CN112174201A - Preparation method of sulfide-based solid electrolyte - Google Patents
Preparation method of sulfide-based solid electrolyte Download PDFInfo
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- CN112174201A CN112174201A CN202010985898.8A CN202010985898A CN112174201A CN 112174201 A CN112174201 A CN 112174201A CN 202010985898 A CN202010985898 A CN 202010985898A CN 112174201 A CN112174201 A CN 112174201A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/002—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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 relates to a preparation method of a sulfide-based solid electrolyte, which comprises the following steps: vacuum drying the raw materials, weighing the dried raw materials according to a metering ratio under an inert atmosphere, mixing and grinding to obtain mixed powder; transferring the mixed powder into a high-pressure reaction kettle, adding a solvent, sealing the reaction kettle, and placing the reaction kettle in a muffle furnace for heat treatment; cooling, adding acetone to precipitate solid, filtering the powder, washing with ethanol, and vacuum drying to obtain primary material; and carrying out heat treatment on the initial material under an inert atmosphere to obtain a final product. Na produced in the present invention3XS4(X = P, Sb) good reproducibility of solid electrolyte batches and high ionic conductivity; the method has the advantages of simple operation, low cost, high efficiency and high purity,is beneficial to large-scale preparation.
Description
Technical Field
The invention belongs to the field of solid electrolyte of a sodium ion battery, and particularly relates to a lithium ion batterySulfide-based solid electrolyte Na in all-solid-state sodium ion battery3XS4(X = P, Sb).
Background
In recent years, with the rise of new energy automobiles and the rapid development of pure electric vehicles and hybrid electric vehicles, the demand of lithium ion secondary batteries is greatly increased, and the demand of lithium resources is undoubtedly increased, and it is worth noting that the abundance of lithium in earth crust is only 0.0065%, the demand of an energy storage system for lithium resources is also huge, and the development of lithium batteries is undoubtedly benefited by price. Meanwhile, sodium which is the sixth most abundant element on earth and has the same main group with lithium attracts people, the abundance of the sodium element in the earth crust is 2.74 percent, which is 420 times as much as that of the lithium element, and the refining process of the sodium element is simpler. As a candidate of a battery energy storage system, a sodium ion secondary battery has advantages of low cost, good safety and the like compared with a lithium ion secondary battery, and research on a positive electrode material of the sodium ion secondary battery becomes one of the focuses of people. However, sodium metal anodes have been problematic due to uncontrolled dendrite growth and side effects with liquid electrolytes. While all-solid-state sodium batteries are a promising solution to prevent sodium dendrite growth and eliminate the potential safety hazard caused by flammable organic electrolytes. Currently, among solid electrolytes, all-solid-state sodium ion battery sulfide-based solid electrolytes such as cubic phase Na3PS4Has better formability, lower grain boundary resistance and comparable ionic conductivity, thereby having wide application prospect. However, to realize practical application of sulfide solid electrolytes, optimization of the synthesis method is required to reduce the cost. Electrolytes are typically synthesized by mechanochemical and solid phase techniques. For example, chinese patent publication No. CN108390094A discloses a method for preparing an air-stable sodium ion sulfide solid electrolyte material having a room temperature sodium ion conductivity of about 10-4s/cm, the manufacturing process comprises the steps of firstly ball-milling and mixing materials at a high speed for 15 hours, then carrying out die-pressing and sheeting, and carrying out heat treatment at 550 ℃ in vacuum for 24 hours to obtain the sulfide electrolyte. Is not easy to enterThe industrial scale production is realized. Therefore, a method for preparing the sulfide-based solid electrolyte, which is simple and efficient to operate, environment-friendly, low in cost, high in batch repetition rate and easy to realize in batch, needs to be further explored.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfide-based solid electrolyte Na for an all-solid-state sodium ion battery, which is simple and efficient to operate and easy for industrial production3XS4(X = P, Sb).
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for producing a sulfide-based solid electrolyte, comprising:
step one, drying the raw materials in vacuum at the drying temperature of 50-100 ℃ for 6-20 hours; preparation of Na3PS4When the raw material is Na2S and P2S5(ii) a Preparation of Na3SbS4When the raw material is Na2S, S and Sb2S3；
Weighing the dried raw materials according to a metering ratio under an inert atmosphere, and mixing and grinding the raw materials to obtain mixed powder;
transferring the mixed powder into a high-pressure reaction kettle, adding a solvent, sealing the reaction kettle, and placing the reaction kettle in a muffle furnace for heat treatment;
step four, adding acetone to precipitate solids after cooling, filtering the powder, washing with ethanol, and drying in vacuum to obtain a primary material;
and fifthly, carrying out heat treatment on the primary material under the inert atmosphere to obtain a final product. The heat treatment temperature is 200-500 ℃, and the heat preservation time is 1-3 h.
Further, Na was prepared3PS4Or Na3SbS4In the third step, the solvent is one of polar solvent alcohol and nitrile. On the basis, in the third step, adding a solvent into the high-pressure reaction kettle under the inert atmosphere and then sealing; and step four, adding acetone into the inert atmosphere after cooling to precipitate the solid.
Further, preparation of Na3SbS4In the third step, the solvent is polar solvent deionized water. On the basis, in the third step, after the mixed powder is transferred to a high-pressure reaction kettle in an inert atmosphere, deionized water is quickly added into the reaction kettle in the air, and then the reaction kettle is sealed; in the fourth step, acetone is added into the air after the temperature is reduced to precipitate the solid.
Further, in the third step, the mass of the added polar solvent is 120-180% of the mass of the raw materials.
Further, in the third step, the heat treatment temperature is 100-200 ℃ and the time is 5-20 h.
Further, the following steps: in the fourth step, the vacuum drying temperature is 50-80 ℃ and the time is 5-8 h.
According to another aspect of the invention, a method is also claimed for obtaining a sulfide-based solid electrolyte Na3PS4Or Na3SbS4。
Compared with the prior art, the invention has the beneficial effects that (1) the Na prepared in the invention3XS4(X = P, Sb) good reproducibility of solid electrolyte batches and high ionic conductivity; (2) simple operation, low cost, high efficiency and high purity, and is beneficial to large-scale preparation.
Drawings
FIG. 1 shows different batches of Na prepared with acetonitrile according to the invention3PS4Nyquist plot of solid electrolyte at 25 ℃.
FIG. 2 shows different batches of Na prepared with ethanol according to the invention3SbS4Nyquist plot of solid electrolyte at 25 ℃.
FIG. 3 shows different batches of Na prepared with deionized water according to the invention3SbS4Nyquist plot of solid electrolyte at 25 ℃.
Detailed Description
A typical embodiment of the present invention provides a sulfide-based solid electrolyte Na3XS4(X = P, Sb), comprising:
step one, drying the raw materials in vacuum at the drying temperature of 50-100 ℃ for 6-20 hours; preparation of Na3PS4When the raw material is Na2S and P2S5(ii) a Preparation of Na3SbS4When the raw material is Na2S, S and Sb2S3；
Weighing the dried raw materials according to a metering ratio under an inert atmosphere, and mixing and grinding the raw materials to obtain mixed powder;
transferring the mixed powder into a high-pressure reaction kettle, adding a solvent, sealing the reaction kettle, and placing the reaction kettle in a muffle furnace for heat treatment;
step four, adding acetone to precipitate solids after cooling, filtering the powder, washing with ethanol, and drying in vacuum to obtain a primary material;
and fifthly, carrying out heat treatment on the primary material under the inert atmosphere to obtain a final product. The heat treatment temperature is 200-500 ℃, and the heat preservation time is 1-3 h.
In the above embodiment, the vacuum drying temperature in the first step is set to 50-100 ℃, and the drying time is 6-20 hours, so as to prevent the sublimation loss of sulfur in the raw material caused by the overhigh vacuum drying temperature. In step two, Na is prepared3PS4The raw material metering ratio is 3Na2S:P2S5(ii) a Preparation of Na3SbS4The raw material metering ratio is 3Na2S:2S:Sb2S3。
The solvent in the third step is one of polar solvent deionized water, alcohols and nitriles, and the polar solvent can increase the solubility of the raw materials and promote the synthesis reaction of the raw materials. Acetonitrile is preferably used as the nitrile, and ethanol, methanol, propanol or pentanol is preferably used as the alcohol.
Due to the synthesis of Na3PS4Of raw material P2S5Can be hydrolyzed when meeting water, and the deionized water can only be used for synthesizing Na3SbS4And step three, transferring the mixed powder to a high-pressure reaction kettle in an inert atmosphere, quickly adding deionized water into the reaction kettle in air, sealing, and then putting the reaction kettle into a muffle furnace for heating. And step four, adding acetone into the air after cooling to precipitate the solid.
Alcohols or nitriles as Na3PS4Or Na3SbS4Adding the solvent into the high-pressure reaction kettle in an inert atmosphere and then sealing. And step four, adding acetone in an inert atmosphere after cooling to precipitate solids.
In a preferred embodiment, in the third step, the mass of the added solvent is 120-180% of the mass of the raw material, and preferably, the mass of the added solvent is 150% of the mass of the raw material
In a preferred embodiment, in the third step, the heat treatment temperature of the muffle furnace is 100-200 ℃, and the heat preservation time is 5-20 h. Heating to 100-200 ℃ creates a high-temperature and high-pressure reaction environment, which is beneficial to the dissolution and reaction of raw materials.
Preferably, the vacuum drying temperature in the fourth step is 50-80 ℃, and the drying time is 5-8 h.
And in the second step, the third step and the fifth step, the inert atmosphere is one of helium, neon and argon.
The raw materials are placed in a reaction kettle to be heated, the agglomeration and connection among raw material particles are destroyed under the high-temperature and high-pressure environment, the particles enter a solution in the form of ions or ion clusters, crystal nuclei are formed in strong convection, the crystal nuclei grow, and then crystal grains are formed. The method can obtain powder with uniform and smaller size (nanometer scale), and can increase the specific surface area of particles and make the particles more easily compact. After the final heat treatment, the alternating current impedance test is carried out on the obtained sulfide solid electrolyte, and the experimental result shows that the sulfide solid electrolyte for the all-solid-state sodium ion battery prepared by the invention has good ion conductivity which is more than 10 at room temperature-4S·cm-1。
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
The sodium sulfide and phosphorus pentasulfide are dried in vacuum at 100 ℃ for 5 h. Weighing sodium sulfide and phosphorus pentasulfide with a molar ratio of 3:1 in an argon atmosphere glove box, grinding for 20min, transferring to a high-pressure reaction kettle, adding acetonitrile according to a mass ratio of 120%, sealing the reaction kettle, and performing heat treatment for 10h at 150 ℃ by using a muffle furnace. Cooling, adding acetone into glove box to precipitate solid, filtering, washing with ethanol for three times, vacuum drying at 80 deg.C for 5 hr to obtain primary material, and heat treating at 250 deg.C for 3 hr under argon atmosphere to obtain Na3PS4A solid electrolyte.
To obtain Na3PS4After the solid electrolyte was subjected to AC impedance test for ionic conductivity, the above electrolyte material was pressed into a solid electrolyte sheet having a diameter of 10mm and a thickness of 1mm by a solid battery mold in an argon atmosphere glove box, followed by AC impedance test at room temperature by an electrochemical workstation, as shown in FIG. 1, and sodium ionic conductivity was 2.3 (+ -0.3). times.10 at 25 ℃ as measured-4S·cm-1Indicating that Na was prepared in this example3PS4The solid electrolyte has good batch repeatability and high room-temperature ionic conductivity.
Example 2
The sodium sulfide, sulfur and antimony sulfide were dried in vacuo at 50 ℃ for 15 h. Weighing sodium sulfide, sulfur and antimony sulfide in a molar ratio of 3:2:1 in an argon atmosphere glove box, grinding for 20min, transferring into a high-pressure reaction kettle, adding ethanol according to a mass ratio of 140%, sealing the reaction kettle, and heating to 150 ℃ by using a muffle furnace for heat treatment for 10 h. Cooling, adding acetone into glove box to precipitate solid, filtering, washing with ethanol for three times, vacuum drying at 80 deg.C for 5 hr to obtain primary material, and heat treating at 350 deg.C for 3 hr under argon atmosphere to obtain Na3SbS4A solid electrolyte.
Na prepared in this example was tested as in example 13SbS4The ionic conductivity of the solid electrolyte was 5.5 (+ -0.3). times.10 in terms of sodium ion conductivity at 25 ℃ as shown in FIG. 2-4S·cm-1Indicating that Na was prepared in this example3SbS4The solid electrolyte has good batch repeatability and room temperature separationThe sub-conductivity is high.
Example 3
The sodium sulfide, sulfur and antimony sulfide were dried in vacuo at 50 ℃ for 20 h. Weighing sodium sulfide, sulfur and antimony sulfide in a molar ratio of 3:2:1 in an argon atmosphere glove box, grinding for 20min, transferring into a high-pressure reaction kettle, taking the reaction kettle out of the glove box, quickly adding deionized water in air according to a mass ratio of 160%, sealing the reaction kettle, and heating to 150 ℃ by using a muffle furnace for heat treatment for 10 h. Cooling, adding acetone into air to precipitate solid, filtering, washing with ethanol for three times, and vacuum drying at 80 deg.C for 5 hr to obtain hydrate Na3SbS4·9H2O, then heating to 150 ℃, keeping the temperature for 5h to remove water in the hydrate to obtain a primary material, and finally carrying out heat treatment on the primary material at 300 ℃ for 3h under the argon atmosphere to obtain Na3SbS4A solid electrolyte.
Na prepared in this example was tested as in example 13SbS4The ionic conductivity of the solid electrolyte was 4.6 (. + -. 0.3). times.10 in terms of sodium ion conductivity at 25 ℃ as shown in FIG. 3-4S·cm-1Indicating that Na was prepared in this example3SbS4The solid electrolyte has good batch repeatability and high room-temperature ionic conductivity.
Example 4
The sodium sulfide and phosphorus pentasulfide raw materials are dried for 5 hours in vacuum at 80 ℃. Weighing sodium sulfide and phosphorus pentasulfide in a molar ratio of 3:1 in an argon atmosphere glove box, grinding for 20min, transferring to a high-pressure reaction kettle, adding methanol in a mass ratio of 170%, sealing the reaction kettle, and performing heat treatment for 20h at 100 ℃ by using a muffle furnace. Cooling, adding acetone into glove box to precipitate solid, filtering, washing with ethanol for three times, vacuum drying at 80 deg.C for 5 hr to obtain primary material, and heat treating at 300 deg.C for 2 hr under argon atmosphere to obtain Na3PS4A solid electrolyte.
Na prepared in this example was tested as in example 13PS4The ionic conductivity of the solid electrolyte showed that the sodium ion conductivity at 25 ℃ was 2.5 (+ -0.3). times.10-4S·cm-1Indicating that Na was prepared in this example3PS4The solid electrolyte has good batch repeatability and high room-temperature ionic conductivity.
Example 5
The sodium sulfide, sulfur and antimony sulfide were dried in vacuo at 50 ℃ for 20 h. Weighing sodium sulfide, sulfur and antimony sulfide in a molar ratio of 3:2:1 in an argon atmosphere glove box, grinding for 20min, transferring to a high-pressure reaction kettle, adding acetonitrile according to a mass ratio of 180%, sealing the reaction kettle, and performing heat treatment for 5h at 200 ℃ by using a muffle furnace. Cooling, adding acetone into glove box to precipitate solid, filtering, washing with ethanol for three times, vacuum drying at 50 deg.C for 5 hr to obtain primary material, and heat treating at 450 deg.C for 1 hr under argon atmosphere to obtain Na3SbS4A solid electrolyte.
Na prepared in this example was tested as in example 13SbS4The ionic conductivity of the solid electrolyte showed that the sodium ion conductivity at 25 ℃ was 5.8 (. + -. 0.3). times.10-4S·cm-1Indicating that Na was prepared in this example3SbS4The solid electrolyte has good batch repeatability and high room-temperature ionic conductivity.
Example 6
The sodium sulfide, sulfur and antimony sulfide were dried in vacuo at 60 ℃ for 10 h. Weighing sodium sulfide, sulfur and antimony sulfide in a molar ratio of 3:2:1 in an argon atmosphere glove box, grinding for 20min, transferring into a high-pressure reaction kettle, taking the reaction kettle out of the glove box, quickly adding deionized water in air according to a mass ratio of 150%, sealing the reaction kettle, and performing heat treatment at 150 ℃ for 15h by using a muffle furnace. Cooling, adding acetone into air to precipitate solid, filtering, washing with ethanol for three times, and vacuum drying at 80 deg.C for 5 hr to obtain hydrate Na3SbS4·9H2O, then preserving heat at 150 ℃ for 5h to remove water in the hydrate to obtain a primary material, and finally carrying out heat treatment on the primary material at 200 ℃ for 3h under the argon atmosphere to obtain Na3SbS4A solid electrolyte.
Na prepared in this example was tested as in example 13SbS4The ionic conductivity of the solid electrolyte showed that the sodium ion conductivity at 25 ℃ was 5.8 (. + -. 0.3). times.10-4S·cm-1To show the true natureNa prepared in example3SbS4The solid electrolyte has good batch repeatability and high room-temperature ionic conductivity.
Claims (9)
1. A process for preparing the sulfide-base solid electrolyte (Na)3XS4(X = P, Sb), comprising:
step one, drying the raw materials in vacuum at the drying temperature of 50-100 ℃ for 6-20 hours; preparation of Na3PS4When the raw material is Na2S and P2S5(ii) a Preparation of Na3SbS4When the raw material is Na2S, S and Sb2S3；
Weighing the dried raw materials according to a metering ratio under an inert atmosphere, and mixing and grinding the raw materials to obtain mixed powder;
transferring the mixed powder into a high-pressure reaction kettle, adding a solvent, sealing the reaction kettle, and placing the reaction kettle in a muffle furnace for heat treatment;
step four, adding acetone to precipitate solids after cooling, filtering the powder, washing with ethanol, and drying in vacuum to obtain a primary material;
step five, carrying out heat treatment on the primary material under inert atmosphere to obtain a final product; the heat treatment temperature is 200-500 ℃, and the heat preservation time is 1-3 h.
2. The method of claim 1, wherein: preparation of Na3PS4Or Na3SbS4In the third step, the solvent is one of polar solvent alcohol and nitrile.
3. The method of claim 2, wherein: in the third step, adding a solvent into the high-pressure reaction kettle in an inert atmosphere and then sealing; and step four, adding acetone into the inert atmosphere after cooling to precipitate the solid.
4. The method of claim 1, wherein: preparation of Na3SbS4In the third step, the solvent is polar solvent deionized water.
5. The method of claim 4, wherein: in the third step, after the mixed powder is transferred to a high-pressure reaction kettle in an inert atmosphere, deionized water is quickly added into the reaction kettle in the air, and then the reaction kettle is sealed; in the fourth step, acetone is added into the air after the temperature is reduced to precipitate the solid.
6. The method according to claim 2 or 4, characterized in that: in the third step, the mass of the added polar solvent is 120-180% of the mass of the raw materials.
7. The method according to any one of claims 1 to 5, wherein: in the third step, the heat treatment temperature is 100-200 ℃ and the time is 5-20 h.
8. The method of claim 7, wherein: in the fourth step, the vacuum drying temperature is 50-80 ℃ and the time is 5-8 h.
9. Sulfide-based solid electrolyte Na obtained by the method according to any one of claims 1 to 83PS4Or Na3SbS4。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117023534A (en) * | 2023-08-16 | 2023-11-10 | 黄冈师范学院 | Low-cost preparation method of sodium ion sulfide solid electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108190845A (en) * | 2018-01-31 | 2018-06-22 | 湖南省正源储能材料与器件研究所 | A kind of method for preparing lithium sulfide |
| CN110534801A (en) * | 2019-09-05 | 2019-12-03 | 中国科学院宁波材料技术与工程研究所 | All solid state electrolyte material and preparation method thereof and solid state secondary battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190845A (en) * | 2018-01-31 | 2018-06-22 | 湖南省正源储能材料与器件研究所 | A kind of method for preparing lithium sulfide |
| CN110534801A (en) * | 2019-09-05 | 2019-12-03 | 中国科学院宁波材料技术与工程研究所 | All solid state electrolyte material and preparation method thereof and solid state secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117023534A (en) * | 2023-08-16 | 2023-11-10 | 黄冈师范学院 | Low-cost preparation method of sodium ion sulfide solid electrolyte |
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Application publication date: 20210105 |