CN113054245B - Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery - Google Patents

Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery Download PDF

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CN113054245B
CN113054245B CN202110273750.6A CN202110273750A CN113054245B CN 113054245 B CN113054245 B CN 113054245B CN 202110273750 A CN202110273750 A CN 202110273750A CN 113054245 B CN113054245 B CN 113054245B
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inorganic metal
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CN113054245A (en
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邓志
倪地兴
李帅
赵予生
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Southwest University of Science and Technology
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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The application provides an anti-perovskite solid electrolyte material, a preparation method thereof, a solid electrolyte sheet and an all-solid-state battery, and belongs to the technical field of all-solid-state lithium ion batteries. The anti-perovskite solid electrolyte material comprises: cubic phase Li 3‑x M x/n AX and lamellar phase Li 7‑ y M y/n A 2 X 3 Wherein 0 is<x<0.5，0<y<1, M is a metal ion, A is a divalent anion, X is a monovalent anion, and n is the valence state of the doped metal ion. The preparation method comprises the following steps: mixing Li 2 A. Mixing an inorganic metal compound and LiX, keeping the temperature for 2 hours at the temperature of 250-600 ℃, and then cooling; wherein A is a divalent anion and B is a monovalent anion. The anti-perovskite solid electrolyte material is doped with metal ions, an ion diffusion channel is optimized, and the ion mobility is improved, so that the ion conductivity of the electrolyte is improved.

Description

Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery
Technical Field
The application relates to the technical field of all-solid-state lithium ion batteries, in particular to an anti-perovskite solid electrolyte material, a preparation method thereof, a solid electrolyte sheet and an all-solid-state battery.
Background
At present, the main component in the all-solid-state lithium ion battery is a solid electrolyte sheet, and the existing solid electrolyte sheet has the problems of low ionic conductivity, poor interface stability and the like. Therefore, the development of a solid electrolyte sheet having high ionic conductivity and interfacial stability is a key driving the development of all-solid lithium ion batteries.
The solid electrolyte with the anti-perovskite structure generally has more ideal performance, such as lower activation energy, higher ionic conductivity and the like, and very low electronic conductivity, and more importantly, the material is stable to lithium metal, has good thermal stability in a certain temperature range, and has better application space. However, the ion conductivity of the current anti-perovskite solid electrolyte is still greatly different from that of a liquid electrolyte, and further improvement is still needed.
Disclosure of Invention
The application aims to provide an anti-perovskite solid electrolyte material, a preparation method thereof, a solid electrolyte sheet and an all-solid-state battery, and the ion conductivity of the electrolyte is further improved by doping metal ions in a lamellar phase and a cubic phase.
In a first aspect, the present application provides an anti-perovskite solid state electrolyte material comprising: cubic phase Li 3-x M x/n AX and lamellar phase Li 7-y M y/n A 2 X 3 Wherein, 0<x<0.5，0<y<1, M is a metal element, A is a divalent anion, X is a monovalent anion, and n is the valence state of the doped metal ion.
In the application, metal ions are doped in both the lamellar anti-perovskite structural phase and the cubic anti-perovskite structural phase, so that an ion diffusion channel can be optimized, and the ion mobility is improved, thereby improving the ion conductivity of the electrolyte. And metal ions are doped in the layered phase, so that the structure of the layered phase of the metastable phase is more stable, and the metastable phase can stably exist in two opposite perovskite materials.
Optionally, M is an alkaline earth metal ion or/and a transition metal ion. Alternatively, M is Ca 2+ 、Mg 2+ 、Ba 2+ 、Sr 2+ 、Sc3 + 、Al 3+ 、Ga 3+ And Ti 4+ One or more of (a). A is O 2- 、S 2- And Se 2- One or more of (a). X is F - 、Cl - 、Br - 、I - 、NO 2 - 、NH 2 - 、BH 4 - And BF 4 - One or more of (a).
In one possible embodiment, the lamellar phase is present in an amount of 25% to 80% by weight. The higher content of the layered anti-perovskite structure phase enables the ionic conductivity of the electrolyte to be higher.
In a second aspect, the present application provides a method for preparing an anti-perovskite solid-state electrolyte material, comprising: mixing Li 2 A. Mixing an inorganic metal compound and LiX, carrying out heat treatment at the temperature of 250-600 ℃, and then cooling; wherein A is a divalent anion and X is a monovalent anion.
Mixing Li 2 A. After inorganic metal compound and LiX are mixed and subjected to heat treatment, a two-phase anti-perovskite solid electrolyte material containing a part of cubic anti-perovskite structural phase and a layered anti-perovskite structural phase which are mixed can be obtained, and the reaction principle is as follows: li 2 A+MB z +LiX→Li 3-x M x/n AX+Li 7-y M y/n A 2 X 3 . The method can simultaneously dope metal ions into the two-phase-opposition perovskite solid electrolyte, and after metal doping, the metastable-phase lamellar phase structure is more stable, can stably exist in two-phase-opposition perovskite materials, and the process is simpler.
Optionally, the inorganic metal compound is an alkaline earth inorganic metal compound or/and a transition inorganic metal compound. Further, the inorganic metal compound includes at least one of a metal oxide, a metal sulfide, and a metal selenide.
Optionally, the metal oxide comprises CaO, MgO, BaO, SrO, Al 2 O 3 ，Ga 2 O 3 ，Sc 2 O 3 ，TiO 2 One or more of (a).
In one possible embodiment, the cooling rate after the heat treatment is not less than 100 ℃/s. Optionally, the cooling speed is 100-; furthermore, the cooling speed is 160-.
Optionally, the heat-treated product is cooled in liquid nitrogen.
In one possible embodiment, the mixing is ball milled under an inert gas blanket or a stabilizing organic solvent blanket. The particles of the raw material may be made finer for subsequent heat treatment.
Optionally, the rotation speed of the ball mill is within the range of 200-600 rpm; the stabilizing organic solvent comprises one or more of hexane, heptane, octane, benzene, toluene, p-xylene.
In one possible embodiment, Li 2 A. The particle diameters of the inorganic metal compound and LiX are both in the range of 0.5 to 50 μm. After the raw materials in the particle size range are subjected to heat treatment, the metal ion doping effects of the cubic anti-perovskite structure phase and the lamellar anti-perovskite structure phase are better, and the reaction efficiency is higher.
In a third aspect, the present application provides a solid electrolyte sheet comprising the above-described anti-perovskite solid electrolyte material.
In a fourth aspect, the present application provides an all-solid-state battery comprising the above-described solid electrolyte sheet.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
Fig. 1 is an XRD pattern of a solid electrolyte material provided in comparative examples 1 to 3, examples 1 to 2;
fig. 2 is a graph comparing the ac impedance of a solid electrolyte sheet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.
The application provides a preparation method of an anti-perovskite solid electrolyte material, which comprises the following steps:
s10, preparing raw materials
The raw materials are respectively Li 2 A. An inorganic metal compound and LiX, wherein A is a divalent anion and X is a monovalent anion.
Alternatively, A is O 2- 、S 2- And Se 2- Is one or more of, X is F - 、Cl - 、Br - 、I - 、NO 2 - 、NH 2 - 、BH 4 - And BF 4 - One or more of (a).
For example: raw material Li 2 A comprises Li 2 O、Li 2 S and Li 2 One or more of Se.
The LiX raw material comprises LiF, LiCl, LiBr, LiI and LiNO 2 、LiNH 2 、LiBH 4 And LiBF 4 One or more of (a).
The inorganic metal compound is an alkaline earth inorganic metal compound or/and a transition inorganic metal compound. Optionally, the inorganic metal compound comprises at least one of a metal oxide, a metal sulfide, and a metal selenide.
If the inorganic metal compound is a metal oxide, the metal oxide includes CaO, MgO, BaO, SrO, Al 2 O 3 、Ga 2 O 3 、Sc 2 O 3 And TiO 2 One or more of (a).
If the inorganic metal compound is a metal sulfide, the metal sulfide includes CaS, MgS, BaS, SrS, Al 2 S 3 、Ga 2 S 3 、Sc 2 S 3 And TiS 2 One or more of (a).
If the inorganic metal compound is a metal selenide, the metal selenide comprises CaSe, MgSe, BaSe, SrSe, Al 2 Se 3 、Ga 2 Se 3 、Sc 2 Se 3 And TiSe 2 One or more of (a).
Alternatively, Li 2 A. The molar ratio of the inorganic metal compound to the LiX is 1 (0-0.2) to 1-1.5. For example: li 2 A. The molar ratio of the inorganic metal compound to LiX is 1:0.01:1, 1:0.1:1.2 or 1:0.2: 1.5.
S20, mixing the raw materials
Mixing Li 2 A. And uniformly mixing the inorganic metal compound and the LiX to obtain the precursor. Optionally, the raw materials are mixed in a ball milling mode, so that the raw materials can be mixed more uniformly, and the particles of the raw materials can be formedThe diameter is smaller, so that the subsequent reaction can be carried out.
Optionally, the ball milling is performed under the protection of inert gas or stable organic solvent; the rotation speed of the ball mill is 200-600 rpm.
Further, the stabilizing organic solvent comprises one or more of hexane, heptane, octane, benzene, toluene, p-xylene, and similar alkane analogs or derivatives or ether organic liquids. The inert gas is argon, nitrogen, helium, etc.
After ball milling, Li 2 A. The particle diameters of the inorganic metal compound and LiX are each in the range of 0.5 to 50 μm for subsequent heat treatment. Illustratively, the precursor has a particle size in the range of 0.5-10 μm, 10-20 μm, 20-30 μm, or 30-40 μm.
S30, heat treatment is carried out on the precursor
The heat treatment is carried out at the temperature of 250-600 ℃, and then the cooling is carried out. Mixing Li 2 A. After inorganic metal compound and LiX are mixed and subjected to heat treatment, a two-phase anti-perovskite solid electrolyte material containing a part of cubic anti-perovskite structural phase and a part of layered anti-perovskite structural phase which are mixed can be obtained, and the reaction principle is as follows: li 2 A+MB z +LiX→Li 3-x M x/n AX+Li 7- y M y/n A 2 X 3 . The method can be used for simultaneously doping metal ions in the two-phase anti-perovskite solid electrolyte, and after metal doping, the metastable-phase lamellar phase structure is more stable and can be stably stored in two opposite perovskite materials, and the process is simpler.
Optionally, the heat treatment temperature is 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the heat preservation time of the heat treatment is 2h, 2.5h or 3 h.
Alternatively, the cooling method may be rapid cooling, which may make the two-phase anti-perovskite material contain more lamellar anti-perovskite structure phase, thereby improving the ionic conductivity of the electrolyte.
Optionally, the cooling rate is not less than 100 ℃/s; the cooling speed is 100-; the cooling rate is 160-250 ℃/s. The cooling speed is high, the mass percentage of the lamellar phase can be higher, and the ionic conductivity of the electrolyte is further improved. Further, the product was cooled in liquid nitrogen. In other embodiments, the heat-treated product can be directly taken out and placed in a normal-temperature or low-temperature container for rapid cooling, so as to generate the anti-perovskite material with the lamellar phase and increase the ionic conductivity of the electrolyte. The reactor with the product after heat treatment can also be directly placed in liquid nitrogen for rapid cooling of the product.
The anti-perovskite solid electrolyte material prepared by the preparation method comprises cubic phase Li 3-x M x/n AX and lamellar phase Li 7-y M y/n A 2 X 3 Wherein, 0<x<0.5，0<y<1 and n are the valence states of the doped metal ions. Wherein the selection of M, A and X is consistent with the selection of M, A and X in the raw materials.
For example: m is Ca 2+ 、Mg 2+ 、Ba 2+ 、Sr 2+ If n is 2; m is Sc3 + 、Al 3+ 、Ga 3+ If n is 3; m is Ti 4+ And n is 4. A is O 2- ，S 2- ，Se 2- One or more of (a). X is F - 、Cl - 、Br - 、I - 、NO 2 - 、NH 2 - 、BH 4 - And BF 4 - One or more of (a).
Illustratively, x is 0.1, y is 0.1, and M is Ca 2+ A is O 2- X is Cl - Then the anti-perovskite solid electrolyte material is cubic phase Li 2.9 Ca 0.1/2 OCl and lamellar phase Li 6.9 Ca 0.1/2 O 2 Cl 3 (ii) a x is 0.2, y is 0.3, and M is Ga 3+ A is O 2- X is Br - Then the anti-perovskite solid electrolyte material is cubic phase Li 2.8 Ga 0.2/3 OBr and lamellar phase Li 6.7 Ga 0.3/3 O 2 Br 3 (ii) a x is 0.3, y is 0.5, M is Ti 4+ A is S 2- X is (NH) 2 ) - Then the anti-perovskite solid state electrolysisThe material is cubic phase Li 2.7 Ti 0.3/4 S(NH 2 ) And a lamellar phase Li 6.5 Ti 0.5/4 S 2 (NH 2 ) 3 (ii) a x is 0.4, y is 0.7, M is Ca 2+ A is O 2- X is Br - Then the anti-perovskite solid electrolyte material is cubic phase Li 2.6 Ca 0.4/2 OBr and lamellar phase Li 6.3 Ca 0.7/2 O 2 Br 3 。
Optionally, the content of the lamellar phase is 25% to 80% by mass, and the higher content of the lamellar anti-perovskite structure phase enables the ionic conductivity of the electrolyte to be higher.
Further, the mass percent of the lamellar phase is 50-80%.
The anti-perovskite solid electrolyte material can be used for preparing a solid electrolyte sheet. The method comprises the following specific steps: grinding the anti-perovskite solid electrolyte material obtained after rapid cooling to obtain electrolyte particles, and then pressing into a sheet at normal temperature to obtain a solid electrolyte sheet; or pressed into a sheet at a high temperature and then cooled to obtain a solid electrolyte sheet.
The solid electrolyte sheet can be used for preparing all-solid batteries, and has higher ionic conductivity.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
With Li 2 O, LiBr, CaO as raw materials, Li 2 The mol ratio of O, LiBr and CaO is 1:1.1:0.05, the mol ratio of elements of lithium, oxygen, bromine and calcium is 3.1:1.05:1.1:0.05, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of a ball mill is 400rpm, the ball milling is carried out for 5min each time, the rest is carried out for 10min, and the total ball milling time is 20h, thus obtaining the precursor. Carrying out heat treatment on the precursor, wherein the heat treatment temperature is 280 ℃, the heat preservation time is 8h, and after the heat preservation process is finishedThe molten sample was placed in a liquid nitrogen environment for cooling.
Example 2
With Li 2 O, LiBr, CaO as raw materials, Li 2 The mol ratio of O, LiBr and CaO is 1:1.1:0.1 respectively, the mol ratio of elements of lithium, oxygen, bromine and calcium is 3.1:1.1:1.1:0.1, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of a ball mill is 400rpm, the ball milling is carried out for 5min each time, the rest is carried out for 10min, and the total ball milling time is 20h, thus obtaining the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 280 ℃, the heat preservation time is 8h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Example 3
With Li 2 O、LiBr、Ga 2 O 3 As a raw material, Li 2 O、LiBr、Ga 2 O 3 The molar ratio of the elements is 1:1.1:0.05, the molar ratio of the elements of lithium, oxygen, bromine and gallium is 3.1:1.15:1.1:0.1, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of the ball mill is 400rpm, each ball milling is 5min, the rest is 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 5h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Example 4
With Li 2 O、LiBr、Ga 2 O 3 As a raw material, Li 2 O、LiBr、Ga 2 O 3 The molar ratio of the elements is 1:1.2:0.05, the molar ratio of the elements of lithium, oxygen, bromine and gallium is 3.2:1.15:1.2:0.1, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of the ball mill is 400rpm, each ball milling is 5min, the rest is 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 5h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Example 5
With Li 2 S、LiI、Sc 2 S 3 As a raw material, Li 2 S、LiI、Sc 2 S 3 In a molar ratio of 1:1.1:0.05, respectively, and the molar ratio of the elements of lithium, sulfur, iodine and scandium in a molar ratio of 3.1:1.15:1.1:0.1, respectivelyThe raw materials are mixed and then ball-milled under the protection of argon, the rotating speed of the ball mill is 400rpm, each ball milling is carried out for 5min, the rest is carried out for 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 250 ℃, the heat preservation time is 2h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Example 6
With Li 2 S、LiI、Sc 2 S 3 As a raw material, Li 2 S、LiI、Sc 2 S 3 The molar ratio of the lithium, the sulfur, the iodine and the scandium is 1:1.2:0.05, the molar ratio of the elements of the lithium, the sulfur, the iodine and the scandium is 3.2:1.15:1.2:0.1, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of the ball mill is 400rpm, each ball milling is 5min, the rest is 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 250 ℃, the heat preservation time is 2h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Comparative example 1
With Li 2 O, LiBr as raw material, Li 2 O, LiBr, the molar ratio of lithium to oxygen to bromine is 1:1, the molar ratio of lithium to oxygen to bromine is 3:1:1, the raw materials are mixed and ball milled under the protection of argon, the rotating speed of the ball mill is 400rpm, the ball milling is carried out for 5min each time, the rest is carried out for 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 280 ℃, the heat preservation time is 8h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Comparative example 2
With Li 2 O, LiBr as raw material, Li 2 O, LiBr, the molar ratio of lithium, oxygen and bromine is 1:1.05, the raw materials are mixed and ball milled under the protection of argon, the rotating speed of the ball mill is 400rpm, the ball milling is carried out for 5min each time, the rest is carried out for 10min, and the total ball milling time is 20h, thus obtaining the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 280 ℃, the heat preservation time is 8h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Comparative example 3
With Li 2 O, LiBr as raw material, Li 2 O, LiBr molar ratio of 1:1.1, moles of lithium, oxygen and bromineThe ratio of the raw materials is 3.1:1:1.1, the raw materials are mixed and then ball milled under the protection of argon, the rotating speed of a ball mill is 400rpm, each ball milling is 5min, the rest is 10min, and the total ball milling time is 20h to obtain the precursor. And (3) carrying out heat treatment on the precursor, wherein the heat treatment temperature is 280 ℃, the heat preservation time is 8h, and after the heat preservation process is finished, placing the molten sample into a liquid nitrogen environment for cooling.
Experimental example 1
Fig. 1 is an XRD pattern of the solid electrolyte material provided in comparative examples 1 to 3 and examples 1 to 2. As can be seen from fig. 1, the contents of the layered anti-perovskite structure phase in comparative example 1, comparative example 2, comparative example 3, example 1 and example 2 gradually increase. It is shown that examples 1 and 2 of the present application provide an anti-perovskite material having a higher content of a lamellar phase. And as can be seen from the XRD patterns of the solid electrolyte materials provided in examples 1 and 2, the solid electrolyte material has no hetero-peak of the inorganic metal compound other than the peaks of the layered perovskite structure phase and the cubic perovskite structure phase, indicating that metal ions have been doped into the layered perovskite structure phase and the cubic perovskite structure phase.
The anti-perovskite solid electrolyte materials provided in comparative examples 1 to 3 and examples 1 to 2 were used for the preparation of solid electrolyte sheets, and the anti-perovskite solid electrolyte materials were ground into powders and, after hot pressing into solid electrolyte sheets, were placed in liquid nitrogen for cooling. Fig. 2 is a graph comparing the ac impedance of a solid electrolyte sheet. As can be seen from fig. 2, the resistance value of the electrolyte sheet gradually decreases and the ionic conductivity gradually increases along the order of comparative example 1, comparative example 2, comparative example 3, example 1, and example 2. It is shown that the ion conductivity of the solid electrolyte sheets provided in examples 1 and 2 of the present application is higher.
The content of the layered opposite perovskite material in the solid electrolyte material and the ionic conductivity of the solid electrolyte sheet were analyzed according to fig. 1 and 2. The ion conductivity of the anti-perovskite solid electrolyte in comparative example 1 was 1.1X 10 -5 S/cm, the content of the layered opposite perovskite is 25 percent; in comparative example 2, the content of lamellar anti-perovskite structural phase in the anti-perovskite solid electrolyte reaches 50%, and the ionic conductivity is 9.6 multiplied by 10 -5 S/cm; trans-perovskite in comparative example 3The content of the lamellar anti-perovskite structure phase in the mineral solid electrolyte reaches 60 percent, but the mineral solid electrolyte contains certain LiBr mixed phases (peaks appearing at about 28 degrees 2 theta and about 32.5 degrees 2 theta), and the ionic conductivity is 9.2 multiplied by 10 -5 S/cm; the content of the lamellar anti-perovskite structure phase in the anti-perovskite solid electrolyte in example 1 reaches 66%, no LiBr impurity phase exists (no peak appears at about 28 ° and about 32.5 ° 2 θ), and the ionic conductivity is 1.8 × 10 -4 S/cm; in example 2, the content of the lamellar anti-perovskite structure phase in the anti-perovskite solid electrolyte reaches 75%, and the electrolyte has no LiBr impurity phase (no peaks appear around 28 ° and around 32.5 °), and has an ionic conductivity of 3 × 10 -4 S/cm。
It can be seen from comparison among examples 1, 2 and comparative example 3 that, under the condition of the same proportion of other raw materials, the addition of CaO in different contents in examples 1 and 2 can make the lamellar phase content in the two-phase anti-perovskite solid electrolyte material higher and the ionic conductivity higher. Furthermore, as can be seen from comparative example 3, in Li 2 O, LiBr, the LiBr content is relatively high when the molar ratio is 1:1.1, so LiBr mixed phase appears in the XRD pattern; in example 1, however, Li 2 The molar ratios of O, LiBr and CaO were 1:1.1:0.05, respectively, and Li in example 2 2 The molar ratio of O, LiBr and CaO is 1:1.1:0.1 respectively, LiBr mixed phases do not appear in an XRD (X-ray diffraction) diagram, which shows that in the application, the addition of CaO in the raw materials is gradually increased, so that more LiBr and Li can be added 2 O reacts with CaO, so that more lamellar phases are contained in the material.
As can be seen from comparative examples 1 to 3, Li 2 O, LiBr is gradually increased from 1:1 to 1:1.1, the content of the lamellar phase in the two-phase anti-perovskite solid electrolyte material is gradually increased.
Table 1 shows the preparation methods and properties of the anti-perovskite solid electrolyte materials provided in examples 1 to 8 and comparative example 1.
TABLE 1 preparation method and Properties of anti-perovskite solid electrolyte Material
Figure BDA0002973745070000101
In Table 1, it is clear from examples 1 and 2 that the amount of CaO added to the raw material is gradually increased, and that LiBr and Li can be increased more 2 O reacts with CaO, so that more lamellar phases are contained in the material, and the ionic conductivity of the material is higher. As is clear from examples 3 and 4, Ga is added to the raw materials 2 O 3 The increasing can lead more LiBr and Li 2 O and Ga 2 O 3 The reaction occurs, resulting in a material with more lamellar phases and thus a higher ionic conductivity. It can be seen from examples 5 and 6 that Sc is added to the starting material 2 S 3 Gradually increase Li 2 S and LiI and Sc 2 S 3 The reaction occurs, so that the material contains more lamellar phase, and the ionic conductivity is higher.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (14)

1. A method for preparing an anti-perovskite solid electrolyte material is characterized by comprising the following steps:
mixing Li 2 A. Mixing an inorganic metal compound and LiX, carrying out heat treatment at the temperature of 250-600 ℃, and then cooling; the cooling speed is not less than 100 ℃/s;
wherein the anti-perovskite solid state electrolyte material comprises cubic phase Li x3- M x/n AX and lamellar phase Li y7- M y/n A 2 X 3 ，0<x<0.5，0<y<1, M is a metal ion, A is a divalent anion, X is a monovalent anion, and n is the valence state of the doped metal ion.
2. The production method according to claim 1, wherein the inorganic metal compound is an alkaline earth inorganic metal compound or/and a transition inorganic metal compound.
3. The production method according to claim 2, wherein the inorganic metal compound includes at least one of a metal oxide, a metal sulfide, and a metal selenide.
4. The method according to claim 3, wherein the metal oxide comprises CaO, MgO, BaO, SrO, Al 2 O 3 ，Ga 2 O 3 ，Sc 2 O 3 ，TiO 2 One or more of (a).
5. The method according to claim 1, wherein A is O 2- 、S 2- And Se 2- One or more of (a).
6. The method according to claim 1, wherein X is F - 、Cl - 、Br - 、I - 、NO 2 - 、NH 2 - 、BH 4 - And BF 4 - One or more of (a).
7. The method according to claim 1, wherein the lamellar phase is present in an amount of 25 to 80% by mass.
8. The method as claimed in claim 1, wherein the cooling rate is 100 ℃ and 800 ℃/s.
9. The method as claimed in claim 1, wherein the cooling rate is 160 ℃ per second and 250 ℃ per second.
10. The method according to claim 1, wherein the heat-treated product is cooled in liquid nitrogen.
11. The preparation method of claim 1, wherein the mixing is performed by ball milling under the protection of inert gas or stable organic solvent.
12. The method as claimed in claim 11, wherein the rotation speed of the ball mill is within the range of 200-600 rpm.
13. The method of claim 11, wherein the stable organic solvent comprises one or more of hexane, heptane, octane, benzene, toluene, and p-xylene.
14. The production method according to any one of claims 1 to 13, characterized in that the Li 2 A. The particle size of the inorganic metal compound and the particle size of the LiX are both in the range of 0.5 to 50 μm.
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