CN110867606A - Preparation method of sulfide solid electrolyte - Google Patents
Preparation method of sulfide solid electrolyte Download PDFInfo
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- CN110867606A CN110867606A CN201910991235.4A CN201910991235A CN110867606A CN 110867606 A CN110867606 A CN 110867606A CN 201910991235 A CN201910991235 A CN 201910991235A CN 110867606 A CN110867606 A CN 110867606A
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- aromatic compound
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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 provides a method for preparing a sulfide solid electrolyte which is composed of Li, P and S elements and has freely controllable components at low cost, comprising the following steps: adding elemental sulfur and phosphorus pentasulfide into an organic ether solution of a metal lithium-aromatic compound, and mixing to obtain a mixed solution; and (3) sequentially carrying out mixing reaction, separation and precipitation, drying and heat treatment on the mixed solution to obtain the sulfide solid electrolyte containing Li, P and S as constituent elements. The preparation method of the sulfide solid electrolyte has the advantages of cheap and easily-obtained raw materials, simple process, safe production, easy adjustment of product components and capability of greatly reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to a preparation method of a sulfide solid electrolyte.
Background
Solid electrolytes are mainly composed of three major classes of polymers, oxides and sulfides. Sulfide electrolytes are considered to be the most promising solid electrolyte materials due to their highest lithium ion conductivity and relatively "soft" mechanical properties (good solid-solid interface contact can be achieved by low temperature pressing only).
A variety of sulfide solid electrolytes have been developed and used at present, and among them, a system which is relatively simple and receives much attention is a sulfide solid electrolyte containing Li, P and S as constituent elements (LPS system). The system has higher ion conductivity (>10−4S cm−1) And without any additional elements (Si, Ge, Al) added. At present, the common synthesis methods of the system are three methods, namely a high-temperature solid-phase reaction method, a mechanochemical method and a liquid-phase method. The high-temperature solid-phase reaction needs to consider the requirement of a sealed reaction container and the quenching step introduced under certain conditions, and the synthesis process is long in time consumption and high in energy consumption; the mechanochemical method firstly prepares an amorphous phase LPS system by ball milling, and then obtains the glass-ceramic solid electrolyte with higher conductivity by an annealing step, and the repeatability and the uniformity of ball milling products are considered to be a method with large-scale production potential; liquid phase synthesis, although having a reduced residual conductivity due to a portion of the solvent, has attracted researchers' attention in recent years by virtue of its simple and easy synthesis process and nanostructured products. Patent CN103500853B is that lithium sulfide, phosphorus pentasulfide and organic solution are mixed, the mixed solution is stirred, centrifuged, filtered and dried in sequence to obtain a primary material, and the primary material is subjected to heat treatment to obtain (100-x) Li2S·xP2S5A sulfide solid electrolyte. The patent application CN109326820A dissolves red phosphorus and orthorhombic sulfur in alcohol organic solvent, and reacts under microwave irradiation to obtain liquid P2S5(ii) a Then adding it into Li2S is dissolved in an alcohol organic solvent to form a source solution, and the source solution is sprayed to an evaporation area through a pulse nozzle, so that the lithium ion solid electrolyte P is obtained on the substrate2S5-Li2S and a positive electrode composite layer. Patent application CN109698383A uses Li2S and P2S5Stirring the raw materials in tetrahydrofuran and acetonitrile, immersing the polished substrate in the obtained solution, standing, taking out, and hot pressingAnd (4) processing and stripping the substrate to obtain the ultrathin solid electrolyte of the lithium battery. Patent application CN108075182A, which considers the problem of non-uniformity caused by the material easily sticking to the wall surface of the container used in mechanical grinding in the dry state, provides a method for manufacturing a sulfide-based solid electrolyte by a wet process, by adding a solvent to a mixture containing lithium sulfide and a sulfide of a group 14 or group 15 element to prepare a slurry; and preparing the sulfide electrolyte by subsequent grinding of the slurry, drying of the slurry and heat treatment. According to the technical scheme, lithium sulfide is used as a raw material, so that the production cost is high, and the industrial production is not facilitated.
Disclosure of Invention
Based on the problems, the invention provides a method for preparing a sulfide solid electrolyte which is composed of Li, P and S elements and has freely controllable components at low cost, the synthesis method uses an ether solution of metallic lithium-aromatic compound, elemental sulfur and phosphorus pentasulfide as raw materials, the raw materials have low cost, the process is simple, the production is safe, and the method is beneficial to the large-scale production of the sulfide solid electrolyte.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a sulfide solid electrolyte comprises the following steps:
A. adding elemental sulfur and phosphorus pentasulfide into an organic ether solution of a metal lithium-aromatic compound according to a proportion to obtain a mixed solution;
B. and (3) sequentially carrying out mixing reaction, separation and precipitation, drying and heat treatment on the mixed solution to obtain the sulfide solid electrolyte containing Li, P and S as constituent elements.
Further, the organic ether in the organic ether solution of the metallic lithium-aromatic compound is one or more of monoethers such as diethyl ether, diphenyl ether, divinyl ether, and the like, mixed ethers such as methyl ethyl ether, ethyl vinyl ether, anisole, and the like, ethers formed from polyhydric alcohols such as ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, and the like, cyclic ethers such as tetrahydrofuran, and thioethers such as methyl ethyl sulfide, and the like, but is not limited to the above listed ethers.
Further, the aromatic compound in the organic ether solution of the metal lithium-aromatic compound may be one or a mixture of several of monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and styrene, fused ring aromatic hydrocarbons such as biphenyl and p-terphenyl, polycyclic aromatic hydrocarbons such as naphthalene and anthracene, polyphenyl aliphatic hydrocarbons such as diphenylmethane, and non-benzene aromatic hydrocarbons such as azulene, but is not limited to the above-listed aromatic compounds.
Further, the concentration of the aromatic compound in the organic ether solution of the metallic lithium-aromatic compound is 0.1 to 10 mol/L, preferably 0.2 to 5 mol/L.
Further, the concentration of the metallic lithium in the organic ether solution of the metallic lithium-aromatic compound is 0.1-20 mol/L, preferably 0.2-10 mol/L, and the reaction rate and the reaction time can be adjusted and controlled by adjusting the concentration of the metallic lithium.
Further, the drying in the step B is carried out under the protection of a vacuum environment or an inert atmosphere, the drying temperature is 25-200 ℃, and the drying time is 1-24 hours.
Further, the heat treatment in the step B is performed under the protection of a vacuum environment or an inert atmosphere, the heat treatment temperature is 100-400 ℃, and the heat treatment time is 1-12 hours.
Compared with the prior art, the preparation method of the low-cost sulfide solid electrolyte has the following advantages: the method has the advantages of low-cost and easily-obtained raw materials, simple process and capability of greatly reducing the preparation cost; no harmful gas is generated in the preparation process, the reaction is mild and controllable, and the production safety can be effectively ensured; in addition, the composition of the sulfide solid electrolyte product composed of Li, P and S elements obtained by the method is easy to adjust relative to the raw materials of lithium sulfide and phosphorus pentasulfide.
Drawings
FIG. 1 shows a glass-ceramic phase Li prepared in example 1 of the present invention3PS4XRD pattern of sulfide solid electrolyte and orthorhombic system Li3PS4Comparison of PDF cards 76-0973;
FIG. 2 shows Li as a glass-ceramic phase prepared in example 1 of the present invention3PS4Sulfide solid state electricityConductivity data of the electrolyte from low temperature to high temperature and an arrhenius conductivity map thereof;
FIG. 3 shows Li as a glass-ceramic phase prepared in example 1 of the present invention3PS4Constant voltage dc polarization curve of sulfide solid electrolyte at room temperature.
Detailed Description
In order to make the objects, technical solutions and process advantages of the present invention more clear, the present invention is described in detail below with reference to the following embodiments and accompanying drawings. Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
Example 1:
step 1: preparing an anhydrous glycol dimethyl ether solution of metal lithium-biphenyl: weighing 30.842 g of biphenyl, dissolving the biphenyl into an anhydrous glycol dimethyl ether solvent with a corresponding volume according to the concentration of 1 mol/L, adding 1.3882 g of metal lithium wires with the length of 1 cm and the width of 1 mm when the biphenyl is completely dissolved, and standing at room temperature until the metal lithium wires are completely dissolved;
step 2: 3.206 g of elemental sulfur and 7.408 g of phosphorus pentasulfide are weighed and added into the anhydrous glycol dimethyl ether solution of the metal lithium-biphenyl, and the mixture is stirred for 6 hours at the temperature of 80 ℃ to obtain suspension;
and step 3: separating the precipitate and the supernatant with a centrifuge at 8000 r/min for 20 min, recovering the supernatant for reuse, centrifuging and washing the precipitate with anhydrous ethylene glycol dimethyl benzene for 3 times at 6000 r/min for 10 min; then the precipitate is dried for 12 hours at 100 ℃ in a vacuum drying oven and is heat treated for 10 hours under the protection of argon atmosphere at 180 ℃ in sequence to obtain the glass-ceramic phase Li3PS4A sulfide solid electrolyte.
The obtained electrolyte material was subjected to XRD measurement, and the obtained XRD pattern was as shown in fig. 1. As can be seen from FIG. 1, orthorhombic Li can be prepared by this method3PS4Sulfide electrolyte corresponding to PDF card76-0973, which had a bulge at 11.5 ° and a peak at 21.5 ° from the substrate and PE protective material used in the XRD testing. The electrochemical performance of the synthesized sulfide electrolyte material is tested, the sulfide electrolyte material is pressed into sheets under the pressure of 420 MPa, the sheets are pressed into electrolyte sheets with the diameter of 10mm and the thickness of 1 mm, carbon sheets are used as ion blocking electrodes on two sides of each electrolyte sheet to assemble test batteries, and alternating current impedance tests are carried out at different temperatures, and the results are shown in figure 2. As can be seen from fig. 2, the sulfide solid electrolyte material prepared in this example has a high conductivity property, and the room-temperature conductivity is 1.73 × 10−4S cm−1And the activation energy of the synthesized sulfide electrolyte material was calculated to be 0.356 eV. In addition, the sulfide electrolyte powder was pressed into sheets under a pressure of 420 MPa, and after pressing into electrolyte sheets having a diameter of 10mm and a thickness of 1 mm, both sides were assembled into test cells using carbon sheets as ion blocking electrodes, and a dc polarization test was performed at a dc voltage of 20 mV to distinguish between electron conductivity and ion conductivity, and the test results are shown in fig. 3. As can be seen from FIG. 3, Li prepared in example 1 of the present invention3PS4The electronic conductivity of the sulfide electrolyte material was 5.09 × 10−9S cm−1And is suitable for solid electrolyte material in all-solid-state batteries.
Example 2:
step 1: preparing an anhydrous tetrahydrofuran solution of metal lithium-naphthalene: weighing 25.636 g of naphthalene, dissolving the naphthalene in an anhydrous tetrahydrofuran solvent with a corresponding volume according to the concentration of 2 mol/L, adding 1.3882 g of metal lithium dices with the length of 2 mm, the width of 2 mm and the thickness of 0.5 mm when the biphenyl is completely dissolved, and standing until the metal lithium dices are completely dissolved;
step 2: 3.206 g of elemental sulfur and 9.525 g of phosphorus pentasulfide are weighed and added into the anhydrous tetrahydrofuran solution of the metal lithium-naphthalene, and the mixture is stirred for 8 hours at room temperature to obtain suspension;
and step 3: separating the precipitate and the supernatant with a centrifuge at 8000 r/min for 20 min, recovering the supernatant for reuse, centrifuging the precipitate with anhydrous tetrahydrofuran for 3 times at 6000 r/min for 10 min; then the precipitate is dried in sequence in a vacuum drying oven at 80 DEG CDrying for 10 h, and carrying out heat treatment for 1 h at the temperature of 260 ℃ under the argon protective atmosphere to obtain the glass-ceramic phase Li7P3S11A sulfide solid electrolyte.
Example 3:
step 1: preparing an anhydrous glycol dimethyl ether solution of metal lithium-biphenyl: weighing 30.842 g of biphenyl, dissolving the biphenyl into an anhydrous glycol dimethyl ether solvent with a corresponding volume according to the concentration of 1 mol/L, adding 1.3882 g of metal lithium wires with the length of 1 cm and the width of 1 mm when the biphenyl is completely dissolved, and standing at room temperature until the metal lithium wires are completely dissolved;
step 2: weighing 1.603 g of elemental sulfur and 11.112 g of phosphorus pentasulfide, adding the elemental sulfur and 11.112 g of phosphorus pentasulfide into the anhydrous glycol dimethyl ether solution of the metal lithium-biphenyl, and stirring for 6 hours at 80 ℃ to obtain a suspension;
and step 3: separating the precipitate and the supernatant with a centrifuge at 8000 r/min for 20 min, recovering the supernatant for reuse, centrifuging and washing the precipitate with anhydrous ethylene glycol dimethyl benzene for 3 times at 6000 r/min for 10 min; then the precipitate is dried for 10 hours at 100 ℃ in a vacuum drying oven and is thermally treated for 5 hours under the protection of argon atmosphere at 350 ℃ in sequence to obtain the glass-ceramic phase Li4P2S6A sulfide solid electrolyte.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a sulfide solid electrolyte is characterized by comprising the following steps:
A. adding elemental sulfur and phosphorus pentasulfide into an organic ether solution of a metal lithium-aromatic compound according to a proportion to obtain a mixed solution;
B. and (3) sequentially carrying out mixing reaction, separation and precipitation, drying and heat treatment on the mixed solution to obtain the sulfide solid electrolyte containing Li, P and S as constituent elements.
2. The method according to claim 1, wherein the organic ether in the organic ether solution of the metallic lithium-aromatic compound is one or more selected from the group consisting of monoethers such as diethyl ether, diphenyl ether, and divinyl ether, mixed ethers such as methyl ethyl ether, ethyl vinyl ether, and anisole, ethers formed from polyols such as ethylene glycol dimethyl ether and ethylene glycol monomethyl ether, cyclic ethers such as tetrahydrofuran, and thioethers such as methyl ethyl sulfide, but not limited to the above-mentioned ethers.
3. The method according to claim 1, wherein the aromatic compound in the organic ether solution of the metallic lithium-aromatic compound is one or more selected from the group consisting of monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and styrene, fused ring aromatic hydrocarbons such as biphenyl and p-terphenyl, polyphenylalkyl hydrocarbons such as naphthalene and anthracene, polyphenylalkyl hydrocarbons such as diphenylmethane, and non-benzene aromatic hydrocarbons such as azulene, but not limited to the above-listed aromatic compounds.
4. The method according to claim 1, wherein the concentration of the aromatic compound in the organic ether solution of the metallic lithium-aromatic compound is 0.1 to 10 mol/L.
5. The method according to claim 4, wherein the concentration of the aromatic compound in the organic ether solution of the metallic lithium-aromatic compound is 0.2 to 5 mol/L.
6. The method according to claim 1, wherein the concentration of metallic lithium in the organic ether solution of metallic lithium-aromatic compound is 0.1 to 20mol/L, and the reaction rate and reaction time can be controlled by adjusting the concentration of metallic lithium.
7. The method according to claim 6, wherein the concentration of metallic lithium in the organic ether solution of metallic lithium-aromatic compound is 0.2 to 10 mol/L.
8. The method according to claim 1, wherein the drying in step B is performed under a vacuum environment or under an inert atmosphere, the drying temperature is 25-200 ℃, and the drying time is 1-24 hours.
9. The method as claimed in claim 1, wherein the heat treatment in step B is performed under vacuum or inert atmosphere protection at a temperature of 100 ℃ to 400 ℃ for 1-12 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517288A (en) * | 2020-05-07 | 2020-08-11 | 天目湖先进储能技术研究院有限公司 | Method for synthesizing lithium sulfide |
| CN112768762A (en) * | 2021-02-26 | 2021-05-07 | 浙江锋锂新能源科技有限公司 | Carbon-containing sulfide solid electrolyte for solid lithium battery and preparation method thereof |
| CN113506918A (en) * | 2021-07-09 | 2021-10-15 | 郑州新世纪材料基因组工程研究院有限公司 | Preparation method of inorganic solid electrolyte |
| CN114455613A (en) * | 2022-01-07 | 2022-05-10 | 天津大学 | Preparation method of sulfide electrolyte, sulfide electrolyte and application of sulfide electrolyte |
| WO2022154428A1 (en) * | 2021-01-15 | 2022-07-21 | 한국전기연구원 | Method for preparing solid electrolyte, solid electrolyte prepared thereby, and all-solid-state battery comprising same |
| KR20220103597A (en) * | 2021-01-15 | 2022-07-22 | 한국전기연구원 | Method for producing solid electrolyte, solid electrolyte prepared therefrom, and all-solid-state battery comprising the same |
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| WO2021145248A1 (en) * | 2020-01-17 | 2021-07-22 | 三菱瓦斯化学株式会社 | METHOD FOR PRODUCING SULFIDE SOLID ELECTROLYTE INCLUDING Sn |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517288A (en) * | 2020-05-07 | 2020-08-11 | 天目湖先进储能技术研究院有限公司 | Method for synthesizing lithium sulfide |
| WO2022154428A1 (en) * | 2021-01-15 | 2022-07-21 | 한국전기연구원 | Method for preparing solid electrolyte, solid electrolyte prepared thereby, and all-solid-state battery comprising same |
| KR20220103597A (en) * | 2021-01-15 | 2022-07-22 | 한국전기연구원 | Method for producing solid electrolyte, solid electrolyte prepared therefrom, and all-solid-state battery comprising the same |
| KR102542111B1 (en) * | 2021-01-15 | 2023-06-12 | 한국전기연구원 | Method for producing solid electrolyte, solid electrolyte prepared therefrom, and all-solid-state battery comprising the same |
| CN112768762A (en) * | 2021-02-26 | 2021-05-07 | 浙江锋锂新能源科技有限公司 | Carbon-containing sulfide solid electrolyte for solid lithium battery and preparation method thereof |
| CN112768762B (en) * | 2021-02-26 | 2023-08-22 | 浙江锋锂新能源科技有限公司 | Carbon sulfide-containing solid electrolyte for solid lithium battery and preparation method thereof |
| CN113506918A (en) * | 2021-07-09 | 2021-10-15 | 郑州新世纪材料基因组工程研究院有限公司 | Preparation method of inorganic solid electrolyte |
| CN114455613A (en) * | 2022-01-07 | 2022-05-10 | 天津大学 | Preparation method of sulfide electrolyte, sulfide electrolyte and application of sulfide electrolyte |
| CN114455613B (en) * | 2022-01-07 | 2023-11-07 | 天津大学 | Sulfide electrolyte preparation method, sulfide electrolyte and application thereof |
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