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CN111082128A - A high-power all-solid-state battery and its preparation - Google Patents

A high-power all-solid-state battery and its preparation Download PDF

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CN111082128A
CN111082128A CN201911342394.8A CN201911342394A CN111082128A CN 111082128 A CN111082128 A CN 111082128A CN 201911342394 A CN201911342394 A CN 201911342394A CN 111082128 A CN111082128 A CN 111082128A
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solid
state battery
ion conductor
fast ion
sulfide
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CN111082128B (en
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崔光磊
王延涛
鞠江伟
徐红霞
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract

本发明属于电池技术领域，涉及一种高功率全固态电池及其制备。高功率全固态电池，包括正极、固态电解质和负极，所述正极为硫化物快离子导体与导电剂混磨得到，固态电解质为离子传输介质；其中硫化物快离子导体为xLi2S:(1‑x)P2S5(x＝0.6‑0.8),Li3PS4,Li10MxP3‑xS12(0≤x≤2,M＝Si,Ge,Sn),Li6PS5X(X＝Cl,Br,I)中的一种或几种的组合。本发明固态电池从原子尺度上修饰了电池活性材料的离子和电子传输通道，提高了电池的高倍率性能。为开发高安全、高容量、快速充放电电池提供了参考。The invention belongs to the technical field of batteries, and relates to a high-power all-solid-state battery and its preparation. A high-power all-solid-state battery, comprising a positive electrode, a solid-state electrolyte and a negative electrode, the positive electrode is obtained by mixing a sulfide fast ion conductor and a conductive agent, and the solid electrolyte is an ion transport medium; wherein the sulfide fast ion conductor is xLi 2 S:(1 ‑x)P 2 S 5 (x=0.6‑0.8),Li 3 PS 4 ,Li 10 M x P 3‑x S 12 (0≤x≤2,M=Si,Ge,Sn),Li 6 PS 5 One or a combination of X (X=Cl, Br, I). The solid-state battery of the invention modifies the ion and electron transport channels of the battery active material on the atomic scale, and improves the high rate performance of the battery. It provides a reference for the development of high-safety, high-capacity, and fast charge-discharge batteries.

Description

High-power all-solid-state battery and preparation thereof
Technical Field
The invention belongs to the technical field of batteries, and relates to a high-power all-solid-state battery and a preparation method thereof.
Background
An all solid-state lithium battery using a solid electrolyte has received much attention from both academic and industrial fields due to its high safety and high energy density, as compared to a commercial lithium ion battery using a liquid electrolyte. However, compared with liquid batteries, the existing all-solid batteries can not work normally at a higher rate, and the essential analysis is mainly that the contact between the active substance in the electrode and the solid electrolyte or the conductive agent can only depend on a simple solid-solid contact mode, and the simple mixing of the active substance in the electrode, the solid electrolyte and the conductive agent can not ensure that the active substance can contact both the electrolyte (ensuring ion transmission) and the conductive agent (ensuring electron transmission), and the mode can not ensure that the ion or electron transmission channel is continuous and smooth. At present, relevant improvement measures are not reported, so that an all-solid-state battery anode is urgently needed to be designed, active materials are ensured to be in contact with both a solid electrolyte and a conductive agent, and rapid ion and electron transmission is realized.
Disclosure of Invention
The invention aims to provide a high-power all-solid-state battery and preparation thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-power all-solid-state battery comprises a positive electrode, a solid electrolyte and a negative electrode, wherein the positive electrode is obtained by mixing and grinding a sulfide fast ion conductor and a conductive agent, and the solid electrolyte is an ion transmission medium; wherein the sulfide fast ion conductor is xLi2S:(1-x)P2S5(x＝0.6-0.8),Li3PS4,Li10MxP3-xS12(0≤x≤2,M＝Si,Ge,Sn),Li6PS5And X (X ═ Cl, Br, I) is one or a combination of more of the above.
Discharging the all-solid-state battery at low voltage until the electrochemical stability window of the sulfide fast ion conductor is lower than the electrochemical stability window of the all-solid-state battery; or charged to a voltage above the electrochemical stability window of the sulfide fast ion conductor at low voltage.
The mass ratio of the sulfide fast ion conductor to the conductive agent is 2: 8-8: 2, preferably 7: 3-4: 6.
the solid electrolyte is a sulfide fast ion conductor, an oxide fast ion conductor or a polymer solid electrolyte, wherein the sulfide fast ion conductor is xLi2S:(1-x)P2S5(x＝0.6～0.8),Li3PS4,Li10MxP3-xS12(0≤x≤2,M＝Si,Ge,Sn),Li6PS5One or more of X (Cl, Br, I); the oxide fast ion conductor is Li1- xAlxTi2-x(PO4)3(0.1<x<0.6)、Li3xLa(2/3)-xTiO3(0.04<x<0.15)、Li5La3M2O12(M＝Ta,Nb)、Li5+ xAxLa3-XM2O12(x＝0,1,A＝Ca,Sr,Ba,M＝Nb,Ta,Bi)、γ-Al2O3One or more of the above; the polymer solid electrolyte is composed of a polymer and a lithium salt.
The polymer is one or more of polyoxyethylene, polyoxypropylene, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl carbonate, polyvinylpyrrolidone, polymethyl methacrylate, polyvinylidene fluoride, polyethylene glycol acrylate, polydivinyl sulfide and derivatives thereof; the lithium salt is lithium perchlorate (LiClO)4) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoro (CF)3SO3Li), lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and lithium bis (fluoro) sulfonyl imide (LiFSI).
A preparation method of a high-power all-solid-state battery comprises the steps of preparing a positive electrode, a solid electrolyte and a negative electrode; or the negative electrode, the solid electrolyte and the positive electrode are sequentially laminated to form the integrated all-solid-state lithium battery with the sandwich structure.
The negative active material is one of a metal lithium sheet, a metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene and a silicon carbon negative electrode;
the all-solid-state battery discharges the battery to be below the electrochemical stability window of the sulfide fast ion conductor or charges the battery to be above the electrochemical stability window of the sulfide fast ion conductor, and then charges or discharges the battery for use.
The all-solid-state battery is firstly discharged to be below the electrochemical stability window of the sulfide fast ion conductor or charged (3-5V) to be above the electrochemical stability window of the sulfide fast ion conductor under the low voltage of 0-1.5V, so that the sulfide fast ion conductor in the contact part with the conductive agent is decomposed to generate a battery active substance with capacity, the active substance is generated in situ by electrochemical reaction, and the active substance is in atomic-level contact with the sulfide fast ion conductor and the conductive agent, so that the active substance has excellent ion and electron transmission in the subsequent oxidation reduction process, the solid-solid interface impedance is reduced, and the high multiplying power and the high cycle stability of the all-solid-state battery are improved.
A method for improving the efficiency of solid-state battery features that the solid-state battery containing sulfide fast ion conductor as positive electrode material or said all-solid-state battery is charged at 0-1.5V to below the electrochemical stability window of sulfide fast ion conductor or charged (3-5V) to above the electrochemical stability window of sulfide fast ion conductor, so realizing high multiplying power and high cyclic stability.
The working principle of the battery is that the battery is firstly discharged to be below the electrochemical stability window of the sulfide fast ion conductor or charged to be above the electrochemical stability window of the sulfide fast ion conductor, and only the sulfide fast ion conductor in contact with the conductive agent in the positive electrode can be decomposed and generate Li in the process2S,P2S5,Li2SnEtc. by-products, wherein Li2S，Li2SnIs an electrochemically active material, and the generated byproducts can prevent the decomposition of the electrolyte in the subsequent charge and discharge processes due to the inertia of electrons and ions (the electrolyte in the positive electrode does not have redox reaction if not contacting with the electrons). Li produced at the end of discharge2S production of Li during charging2SnOr end of charge generationLi of (2)2SnGeneration of Li during discharge2And S. After that, the electrochemical reaction during the charge and discharge of the battery is as follows:
Figure BDA0002331785820000021
the invention has the advantages that:
the solid-state battery modifies ion and electron transmission channels of the battery active material on an atomic scale, and improves the high-rate performance of the battery. Provides reference for developing high-safety, high-capacity and rapid charge and discharge batteries.
The method is suitable for all-solid-state batteries taking a sulfide fast ion conductor and a conductive agent as electrode components, the generated sulfide by-product is used as an active material of the battery to further improve the rate capability, and the generated by-product is tightly contacted with a sulfide electrolyte on an atomic scale to realize rapid ion and electron transmission.
The high-power all-solid-state battery of the invention utilizes sulfide electrolyte to spontaneously decompose into Li at low voltage2By-products such as S, utilizing the characteristics of the produced Li2S is used as the positive electrode active material of the battery. Due to Li generation2S is spontaneously generated in situ, so that the active material is in close contact with the sulfide electrolyte and the conductive agent on an atomic scale, the solid-solid interface impedance is greatly reduced, and the rapid transmission of ions and electrons is facilitated. An all-solid-state battery assembled in this manner can be at 25mA cm-2The current density of the battery can be stably circulated, and the battery capacity can be as high as 1.54mAhcm-2. And the proportion of the sulfide electrolyte and the conductive agent in the anode material is further regulated and controlled, so that the all-solid-state lithium battery with different capacities, high multiplying power and high cycle stability can be obtained.
Drawings
Fig. 1 is a schematic diagram illustrating generation of active materials in an all-solid-state electrode positive electrode according to an embodiment of the present invention; a, a schematic diagram of the discharge process of the battery in the first cycle; b is a schematic diagram of the change of the material of the first cycle discharge end of the battery.
Fig. 2 is a graph of capacity versus voltage for different cycles of the high power all-solid battery provided in embodiment 1 of the present invention.
Fig. 3 is a graph showing a relationship between capacity and voltage in a stable state of the high-power all-solid battery provided in embodiment 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
The high-power all-solid-state battery comprises three parts of a positive electrode, an electrolyte and a negative electrode, wherein the positive electrode part is a mixture of a sulfide fast ion conductor and a conductive agent according to a certain proportion, and the electrolyte is a solid fast ion conductor or a polymer electrolyte. The battery is firstly discharged to be below the electrochemical stability window of the sulfide fast ion conductor or above the electrochemical stability window of the charged sulfide fast ion conductor, and only the sulfide fast ion conductor in contact with the conductive agent in the positive electrode can be decomposed and Li is generated in the process2S,P2S5,Li2SnEtc. by-products, wherein Li2S，Li2SnIs an electrochemically active material, and the generated byproducts can prevent the decomposition of the electrolyte in the subsequent charge and discharge processes due to the inertia of electrons and ions (the electrolyte in the positive electrode does not have redox reaction if not contacting with the electrons). Li produced at the end of discharge2S production of Li during charging2SnOr Li generated at the end of charge2SnGeneration of Li during discharge2And S. After that, the electrochemical reaction during the charge and discharge of the battery is as follows:
Figure BDA0002331785820000031
the generated sulfide by-product is used as an active material of the battery to further improve the rate capability, and the generated by-product is tightly contacted with sulfide electrolyte on an atomic scale, so that rapid ion and electron transmission is realized.
Example 1
Mixing Li3PS4And is electrically conductiveAnd mixing the carbon black according to the mass ratio of 7:3, fully grinding and mixing to obtain the composite positive electrode. For an all-solid-state battery taking a sulfide fast ion conductor as an electrolyte, a cold pressing method can be adopted to prepare the all-solid-state battery, and the method specifically comprises the following steps: first 0.1g of Li was taken3PS4The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charge-discharge instrument, and transverse current discharge is firstly carried out to 1V (vs+) After the discharge, the battery is subjected to cross-current charging to reach a voltage of 4V (vs+). The charge and discharge test is then performed in the voltage interval 1-4V (see fig. 1 and 2).
The cell obtained by the above example was subjected to a transverse current charge and discharge test, in which a high-capacity active material had been generated at the time of the first discharge to 1V and the redox reactions occurring in the subsequent charge and discharge of the cell were all based on the generated active material.
As can be seen from the figure, the battery was first discharged to Li3PS4Below the electrochemical stability window, the reactions that occur are different following normal charge and discharge. Upon discharge of the first turn, Li3PS4Will decompose at low voltage to produce Li2S and other by-products, Li when the battery is charged2S will generate Li2SnAnd contributes capacity. Due to Li3PS4Is irreversible and other by-products formed can also inhibit Li3PS4Further decomposition, which ensures an ion transport channel in the positive electrode. Whereas in the subsequent electrochemical reaction of the cell, only Li occurs2S and Li2SnA redox reaction therebetween.
Example 2
Mixing Li7P3S11And mixing the graphite powder and graphene according to a mass ratio of 5:5, fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, the method can be adoptedThe cold pressing method is used for preparing the all-solid-state battery, and specifically comprises the following steps: first 0.1g of Li was taken7P3S11The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charging and discharging instrument, and transverse current charging is firstly carried out to 4.5V (vs+) After the charging, the battery carries out transverse current discharge to the voltage of 1V (vs+). The charge and discharge test is then performed in the voltage interval 1-4V (see fig. 1 and 3).
The battery obtained by using the above example was subjected to a transverse current charge and discharge test, in which a high-capacity active material was generated at the time of the first charge to 4.5V and the redox reactions occurring in the subsequent charge and discharge of the battery were all based on the generated active material.
As can be seen from the figure, the resistance of the cell reaction kinetics is greatly reduced due to the in-situ generation of high-capacity active species, which leads to a reduction in the electrochemical polarization of the cell reaction and a cell efficiency approaching 100%.
Example 3
Mixing Li10GeP2S12Mixing with super P according to the mass ratio of 4:6, fully grinding and mixing to obtain the composite positive electrode. For the all-solid-state battery taking the sulfide fast ion conductor as the electrolyte, the cold pressing method can be adopted to prepare the all-solid-state battery. First 0.1g of Li was taken10GeP2S12The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charge-discharge instrument, and transverse current discharge is firstly carried out to 0.5V (vs+) After the discharge, the battery is subjected to cross-current charging to reach a voltage of 4V (vs+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
Example 4
Mixing Li10SnP2S12Mixing with super P according to the mass ratio of 4:6, fully grinding and mixing to obtain the composite positive electrode. For the all-solid-state battery taking the sulfide fast ion conductor as the electrolyte, the cold pressing method can be adopted to prepare the all-solid-state battery. First 0.1g of Li was taken10SnP2S12The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charging and discharging instrument, and transverse current charging is firstly carried out to 4.5V (vs+) After the charging, the battery carries out transverse current discharge to the voltage of 1V (vs+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
Example 5
0.7Li2S:0.3P2S5And conductive carbon black according to the mass ratio of 5:5 mixing, fully grinding and mixing to obtain the composite positive electrode. For the all-solid-state battery taking the sulfide fast ion conductor as the electrolyte, the cold pressing method can be adopted to prepare the all-solid-state battery. First 0.1g of Li was taken10GeP2S12The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charge-discharge instrument, and transverse current discharge is firstly carried out to 0.8V (vs+) After the discharge, the battery is subjected to cross-current charging to reach a voltage of 4V (vs+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
Example 6
Mixing Li10SiP2S12And mixing the graphite with the graphite according to the mass ratio of 7:3, fully grinding and mixing to obtain the composite positive electrode. For sulfide-based fast ion conductorsThe all-solid-state battery is an electrolyte, and can be prepared by adopting a cold pressing method. First 0.1g of Li was taken10SiP2S12The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charging and discharging instrument, and transverse current charging is firstly carried out to 4.5V (vs+) After the charging, the battery carries out cross current discharge to the voltage of 0.5V (vs. Li/Li)+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
Example 7
Mixing Li6PS5And mixing Cl and Keqin black according to the mass ratio of 6:4, and fully grinding and mixing to obtain the composite positive electrode. For the all-solid-state battery taking the sulfide fast ion conductor as the electrolyte, the cold pressing method can be adopted to prepare the all-solid-state battery. First 0.1g of Li was taken10GeP2S12The sheet was left in a swegelok type cell under a pressure of 100Mpa for 1min, and then 10mg of the above composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300Mpa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charging and discharging instrument, and transverse current charging is firstly carried out to 5.5V (vs+) After the charging, the battery carries out transverse current discharge to the voltage of 1V (vs+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
Example 8
Mixing Li6PS5And mixing Br and KS graphite according to a mass ratio of 5:5, and fully grinding and mixing to obtain the composite positive electrode. For the all-solid-state battery taking the sulfide fast ion conductor as the electrolyte, the cold pressing method can be adopted to prepare the all-solid-state battery. First 0.1g of Li was taken6PS5Placing Cl in a swegelok type battery, maintaining the pressure at 100Mpa for 1min, and then spreading 10mg of the composite anode powder on one side of an electrolyte sheet uniformlyAnd maintaining the pressure at 300MPa for 5 min. And finally, placing the lithium sheet or the lithium indium alloy sheet on the other side of the electrolyte and maintaining the pressure at 50MPa for 5 min. Finally, the battery is placed on a constant current charge-discharge instrument, and transverse current discharge is firstly carried out to 1V (vs+) After the discharge, the battery is subjected to cross-current charging to reach a voltage of 4V (vs+). The charge and discharge test was then performed in the voltage interval 1-4V (see fig. 1).
As can be seen from the above examples, fig. 1, in which active materials are generated in the positive electrode after the battery is assembled and discharged at low voltage, the decomposition of the sulfide fast ion conductor at low voltage occurs during the first cycle of discharge; formation of high-capacity electrochemically active material Li after battery first-cycle discharge2And S. After the battery is assembled and charged under high voltage, active substances in the positive electrode are generated visibly, and the decomposition of the sulfide fast ion conductor under high voltage can also occur in the first-week charging process; formation of high-capacity electrochemically active material Li after battery first-cycle discharge2Sn/S。

Claims (10)

1.一种高功率全固态电池，包括正极、固态电解质和负极，其特征在于，所述正极为硫化物快离子导体与导电剂混磨得到，固态电解质为离子传输介质；其中硫化物快离子导体为xLi2S:(1-x)P2S5(x＝0.6-0.8),Li3PS4,Li10MxP3-xS12(0≤x≤2,M＝Si,Ge,Sn),Li6PS5X(X＝Cl,Br,I)中的一种或几种的组合。1. a high-power all-solid-state battery, comprising positive electrode, solid-state electrolyte and negative electrode, is characterized in that, described positive electrode is that sulfide fast ion conductor and conductive agent are mixed and ground, and solid-state electrolyte is ion transport medium; Wherein sulfide fast ion The conductor is xLi 2 S: (1-x)P 2 S 5 (x=0.6-0.8), Li 3 PS 4 , Li 10 M x P 3-x S 12 (0≤x≤2, M=Si, Ge , Sn), Li 6 PS 5 X (X=Cl, Br, I) one or a combination of several. 2.按权利要求1所述的高功率全固态电池，其特征在于：对所述全固态电池低压下进行放电至硫化物快离子导体电化学稳定窗口以下，所呈现的全固态电池；或充电至硫化物快离子导体电化学稳定窗口以上，所呈现的全固态电池。2. The high-power all-solid-state battery according to claim 1, characterized in that: the all-solid-state battery is discharged under low pressure to below the electrochemical stability window of the sulfide fast ion conductor, and the presented all-solid-state battery; or charging Above the electrochemical stability window of sulfide fast ionic conductors, the presented all-solid-state battery. 3.按权利要求1所述的高功率全固态电池，其特征在于：所述硫化物快离子导体与导电剂的质量比例为2：8-8：2。3 . The high-power all-solid-state battery according to claim 1 , wherein the mass ratio of the sulfide fast ion conductor to the conductive agent is 2:8-8:2. 4 . 4.按权利要求1所述的高功率全固态电池，其特征在于：所述固态电解质硫化物快离子导体、氧化物快离子导体或聚合物固态电解质，其中硫化物快离子导体为xLi2S:(1-x)P2S5(x＝0.6-0.8),Li3PS4,Li10MxP3-xS12(0≤x≤2,M＝Si,Ge,Sn),Li6PS5X(X＝Cl,Br,I)中的一种或几种的组合；氧化物快离子导体为Li1-xAlxTi2-x(PO4)3(0.1<x<0.6)、Li3xLa(2/3)-xTiO3(0.04<x<0.15)、Li5La3M2O12(M＝Ta,Nb)、Li5+xAxLa3-XM2O12(x＝0,1,A＝Ca,Sr,Ba,M＝Nb,Ta,Bi)、γ-Al2O3中的一种或几种；聚合物固态电解质由聚合物和锂盐组成。4. The high-power all-solid-state battery according to claim 1, wherein the solid electrolyte sulfide fast ion conductor, oxide fast ion conductor or polymer solid electrolyte, wherein the sulfide fast ion conductor is xLi 2 S : (1-x)P 2 S 5 (x=0.6-0.8), Li 3 PS 4 , Li 10 M x P 3-x S 12 (0≤x≤2, M=Si,Ge,Sn),Li 6 PS 5 X (X=Cl, Br, I) one or a combination of several; the oxide fast ion conductor is Li 1-x Al x Ti 2-x (PO 4 ) 3 (0.1<x<0.6 ), Li 3x La (2/3)-x TiO 3 (0.04<x<0.15), Li 5 La 3 M 2 O 12 (M=Ta, Nb), Li 5+x A x La 3-X M 2 One or more of O 12 (x=0,1, A=Ca, Sr, Ba, M=Nb, Ta, Bi), γ-Al 2 O 3 ; polymer solid electrolyte is composed of polymer and lithium salt composition. 5.按权利要求4所述的高功率全固态电池，其特征在于：所述聚合物为聚氧乙烯、聚氧丙烯、聚丙烯腈、聚氯乙烯、聚苯乙烯、聚碳酸乙烯酯、聚乙烯吡咯烷酮、聚甲基丙烯酸甲酯、聚偏氟乙烯、聚丙烯酸乙二醇酯、聚二乙烯基硫及其衍生物中的一种或几种；锂盐为高氯酸锂(LiClO4)、双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiDFOB)、三氟甲磺酸锂(CF3SO3Li)、双三氟甲基磺酰亚胺锂(LiTFSI)、双氟磺酰亚胺锂(LiFSI)中的一种或几种的组合。5. The high-power all-solid-state battery according to claim 4, wherein the polymer is polyoxyethylene, polyoxypropylene, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl carbonate, polyvinyl One or more of vinylpyrrolidone, polymethylmethacrylate, polyvinylidene fluoride, polyethylene glycol acrylate, polydivinyl sulfide and its derivatives; the lithium salt is lithium perchlorate (LiClO 4 ) , Lithium Bisoxalate Borate (LiBOB), Lithium Difluorooxalate Borate (LiDFOB), Lithium Trifluoromethanesulfonate (CF 3 SO 3 Li), Lithium Bistrifluoromethanesulfonimide (LiTFSI), Bisfluorosulfonyl One or a combination of lithium imide (LiFSI). 6.一种权利要求1所述的高功率全固态电池的制备方法，其特征在于：按述正极、固态电解质和负极；或负极、固态电解质和正极的顺序叠压形成三明治结构一体化全固态锂电池。6. A method for preparing a high-power all-solid-state battery according to claim 1, characterized in that: the positive electrode, the solid-state electrolyte and the negative electrode are laminated in the order of the negative electrode, the solid-state electrolyte and the positive electrode to form a sandwich structure integrated all-solid state lithium battery. 7.按权利要求6所述的高功率全固态电池的制备方法，其特征在于：所述的负极活性材料为金属锂片、金属锂合金、石墨、硬碳、二硫化钼、钛酸锂、石墨烯和硅碳负极中的一种。7. by the preparation method of the described high-power all-solid-state battery of claim 6, it is characterized in that: described negative electrode active material is metal lithium sheet, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, One of graphene and silicon carbon anodes. 8.按权利要求6所述的高功率全固态电池的制备方法，其特征在于，所述全固态电池对电池放电至硫化物快离子导体电化学稳定窗口以下或充电至硫化物快离子导体电化学稳定窗口以上，而后对其进行充电或放电使用。8. by the preparation method of the high-power all-solid-state battery according to claim 6, it is characterized in that, described all-solid-state battery is discharged to the battery to below the electrochemical stability window of sulfide fast ion conductor or charged to the sulfide fast ion conductor electrochemical stability window. Above the chemical stability window, it is then charged or discharged for use. 9.按权利要求6所述的高功率全固态电池的制备方法，其特征在于，对所述全固态电池首先对电池在0-1.5V的低压下放电至硫化物快离子导体电化学稳定窗口以下或充电(3-5v)至硫化物快离子导体电化学稳定窗口以上，使与导电剂接触部分的硫化物快离子导体进行分解产生具有容量的电池活性物质，该活性物质由电化学反应原位生成，使其与硫化物快离子导体、导电剂都有原子级的接触，使其在后续氧化还原过程中离子、电子的传输快速，降低固-固界面阻抗，进而实现全固态电池的高倍率、高循环稳定性。9. The preparation method of the high-power all-solid-state battery according to claim 6, wherein the all-solid-state battery is first discharged to the sulfide fast ion conductor electrochemical stability window at a low voltage of 0-1.5V for the all-solid-state battery Below or charged (3-5v) to above the electrochemical stability window of the sulfide fast ion conductor, the sulfide fast ion conductor in contact with the conductive agent is decomposed to produce a battery active material with capacity, which is composed of electrochemical reactants. It is formed in situ, making it in atomic-level contact with sulfide fast ion conductors and conductive agents, so that ions and electrons can be transported quickly in the subsequent redox process, reducing the solid-solid interface impedance, thereby realizing the high performance of the all-solid-state battery. Multiplier, high cycle stability. 10.一种提高固态电池效率的方法，其特征在于：对含硫化物快离子导体为正极材料的固态电池，或权利要求1所述的全固态电池首先对电池在0-1.5V的低压下放电至硫化物快离子导体电化学稳定窗口以下或充电(3-5v)至硫化物快离子导体电化学稳定窗口以上，进而可实现全固态电池的高倍率、高循环稳定性。10. A method for improving the efficiency of a solid-state battery, characterized in that: for a solid-state battery with a sulfide-containing fast ion conductor as a positive electrode material, or for the all-solid-state battery according to claim 1, the battery is first subjected to a low voltage of 0-1.5V. Discharge to below the electrochemical stability window of the sulfide fast ion conductor or charge (3-5v) to above the electrochemical stability window of the sulfide fast ion conductor, thereby achieving high rate and high cycle stability of the all-solid-state battery.
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