3) Pour the slurry into the lower mold, where the slurry height is 3mm. Then place a stainless steel screen with a mesh size of 200μm on the surface of the slurry and allow the slurry to pass through the screen. Then press the upper mold with openings at both ends onto the screen and inject the slurry. The slurry height in the upper mold is 5mm.

[0056] (4) Ethanol was used as a flocculant and poured from the top of the slurry to initiate the phase inversion process. After 10 hours of phase inversion, the membrane was demolded, the screen was removed, and the membrane preform was cut off at the interface where the screen was located. The resulting electrolyte preform was soaked in water for 6 hours to displace the remaining solvent N-methylpyrrolidone. Then, the electrolyte preform was dried in an oven at 80°C for 6 hours to obtain an electrolyte preform with vertically distributed channels inside.

[0057] (5) High-temperature sintering of the electrolyte blank: First, heat the temperature to 600℃ at 5℃ / min and hold for 30min to remove volatile substances; then heat the temperature to 850℃ at 5℃ / min and hold for 2h; then heat the temperature to 1200℃ at 5℃ / min and hold for 5h; after completion, cool the temperature to 500℃ at 5℃ / min and then let it cool naturally to obtain a support with vertically distributed channels inside and a dense layer on the upper surface.

[0058] (6) Add 3g Li 6.75 La3Zr 1.75 Ta 0.25 O 12 The powder, 0.1g PVP40000, and 30ml ethanol were ball-milled in a ball mill jar for 10 hours to obtain a grid layer slurry. The grid layer slurry was sprayed onto the upper surface of the support in step (5) using a spray gun, and then co-sintered: first, the temperature was raised to 600℃ at 5℃ / min and held for 90 minutes to remove volatile substances; then, the temperature was raised to 1350℃ at 5℃ / min and held for 3 hours; finally, the temperature was lowered to 500℃ at 5℃ / min and allowed to cool naturally to obtain a composite ceramic electrolyte with a grid layer on the upper surface.

[0059] (7) Take 0.67g LiNi2O4 powder, 0.15g polyethylene oxide, 0.08g conductive carbon black, and 0.1g lithium bis(trifluoromethanesulfonyl)imide. Dissolve the above raw materials in 7g dimethyl sulfoxide and then heat and stir for 10h to obtain a positive electrode material slurry.

[0060] (8) Invert the composite ceramic electrolyte from step (6) so that the lower end of the channel in the support faces upward. Then, drop the positive electrode material slurry onto the lower end. Then, use a vacuum device to draw negative pressure downward so that the positive electrode material slurry fills the channel in the support. After drying, repeat the filling process 3 times to ensure the filling amount, and thus obtain the microchannel structure solid ceramic composite electrolyte.

[0061] Example 3

[0062] A method for preparing a microchannel structured solid ceramic composite electrolyte includes the following steps:

[0063] (1) Take 20.0011g of Li 0.34 La 0.51TiO3 powder, 6.0024g polysulfone, 72.0181g N-methylpyrrolidone and 0.5854g polyvinylpyrrolidone were weighed and placed in a ball mill jar, and ball milled for 10 hours using a planetary ball mill to form a premixed material.

[0064] (2) The premixed slurry is placed in a vacuum-assisted device for degassing. The vacuum degree is set at 0.1 MPa. After degassing for 20 minutes, a uniformly mixed electrolyte slurry is obtained.

[0065] (3) Pour the slurry into the lower mold, where the slurry height is 1mm. Then place a stainless steel screen with a sieve hole of 100μm on the surface of the slurry and allow the slurry to pass through the screen. Then press the upper mold with openings at both ends onto the screen and inject the slurry. The slurry height in the upper mold is 3mm.

[0066] (4) Water was used as a flocculant and poured from the top of the slurry to initiate the phase inversion process. After 3 hours of phase inversion, the membrane was demolded, the screen was removed, and the membrane preform was cut off at the interface where the screen was located. The resulting electrolyte preform was soaked in water for 4 hours to displace the remaining solvent N-methylpyrrolidone. Then, the electrolyte preform was dried in an oven at 40°C for 24 hours to obtain an electrolyte preform with vertically distributed channels inside.

[0067] (5) High-temperature sintering of the electrolyte blank: First, heat the temperature to 300℃ at 5℃ / min and hold for 90min to remove volatile substances; then heat the temperature to 800℃ at 5℃ / min and hold for 2h; then heat the temperature to 1100℃ at 5℃ / min and hold for 20h; after completion, cool the temperature to 500℃ at 5℃ / min and then let it cool naturally to obtain a support with vertically distributed channels inside and a dense layer on the upper surface.

[0068] (6) Add 3g Li 6.55 La3Zr2Ga 0.15 O 12 0.1g PVP40000 and 30ml ethanol were ball-milled in a ball mill jar for 10h to obtain a grid layer slurry. The grid layer slurry was sprayed onto the upper surface of the support in step (5) using a spray gun, and then co-sintered: first, the temperature was raised to 500℃ at 5℃ / min and held for 30min to remove volatile substances; then, the temperature was raised to 1200℃ at 5℃ / min and held for 20h; finally, the temperature was lowered to 500℃ at 5℃ / min and allowed to cool naturally to obtain a composite ceramic electrolyte with a grid layer on the upper surface.

[0069] (7) Take 0.67g LiAlO2 powder, 0.15g polyethylene oxide, 0.08g conductive carbon black, and 0.1g lithium bis(trifluoromethanesulfonyl)imide. Dissolve the above raw materials in 7g dimethyl sulfoxide and then heat and stir for 10h to obtain positive electrode material slurry.

[0070] (8) Invert the composite ceramic electrolyte from step (6) so that the lower end of the channel in the support faces upward. Then, drop the positive electrode material slurry onto the lower end. Then, use a vacuum device to draw negative pressure downward so that the positive electrode material slurry fills the channel in the support. After drying, repeat the filling process 3 times to ensure the filling amount, and thus obtain the microchannel structure solid ceramic composite electrolyte.

[0071] Example 4

[0072] A method for preparing a microchannel structured solid ceramic composite electrolyte includes the following steps:

[0073] (1) Take 20.0027g of Li 0.34 La 0.51 TiO3 powder, 4.8745 g polysulfone, 82.1936 g N-methylpyrrolidone and 0.5854 g polyvinylpyrrolidone were weighed and placed in a ball mill jar, and ball milled for 10 hours using a planetary ball mill to form a premixed material.

[0074] (2) The premixed slurry is placed in a vacuum-assisted device for degassing. The vacuum degree is set at 0.1 MPa. After degassing for 20 minutes, a uniformly mixed electrolyte slurry is obtained.

[0075] (3) Pour the slurry into the lower mold, where the slurry height is 2mm. Then place a stainless steel screen with a sieve hole of 50μm on the surface of the slurry and allow the slurry to pass through the screen. Then press the upper mold with openings at both ends onto the screen and inject the slurry, where the slurry height in the upper mold is 5mm.

[0076] (4) Ethanol was used as a flocculant and poured from the top of the slurry to initiate the phase inversion process. After 8 hours of phase inversion, the membrane was demolded, the screen was removed, and the membrane preform was cut off at the interface where the screen was located. The resulting electrolyte preform was soaked in water for 5 hours to displace the remaining solvent N-methylpyrrolidone. Then, the electrolyte preform was dried in an oven at 50°C for 20 hours to obtain an electrolyte preform with vertically distributed channels inside.

[0077] (5) High-temperature sintering of the electrolyte blank: First, heat the temperature to 400℃ at 5℃ / min and hold for 60min to remove volatile substances; then heat the temperature to 800℃ at 5℃ / min and hold for 2h; then heat the temperature to 1150℃ at 5℃ / min and hold for 10h; after completion, cool the temperature to 500℃ at 5℃ / min and then let it cool naturally to obtain a support with vertically distributed channels inside and a dense layer on the upper surface.

[0078] (6) Add 3g Li 6.55 La3Zr2Ga 0.15 O12 0.1g PVP40000 and 30ml ethanol were ball-milled in a ball mill jar for 10h to obtain a grid layer slurry. The grid layer slurry was sprayed onto the upper surface of the support in step (5) using a spray gun, and then co-sintered: first, the temperature was raised to 700℃ at 5℃ / min and held for 60min to remove volatile substances; then, the temperature was raised to 1300℃ at 5℃ / min and held for 10h; finally, the temperature was lowered to 500℃ at 5℃ / min and then allowed to cool naturally to obtain a grid layer composite ceramic electrolyte on the upper surface.

[0079] (7) Take 0.67g LiMnPO4 powder, 0.15g polyethylene oxide, 0.08g conductive carbon black, and 0.1g lithium bis(trifluoromethanesulfonyl)imide. Dissolve the above raw materials in 7g dimethyl sulfoxide and then heat and stir for 10h to obtain a positive electrode material slurry.

[0080] (8) Invert the composite ceramic electrolyte from step (6) so that the lower end of the channel in the support faces upward. Then, drop the positive electrode material slurry onto the lower end. Then, use a vacuum device to draw negative pressure downward so that the positive electrode material slurry fills the channel in the support. After drying, repeat the filling process 3 times to ensure the filling amount, and thus obtain the microchannel structure solid ceramic composite electrolyte.

[0081] Performance testing:

[0082] The prepared half-cell was bonded to aluminum foil with a conductive agent, and the smooth surface was coated with dissolved polyethylene oxide and then dried. Finally, in a glove box, the lithium sheet was placed on the surface of the barrier layer of the composite electrolyte prepared in step (8) of Example 1, and sealed with a button cell to prepare the battery. The battery was placed in a constant temperature oven and tested using a blue electric test system. The activation charging current was 50 μA, the discharge current was 50 μA, and the charge-discharge test was performed. Finally, a cycle test was performed at this current. At the same time, a single-phase electrolyte Li 0.34 La 0.51 TiO3 replaces the composite electrolyte Li 0.34 La 0.51 TiO3- Li 6.55 La3Zr2Ga 0.15 O 12 The same test was performed, and the results were as follows: Figure 3 , Figure 4 As shown.

[0083] from Figure 3 This shows that, under the same test conditions, the composite electrolyte has a higher charge-discharge capacity. From... Figure 4 As can be seen from the results, under the same test conditions, the composite electrolyte significantly improves the battery charge and discharge stability due to the barrier layer that can directly contact the Li metal.

[0084] The above description merely illustrates several embodiments of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make modifications, substitutions, and improvements without departing from the concept and scope of the present invention, and these all fall within the protection scope of the present invention. Therefore, the patent protection scope of the present invention should be determined by the described claims.

Claims

1. A method for preparing a ceramic composite electrolyte for solid-state lithium batteries, characterized in that, The methods and steps include the following: Phase transformation method for preparing supports (1) A premixed slurry is obtained by uniformly mixing solid electrolyte powder, polysulfone, N-methylpyrrolidone and polyvinylpyrrolidone; (2) The premixed slurry is subjected to degassing in a vacuum-assisted device to obtain an electrolyte slurry; (3) Pour the electrolyte slurry into the lower mold, then place the screen on the surface of the slurry and let the slurry pass through the screen; press the upper mold on the screen and inject the electrolyte slurry; then add water to carry out phase conversion. After the phase conversion is completed, take out the electrolyte blank, tear off the screen and cut the electrolyte blank from the interface where the screen is located, and dry it. (4) The electrolyte blank dried in step (3) is sintered to obtain a support with vertically distributed channels inside and a dense layer on the upper surface; the sintering process is as follows: first, the electrolyte blank is heated to 300~600℃ and held for 0.5~1.5h; then the temperature is raised to 1100~1200℃ and held for 5~20h, cooled to room temperature, the sample position is adjusted to prevent sticking to the wall, the temperature is raised to 500~800℃ and held for 0.5~2h; finally, the temperature is raised to 1200~1350℃ and held for 3~20h to obtain the electrolyte blank. The solid electrolyte powder is Li 0.34 La 0.51 TiO3, Li 0.06 La 0.66 Ti 0.93 Al 0.03 O3, LiSr2Ti2NbO9, LiTi2(PO4)3, LiGe2(PO4)3, Li 1.3 Al 0.3 Ti 1.7 Any one of (PO4)3; Barrier layer preparation (1) The powder used for the barrier layer is mixed with polyvinylpyrrolidone and dispersed in ethanol to obtain the barrier layer slurry; (2) The grid layer slurry is uniformly sprayed onto the upper surface of the support by spraying method and then co-sintered; the co-sintering process is as follows: first, the support with the grid layer slurry sprayed is heated to 500~800℃ and kept at that temperature for 0.5~2h; then the temperature is raised to 900~1200℃ and kept at that temperature for 3~20h to obtain the composite ceramic electrolyte; The powder used for the barrier layer is Li7La3Zr2O 12 Li5La3Nb2O 12 Li5La3Ta2O 12 Li 6.75 La3Zr 1.75 Ta 0.25 O 12 Li 6.55 La3Zr2Ga 0.15 O 12 Any one of them; The composite ceramic electrolyte is inverted so that the lower opening of the channel in the support faces upward. Then, positive electrode material slurry is dripped onto the lower opening. A vacuum device is used to draw negative pressure downward to fill the channel of the support with positive electrode material slurry. After drying, the filling is repeated 3 times to ensure the filling amount, thus obtaining the solid lithium battery ceramic composite electrolyte.

2. The method for preparing the solid-state lithium battery ceramic composite electrolyte according to claim 1, characterized in that, In step (3) of the phase transformation method for preparing the support, the drying temperature is 40~80℃ and the time is 6~24h.

3. A solid-state lithium battery ceramic composite electrolyte prepared according to claim 1 or 2, characterized in that, The support has a positive electrode material; the positive electrode material covers the inner surface of the channel or fills the channel; The surface of the barrier layer is also covered with a layer of battery negative electrode material.

4. The solid-state lithium battery ceramic composite electrolyte according to claim 3, characterized in that, The thickness of the support is 100-1000μm, and the thickness of the barrier layer is 10-50μm.

5. The solid-state lithium battery ceramic composite electrolyte according to claim 3, characterized in that, The cathode material includes any one of LiMO2, LiM2O4, and LiMPO4; in LiMO2, M is at least one of Co, Ni, Mn, and Al; in LiM2O4, M is at least one of Ni and Mn; and in LiMPO4, M is at least one of Fe, Mn, Co, and Ni.

6. The solid-state lithium battery ceramic composite electrolyte according to claim 3, characterized in that, The negative electrode material includes any one of carbon, metallic lithium, and lithium-titanium composite oxide.

7. The application of the solid-state lithium battery ceramic composite electrolyte according to any one of claims 3-6 in energy storage batteries.

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