CN114436675A - Composite material and preparation method thereof - Google Patents

Composite material and preparation method thereof Download PDF

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CN114436675A
CN114436675A CN202011205726.0A CN202011205726A CN114436675A CN 114436675 A CN114436675 A CN 114436675A CN 202011205726 A CN202011205726 A CN 202011205726A CN 114436675 A CN114436675 A CN 114436675A
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solid electrolyte
oxide solid
lithium
composite material
coating layer
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不公告发明人
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Evergrande New Energy Technology Shenzhen Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5018—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with fluorine compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte

Abstract

The application relates to the technical field of battery materials, in particular to a composite material and a preparation method thereof. The composite material comprises an oxide solid electrolyte and a lithium halide coating layer coated on the surface of the oxide solid electrolyte. The lithium halide coating layer can not only enhance the stability of the oxide solid electrolyte to air and prevent the generation of LiOH and Li on the surface of the oxide solid electrolyte2CO3The pollutants can also enhance the wettability of the oxide solid electrolyte to lithium metal, so that the interface impedance is reduced, and meanwhile, the lithium ions can be inhibited from depositing in the oxide solid electrolyte, and the growth of lithium dendrites is inhibited; therefore, the composite material is used as a solid electrolyte for a lithium ion battery, so that the cycle life of the battery can be prolongedAnd has very good application prospect.

Description

Composite material and method for producing the same
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a composite material and a preparation method thereof.
Background
Solid-state batteries are representative of the next generation of high safety energy storage solutions, and the core technology thereof lies in the preparation of solid-state electrolytes. Currently, mainstream solid electrolytes can be classified into 3 types: polymer solid electrolytes, oxide solid electrolytes, and sulfide solid electrolytes. Polymer solid electrolyte has low room temperature ionic conductivity (about 10)-6-10-7S/cm order) and sulfide solid electrolyte is unstable to air and water (is prone to generation of H)2S highly toxic gas) and is expensive. Oxide solid electrolyte has moderate room temperature ionic conductivity (about 10)-4Amount of S/cmGrade), strong chemical stability and low cost.
The major problem with oxide solid electrolytes is the tendency to form surface contaminants, such as LiOH, Li, during the preparation or formation process2CO3Etc., these components have poor wetting to lithium metal, increasing interfacial resistance; in addition, oxide solid electrolytes have a certain electron conductivity, Li+Can deposit in the interior thereof to form lithium dendrites. At present, surface pollutants are mainly removed through a physical or chemical method to expose the surface of a fresh oxide solid electrolyte, but the scheme cannot ensure that the pollutants are not generated in the subsequent process and cannot relieve the problem of lithium dendrite growth in the oxide.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The application aims to provide a composite material and a preparation method thereof, and aims to solve the technical problem that pollutants are easily generated on the surface of the existing oxide solid electrolyte, so that lithium dendrite grows inside.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a composite material comprising an oxide solid electrolyte and a lithium halide coating layer coated on a surface of the oxide solid electrolyte.
In the composite material provided by the application, the surface of the oxide solid electrolyte is coated with the lithium halide coating layer, and the lithium halide coating layer can enhance the stability of the oxide solid electrolyte to air so as to prevent LiOH and Li from being generated on the surface of the oxide solid electrolyte2CO3And the like, and can also enhance the wettability of the oxide solid electrolyte to lithium metal, so that the coated oxide solid electrolyte is more closely contacted with an electrode, thereby reducing the interface impedance, and meanwhile, the electronic conductivity of the lithium halide coating layer is very low, thereby inhibiting the lithium ions from depositing in the oxide solid electrolyte and preventing the growth of lithium dendrites; therefore, the composite material used as a solid electrolyte for a lithium ion battery can prolong the cycle life of the battery and has very important applicationAnd 4, application prospect.
In some embodiments, the lithium halide cladding layer has a thickness of 10-100 nm.
In some embodiments, the oxide solid electrolyte is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle.
In some embodiments, when the oxide solid electrolyte is selected from an oxide solid electrolyte sheet, the oxide solid electrolyte sheet has a thickness of 1 to 100 μm;
when the oxide solid electrolyte is selected from oxide solid electrolyte particles, the oxide solid electrolyte particles have a particle diameter of 0.01 to 50 μm.
In some embodiments, the oxide solid state electrolyte is selected from any one of a lithium lanthanum zirconium oxide solid state electrolyte, a lithium lanthanum titanium oxide solid state electrolyte, a lithium aluminum germanium phosphate solid state electrolyte, and a lithium aluminum titanium phosphate solid state electrolyte; and/or the presence of a gas in the gas,
the lithium halide coating layer is selected from any one of a lithium fluoride coating layer, a lithium chloride coating layer and a lithium bromide coating layer.
In a second aspect, the present application provides a method for preparing a composite material, comprising the steps of:
providing an oxide solid electrolyte;
and placing the oxide solid electrolyte into a solution containing halogen ions, and generating a lithium halide coating layer on the surface of the oxide solid electrolyte to obtain the composite material.
LiOH and Li are generally generated on the surface of oxide solid electrolyte2CO3And the like, the method for preparing the composite material provided by the application carries out reaction by putting the oxide solid electrolyte into a solution containing halogen ions, so that LiOH and Li on the surface of the oxide solid electrolyte2CO3The pollutants react with halogen ions in the solution to form a lithium halide coating layer which is stable to air on the surface of the oxide solid electrolyte, so that the pollutants are converted into a lithium halide protective layer through a chemical reaction, the pollutants can be prevented from being generated again on the surface of the oxide solid electrolyte, and the pollutants can be enhancedThe wettability of the oxide solid electrolyte to lithium metal can prevent the growth of lithium dendrites; therefore, the composite material obtained by the preparation method can be used as a solid electrolyte for a lithium ion battery, can prolong the cycle life of the battery, and has a very good application prospect.
In some embodiments, the step of placing the oxide solid electrolyte in a solution containing halogen ions to form a lithium halide coating layer on a surface of the oxide solid electrolyte comprises: and placing the oxide solid electrolyte in a solution containing halogen ions, and standing for 5-30min at the temperature of 0-50 ℃.
In some embodiments, the solution containing halide ions is an ammonium halide solution.
In some embodiments, the ammonium halide solution is an amine fluoride solution and the generated lithium halide coating layer is a lithium fluoride coating, or the ammonium halide solution is an amine chloride solution and the generated lithium halide coating layer is a lithium chloride coating, or the ammonium halide solution is an amine bromide solution and the generated lithium halide coating layer is a lithium bromide coating; and/or the presence of a gas in the gas,
the mass concentration of the ammonium halide solution is 0.5-1.5 mg/ml.
In some embodiments, the oxide solid electrolyte is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle; and/or the presence of a gas in the gas,
the oxide solid electrolyte is selected from any one of lithium lanthanum zirconium oxide solid electrolyte, lithium lanthanum titanium oxide solid electrolyte, lithium aluminum germanium phosphate solid electrolyte and lithium aluminum titanium phosphate solid electrolyte.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method of making a composite material provided in an embodiment of the present application;
fig. 2 is a graph comparing the wetting of Li metal by an oxide solid electrolyte coated with a lithium halide coating layer and an uncoated oxide solid electrolyte provided in examples of the present application;
FIG. 3 is a graph comparing electrochemical impedance spectra of an oxide solid electrolyte coated with a lithium halide coating with an uncoated oxide solid electrolyte provided in examples of the present application;
fig. 4 is a graph comparing transient current responses of symmetric cells prepared from the oxide solid electrolyte coated with lithium halide coating and uncoated oxide solid electrolyte provided in examples of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In a first aspect, embodiments of the present application provide a composite material, including an oxide solid electrolyte and a lithium halide coating layer coated on a surface of the oxide solid electrolyte.
In the composite material provided by the application, the surface of the oxide solid electrolyte is coated with the lithium halide coating layer, and the lithium halide coating layer can enhance the stability of the oxide solid electrolyte to air so as to prevent LiOH and Li from being generated on the surface of the oxide solid electrolyte2CO3And the like, and can enhance the wettability of the oxide solid electrolyte to lithium metal, so that the coated oxide solid electrolyte is in closer contact with an electrode, thereby reducing the interface impedance, and the likeThe electronic conductivity of the lithium halide coating layer is low, so that lithium ions can be inhibited from depositing in the oxide solid electrolyte, and the growth of lithium dendrites can be inhibited; therefore, the composite material can be used as a solid electrolyte for a lithium ion battery, can prolong the cycle life of the battery, and has a very good application prospect.
In some embodiments, the oxide solid electrolyte is selected from any one of a Lithium Lanthanum Zirconium Oxide (LLZO) solid electrolyte, a Lithium Lanthanum Titanium Oxide (LLTO) solid electrolyte, a Lithium Aluminum Germanium Phosphate (LAGP) solid electrolyte, and a Lithium Aluminum Titanium Phosphate (LATP) solid electrolyte; among them, LLZO solid electrolyte is preferable, and LiOH and Li are more easily generated on the surface of LLZO in general2CO3The effect of the contaminant, and therefore the lithium halide coating, on the improvement of LLZO is most pronounced.
In some embodiments, the oxide solid electrolyte is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle. Namely, the lithium halide coating layer can be coated on the surface of the oxide solid electrolyte sheet to form a coating layered composite material sheet, and can also be coated on the surface of the oxide solid electrolyte particles to form composite material particles with a core-shell structure. Further, when the oxide solid electrolyte is selected from the oxide solid electrolyte sheet, the oxide solid electrolyte sheet has a thickness of 1 to 100 μm; the thinner the oxide solid electrolyte sheet, the lower the impedance, and the preferable thickness of the industrially produced solid electrolyte is 20 to 50 μm, more preferably about 35 μm, in combination with the actual industrial productivity; when the oxide solid electrolyte is selected from oxide solid electrolyte particles having a particle size of 0.01 to 50 μm, a higher compacted density can be obtained with a smaller particle size of the oxide solid electrolyte particles, a higher ionic conductivity, and a commercial particle size of 1 to 30 μm is preferred in conjunction with practical industrial production costs. In some embodiments, the lithium halide cladding layer has a thickness of 10-100nm, and if the thickness is too low, the protective layer is not effective, and if the thickness is too high, the interfacial resistance increases, so that the lithium halide cladding layer within the above-mentioned thickness range provides the best combination of protection and interfacial resistance.
In some embodiments, the lithium halide coating is selected from any one of a lithium fluoride coating, a lithium chloride coating, and a lithium bromide coating. Lithium halide coatings of the above kind all enhance the stability of the oxide solid electrolyte, enhance the wettability of the oxide solid electrolyte to lithium metal, and lithium dendrite growth; among them, the lithium fluoride coating layer has the best effect.
In a second aspect, embodiments of the present application provide a method for preparing a composite material, as shown in fig. 1, the method includes the following steps:
s01: providing an oxide solid electrolyte;
s02: and placing the oxide solid electrolyte into a solution containing halogen ions, and generating a lithium halide coating layer on the surface of the oxide solid electrolyte to obtain the composite material.
According to the preparation method of the composite material, the obtained composite material comprises an oxide solid electrolyte and a lithium halide coating layer coated on the surface of the oxide solid electrolyte. Because oxide solid electrolytes can form contaminants, such as LiOH, Li, on the surface during preparation or production2CO3And the like, and the preparation method provided by the application carries out reaction by putting the prepared oxide solid electrolyte into a solution containing halogen ions, so that LiOH and Li on the surface of the oxide solid electrolyte2CO3The pollutants react with halogen ions in the solution, so that a lithium halide coating layer stable to air is generated on the surface of the oxide solid electrolyte, and the pollutants are converted into a lithium halide protective layer through a chemical reaction, so that the pollutants can be prevented from being generated on the surface of the oxide solid electrolyte again, the wettability of the oxide solid electrolyte to lithium metal can be enhanced, and the growth of lithium dendrites can be prevented; therefore, the composite material obtained by the preparation method can be used as a solid electrolyte for a lithium ion battery, can prolong the cycle life of the battery, and has a very good application prospect.
In some embodiments, the oxide solid electrolyte provided in step S01 is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle; further, when the oxide solid electrolyte is selected from the oxide solid electrolyte sheet, the oxide solid electrolyte sheet has a thickness of 1 to 100 μm; when the oxide solid electrolyte is selected from the oxide solid electrolyte particles, the oxide solid electrolyte particles have a particle diameter of 0.01 to 50 μm. Further, the oxide solid electrolyte is selected from any one of a lithium lanthanum zirconium oxide solid electrolyte, a lithium lanthanum titanium oxide solid electrolyte, a lithium aluminum germanium phosphate solid electrolyte and a lithium aluminum titanium phosphate solid electrolyte.
In some embodiments, the step of placing the oxide solid electrolyte in a solution containing halogen ions to form a lithium halide coating layer on the surface of the oxide solid electrolyte comprises: placing the oxide solid electrolyte in a solution containing halogen ions, and standing for 5-30min at 0-50 ℃, wherein the oxide solid electrolyte can fully react to generate a lithium halide coating layer under the condition.
In some embodiments, the solution containing halide ions is an ammonium halide solution. Specifically, the ammonium halide solution is an amine fluoride solution, the generated lithium halide coating layer is coated with lithium fluoride, or the ammonium halide solution is an amine chloride solution, the generated lithium halide coating layer is coated with lithium chloride, or the ammonium halide solution is an amine bromide solution, and the generated lithium halide coating layer is coated with lithium bromide.
Further, the mass concentration of the ammonium halide solution is 0.5-1.5 mg/ml. Specifically, the solvent may be selected from dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), and the like.
In some embodiments, after a lithium halide coating layer is formed on the surface of the oxide solid electrolyte, the composite material may be further dried. Specifically, the oxide solid electrolyte can be placed in a solution containing halogen ions for standing treatment, taken out after the reaction generates a lithium halide coating layer, and dried for 5-15min at the temperature of 150-.
In the examples of the present application, lithium lanthanum zirconium oxide powder (reference: Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries; doi.org/10.1021/acs.chemrev.9b00427), lithium lanthanum titanium oxide powder (reference: A review on structural characteristics, lithium ion differentiation behavor and temperature dependence, respectively) can be prepared by conventional Solid phase methodof conductivity in perovskite-type solid electrolyte Li3xLa2/3-xTiO3(ii) a 10.1142/S179360471730002X), and lithium aluminum germanium phosphate powder (reference: synthesis and Properties of NASICON-type LATP and LAGP Solid Electrolytes; dx, doi, org/10.1002/cssc, 201900725)
In one embodiment of the present application, Lithium Lanthanum Zirconium Oxide (LLZO) powder is prepared by a conventional solid phase method, hot pressed into a sheet and left to stand in air for use. Reacting NH4Dissolving F in dimethyl sulfoxide (DMSO) to form a solution, immersing the LLZO flakes in NH4Standing in F/DMSO solution to make NH4F with LiOH, Li2CO3Reacting with pollutants to generate a LiF protective layer, taking out and drying in a heating environment to obtain the composite material. The LiF layer is stable in air, so that the pollutant can be prevented from being formed on the surface of the LLZO again, the Li metal is enhanced to be wetted, and the interface resistance is reduced; LiF has low electronic conductivity, and can inhibit the growth of Li dendrites to the inside of LLZO and inhibit the growth of the Li dendrites.
The composite material provided by the application or the composite material obtained by the preparation method provided by the application is used as a solid electrolyte for preparing an all-solid-state power battery, so that the cycle life of the battery can be prolonged.
The following description will be given with reference to specific examples.
Example 1
Preparing Lithium Lanthanum Zirconium Oxide (LLZO) powder by a solid phase method, and hot-pressing at 1250 ℃ into slices for later use. Adding 5mg of NH4F was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4F solution, immersing LLZO flakes in NH4And standing the solution F for 15min at 20 ℃, taking out, and drying the solution F for 10min at 180 ℃ to obtain the composite material.
Example 2
Lithium Lanthanum Titanium Oxide (LLTO) powder is prepared by a solid phase method and is hot pressed into thin slices for standby at 1250 ℃. Adding 5mg of NH4F was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4F solution, immersing LLTO flakes in NH4And standing the solution F for 15min at 15 ℃, taking out, and drying the solution F for 10min at 180 ℃ to obtain the composite material.
Example 3
Preparing germanium aluminum lithium phosphate (LAGP) powder by a solid phase method, and hot-pressing the powder into a sheet at 1250 ℃ for later use. Adding 5mg of NH4F was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4Solution F, immersing LAGP sheet in NH4And standing the solution F for 15min at 25 ℃, taking out, and drying the solution F for 10min at 180 ℃ to obtain the composite material.
Example 4
Preparing Lithium Lanthanum Zirconium Oxide (LLZO) powder by a solid phase method, and hot-pressing at 1250 ℃ into slices for later use. Adding 5mg of NH4F was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4F solution, immersing LLZO flakes in NH4Stirring the solution F, standing the solution at 50 ℃ for 15min, then carrying out solid-liquid separation, taking out the solution, and then drying the solution at 180 ℃ for 10min to obtain the composite material.
Example 5
Preparing Lithium Lanthanum Zirconium Oxide (LLZO) powder by a solid phase method, and hot-pressing at 1250 ℃ into slices for later use. Adding 5mg of NH4Cl was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4Cl solution, immersing LLZO flakes in NH4And (3) standing the solution in Cl solution for 15min at 5 ℃, taking out the solution, and then drying the solution at 180 ℃ for 10min to obtain the composite material.
Example 6
Preparing Lithium Lanthanum Zirconium Oxide (LLZO) powder by a solid phase method, and hot-pressing at 1250 ℃ into slices for later use. 1mg of NH4Br was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4Br solution, immersing LLZO flakes in NH4And (3) standing the solution in Br for 15min at 25 ℃, taking out, and drying the solution for 10min at 180 ℃ to obtain the composite material.
Example 7
Preparing Lithium Lanthanum Zirconium Oxide (LLZO) powder by a solid phase method, and hot-pressing at 1250 ℃ into slices for later use. Adding 10mg of NH4Br was dissolved in 6mL of dimethyl sulfoxide (DMSO), and stirred for 24 hours to obtain NH4Br solution, immersing LLZO flakes in NH4And (3) standing the solution in Br for 15min at 25 ℃, taking out, and drying the solution for 10min at 180 ℃ to obtain the composite material.
Comparative example 1
Preparing Lithium Lanthanum Zirconium Oxygen (LLZO) powder by a solid phase method, and hot-pressing into slices at 1250 ℃.
Comparative example 2
Preparing Lithium Lanthanum Zirconium Oxygen (LLZO) powder by a solid phase method, and hot-pressing the powder into slices at 1250 ℃; the whole process is carried out in a glove box, 400#, 800#, 1500# and 300# sandpaper is used for treating the surface of the LLZO sheet in sequence, and then the LLZO sheet is cleaned by alcohol and dried for standby.
Comparative example 3
Preparing Lithium Lanthanum Zirconium Oxygen (LLZO) powder by a solid phase method, and hot-pressing into slices at 1250 ℃. The entire process was carried out in a glove box, soaking the LLZO flakes with 20 wt.% HCl for 10 minutes, followed by rinsing with alcohol and drying for use.
Comparative example 4
Preparing Lithium Lanthanum Titanium Oxide (LLTO) powder by a solid phase method, and hot-pressing the powder into slices at 1250 ℃.
Comparative example 5
Preparing Lithium Lanthanum Titanium Oxide (LLTO) powder by a solid phase method, and hot-pressing the powder into slices at 1250 ℃; the whole process is carried out in a glove box, and 400#, 800#, 1500# and 300# sandpaper are sequentially used for treating the surface of the LLTO sheet, and then the LLTO sheet is cleaned by alcohol and dried for standby.
Comparative example 6
Preparing Lithium Lanthanum Titanium Oxide (LLTO) powder by a solid phase method, and hot-pressing the powder into slices at 1250 ℃. All the way in a glove box, LLTO flakes were soaked with 20 wt.% HCl for 10 minutes, then rinsed with alcohol, dried and ready for use.
Comparative example 7
Preparing germanium aluminum lithium phosphate (LAGP) powder by a solid phase method, and hot pressing into a sheet at 1250 ℃.
Comparative example 8
Preparing germanium aluminum lithium phosphate (LAGP) powder by a solid phase method, and hot-pressing the powder into a sheet at 1250 ℃; the whole process is carried out in a glove box, 400#, 800#, 1500# and 300# sandpaper is used for treating the surface of the LAGP sheet in sequence, and then the LAGP sheet is cleaned by alcohol and dried for standby.
Comparative example 9
Preparing germanium aluminum lithium phosphate (LAGP) powder by a solid phase method, and hot pressing into a sheet at 1250 ℃. The entire process was carried out in a glove box, and the LAGP sheets were soaked with 20 wt.% HCl for 10 minutes, then rinsed with alcohol, and dried for use.
Performance testing
FIG. 2 is a schematic diagram showing wetting of untreated LLZO (FIG. 2a) of comparative example 1 and LLZO (FIG. 2b) surface coated with LiF coating of example 1 to lithium metal. Untreated LLZO surfaces have contaminants such as LiOH, Li2CO3And the like, the wetting to lithium metal is poor, the contact angle is large, while the LLZO surface of example 1 has a LiF layer, and the wetting to lithium metal is good. Therefore, the embodiment of the application can enhance the wettability of the LLZO to the lithium metal negative electrode, so that the contact between the solid electrolyte and the electrode is tighter, and the interface impedance is reduced.
FIG. 3 is an electrochemical impedance spectrum of the untreated LLZO of comparative example 1 and the LLZO of example 1 surface-coated with LiF coating layer (FIG. 3a) and an electrochemical impedance spectrum of the LLZO of example 1 surface-coated with LiF coating layer after standing in air (FIG. 3 b). As can be seen from the figure, the interface resistance of LLZO and Li metal electrodes coated with LiF coating layer on the surface of example 1 is smaller because LiF replaces LiOH and Li2CO3And pollutants are solved, so that the wetting of the LLZO to the Li metal is improved; in addition, the resistance of the LLZO coated with the LiF coating layer on the surface of the LLZO in example 1 is not obviously increased after the LLZO is placed in the air, which shows that the LiF protective layer plays a role in enhancing the stability of the LLZO to the air.
FIG. 4 is a graph comparing the transient current responses of the symmetrical cell consisting of the untreated LLZO of comparative example 1 and the LLZO of example 1 surface-coated with LiF coating layer with the irreversible stainless steel electrode, respectively. As can be seen from the graph, the symmetrical battery current composed of the two LLZO types mentioned above increases instantaneously at the instant of current application; subsequently, the current of comparative example 1 slowly decreased, indicating that it has a certain electronic conductivity, while the corresponding current of example 1 instantly decreased to zero, indicating that the formed LiF coating layer has an extremely low electronic conductivity, which is important for inhibiting lithium ions from depositing inside the LLZO and forming lithium dendrites.
The solid electrolytes of examples 1 to 7 and comparative examples 1 to 9 described above may be hot-pressed into a 3mm sheet row impedance test for more convenient impedance test (the thickness of the solid electrolyte sheet is preferably 20 to 50 μm when actually assembled into a full cell). The testing steps include: and cleaning and drying the electrolyte sheet, coating silver paste on two sides, drying at 80 ℃ for 10min, and then carrying out impedance test by using a high-frequency electrochemical impedance tester, wherein the frequency range is 10 MHz-0.1 Hz. After reading the internal resistance and interfacial resistance data, the electrolyte sheet was placed in air for 50h, the above resistance test was repeated, and the interfacial resistance data was recorded, with the results shown in table 1.
TABLE 1
Internal resistance of body phase (omega) Initial interface impedance (omega) Static back interface impedance (omega)
Example 1 64 121 125
Example 2 63 136 139
Example 3 61 134 140
Example 4 70 129 130
Example 5 58 123 139
Example 6 56 122 140
Comparative example 7 67 131 131
Comparative example 1 71 151 150
Comparative example 2 54 123 155
Comparative example 3 55 121 153
Comparative example 4 69 157 158
Comparison ofExample 5 60 122 156
Comparative example 6 59 123 155
Comparative example 7 69 158 158
Comparative example 8 61 127 155
Comparative example 9 61 125 158
From the data in table 1, it can be seen that: ammonium salts of F, Br and Cl have good coating effects on LLZO, LLTO and LAGP, can remove surface impurities, reduce interface impedance and are stable in air; wherein NH4F has the most outstanding effect on LLZO, and the higher the standing reaction temperature is, the thicker the protective layer is, the internal resistance is increased, but the air isolation and secondary pollution prevention capabilities are stronger.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A composite material is characterized by comprising an oxide solid electrolyte and a lithium halide coating layer coated on the surface of the oxide solid electrolyte.
2. The composite material of claim 1, wherein the lithium halide cladding layer has a thickness of 10 nm to 100 nm.
3. The composite material of claim 1, wherein the oxide solid electrolyte is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle.
4. The composite material according to claim 3, wherein when the oxide solid electrolyte is selected from an oxide solid electrolyte sheet, the oxide solid electrolyte sheet has a thickness of 1 to 100 μm;
when the oxide solid electrolyte is selected from oxide solid electrolyte particles, the oxide solid electrolyte particles have a particle diameter of 0.01 to 50 μm.
5. The composite material according to any one of claims 1 to 4, wherein the oxide solid state electrolyte is selected from any one of a lithium lanthanum zirconium oxide solid state electrolyte, a lithium lanthanum titanium oxide solid state electrolyte, a lithium aluminum germanium phosphate solid state electrolyte, and a lithium aluminum titanium phosphate solid state electrolyte; and/or the presence of a gas in the gas,
the lithium halide coating layer is selected from any one of a lithium fluoride coating layer, a lithium chloride coating layer and a lithium bromide coating layer.
6. The preparation method of the composite material is characterized by comprising the following steps:
providing an oxide solid electrolyte;
and placing the oxide solid electrolyte into a solution containing halogen ions, and generating a lithium halide coating layer on the surface of the oxide solid electrolyte to obtain the composite material.
7. The method of preparing a composite material according to claim 6, wherein the step of placing the oxide solid electrolyte in a solution containing halogen ions to form a lithium halide coating layer on the surface of the oxide solid electrolyte comprises: and placing the oxide solid electrolyte in a solution containing halogen ions, and standing for 5-30min at the temperature of 0-50 ℃.
8. The method of claim 6, wherein the solution containing halide ions is an ammonium halide solution.
9. The method according to claim 8, wherein the ammonium halide solution is an amine fluoride solution and the lithium halide coating layer is formed as a lithium fluoride coating, or the ammonium halide solution is an amine chloride solution and the lithium halide coating layer is formed as a lithium chloride coating, or the ammonium halide solution is an amine bromide solution and the lithium halide coating layer is formed as a lithium bromide coating; and/or the presence of a gas in the gas,
the mass concentration of the ammonium halide solution is 0.5-1.5 mg/ml.
10. The method for producing a composite material according to any one of claims 6 to 9, wherein the oxide solid electrolyte is selected from an oxide solid electrolyte sheet or an oxide solid electrolyte particle; and/or the presence of a gas in the gas,
the oxide solid electrolyte is selected from any one of lithium lanthanum zirconium oxide solid electrolyte, lithium lanthanum titanium oxide solid electrolyte, lithium aluminum germanium phosphate solid electrolyte and lithium aluminum titanium phosphate solid electrolyte.
CN202011205726.0A 2020-11-02 2020-11-02 Composite material and preparation method thereof Pending CN114436675A (en)

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