CN114976222A - Core-shell structure sulfide solid electrolyte, preparation method and all-solid-state battery - Google Patents

Core-shell structure sulfide solid electrolyte, preparation method and all-solid-state battery Download PDF

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CN114976222A
CN114976222A CN202210793193.5A CN202210793193A CN114976222A CN 114976222 A CN114976222 A CN 114976222A CN 202210793193 A CN202210793193 A CN 202210793193A CN 114976222 A CN114976222 A CN 114976222A
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solid electrolyte
sulfide solid
core
shell
sulfide
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许晓雄
陈伟林
唐光盛
林久
忻粒
李家明
王亚涛
戈志敏
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Zhejiang Funlithium New Energy Tech 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
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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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • 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
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Abstract

The invention discloses a core-shell structure sulfide solid electrolyte, a preparation method and an all-solid-state battery, belonging to the field of all-solid-state batteries, wherein the core-shell structure sulfide solid electrolyte comprises core-shell particles, and the core-shell particles comprise an inner core and a shell layer for coating the inner core; the inner core is sulfide solid electrolyte, and the shell layer is oxide solid electrolyte. Due to the existence of the oxide solid electrolyte layer, the stability of the sulfide solid electrolyte to metal lithium and air is ensured, and the probability of oxidation when the sulfide solid electrolyte is in contact with a positive electrode material is reduced. Meanwhile, the preparation method is simple and suitable for large-scale production, and in addition, the lithium-ion battery is combined with a metal lithium cathode and a high-voltage anode, so that the electrical property of the all-solid-state battery can be effectively improved.

Description

Core-shell structure sulfide solid electrolyte, preparation method and all-solid-state battery
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a sulfide solid electrolyte with a core-shell structure, a preparation method of the sulfide solid electrolyte and an all-solid-state battery.
Background
In recent years, in order to improve safety, attention has been paid to all-solid-state secondary batteries using a solid electrolyte instead of a liquid electrolyte.
Because of the incombustibility of the solid electrolyte, the lithium metal all-solid-state battery based on the sulfide solid electrolyte not only has high energy density, but also has high safety performance. However, in the practical application process, the sulfide solid electrolyte is unstable to water and oxygen, and hydrogen sulfide highly toxic gas can be generated after reaction, so that the traditional sulfide solid electrolyte is difficult to normally use in a drying room with a dew point of-45 ℃. In addition, the sulfide solid electrolyte and the anode or lithium metal are unstable, and if a coating layer which is stable to the anode or the lithium metal is coated on the surface of the sulfide solid electrolyte, the performance of the battery can be effectively improved. Therefore, the preparation of a sulfide solid electrolyte with ultra-high air stability and stability to the positive electrode or lithium metal is a problem which needs to be solved urgently at present.
Chinese patent CN110400967A discloses a sulfide solid electrolyte with a three-layer core-shell structure and a preparation method thereof. The invention combines Li-Argyrodite solid electrolyte or LGPS-type solid electrolyte with P 2 S 5 Mixing, heat treating to obtain intermediate powder containing O 2 The multilayer sulfide solid electrolyte is placed in the atmosphere for 0 to 100 hours, and the multilayer sulfide solid electrolyte which takes Li-Argyrodite solid electrolyte or LGPS-type solid electrolyte as an inner core, Li-P-S as an intermediate layer and Li-P-S-O as an outermost layer is obtained. Although the invention improves the air stability of the electrolyte material to a certain extent, the ionic conductivity of the Li-P-S layer and the Li-P-S-O layer is lower, and the ionic conductivity of the material is obviously reduced along with the increase of the thickness of the nuclear layer.
Chinese patent CN114388803A discloses a passivation layer sulfide solid electrolyte and a preparation method and application thereof. The tin tetrachloride vapor is taken out by inert gas, and reacts on the surface of the initial sulfide solid electrolyte powder to generate a layer of tin-doped sulfide solid electrolyte layer (passivation layer), and the passivation layer has good air stability and high electrical conductivity. However, the passivation layer containing tin on the surface is unstable with lithium metal, and tin element is very easy to be reduced by lithium metal, thereby forming metallic tin or compound with low ionic conductivity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfide solid electrolyte with a core-shell structure, a preparation method and an all-solid-state battery, and aims to solve the problems of poor air stability and poor stability of a ternary positive electrode or a lithium metal negative electrode of the conventional sulfide solid electrolyte.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a sulfide solid electrolyte with a core-shell structure is characterized in that: the core-shell particle comprises an inner core and a shell layer for coating the inner core; the inner core is sulfide solid electrolyte, and the shell layer is oxide solid electrolyte.
Preferably, the sulfide solid electrolyte includes at least one of a binary sulfide solid electrolyte, an LGPS type crystal sulfide solid electrolyte, a Thio-LiSICON series, a langugite type crystal sulfide solid electrolyte, and a mixed conductor sulfide solid electrolyte.
Preferably, the binary sulfide solid electrolyte is Li 2 S-P 2 S 5 As a host, specifically (100-a) Li 2 S·a P 2 S 5 ，a＝20～40；b Li 2 S·a P 2 S 5 ·c LiBr·d LiI，b:a＝3～4，(c+d)/(a+b+c+d)＝5～50％。
Preferably, the mixed conductor sulfide solid electrolyte is Li 7-a M b P 1-b S 6-a X a Wherein a and b satisfy 0 < a < 2 and 0 < b < 1; m is a transition metal; x is at least one of halogen elements Cl, Br and I.
Preferably, the transition metal is at least one of Sc, Ti, V, Cr, Fe, Ni, Nb, Zn and Y.
Preferably, the oxide solid electrolyte is one or more of NASICON type solid electrolyte, Garnet type solid electrolyte, perovskite type solid electrolyte and LISICON type solid electrolyte.
Preferably, the thickness of the shell layer is 2nm to 500nm, and the particle size diameter of the core-shell particle is 2nm to 500 nm.
A preparation method of a sulfide solid electrolyte with a core-shell structure comprises the following steps:
s1, suspending the sulfide solid electrolyte in a fluidized bed reactor by using a carrier gas, atomizing the oxide solid electrolyte solution, introducing the atomized oxide solid electrolyte solution into the fluidized bed reactor, controlling the temperature of the fluidized bed reactor to enable the oxide solid electrolyte powder to be adsorbed and deposited on the surface of the sulfide solid electrolyte, and simultaneously evaporating the solvent to dryness;
and S2, calcining the sulfide solid electrolyte coated by the oxide solid electrolyte to obtain the sulfide solid electrolyte with the core-shell structure.
Preferably, the temperature of the fluidized bed reactor in the step S1 is 70-180 ℃; and/or the sintering temperature in the step S2 is 100-750 ℃, and the heat preservation time is 1-20 h.
The all-solid-state battery comprises the sulfide solid electrolyte with the core-shell structure in at least one of a positive electrode layer, a negative electrode layer and an electrolyte layer.
Compared with the prior art, the sulfide solid electrolyte with the core-shell structure, the preparation method and the all-solid-state battery have the advantages that:
1) the sulfide solid electrolyte has a core-shell structure, and the oxide solid electrolyte of a shell layer has higher ionic conductivity. Under the condition of room temperature, the ionic conductivity of the oxide solid electrolyte can reach 10 -3 S/cm, comparable to the level of ionic conductivity of most sulfide electrolytes. Therefore, the ion conductivity of the oxide electrolyte coating layer is more matched with that of the sulfide electrolyte than that of other coating layers, and the two coating layers have less influence on the ion conductivity of the sulfide electrolyte when being compounded together.
(2) This applicationThe sulfide solid electrolyte has a core-shell structure, and the oxide solid electrolyte of the shell layer is extremely stable to water and oxygen. P-S bond in sulfide electrolyte reacts with water, and P-S bond is broken to generate H 2 S, the breaking of P-O bonds is difficult to change by replacing S with pure O, oxygen-containing compounds with low ionic conductivity are generated on the surface of the sulfide electrolyte along with the breaking of the P-O bonds on the surface, and the P-S bonds are broken along with the continuous reaction. The sulfide solid electrolyte coated by the oxide solid electrolyte can effectively isolate the reaction with water, so that the sulfide solid electrolyte can be applied to a common dry room or a common room, and the environmental control cost is reduced.
(3) The sulfide solid electrolyte has a core-shell structure, and the oxide solid electrolyte of a shell layer has a wider stable electrochemical window. The electrochemical stability window of the traditional sulfide solid electrolyte is 1.7-3.5V, so that more side reactions can be generated and various byproducts can be generated in the practical application process, and the battery performance is influenced. In addition, sulfide and electrolyte are unstable with the current common ternary positive electrode, and a space charge layer can be formed, so that the performance of the battery is influenced. The stable electrochemical window of the oxide electrolyte coating layer adopted by the method is 0-5V, and the compatibility between the oxide solid electrolyte and the ternary cathode material and the lithium metal is good, so that the performance of the battery can be effectively improved by the strategy.
(4) The sulfide solid electrolyte has a core-shell structure, and the oxide solid electrolyte of a shell layer has a higher Young modulus. The Young modulus of the sulfide electrolyte is low, and when lithium dendrite is generated in the negative electrode, the sulfide electrolyte layer is easy to pierce. The Young modulus of the oxide solid electrolyte is far higher than that of the sulfide solid electrolyte, and the growth of lithium dendrite can be inhibited to a greater extent, so that the performance of the battery is improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples of the following,
A sulfide solid electrolyte with a core-shell structure comprises core-shell particles, wherein the core-shell particles comprise an inner core and a shell layer for coating the inner core; the inner core is sulfide solid electrolyte, and the shell layer is oxide solid electrolyte. The thickness of the shell layer is 2 nm-500 nm, preferably 5nm, 50nm, 100nm, 200nm, 300nm and 400 nm; the particle size diameter of the core-shell particles is 2nm to 500nm, preferably 50nm, 100nm, 200nm, 250nm, 300nm, 350nm, 400nm and 450 nm.
The sulfide solid electrolyte includes at least one of a binary sulfide solid electrolyte, an LGPS type crystal sulfide solid electrolyte, a Thio-LiSICON series, a Geranite type crystal sulfide solid electrolyte, and a mixed conductor sulfide solid electrolyte.
Binary sulfide solid electrolyte with Li 2 S-P 2 S 5 As a host, specifically (100-a) Li 2 S·a P 2 S 5 ，a＝20～40；b Li 2 S·a P 2 S 5 C LiBr d LiI, b, a is 3-4, and (c + d)/(a + b + c + d) is 5-50%. Mixed conductor sulfide solid electrolytes, in particular Li 7-a M b P 1-b S 6-a X a Wherein a and b satisfy 0 < a < 2 and 0 < b < 1; m is a transition metal; x is at least one of halogen elements Cl, Br and I. Wherein the transition metal is at least one of Sc, Ti, V, Cr, Fe, Ni, Nb, Zn and Y.
The oxide solid electrolyte is one or more of NASICON type solid electrolyte, Garnet type solid electrolyte, perovskite type solid electrolyte and LISICON type solid electrolyte.
Comparative examples 1,
This comparative example prepared the Geranite type sulfide solid electrolyte Li commonly used in the prior art 6 PS 5 Cl, raw material: li 2 S，P 2 S 5 ，LiCl。
In a glove box under argon atmosphere, Li 2 S、P 2 S 5 LiCl with the chemical formula Li 6 PS 5 And (3) weighing 40g of raw materials by Cl according to the corresponding stoichiometric ratio of 25:5:10, putting the raw materials and 500g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, and carrying out ball milling at 550rpm for 3 hours to obtain a precursor. Transferring the precursor into a sintering furnace for sintering at 550 ℃ for 5h to obtain sulfide solid after grinding and crushingElectrolyte powder Li 6 PS 5 Cl。
Examples 1,
Suspending 20g of the digermite sulfide solid electrolyte obtained in comparative example 1 in a fluidized bed reactor by using a carrier gas, atomizing 10mL of NASICON type solid electrolyte LATP solution (solid content is 1%), introducing the atomized solution into the fluidized bed reactor, wherein the solvent is dimethylbenzene, controlling the temperature of the fluidized bed reactor to be 70 ℃, so that LATP powder is adsorbed and deposited on the surface of the sulfide solid electrolyte, and simultaneously evaporating the solvent. After the reaction is finished, carrying out high-temperature calcination on the sulfide solid electrolyte coated with the LATP on the surface to obtain the sulfide solid electrolyte with the core-shell structure, wherein the sintering temperature is 500 ℃, and the heat preservation time is 10 hours.
Examples 2,
Suspending 20g of the digermite sulfide solid electrolyte obtained in comparative example 1 in a fluidized bed reactor by using a carrier gas, atomizing 10mL of NASICON inorganic solid electrolyte LAGP solution (solid content is 1%), introducing the atomized solution into the fluidized bed reactor, wherein the solvent is toluene, controlling the temperature of the fluidized bed reactor to be 70 ℃, adsorbing and depositing LAGP powder on the surface of the sulfide solid electrolyte, and simultaneously evaporating the solvent. After the reaction is finished, carrying out high-temperature calcination on the sulfide solid electrolyte coated with the LAGP at the sintering temperature of 500 ℃ for 10h to obtain the sulfide solid electrolyte with the core-shell structure.
Examples 3,
Suspending 20g of the digermite sulfide solid electrolyte obtained in comparative example 1 in a fluidized bed reactor by using a carrier gas, atomizing 10mL of a Garnet type solid electrolyte LLZO solution (with a solid content of 1%) and then introducing the atomized solution into the fluidized bed reactor, wherein the solvent is petroleum ether, the temperature of the fluidized bed reactor is controlled to be 70 ℃, the LLZO powder is adsorbed and deposited on the surface of the sulfide solid electrolyte, and meanwhile, the solvent is evaporated. After the reaction is finished, carrying out high-temperature calcination on the sulfide solid electrolyte coated with the LLZO on the surface to obtain the sulfide solid electrolyte with the core-shell structure, wherein the sintering temperature is 500 ℃, and the heat preservation time is 10 hours.
Examples 4,
The difference from example 3 is that the LLZO solution has a solids content of 2%.
Examples 5,
The difference from example 3 is that the temperature of the fluidized bed reactor was controlled to 180 ℃.
Examples 6,
The difference from example 3 is that the sintering temperature is 100 ℃ and the holding time is 20 h.
Example 7,
The difference from example 3 is that the sintering temperature is 750 ℃ and the holding time is 1 h.
Comparative examples 2,
This comparative example prepared an LGPS type crystalline sulfide solid electrolyte Li which was commonly used in the prior art 10 GeP 2 S 12 Raw materials: li 2 S，GeS 2 ，P 2 S 5 。
In a glove box under argon atmosphere, Li 2 S，P 2 S 5 ，GeS 2 In the chemical formula Li 10 GeP 2 S 12 Weighing 40g of raw materials according to the corresponding stoichiometric ratio, putting the raw materials and 500g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, and carrying out ball milling at 550rpm for 3 hours to obtain a precursor. Transferring the precursor into a sintering furnace for sintering at 650 ℃ for 5h to obtain sulfide solid electrolyte powder Li after grinding and crushing 10 GeP 2 S 12 。
Example 8,
20g of the LGPS type crystal sulfide solid electrolyte obtained in comparative example 2 was suspended in a fluidized bed reactor with a carrier gas, 10mL of LLZO solution (solid content 1%) was atomized and introduced into the fluidized bed reactor, the solvent was petroleum ether, the temperature of the fluidized bed reactor was controlled at 180 ℃ to cause the LLZO powder to be adsorbed and deposited on the surface of the sulfide solid electrolyte while the solvent was evaporated. After the reaction is finished, carrying out high-temperature calcination on the sulfide solid electrolyte coated with the LLZO on the surface to obtain the sulfide solid electrolyte with the core-shell structure, wherein the sintering temperature is 500 ℃, and the heat preservation time is 10 hours.
Comparative examples 3,
The comparative example prepares the commonly used binary sulfide solid electrolyte Li in the prior art 7 P 3 S 11 Raw materials: li 2 S，P 2 S 5 。
In a glove box under argon atmosphere, Li 2 S，P 2 S 5 In the chemical formula Li 7 P 3 S 11 Weighing 40g of raw materials according to the corresponding stoichiometric ratio, putting the raw materials and 500g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, and carrying out ball milling at 550rpm for 20 hours to obtain a precursor. Transferring the precursor into a sintering furnace for sintering at the sintering temperature of 250 ℃ for 5h, and grinding and crushing to obtain sulfide solid electrolyte powder Li 7 P 3 S 11 。
Examples 9,
Suspending 20g of the binary sulfide solid electrolyte obtained in comparative example 3 in a fluidized bed reactor by using a carrier gas, atomizing 10mL of LLZO solution (with a solid content of 1%) and introducing the atomized solution into the fluidized bed reactor, wherein the solvent is petroleum ether, controlling the temperature of the fluidized bed reactor at 70 ℃, so that the LLZO powder is adsorbed and deposited on the surface of the sulfide solid electrolyte, and simultaneously evaporating the solvent. After the reaction is finished, carrying out high-temperature calcination on the sulfide solid electrolyte coated with the LLZO on the surface to obtain the sulfide solid electrolyte with the core-shell structure, wherein the sintering temperature is 500 ℃, and the heat preservation time is 10 hours.
And (3) testing air stability:
1g of the sulfide solid electrolyte of the comparative example and the example was spread on the bottom of a 150mL jar, placed in a closed space with a dew point of-45 ℃ dry air, and left for a while, and the ion conductivity of the sulfide solid electrolyte before and after the placement was measured.
And (3) ion conductivity test:
the sulfide solid electrolyte powders in the comparative example and the example were pressed into a sheet-like sulfide solid electrolyte having a diameter of 10mm and a thickness of 1mm under a pressure condition of 200MPa with a water content of less than 10 ppm. Then, EIS test was performed at 25 ℃ at room temperature using carbon as a blocking electrode, and the ionic conductivity was calculated.
Cycle testing of all-solid-state batteries:
the assembly method of the all-solid-state battery is as follows: the positive electrode NCM811 has an area capacity of 2mAh/cm2, the N/P ratio is 1.2, the positive electrode and the negative electrode correspondingly comprise the sulfide solid electrolyte in the comparative example and the embodiment, the content is 30 wt%, and the thickness of the electrolyte layer is 100 mu m.
The cycle test method is as follows: the charging and discharging voltage is 3.0-4.25V, the first circle is cycled for 0.05C, the second circle is started to perform 500 charging and discharging cycles at 0.5C, and the larger the discharging capacity retention ratio after 100 weeks, the better the cycle performance.
Figure BDA0003731143320000061
Figure BDA0003731143320000071
When the sulfide solid electrolyte with the core-shell structure is applied to all-solid-state batteries, the existence of the oxide solid electrolyte layer ensures the stability of the sulfide solid electrolyte to metal lithium and air, and reduces the probability of oxidation when the sulfide solid electrolyte is contacted with a positive electrode material. Meanwhile, the preparation method is simple and suitable for large-scale production, and in addition, the lithium-ion battery is combined with a metal lithium cathode and a high-voltage anode, so that the electrical property of the all-solid-state battery can be effectively improved.
Comparing the performances of the comparative example 1 and the examples 1-7; comparison of the properties of comparative example 2 and example 8; as can be seen from comparison of performances of comparative example 3 and example 9, the discharge capacity of the core-shell sulfide solid electrolyte in the first week (0.05C) of the all-solid battery, the coulombic efficiency, the discharge capacity after 100 weeks, and the discharge retention rate after 100 weeks are all significantly improved, and the design superiority of the core-shell sulfide solid electrolyte is confirmed.
Although preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that modifications and variations of the present invention are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A sulfide solid electrolyte with a core-shell structure is characterized in that: the core-shell particle comprises an inner core and a shell layer for coating the inner core; the core is sulfide solid electrolyte, and the shell layer is oxide solid electrolyte.
2. The core-shell structure sulfide solid electrolyte according to claim 1, characterized in that: the sulfide solid electrolyte includes at least one of a binary sulfide solid electrolyte, an LGPS type crystal sulfide solid electrolyte, a Thio-LiSICON series, a Geranite type crystal sulfide solid electrolyte, and a mixed conductor sulfide solid electrolyte.
3. The core-shell structure sulfide solid electrolyte according to claim 2, characterized in that: the binary sulfide solid electrolyte is Li 2 S-P 2 S 5 As a host, specifically (100-a) Li 2 S·a P 2 S 5 ，a＝20～40；b Li 2 S·a P 2 S 5 ·c LiBr·d LiI，b:a＝3～4，(c+d)/(a+b+c+d)＝5～50％。
4. The core-shell structure sulfide solid electrolyte according to claim 2, characterized in that: the mixed conductor sulfide solid electrolyte is Li 7-a M b P 1-b S 6-a X a Wherein a and b satisfy 0 < a < 2 and 0 < b < 1; m is a transition metal; x is at least one of halogen elements Cl, Br and I.
5. The core-shell structure sulfide solid electrolyte according to claim 4, characterized in that: the transition metal is at least one of Sc, Ti, V, Cr, Fe, Ni, Nb, Zn and Y.
6. The core-shell structure sulfide solid electrolyte according to claim 1, characterized in that: the oxide solid electrolyte is one or more of NASICON type solid electrolyte, Garnet type solid electrolyte, perovskite type solid electrolyte and LISICON type solid electrolyte.
7. The core-shell structure sulfide solid electrolyte according to claim 1, characterized in that: the thickness of the shell layer is 2 nm-500 nm, and the particle size diameter of the core-shell particles is 2 nm-500 nm.
8. A preparation method of a sulfide solid electrolyte with a core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
s1, suspending the sulfide solid electrolyte in a fluidized bed reactor by using a carrier gas, atomizing the oxide solid electrolyte solution, introducing the atomized oxide solid electrolyte solution into the fluidized bed reactor, controlling the temperature of the fluidized bed reactor to enable the oxide solid electrolyte powder to be adsorbed and deposited on the surface of the sulfide solid electrolyte, and simultaneously evaporating the solvent to dryness;
and S2, calcining the sulfide solid electrolyte coated by the oxide solid electrolyte to obtain the sulfide solid electrolyte with the core-shell structure.
9. The method for preparing the core-shell sulfide solid electrolyte according to claim 8, wherein: the temperature of the fluidized bed reactor in the step S1 is 70-180 ℃; and/or the sintering temperature in the step S2 is 100-750 ℃, and the heat preservation time is 1-20 h.
10. An all-solid-state battery characterized by: the all-solid-state battery comprising the core-shell sulfide solid electrolyte according to any one of claims 1 to 7 in at least one of a positive electrode layer, a negative electrode layer, and an electrolyte layer.
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CN115986203B (en) * 2023-03-21 2023-06-20 中创新航技术研究院(江苏)有限公司 Solid electrolyte, method for preparing the same, and battery comprising the same
CN117059880A (en) * 2023-07-18 2023-11-14 高能时代(珠海)新能源科技有限公司 Sulfide solid electrolyte material and preparation method and application thereof
CN117059880B (en) * 2023-07-18 2024-04-12 高能时代(珠海)新能源科技有限公司 Sulfide solid electrolyte material and preparation method and application thereof
CN117613369A (en) * 2023-12-20 2024-02-27 高能时代(珠海)新能源科技有限公司 Sulfide solid electrolyte material and preparation method and application thereof

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