CN111082132A - Sulfide solid electrolyte and preparation method thereof - Google Patents

Sulfide solid electrolyte and preparation method thereof Download PDF

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CN111082132A
CN111082132A CN201911265151.9A CN201911265151A CN111082132A CN 111082132 A CN111082132 A CN 111082132A CN 201911265151 A CN201911265151 A CN 201911265151A CN 111082132 A CN111082132 A CN 111082132A
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sulfide solid
sulfide
solid electrolyte
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CN111082132B (en
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宋英杰
徐宁
马倩倩
伏萍萍
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Tianjin B&M Science and Technology Co Ltd
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    • 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
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • 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
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Abstract

The invention discloses a high-stability sulfide solid electrolyte and a preparation method thereof. The method comprises the following steps: firstly, obtaining the oxide modified double-composite sulfide lithium ion battery solid electrolyte through sanding and high-temperature solid-phase reaction, and then coating a lithium phosphate fast ion conductor layer on the surface of the oxide modified double-composite sulfide lithium ion battery solid electrolyte through a magnetron sputtering method. The main benefits of the invention are: the sulfide solid electrolyte is modified by adding the oxide, and metal ions enter crystal lattices, so that the structural stability of the sulfide can be effectively improved; the lithium phosphate fast ion conductor is coated on the surface of the sulfide solid electrolyte, so that the high ion diffusion coefficient of the solid electrolyte can be maintained, and the structural stability of the sulfide can be effectively improved.

Description

Sulfide solid electrolyte and preparation method thereof
Technical Field
The invention relates to the field of solid electrolytes of lithium ion secondary batteries, in particular to a sulfide solid electrolyte and a preparation method thereof.
Background
Under the support of national policies, the new energy automobile industry in China is rapidly developed, and the annual output and sales volume of the new energy automobile industry in China reach more than the general value of the whole world. As is well known, the power battery is a core part of the new energy automobile, wherein the lithium ion battery has obvious advantages in the aspects of cost and energy density, can greatly improve the economy and the use convenience of the new energy automobile, and occupies a dominating position in the field of the power battery. However, the safety of new energy automobiles occurs recently, and the current solution type electrolyte is a flammable organic matter system and has a narrow electrochemical window, so that the problem cannot be thoroughly solved by adopting a common improvement method. The solid electrolyte has wide electrochemical window and high thermal stability, can fundamentally solve the safety problem of the lithium ion battery, greatly simplify the manufacturing and packaging process, improve the energy density of the battery (the specific energy density can be improved by 20 to 50 percent under the existing positive and negative electrode systems), and has reliability and design freedom.
The solid electrolyte is the core of the lithium ion solid battery, and directly determines key performances such as rate performance, safety performance and cycle performance of the lithium ion solid battery. The existing solid electrolyte system mainly comprises sulfide, phosphide and oxide, wherein the ion diffusion coefficient of the sulfide solid electrolyte is optimal and reaches 10-3S/cm order of magnitude basically meets the use requirements of the lithium ion battery, but sulfide has poor stability and can be decomposed when meeting water vapor to generate hydrogen sulfide gas, thereby seriously influencing the practical application of the hydrogen sulfide gas.
Prior art CN108511792A provides a LixMyPzSwThe high-temperature setting composite sulfide solid electrolyte composed of the compound and the compound with the valence of M lower than 4 has the defect that the structural defect of poor stability of the sulfide solid electrolyte cannot be solved essentially, so that the development of the sulfide solid electrolyte with simple preparation and good stability is needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a sulfide solid electrolyte and a preparation method thereof. The method has simple preparation process, and the prepared sulfide solid electrolyte has good stability and excellent lithium ion diffusion capacity.
The technical scheme of the invention is as follows:
a sulfide solid state electrolyte material with a general structural formula of xLi2S·(1-x)GeS2·yM/Li3PO4Wherein M is oxide, x is more than or equal to 0.7 and less than or equal to 0.8, and y is more than or equal to 0.001 and less than or equal to 0.005. Wherein Li2S and GeS2The lithium ion diffusion coefficient is excellent, and the two can form a double complex sulfide network, but when Li is used2When S is too large or too small, an effective sulfide network is difficult to form; m can stabilize the lattice structure of sulfide, the lithium ion diffusion coefficient is influenced by too high content of M, and the effect of stabilizing the lattice structure is difficult to achieve by too low content of M; coating layer Li3PO4Stable structure and high lithium ion diffusion coefficient.
A method for producing a sulfide solid state electrolyte material, comprising the steps of:
1) according to the formula xLi2S·(1-x)GeS2yM, weighing Li according to molar ratio2S、GeS2And M, adding an organic solvent, and sanding in a sand mill to obtain a solid-liquid mixture I with a particle size D500.1 μ M or less, wherein M is an oxide;
2) carrying out spray drying on the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II, wherein the granularity D of the material II5012-18 mu m, and the drying temperature of the spray drying is 120-160 ℃;
3) carrying out heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 500-700 ℃, and the heat treatment time is 2-8 h;
4) taking part of material III to carry out airflow crushing in nitrogen atmosphere to obtain material IV, wherein the particle size D of the material IV50＝2～4μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass ratio of the material III: the material IV is (2-4) 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a sulfide solid electrolyte material product, wherein a sputtering target material adopted in the magnetron sputtering process is lithium phosphate with the purity of 99.9%, and the sputtering gas is Ar. Compared with common solid-phase coating and liquid-phase coating, the magnetic sputtering has the advantage of uniform and controllable coating thickness.
Preferably, in the step 1), x is more than or equal to 0.7 and less than or equal to 0.8, and y is more than or equal to 0.001 and less than or equal to 0.005.
Preferably, M in the step 1) is TiO2、MgO、ZrO2And Al2O3One or more of (a). The oxides have the characteristics of stable structure and good lithium ion compatibility, so the oxides are more suitable for being used as sulfide solid electrolyte materials.
Preferably, the organic solvent in step 1) is cyclohexane or acetone.
Preferably, the sputtering pressure P in the magnetron sputtering in the step 6) is 1-4 Pa. The magnetron sputtering pressure is too low, and the deposition speed is too slow; the sputtering pressure is too high, the deposition speed is too high, and the density of the coating layer is poor.
Preferably, the sputtering time t in the magnetron sputtering in the step 6) is 10-30 min. The magnetron sputtering time is too short, the thickness of a coating layer is not enough, and the stability is poor; too long, too thick coating layer and poor conductivity.
Preferably, the sputtering power PW in the magnetron sputtering in the step 6) is 30W-50W. The magnetron sputtering power is too low, and the deposition speed is too slow; the power is too high, the deposition speed is too fast, and the density of the coating layer is poor.
The application of the sulfide solid electrolyte material in the all-solid-state battery can be used as a solid electrolyte.
The sulfide solid electrolyte material prepared by the preparation method is applied to all-solid batteries.
The invention has the beneficial effects that: the invention firstly obtains the oxide modified double-composite sulfide lithium ion battery solid electrolyte by sanding and high-temperature solid-phase reaction, and then coats a lithium phosphate fast ion conductor layer on the surface of the lithium phosphate fast ion conductor layer by a magnetron sputtering method. The sulfide solid electrolyte is modified by adding the oxide, and metal ions enter crystal lattices, so that the structural stability of the sulfide can be effectively improved; the lithium phosphate fast ion conductor is coated on the surface of the sulfide solid electrolyte, so that the high ion diffusion coefficient of the solid electrolyte can be maintained, and the structural stability of the sulfide can be effectively improved. Compared with the traditional coating method, the magnetron sputtering method has the advantages of uniform coating layer and controllable thickness, and the prepared material has excellent stability and smaller interface impedance.
Drawings
FIG. 1 is a process flow diagram of a high steady state sulfide solid electrolyte.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples.
Example 1
A high steady state sulfide solid state electrolyte comprising the steps of:
1) according to the formula 0.7Li2S.0.3GeS2Weighing Li with 0.001MgO2S、GeS2And MgO, adding cyclohexane, and sanding in a sand mill to obtain a solid-liquid mixture I with a particle size D50＝0.08μm；
2) Spray-drying the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II with a granularity D5012 μm, wherein the spray drying temperature is 120 ℃;
3) performing heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 500 ℃, and the heat treatment time is 8 hours;
4) crushing the material III in a nitrogen atmosphere by air flow to obtain a material IV with a granularity D50＝2μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass of the material III is as follows: the mass of the material IV is 2: 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a final product VI, wherein the purity of a sputtering target material is 99.9 percent of lithium phosphate, the sputtering gas is Ar, the pressure is 1pa, the sputtering time is 30min, and the sputtering power is 30W.
Comparative example 1
1) According to the formula 0.7Li2S.0.3GeS2Weighing Li2S、GeS2Adding cyclohexane, and sanding in a sand mill to obtain a solid-liquid mixture I with a granularity D50＝0.08μm；
The rest is the same, i.e. no MgO modification is performed.
Comparative example 2
Step 6) was deleted, the same as above, i.e. no lithium phosphate coating was performed.
Example 2
A high steady state sulfide solid state electrolyte comprising the steps of:
1) according to the formula 0.8Li2S.0.2GeS2.0.001Al2O3Weighing Li2S、GeS2And Al2O3Adding cyclohexane, and sanding in a sand mill to obtain a solid-liquid mixture I with a granularity D50＝0.09μm；
2) Spray-drying the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II with a granularity D5018 μm, wherein the spray drying temperature is 180 ℃;
3) performing heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 700 ℃, and the heat treatment time is 2 hours;
4) crushing the material III in a nitrogen atmosphere by air flow to obtain a material IV with a granularity D50＝4μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass of the material III is as follows: the mass of the material IV is 2: 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a final product VI, wherein the purity of a sputtering target material is 99.9 percent of lithium phosphate, the sputtering gas is Ar, the pressure is 2pa, the sputtering time is 20min, and the sputtering power is 30W.
Comparative example 3
The rest is the same, and the step 6) is modified in such a way that the material V and the nano-scale lithium phosphate powder are uniformly mixed in a high-speed mixer, and the adding amount of the lithium phosphate is the same as that of the embodiment 2.
Example 3
A high steady state sulfide solid state electrolyte comprising the steps of:
1) according to the formula 0.8Li2S.0.2GeS20.005MgO weighing Li2S、GeS2Adding MgO, adding organic solvent, and sanding in a sand mill to obtain a solid-liquid mixture I with a particle size D50＝0.09μm；
2) Spray-drying the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II with a granularity D50116 μm, wherein the spray drying temperature is 140 ℃;
3) performing heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 6 hours;
4) crushing the material III in a nitrogen atmosphere by air flow to obtain a material IV with a granularity D50＝2μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass of the material III is as follows: the mass of the material IV is 3: 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a final product VI, wherein the purity of a sputtering target material is 99.9 percent of lithium phosphate, the sputtering gas is Ar, the pressure is 2Pa, the sputtering time is 15min, and the sputtering power is 40W.
Comparative example 4
The pressure in step 6) was modified to 0.5Pa compared with example 3, and the rest was the same.
Comparative example 5
Compared with the embodiment 3, the sputtering time of the step 6) is modified to be 60min, and the rest is the same
Comparative example 6
Compared with the embodiment 3, the sputtering power of the step 7) is modified to be 100W, and the rest is the same
Example 4
A high steady state sulfide solid state electrolyte comprising the steps of:
1) according to the formula 0.8Li2S.0.2GeS2.0.001ZrO2Weighing Li2S、GeS2And ZrO2, adding organic solvent, and sanding in a sand mill to obtain a solid-liquid mixture I with a particle size D50＝0.09μm；
2) Spray-drying the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II with a granularity D50116 μm, wherein the spray drying temperature is 140 ℃;
3) performing heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 6 hours;
4) crushing the material III in a nitrogen atmosphere by air flow to obtain a material IV with a granularity D50＝3μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass of the material III is as follows: the mass of the material IV is 2: 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a final product VI, wherein the purity of a sputtering target material is 99.9 percent of lithium phosphate, the sputtering gas is Ar, the pressure is 3Pa, the sputtering time is 10min, and the sputtering power is 30W.
Experimental conditions:
table 1 shows a comparison table of ion conductivity of the solid electrolytes obtained in examples 1 to 4 and comparative examples 1 to 2 and the solid electrolytes after standing in air for 120 hours. The test method is an alternating current impedance method, and the frequency range is 0.1 HZ-1.0 MHz.
TABLE 1 comparison of ionic conductivities
Figure BDA0002312092420000081
As can be seen from the data in the table, the solid electrolyte prepared by the method has higher ionic conductivity and basically meets the application requirements of the lithium ion battery. Comparative example 1 the ionic conductivity was significantly lower due to no oxide modification; after being placed in the air for 120 hours, the ionic conductivity of the electrolyte of the embodiment 1 coated with the oxide and the lithium phosphate is not obviously changed, while the ionic conductivity of the electrolyte of the comparative example 2 coated with the lithium phosphate is rapidly reduced, mainly because the interface stability of the sulfide solid electrolyte is poor, and the sulfide solid electrolyte reacts with moisture in the air to generate hydrogen sulfide gas and destroy the structure of the body.
Compared with the embodiment 2, the comparative example 3 adopts the traditional lithium phosphate solid phase coating method instead of the ion sputtering, the coating layer is not uniform enough, the ion conductivity is low, and after a period of time of placement, because the coating layer is not absolute, the exposed part of the solid electrolyte reacts with the moisture in the air to generate hydrogen sulfide gas, the material structure is damaged, and the conductivity is reduced greatly. Comparative examples 4, 5, 6 changed the magnetron sputtering conditions compared to example 3. Magnetron sputtering is a preparation method which is very sensitive to preparation conditions, when the preparation conditions are changed, if the conditions are not properly selected, the prepared coating layer has the problems of non-uniformity or surface part exposure and the like, and the material performance is influenced.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.

Claims (10)

1. A sulfide solid electrolyte material is characterized in that the general structural formula of the sulfide solid electrolyte material is xLi2S·(1-x)GeS2·yM/Li3PO4Wherein M is oxide, x is more than or equal to 0.7 and less than or equal to 0.8, and y is more than or equal to 0.001 and less than or equal to 0.005.
2. A method for producing a sulfide solid state electrolyte material, characterized by comprising the steps of:
1) according to the formula xLi2S·(1-x)GeS2yM, weighing Li according to molar ratio2S、GeS2And M, adding an organic solvent, and sanding in a sand mill to obtain a solid-liquid mixtureI, particle size D500.1 μ M or less, wherein M is an oxide;
2) carrying out spray drying on the solid-liquid mixture I in a fully-closed spray dryer under the protection of nitrogen to obtain a material II, wherein the granularity D of the material II5012-18 mu m, and the drying temperature of the spray drying is 120-160 ℃;
3) carrying out heat treatment on the material II in a nitrogen atmosphere to obtain a material III, wherein the heat treatment temperature is 500-700 ℃, and the heat treatment time is 2-8 h;
4) taking part of material III to carry out airflow crushing in nitrogen atmosphere to obtain material IV, wherein the particle size D of the material IV50＝2～4μm；
5) Uniformly mixing a material III and a material IV in a nitrogen protection high-speed mixer to obtain a material V, wherein the mass ratio of the material III: the material IV is (2-4) 1;
6) and putting the material V into a magnetron sputtering machine for magnetron sputtering to obtain a sulfide solid electrolyte material product, wherein a sputtering target material adopted in the magnetron sputtering process is lithium phosphate with the purity of 99.9%, and the sputtering gas is Ar.
3. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: in the step 1), x is more than or equal to 0.7 and less than or equal to 0.8, and y is more than or equal to 0.001 and less than or equal to 0.005.
4. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: in the step 1), M is TiO2、MgO、ZrO2And Al2O3One or more of (a).
5. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: in the step 1), the organic solvent is cyclohexane and acetone.
6. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: and 6) sputtering pressure P in the magnetron sputtering is 1-4 Pa.
7. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: and 6) sputtering time t in the magnetron sputtering is 10-30 min.
8. The production method of a sulfide solid state electrolyte material according to claim 2, characterized in that: and 6) sputtering power in the magnetron sputtering is 30-50W.
9. Use of the sulfide solid state electrolyte material according to claim 1 in an all-solid battery.
10. The sulfide solid electrolyte material prepared by the preparation method according to any one of claims 2 to 8 is applied to an all-solid battery.
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Cited By (4)

* Cited by examiner, † Cited by third party
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CN113745651A (en) * 2021-08-27 2021-12-03 深圳市研一新材料有限责任公司 Coated sulfide solid electrolyte and preparation method and application thereof
CN113937346A (en) * 2020-07-13 2022-01-14 比亚迪股份有限公司 Solid electrolyte, preparation method thereof and all-solid-state battery
CN113937345A (en) * 2020-07-13 2022-01-14 比亚迪股份有限公司 Composite solid electrolyte, preparation method thereof and all-solid-state battery
CN115995600A (en) * 2023-03-22 2023-04-21 中国科学院宁波材料技术与工程研究所 Element doped sulfide solid electrolyte with coating layer and preparation method thereof

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