CN113937346A - Solid electrolyte, preparation method thereof and all-solid-state battery - Google Patents

Solid electrolyte, preparation method thereof and all-solid-state battery Download PDF

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CN113937346A
CN113937346A CN202010670273.2A CN202010670273A CN113937346A CN 113937346 A CN113937346 A CN 113937346A CN 202010670273 A CN202010670273 A CN 202010670273A CN 113937346 A CN113937346 A CN 113937346A
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solid electrolyte
electrolyte
oxide
solid
glass
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CN113937346B (en
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胡屹伟
时琢
郭姿珠
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BYD Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present disclosure relates to a solid electrolyte comprising an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic. The solid electrolyte realizes mutual solubility of the oxide solid electrolyte and the sulfide solid electrolyte, and has high ionic conductivity, high strength and high air stability.

Description

Solid electrolyte, preparation method thereof and all-solid-state battery
Technical Field
The application relates to the technical field of lithium batteries, in particular to a solid electrolyte, a preparation method thereof and an all-solid-state battery.
Background
The solid electrolyte refers to a solid material having high ion conductivity. The lithium ion battery used at present contains flammable liquid organic matters, and lithium metal dendrite and uneven deposition appear in circulation, along with the continuous development of the lithium ion battery technology, the demand for the battery with high safety and high energy density is greatly increased, and the solid battery formed by the solid electrolyte can well solve the problems. In inorganic all-solid-state batteries, the solid electrolyte glass is compatible with existing production processes due to its better processability.
Most of the existing solid electrolyte glasses are phosphates, silicates, borates, thiosilicates and thiophosphates, but each solid electrolyte glass has the advantages and the inherent defects, for example, oxides such as phosphates, silicates and borates have high mechanical strength and are stable in air, but the ionic conductivity is very low; and the thiosilicate and the thiophosphate have high ionic conductivity, but are unstable in air, have lower strength and are easier to break. Therefore, the search for a solid electrolyte which simultaneously has high strength, high processability, high ionic conductivity and high stability in air is a problem to be solved in the development process of the solid battery.
Disclosure of Invention
It is an object of the present disclosure to provide a solid electrolyte that combines strength, processability, high ionic conductivity, and stability in air.
In order to achieve the above object, a first aspect of the present disclosure provides a solid electrolyte including an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic.
The oxide solid electrolyte and the sulfide solid electrolyte are mutually soluble due to the existence of the oxide additive, so that the oxide-sulfide solid electrolyte can be formed, wherein the sulfide solid electrolyte has higher ionic conductivity, and the oxide solid electrolyte has higher stability and strength in the air, so that the solid electrolyte disclosed by the invention can simultaneously give consideration to high strength, high processability, high ionic conductivity and high stability in air.
Alternatively, the content of the oxide additive is 0.01 to 20 parts by weight, the content of the oxide solid electrolyte is 50 to 100 parts by weight, and the content of the sulfide solid electrolyte is 5 to 50 parts by weight, relative to 100 parts by weight of the solid electrolyte;
preferably, the oxide additive is contained in an amount of 1 to 5 parts by weight, the oxide solid electrolyte is contained in an amount of 60 to 80 parts by weight, and the sulfide solid electrolyte is contained in an amount of 5 to 20 parts by weight, relative to 100 parts by weight of the solid electrolyte.
Optionally, the oxide additive is selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2At least one of (1).
Optionally, the oxide solid state electrolyte is selected from at least one of a phosphate glass solid state electrolyte, a silicate glass solid state electrolyte, and an anti-perovskite glass solid state electrolyte; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte;
preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte.
Optionally, the oxide solid electrolyte contains a halogen, and the halogen is at least one of fluorine, chlorine, bromine, and iodine.
A second aspect of the present disclosure provides a method of preparing a solid electrolyte, the method comprising the steps of:
s1, mixing and grinding the oxide solid electrolyte, the sulfide solid electrolyte and the oxide additive to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material.
Optionally, the oxide solid state electrolyte is selected from at least one of a phosphate glass solid state electrolyte, a silicate glass solid state electrolyte, and an anti-perovskite glass solid state electrolyte; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte; the oxide additive is selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2At least one of (1).
Preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte; the additive is selected from B2O3、Nb2O5And SnO2At least one of (1).
Further preferably, the oxide solid electrolyte contains a halogen, and the halogen is at least one of fluorine, chlorine, bromine, and iodine.
Optionally, the mass ratio of the oxide solid electrolyte precursor, the sulfide solid electrolyte precursor, and the oxide additive is 1: 0.01-1: 0.0001 to 0.25, preferably 1: 0.05-0.25: 0.01-0.1.
Alternatively, in step S2, the conditions of the melting process include: under inert gas, the temperature is 300-; the quenching treatment is carried out in a treatment mode selected from the following modes: single medium quenching, double medium quenching, graded quenching, surface quenching and isothermal quenching; the inert gas is one of argon, nitrogen and helium.
A third aspect of the present disclosure provides an all-solid-state battery including a positive electrode, a negative electrode, and a solid electrolyte as described above. Compared with the traditional liquid electrolyte battery, the solid electrolyte battery has higher safety due to the existence of the solid electrolyte, and can be matched with a high-voltage positive electrode and a lithium negative electrode to improve the energy density.
Through the technical scheme, the solid electrolyte provided by the disclosure realizes mutual solubility of oxide solid electrolyte glass and sulfide solid electrolyte glass due to the existence of the oxide additive, so that the oxide-sulfide solid electrolyte glass can be formed. The sulfide solid electrolyte can improve the ionic conductivity of an oxide system, and the oxide solid electrolyte can improve the stability and strength of sulfide in air, so that the solid electrolyte can simultaneously give consideration to high strength, high processability, high ionic conductivity and high stability in air.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
A first aspect of the present disclosure provides a solid electrolyte comprising an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic.
The solid electrolyte provided by the present disclosure is a mixed system solid electrolyte compatible with both an oxide solid electrolyte and a sulfide solid electrolyte. The conventional oxide solid electrolyte glass and sulfide solid electrolyte glass cannot be mutually dissolved in a high-temperature molten state, and the inventor obtains the fact that due to the fact that the polarity and the bond energy of additive molecules are between the polarity and the bond energy of the additive molecules, the oxide additive can achieve mutual dissolution of the oxide solid electrolyte and the sulfide solid electrolyte, so that oxide-sulfide mixed system solid electrolyte glass can be formed, the sulfide solid electrolyte can improve the ionic conductivity of an oxide system, the oxide solid electrolyte can improve the stability and the strength of sulfide in air, the mixed system solid electrolyte is constructed, the physical performance of the solid electrolyte is greatly improved, and the solid electrolyte can achieve high ionic conductivity, high strength, high processability and high air stability.
According to the first aspect of the present disclosure, the content of the oxide additive may be 0.01 to 20 parts by weight, the content of the oxide solid electrolyte may be 50 to 100 parts by weight, and the content of the sulfide solid electrolyte may be 5 to 50 parts by weight, with respect to 100 parts by weight of the solid electrolyte. In the present disclosure, the presence of a small amount of oxide additive molecules can connect the oxide and sulfide solid electrolyte glass networks to make them mutually soluble.
In a preferred embodiment of the present disclosure, the oxide additive may be included in an amount of 1 to 5 parts by weight, the oxide solid electrolyte may be included in an amount of 60 to 80 parts by weight, and the sulfide solid electrolyte may be included in an amount of 5 to 20 parts by weight, relative to 100 parts by weight of the solid electrolyte.
According to a first aspect of the present disclosure, the additive may be selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2At least one of (1). The polarity and bond energy of the oxide additive disclosed by the invention are between the molecules of the oxide solid electrolyte and the molecules of the sulfide solid electrolyte, so that the molecules of the oxide solid electrolyte and the molecules of the sulfide solid electrolyte can be well connected to form a space network structure.
According to the first aspect of the present disclosure, the oxide solid-state electrolyte may be selected from at least one of a phosphate glass solid-state electrolyte, a silicate glass solid-state electrolyte, and an anti-perovskite glass solid-state electrolyte; the sulfide solid electrolyte may be selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte.
According to a first aspect of the present disclosure, phosphate glass solid-state electrolytes, silicate glass solid-state electrolytes and anti-perovskite glass solid-state electrolytes may be well known to those skilled in the art. For example, the phosphate glass solid electrolyte may comprise Li having the formulaaXbYcZdPOeWherein a is between 0.5 and 6, X is one or more of Al, Y, Ca, Cr, In, Fe, Se and La, b is between 0 and 0.3, Y is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and the element Hf, c is between 0 and 0.9, Z is one or more of F, Cl, Br and IAnd d is between 0 and 1.5. The silicate glass solid electrolyte may comprise Li having the formulaaXbYcZdSiOeWherein a is between 0.3 and 6, X is one or more of Na, K, Ca, Ba and Al, b is between 0 and 0.5, Y is one or more of Ti, Zr, La, Y, Sb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, c is between 0 and 0.8, Z is one or more of F, Cl, Br and I, and d is between 0 and 1.5.
In a preferred embodiment of the present disclosure, the oxide solid electrolyte is selected from the group consisting of phosphate glass solid electrolytes; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte.
In a preferred embodiment of the present disclosure, the oxide solid electrolyte may contain a halogen, so that the ionic conductivity of the solid electrolyte may be further increased, wherein the halogen may be at least one of fluorine, chlorine, bromine, and iodine.
A second aspect of the present disclosure provides a method of preparing a solid electrolyte, the method comprising the steps of:
s1, mixing and grinding the oxide solid electrolyte, the sulfide solid electrolyte and the oxide additive to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material.
The solid electrolyte prepared by the method realizes mutual solubility of the oxide solid electrolyte and the sulfide solid electrolyte, so that the oxide-sulfide mixed system solid electrolyte can be formed. The sulfide solid electrolyte can improve the ionic conductivity of the oxide solid electrolyte, and the oxide solid electrolyte can improve the stability and strength of the sulfide solid electrolyte in the air, so that the composite solid electrolyte glass has high strength, high stability and high ionic conductivity.
According to a second aspect of the present disclosure, the oxide solid-state electrolyte may be selected from at least one of a phosphate glass solid-state electrolyte, a silicate glass solid-state electrolyte, and an anti-perovskite glass solid-state electrolyte; the sulfide is in a solid stateThe electrolyte may be selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte; the oxide additive may be selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2At least one of (1). Preferably, the oxide solid electrolyte may be selected from phosphate glass solid electrolytes; the sulfide solid electrolyte may be selected from a thiosilicate glass solid electrolyte; the additive may be selected from B2O3、Nb2O5And SnO2At least one of (1).
According to the second aspect of the present disclosure, the oxide solid electrolyte may contain a halogen, which may be at least one of fluorine, chlorine, bromine, and iodine. The present disclosure can further increase the ionic conductivity of the solid electrolyte by introducing a halogen element to the oxide solid electrolyte precursor.
According to the second aspect of the present disclosure, the mass ratio of the oxide solid electrolyte precursor, the sulfide solid electrolyte precursor, and the oxide additive may be 1: 0.01-1: 0.0001 to 0.25, preferably 1: 0.05-0.25: 0.01-0.1.
According to the second aspect of the present disclosure, in step S2, the conditions of the melting process may include: under inert gas, the temperature is 300-; the quenching treatment can be carried out in a treatment mode selected from the following modes: one of single medium quenching, double medium quenching, staged quenching, surface quenching and isothermal quenching; the inert gas may be one of argon, nitrogen and helium.
A third aspect of the present disclosure provides an all-solid-state battery including a positive electrode, a negative electrode, and a solid electrolyte.
The all-solid-state battery in the disclosure has higher safety compared with the conventional liquid electrolyte battery due to the existence of the solid electrolyte, can match a high-voltage positive electrode and a lithium negative electrode, and improves energy density, and can be compatible with the existing production process due to the fact that the solid electrolyte glass has high flexibility as a diaphragm.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The materials, reagents, instruments and equipment used in the examples of the present disclosure are commercially available, unless otherwise specified. The examples of the present disclosure were all performed under an argon atmosphere.
Example 1
16mmol of LiCl and 24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the oxide solid electrolyte.
40mmol of SiS2And 60mmol of Li2And S, adding the materials into a mortar for grinding, mixing fully, placing the materials into a boron nitride crucible, heating the materials to 950 ℃ along with a furnace, keeping the temperature for 30 minutes at a heating rate of 5 ℃/min, taking the materials out after full melting, pouring the materials into a stainless steel mold, and quenching to obtain the sulfide solid electrolyte.
80% by mass of an oxide solid electrolyte and 5% by mass of B2O3Grinding the sulfide solid electrolyte accounting for 15 percent of the mass, grinding and uniformly mixing, putting the mixture into a boron nitride crucible, heating the mixture to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 20 minutes, taking out the mixture, pouring the mixture into a stainless steel mold, and quenching to obtain the solid electrolyte of the embodiment.
Example 2
24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the oxide solid electrolyte.
40mmol of SiS2And 60mmol of Li2S is added into a mortar for grinding, fully mixed and placedHeating the mixture in a boron nitride crucible along with a furnace to 950 ℃, keeping the heating rate at 5 ℃/min for 30 minutes, taking out the mixture after full melting, pouring the mixture into a stainless steel mold, and quenching to obtain the sulfide solid electrolyte.
80% by mass of an oxide solid electrolyte and 5% by mass of B2O3Grinding the sulfide solid electrolyte accounting for 15 percent of the mass, grinding and uniformly mixing, putting the mixture into a boron nitride crucible, heating the mixture to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 20 minutes, taking out the mixture, pouring the mixture into a stainless steel mold, and quenching to obtain the solid electrolyte of the embodiment.
Example 3
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
Mixing 94% by mass of oxide solid electrolyte and 1% by mass of B2O3Grinding the sulfide solid electrolyte accounting for 5 percent of the mass, grinding and uniformly mixing, putting the mixture into a boron nitride crucible, heating the mixture to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 20 minutes, taking out the mixture, pouring the mixture into a stainless steel mold, and quenching to obtain the solid electrolyte of the embodiment.
Example 4
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
50% by mass of an oxide solid electrolyte and 20% by mass of B2O3Grinding the sulfide solid electrolyte accounting for 30 percent of the mass, grinding and uniformly mixing, putting the mixture into a boron nitride crucible, heating the mixture to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 20 minutes, taking out the mixture, pouring the mixture into a stainless steel mold, and quenching to obtain the solid electrolyte of the embodiment.
Example 5
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
Oxide solid electrolyte accounting for 80 percent of the mass and SiO accounting for 5 percent of the mass2Grinding the sulfide solid electrolyte accounting for 15 percent of the mass, then grinding and uniformly mixing,placing the mixture into a boron nitride crucible, heating the mixture to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min, taking out the mixture after keeping the temperature for 20 minutes, pouring the mixture into a stainless steel mold, and quenching the mixture to obtain the solid electrolyte of the embodiment.
Comparative example 1
16mmol of LiCl and 24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the oxide solid electrolyte.
40mmol of SiS2And 60mmol of Li2And S, adding the materials into a mortar for grinding, mixing fully, placing the materials into a boron nitride crucible, heating the materials to 950 ℃ along with a furnace, keeping the temperature for 30 minutes at a heating rate of 5 ℃/min, taking the materials out after full melting, pouring the materials into a stainless steel mold, and quenching to obtain the sulfide solid electrolyte.
Grinding 80 mass percent of oxide solid electrolyte and 20 mass percent of sulfide solid electrolyte, grinding, uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 20 minutes, taking out, pouring into a stainless steel mold, and quenching to obtain the solid electrolyte of the comparative example.
Comparative example 2
16mmol of LiCl and 24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the solid electrolyte of the comparative example.
Comparative example 3
40mmol of SiS2And 60mmol of Li2And S, adding the materials into a mortar for grinding, fully mixing, placing the materials into a boron nitride crucible, heating the materials to 950 ℃ along with a furnace, keeping the temperature at the rate of 5 ℃/min for 30 minutes, taking the materials out after full melting, pouring the materials into a stainless steel mold, and quenching to obtain the solid electrolyte of the comparative example.
Test example 1
The solid electrolytes obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to an ion conductivity test by the following method: coating conductive silver adhesive on two sides of a glass sheet in a glove box, and drying in an oven at 150 ℃ for 1h to remove the solvent. Connecting electrodes at two ends of the glass sheet coated with the conductive silver paste, and carrying out electrochemical impedance test at a frequency of 7MHz-10 mHz.
0.5g of the samples obtained in examples 1 to 5 and comparative examples 1 to 3 was placed in a closed chamber having a capacity of 10L, and tested for H using a sensor2(ii) the concentration of S, to obtain the difference in its stability in air; the thermoformed samples (thickness 200 μm) were tested for bending resistance and the angle at which they broke was recorded to obtain strength data. The specific results are shown in Table 2.
Group of Ionic conductivity H2S content Bending angle Whether or not it is a homogeneous phase
Example 1 10-5-10-4S/cm 7ppm 120° Is that
Example 2 10-6-10-5S/cm 5ppm 160° Is that
Example 3 10-6-10-5S/cm 2ppm 135° Is that
Example 4 10-5-10-4S/cm 53ppm 90° Is that
Example 5 10-6S/cm 7ppm 120° Is that
Comparative example 1 10-7-10-6S/cm 565ppm 30° Whether or not
Comparative example 2 10-8-10-7S/cm 0ppm 160° Is that
Comparative example 3 10-4-10-3S/cm 1383ppm 60° Is that
As can be seen from the data in table 2: the ionic conductivities of the examples 1 to 5 are excellent, and the stability and the strength are generally higher; the product obtained in the comparative example 1 has a non-uniform phase, and the conductivity, the stability and the strength are obviously reduced; comparative example 2 is an oxide solid electrolyte, which has low ionic conductivity although high stability and strength; comparative example 3 is a sulfide solid electrolyte, and although the ionic conductivity was high, the stability was low and the strength was low. It follows that the solid state electrolyte of the present disclosure can combine high strength, high stability, and high ionic conductivity.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. A solid electrolyte, comprising an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive;
wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic.
2. The solid electrolyte according to claim 1, wherein the oxide additive is contained in an amount of 0.01 to 20 parts by weight, the oxide solid electrolyte is contained in an amount of 50 to 100 parts by weight, and the sulfide solid electrolyte is contained in an amount of 5 to 50 parts by weight, relative to 100 parts by weight of the solid electrolyte;
preferably, the oxide additive is contained in an amount of 1 to 5 parts by weight, the oxide solid electrolyte is contained in an amount of 60 to 80 parts by weight, and the sulfide solid electrolyte is contained in an amount of 5 to 20 parts by weight, relative to 100 parts by weight of the solid electrolyte.
3. The solid state electrolyte of claim 1, wherein the oxide additive is selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2At least one of (1).
4. The solid-state electrolyte of claim 1, wherein the oxide solid-state electrolyte is selected from at least one of a phosphate glass solid-state electrolyte, a silicate glass solid-state electrolyte, and an anti-perovskite glass solid-state electrolyte; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte;
preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte.
5. The solid-state electrolyte according to claim 4, wherein a halogen is contained in the oxide solid-state electrolyte, the halogen being at least one of fluorine, chlorine, bromine, and iodine.
6. A method of preparing a solid electrolyte as claimed in any one of claims 1 to 5, characterized in that it comprises the following steps:
s1, mixing and grinding the oxide solid electrolyte, the sulfide solid electrolyte and the oxide additive to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material.
7. The method according to claim 6, wherein the oxide solid-state electrolyte is selected from at least one of a phosphate glass solid-state electrolyte, a silicate glass solid-state electrolyte, and an anti-perovskite glass solid-state electrolyte;
the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte and/or a thiophosphate glass solid electrolyte;
the oxide additive is selected from B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3And SiO2At least one of;
preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid electrolyte is selected from a thiosilicate glass solid electrolyte; the additive is selected from B2O3、Nb2O5And SnO2At least one of (1).
8. The method according to claim 7, wherein the oxide solid electrolyte contains a halogen, the halogen being at least one of fluorine, chlorine, bromine, and iodine.
9. The method of claim 6, wherein in step S2, the conditions of the melt processing include: under inert gas, the temperature is 300-; the quenching treatment mode is one of single medium quenching, double medium quenching, staged quenching, surface quenching and isothermal quenching; the inert gas is one of argon, nitrogen and helium.
10. An all-solid-state battery comprising a positive electrode, a negative electrode and a solid electrolyte, characterized in that the solid electrolyte is a solid electrolyte according to any one of claims 1 to 5.
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