CN112993390A - Solid electrolyte, preparation method thereof and solid battery - Google Patents

Solid electrolyte, preparation method thereof and solid battery Download PDF

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Publication number
CN112993390A
CN112993390A CN202110317524.3A CN202110317524A CN112993390A CN 112993390 A CN112993390 A CN 112993390A CN 202110317524 A CN202110317524 A CN 202110317524A CN 112993390 A CN112993390 A CN 112993390A
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solid electrolyte
lithium
electrolyte
fluorine
solid
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李艳红
熊伟强
石兴菊
谢普
梁世硕
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Kunshan Bao Innovative Energy Technology Co Ltd
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Kunshan Bao Innovative Energy Technology 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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

Abstract

The invention discloses a solid electrolyte, a preparation method thereof and a solid battery, wherein the preparation method of the solid electrolyte comprises the following steps: (1) mixing an oxide solid electrolyte and an auxiliary agent to obtain an electrolyte mixture, wherein the auxiliary agent comprises a stabilizing auxiliary agent and an optionally added lithium source, and the stabilizing auxiliary agent is a fluorine-containing compound; (2) sintering the electrolyte mixture at 800-1300 ℃ to prepare a stable-phase electrolyte; (3) reacting the stable phase electrolyte with HF. The preparation method can form a structure with a stable phase on part or all of the grain boundary and the surface of the material, has good electrochemical compatibility with the metal lithium, reduces the interface impedance with the metal lithium, and improves the cycle performance of the battery.

Description

Solid electrolyte, preparation method thereof and solid battery
Technical Field
The invention relates to the technical field of electrolytes, in particular to a solid electrolyte, a preparation method thereof and a solid battery.
Background
With the increasing demand for miniaturization of electronic components and devices, the safety and driving range of electric vehicles are becoming more anxious, and the research on lithium batteries with higher safety and higher energy density is becoming more urgent, so that solid-state batteries using lithium metal negative electrodes and solid electrolytes instead of liquid electrolytes are becoming a research hotspot in recent years.
Among various solid electrolyte systems, oxide solid electrolytes are widely concerned due to high room temperature lithium ion conductivity, wide electrochemical window and high electrochemical stability, and common oxide electrolytes mainly include garnet-type, perovskite-type, NASICON-type, LISICON-type and LiPON electrolytes. Among these oxide solid electrolytes, the garnet-type LLZO, LLZTO, LLZGO, perovskite-type LLTO and NASICON-type lag, LATP electrolytes are much concerned for their excellent overall performance, but these electrolytes have a large interface impedance when matched with a lithium metal negative electrode, and lithium dendrites still enter grain boundaries and grow along the grain boundaries at high current densities or as the number of cycles of the battery increases; also, there are more serious problems with LLTO and LATP materials in application: ti for lithium metal batteries4+Is easily reduced by metallic lithium, limiting its application.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the solid electrolyte prepared by the method is stable in interface when being in contact with a metal lithium cathode, and has low interface resistance, and the formed battery has good cycle performance.
In a first aspect of the present invention, a method for preparing a solid electrolyte is provided, comprising the following steps:
(1) mixing an oxide solid electrolyte and an auxiliary agent to obtain an electrolyte mixture, wherein the auxiliary agent comprises a stabilizing auxiliary agent and an optionally added lithium source, the stabilizing auxiliary agent is a fluorine-containing compound which is thermally decomposed at 50-1300 ℃, and the fluorine-containing compound is a fluorine-containing lithium salt or a fluorine-containing ammonia salt;
(2) sintering the electrolyte mixture at 800-1300 ℃ to prepare a stable-phase electrolyte;
(3) reacting the stable phase electrolyte with HF.
The preparation method of the solid electrolyte provided by the embodiment of the invention has at least the following beneficial effects:
the embodiment of the invention provides a preparation method of a solid electrolyte, which comprises the steps of mixing an oxide solid electrolyte and a stabilizer, sintering, decomposing a fluorine-containing compound decomposed by heating to form a fluorine-containing substance capable of reacting with lithium, so that a stabilizing additive mixed in an electrolyte mixture can react with lithium in the oxide solid electrolyte or a lithium source in the sintering process to form a stable phase at partial or all grain boundaries of the solid electrolyte material, then reacting with HF to further generate a chemical reaction on the surface of the solid electrolyte material to generate a stable phase, so that partial or all grain boundaries of the material and the surface of the material form the stable phase, the stable phase has good electrochemical compatibility with metallic lithium, thereby preventing the oxide electrolyte material from directly contacting with the metallic lithium, and realizing lower interface impedance of the oxide electrolyte material and the metallic lithium, the interface is stable when the lithium battery contacts with the metal lithium, so that the cycle performance of the battery is improved.
In some embodiments of the present invention, the upper temperature limit for thermal decomposition may be 1300 ℃, the preferred upper temperature limit for thermal decomposition may be 800 ℃ and the lower temperature limit may be 50 ℃.
In some embodiments of the invention, the stabilizing additive is selected from at least one of lithium hexafluorophosphate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, ammonium fluoride, ammonium bifluoride.
In some embodiments of the invention, the auxiliary agent accounts for 0.1 to 1.5 wt% of the mass fraction of the oxide solid electrolyte.
The term "optionally added lithium source" means that a lithium source is optionally added or not added according to the requirement.
In some embodiments of the present invention, the oxide solid electrolyte is at least one selected from a garnet-type solid electrolyte and a perovskite-type solid electrolyte, and the stabilizing additive is added in an amount of 50 to 100% by mass of the additive. That is, when the oxide solid electrolyte is a garnet solid electrolyte or a perovskite solid electrolyte, no lithium source may be added to the assistant, and the content of the stabilizing assistant may reach 100%.
The typical chemical structure formula in the garnet solid electrolyte is A3B2(XO4)3As the solid electrolyte, there can be exemplified LLZO solid electrolyte such as Li7La3Zr2O12. As the perovskite type solid electrolyte, there can be exemplified LLTO solid electrolyte such as Li0.5La0.5TiO3。
In some embodiments of the invention, the oxide solid electrolyte is a NACISION type solid electrolyte, and the addition amount of the stabilizing additive is 40-70% of the mass fraction of the electrolyte mixture. That is, when the oxide solid electrolyte is selected from NACISION type solid electrolytes, the auxiliary agent contains a lithium source.
An example of the NACISION-type solid electrolyte is LiTi2(PO4)3，LiGe2(PO4)3LATP solid electrolytes such as Li1.4Al0.4Ti1.6(PO4)3And the like.
When the oxide solid electrolyte is garnet solid electrolyte, the solid electrolyte formed by the preparation method can inhibit the growth of lithium dendrite and lead the battery to have better cycle performance when being matched with a lithium metal negative electrode, and when the oxide solid electrolyte is perovskite solid electrolyte and NASICON solid electrolyte, the solid electrolyte formed by the preparation method can be matched with the lithium metal negative electrode, Ti4+Is not easy to be reduced by metal lithium and has better stability.
In some embodiments of the present invention, the reaction temperature with HF in step (3) is 30 to 110 ℃, and the reaction time is 10min to 2h, at which the reaction can be accelerated.
In some embodiments of the present invention, step (3) is specifically: introducing HF vapor into the stable phase electrolyte.
In some embodiments of the present invention, step (3) is specifically: and placing the stable-phase electrolyte and the fluorine-containing unstable substance into a closed system, and introducing water vapor into the closed system, wherein the fluorine-containing unstable substance can react with the water vapor to form HF. Preferably, the temperature of the closed system is controlled to be 30-110 ℃, and the reaction lasts for 10 min-2 h. On one hand, the introduced water vapor can react with the oxide solid electrolyte material to form lithium hydroxide on the surface of the material or at an interface without forming a stable phase, on the other hand, the water vapor can react with the fluorine-containing unstable substance to generate hydrogen fluoride, and the generated hydrogen fluoride further reacts with the lithium hydroxide on the surface of the oxide electrolyte or at the interface to generate the stable phase.
In some embodiments of the invention, the fluorine-containing instability species is selected from at least one of ammonium bifluoride, ammonium fluoride, lithium bis-fluorosulfonylimide, lithium hexafluorophosphate, lithium bis-trifluoromethylsulfonyl imide; preferably, the adding amount of the fluorine-containing unstable substance accounts for 2-40% of the mass fraction of the electrolyte mixture.
In some embodiments of the invention, the method further comprises the step of shaping the electrolyte mixture prior to sintering; preferably, the molding mode is tablet molding. In some embodiments, the oxide electrolyte is pressed into a sheet or column shape by a tablet press or a hot press, and the formed oxide electrolyte is convenient for assembling to form a solid-state battery.
In some embodiments of the invention, the lithium source is at least one of lithium hydroxide, lithium chloride, lithium nitrate, lithium sulfate, lithium carbonate. The lithium source can react with the stabilizing additive to form a stable phase at part or all of the grain boundary; meanwhile, the lithium source can be used as a sintering aid at the interface, so that the sintering temperature is reduced, the sintering density is improved, and the conductivity performance of the electrolyte is further improved.
In some preferred embodiments of the invention, the lithium source is lithium hydroxide. Compared with other lithium sources, the used lithium hydroxide can generate water in the subsequent reaction with HF, other impurity ions cannot be introduced, and gas cannot be generated, so that the defect of holes in the electrolyte is caused.
In a second aspect of the present invention, a solid electrolyte is provided, which is prepared according to the above-mentioned method for preparing a solid electrolyte.
In a third aspect of the present invention, a solid-state battery is provided, which includes the above-described solid-state electrolyte.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view showing the wetting angle of a solid electrolyte prepared in example 1 of the present invention and comparative example 1 with molten lithium metal;
FIG. 2 is an electrochemical impedance spectrum of solid electrolytes prepared in example 2 of the present invention and comparative example 2 in a Li/Li symmetrical battery;
FIG. 3 is a graph of cycling data for solid electrolytes prepared in example 2 of the present invention and comparative example 2 in 523 type nickel cobalt lithium manganate ternary positive electrode/solid electrolyte/Li half-cell;
fig. 4 is an electrochemical impedance spectrum of the solid electrolyte prepared in example 3 of the present invention with respect to lithium metal at different times.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The LLTO oxide solid electrolyte used in the examples below was Li0.5La0.5TiO3The preparation process comprises the following steps: weighing lanthanum pentoxide (La) according to stoichiometric ratio2O5) Titanium dioxide (TiO)2) And lithium hydroxide (LiOH) with 20% of excess, selecting alcohol as a solvent, and ball-milling for 12 hours by adopting a ball mill with the rotating speed of 400rpm, wherein the ball-to-material ratio is 4: 1. Drying the alcohol solvent in an oven at 70 ℃ after discharging, crushing by using an agate mortar, sieving by using a 40-mesh sieve, sintering the sieved powder for 12 hours at 1000 ℃,the heating rate is 2 ℃/min, thus obtaining LLTO powder.
The LLZO oxide solid electrolyte is Li7La3Zr2O12The preparation process comprises the following steps: weighing lanthanum pentoxide (La) according to stoichiometric ratio2O5) Zirconium dioxide (ZrO)2) And lithium hydroxide (LiOH) with the excess of 10 percent, selecting alcohol as a solvent, and ball-milling for 8 hours by adopting a ball mill with the rotating speed of 400rpm, wherein the ball-material ratio is 4: 1. And (3) after discharging, drying the alcohol solvent in an oven at 70 ℃, crushing by using an agate mortar, sieving by using a 40-mesh sieve, and sintering the sieved powder at 900 ℃ for 16h at the heating rate of 2 ℃/min to obtain the LLZO powder.
The LATP oxide solid electrolyte is Li1.2Al0.2Ti1.8(PO4)3The preparation process comprises the following steps: weighing aluminum oxide (Al) according to stoichiometric ratio2O3) Titanium dioxide (TiO)2) Ammonium dihydrogen phosphate (NH)4H2PO4) And an excess of 5% lithium carbonate (Li)2CO3) Selecting alcohol as a solvent, and ball-milling for 4 hours by adopting a ball mill with the rotating speed of 200rpm, wherein the ball-material ratio is 3: 1. After discharging, drying the alcohol solvent in an oven at 70 ℃, crushing by using an agate mortar, sieving by using a 40-mesh sieve, and sintering the sieved powder at 750 ℃ for 4 hours for primary sintering, wherein the heating rate is 2 ℃/min; and crushing the sintered material, sieving the crushed material by a 40-mesh sieve, and sintering the sieved powder at 950 ℃ for 8 hours for secondary sintering at the heating rate of 2 ℃/min to obtain the LATP powder. .
Example 1
This example provides a solid electrolyte prepared according to the following steps:
5g of LLTO oxide solid electrolyte Li were weighed0.5La0.5TiO3Adding an auxiliary agent containing 0.0025g of lithium hexafluorophosphate and 0.0025g of lithium hydroxide into the powder, and mixing for 0.5h in a mixer to obtain a uniformly mixed electrolyte mixture.
And pressing the mixed electrolyte mixture into sheets by using a hot press, and sintering at 1150 ℃ for 4 hours to obtain the LLTO oxide electrolyte block.
And (2) placing the block in a platinum dish, placing 2g of ammonium bifluoride beside the block, placing the platinum dish in a vacuum tube furnace, introducing 30s of water vapor into the vacuum tube furnace, controlling the temperature of the tube furnace at 110 ℃, reacting for 2h, and finally cooling to room temperature to obtain the solid electrolyte.
Comparative example 1: comparative example 1 provides a solid electrolyte prepared according to the following steps: 5g of LLTO oxide solid electrolyte Li are taken0.5La0.5TiO3And (3) pressing the mixed electrolyte mixture into a sheet by using a hot press, and sintering at 1150 ℃ for 4 hours to obtain the solid electrolyte.
The interfacial affinity of the solid electrolyte material and the lithium metal is characterized by dropping molten lithium metal on the surface of the solid electrolyte material of example 1 and comparative example 1, respectively, and fig. 1 shows a schematic diagram of the wetting angle comparison between the solid electrolyte material and the lithium metal, wherein the solid electrolyte material prepared by the method of the present invention has a smaller contact angle and better interfacial wettability, and the wetting angle of the solid electrolyte material and the lithium metal is shown in fig. 1 (a) and comparative example 1 (b).
Example 2
This example provides a solid electrolyte prepared according to the following steps:
5g of LLZO oxide solid electrolyte Li was weighed7La3Zr2O12And adding 0.075g of lithium bis (fluorosulfonyl) imide into the powder, and mixing for 6 hours in a mixer to obtain a uniformly mixed electrolyte mixture.
And pressing the mixed electrolyte mixture into sheets by adopting a tablet press, and sintering for 2 hours at 1200 ℃ to obtain the LLZO oxide electrolyte block.
And (2) placing the block in a platinum dish, placing 1g of ammonium fluoride beside the block, placing the platinum dish in a vacuum tube furnace, introducing 30s of water vapor into the vacuum tube furnace, controlling the temperature of the tube furnace at 90 ℃, reacting for 1h, and finally cooling to room temperature to obtain the solid electrolyte.
Comparative example 2: comparative example 1 provides a solid electrolyte prepared according to the following steps: 5g of LLZO oxide solid electrolyte Li was taken7La3Zr2O12And (3) pressing the mixed electrolyte mixture into a sheet by adopting a hot press, and sintering at 1200 ℃ for 2h to obtain the solid electrolyte.
Taking the solid electrolytes prepared in example 2 and comparative example 2, Li/solid electrolyte/Li symmetrical batteries were prepared using the existing method, and then electrochemical impedance spectra of the batteries were measured to characterize the magnitude of interfacial impedance of the solid electrolyte and metallic lithium, and the results are shown in fig. 2, in which (a) represents the solid electrolyte in example 2, and (b) represents the solid electrolyte in comparative example 2. The test result shows that: compared with the solid electrolyte material of comparative example 2, the solid electrolyte prepared by the method of the invention has smaller interface resistance when contacting with metallic lithium, and the effect of improving the interface resistance is more obvious.
Taking the solid electrolytes prepared in the example 2 and the comparative example 2, a battery of 523 type lithium nickel cobalt manganese oxide ternary positive electrode/solid electrolyte/Li metal structure was prepared by using the conventional method, and the cycle performance of the battery was measured, and the results are shown in fig. 3, in which (a) represents the solid electrolyte in the example 2, and (b) represents the solid electrolyte in the comparative example 2. The cycle test results show that: the solid electrolyte prepared by the method has better cycle performance in a half-cell, which shows that the solid electrolyte material has better interface compatibility with a lithium metal cathode and less side reaction.
Example 3
This example provides a solid electrolyte prepared according to the following steps:
5g of LATP oxide solid electrolyte Li was weighed1.2Al0.2Ti1.8(PO4)3Adding an auxiliary agent containing 0.02g of lithium hexafluorophosphate and 0.03g of lithium hydroxide into the powder, and mixing for 8 hours in a mixer to obtain a uniformly mixed electrolyte mixture.
And pressing the mixed electrolyte mixture into sheets by a tablet press, and sintering at 850 ℃ for 5 hours to obtain the LATP oxide electrolyte block.
Placing the block in a platinum dish, placing 0.5g of a mixture of lithium bis (fluorosulfonyl) imide and lithium hexafluorophosphate beside the block, placing the platinum dish in a vacuum tube furnace, introducing 30s of water vapor into the vacuum tube furnace, controlling the temperature of the tube furnace at 50 ℃, reacting for 30min, and finally cooling to room temperature to obtain the solid electrolyte.
The solid electrolyte prepared in the embodiment 3 is assembled into a Li/solid electrolyte/Li symmetric battery, and then the electrochemical impedance spectrum of the battery is tested for the change rule with time, so as to further characterize the interface stability of the solid electrolyte and lithium metal. Fig. 4 shows an electrochemical impedance diagram of the solid electrolyte of example 3 with respect to lithium metal at different times, wherein the intermediate frequency region in the diagram is an interface compatibility contribution of the solid electrolyte material and the lithium metal electrode, and the change of the intermediate frequency region is small with the increase of time, which indicates that the compatibility of the solid electrolyte material and the lithium metal electrode provided by the present invention is good.
Example 4
This example provides a solid electrolyte prepared according to the following steps:
5g of LATP oxide solid electrolyte Li was weighed1.2Al0.2Ti1.8(PO4)3Adding an auxiliary agent containing 0.0525g of lithium bis (trifluoromethyl) sulfonyl imide and 0.0225g of lithium hydroxide into the powder, and mixing in a mixer for 12 hours to obtain a uniformly mixed electrolyte mixture.
And pressing the mixed electrolyte mixture into sheets by using a tablet press, and sintering at 900 ℃ for 10 hours to obtain the LATP oxide electrolyte block.
And (2) placing the block in a platinum dish, placing 1.5g of lithium hexafluorophosphate beside the block, placing the platinum dish in a vacuum tube furnace, introducing 30s of water vapor into the vacuum tube furnace, controlling the temperature of the tube furnace at 70 ℃, reacting for 25min, and finally cooling to room temperature to obtain the solid electrolyte material.
Taking the solid electrolyte prepared in the example, a Li/solid electrolyte/Li symmetric battery was prepared in the manner of example 2, and electrochemical impedance spectra thereof were measured, and experimental results showed that the solid electrolyte of the example has a low interfacial impedance with metallic lithium similar to that of example 2. Taking the solid electrolyte prepared in the embodiment to prepare a battery with a 523 type nickel cobalt lithium manganate ternary positive electrode/solid electrolyte/Li metal structure according to the method of the embodiment 2, and then determining the cycle performance of the battery, the experimental result shows that the solid electrolyte prepared in the embodiment has better cycle performance in a half battery.
Example 5
This example provides a solid electrolyte prepared according to the following steps:
5g of LLTO oxide solid electrolyte Li were weighed0.5La0.5TiO3Adding an auxiliary agent containing 0.0025g of lithium hexafluorophosphate and 0.0025g of lithium hydroxide into the powder, and mixing for 0.5h in a mixer to obtain a uniformly mixed electrolyte mixture.
And pressing the mixed electrolyte mixture into sheets by using a hot press, and sintering at 1300 ℃ for 4 hours to obtain the LLTO oxide electrolyte block.
And (3) placing the block in a platinum dish, placing the platinum dish in a vacuum tube furnace, introducing 30s of vapor of HF aqueous solution into the vacuum tube furnace, controlling the temperature of the tube furnace at 110 ℃, reacting for 2h, and finally cooling to room temperature to obtain the solid electrolyte.
Taking the solid electrolyte prepared in the example, a Li/solid electrolyte/Li symmetric battery was prepared in the manner of example 2, and electrochemical impedance spectra thereof were measured, and experimental results showed that the solid electrolyte of the example has a low interfacial impedance with metallic lithium similar to that of example 2. Taking the solid electrolyte prepared in the embodiment to prepare a battery with a 523 type nickel cobalt lithium manganate ternary positive electrode/solid electrolyte/Li metal structure according to the method of the embodiment 2, and then determining the cycle performance of the battery, the experimental result shows that the solid electrolyte prepared in the embodiment has better cycle performance in a half battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. A method of preparing a solid electrolyte, comprising the steps of:
(1) mixing an oxide solid electrolyte and an auxiliary agent to obtain an electrolyte mixture, wherein the auxiliary agent comprises a stabilizing auxiliary agent and an optionally added lithium source, the stabilizing auxiliary agent is a fluorine-containing compound which is thermally decomposed at 50-1300 ℃, and the fluorine-containing compound is a fluorine-containing lithium salt or a fluorine-containing ammonia salt;
(2) sintering the electrolyte mixture at 800-1300 ℃ to prepare a stable-phase electrolyte;
(3) reacting the stable phase electrolyte with HF.
2. The method for producing a solid electrolyte according to claim 1, wherein the stabilizing auxiliary is at least one selected from the group consisting of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, ammonium fluoride and ammonium bifluoride; preferably, the auxiliary agent accounts for 0.1-1.5 wt% of the mass fraction of the oxide solid electrolyte.
3. The method for preparing a solid electrolyte according to claim 1, wherein the oxide solid electrolyte is at least one selected from garnet-type solid electrolytes and perovskite-type solid electrolytes, and the addition amount of the stabilizing additive is 50-100% by mass of the additive.
4. The method for preparing a solid electrolyte according to claim 1, wherein the oxide solid electrolyte is a NACISION type solid electrolyte, and the stabilizing additive is added in an amount of 40 to 70% by mass based on the mass fraction of the additive.
5. The method for producing a solid electrolyte according to any one of claims 1 to 4, wherein the step (3) is specifically: introducing HF vapor into the stable phase electrolyte.
6. The method for producing a solid electrolyte according to any one of claims 1 to 4, wherein the step (3) is specifically: placing the stable-phase electrolyte and a fluorine-containing unstable substance into a closed system, and introducing water vapor into the closed system, wherein the fluorine-containing unstable substance can react with the water vapor to form HF; preferably, the fluorine-containing labile compound is selected from at least one of ammonium bifluoride, ammonium fluoride, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide; preferably, the addition amount of the fluorine-containing unstable substance accounts for 2-40% of the mass fraction of the oxide solid electrolyte.
7. The method for producing a solid electrolyte according to any one of claims 1 to 4, characterized by further comprising a step of molding the electrolyte mixture before sintering in step (2); preferably, the molding mode is tablet molding.
8. The method of producing a solid electrolyte according to any one of claims 1 to 4, characterized in that the lithium source is at least one of lithium hydroxide, lithium chloride, lithium nitrate, lithium sulfate, lithium carbonate; preferably, the lithium source is lithium hydroxide.
9. A solid electrolyte obtained by the method for producing a solid electrolyte according to any one of claims 1 to 8.
10. A solid-state battery comprising the solid-state electrolyte according to claim 9.
CN202110317524.3A 2021-03-25 2021-03-25 Solid electrolyte, preparation method thereof and solid battery Pending CN112993390A (en)

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Publication number Priority date Publication date Assignee Title
CN113285117A (en) * 2021-06-30 2021-08-20 珠海冠宇电池股份有限公司 Composite solid electrolyte and lithium ion battery comprising same
CN113285117B (en) * 2021-06-30 2024-01-12 珠海冠宇电池股份有限公司 Composite solid electrolyte and lithium ion battery comprising same
CN113782810A (en) * 2021-09-10 2021-12-10 贵州梅岭电源有限公司 Lithium electrolyte of solvent self-sacrificial in-situ protection electrode and preparation and application thereof
CN113782810B (en) * 2021-09-10 2022-06-17 贵州梅岭电源有限公司 Lithium electrolyte of solvent self-sacrificial in-situ protection electrode and preparation and application thereof
CN113921755A (en) * 2021-10-09 2022-01-11 南京林业大学 Composite solid positive electrode for solid lithium battery and preparation method thereof

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Application publication date: 20210618