CN111082128B - High-power all-solid-state battery and preparation thereof - Google Patents

High-power all-solid-state battery and preparation thereof Download PDF

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CN111082128B
CN111082128B CN201911342394.8A CN201911342394A CN111082128B CN 111082128 B CN111082128 B CN 111082128B CN 201911342394 A CN201911342394 A CN 201911342394A CN 111082128 B CN111082128 B CN 111082128B
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ion conductor
fast ion
battery
sulfide
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CN111082128A (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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    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
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    • H01M4/00—Electrodes
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention belongs to the technical field of batteries, and relates to a high-power all-solid-state battery and a preparation method thereof. The 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 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) or a combination of several. 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 a reference for developing a high-safety, high-capacity and rapid charge and discharge battery.

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
All-solid-state lithium batteries employing solid electrolytes are receiving wide attention in academia and industry due to their high safety and high energy density, as compared to commercial lithium ion batteries employing liquid electrolytes. However, compared with liquid batteries, the current all-solid-state battery cannot basically work normally at a higher multiplying power, and basically analysis is mainly because the contact between the active substance and the solid electrolyte or the conductive agent in the electrode can only depend on a simple solid-solid contact mode, and the simple mixing of the active substance in the electrode with the solid electrolyte and the conductive agent cannot ensure that the active substance can contact both the electrolyte (ensuring ion transmission) and the conductive agent (ensuring electron transmission), and the mode cannot ensure that an ion or electron transmission channel is continuous and smooth. At present, related improvement and improvement measures are not reported, so that an all-solid-state battery anode is urgently needed to be designed, and the active material is ensured to be contacted with a solid electrolyte and a conductive agent to realize rapid ion and electron transmission.
Disclosure of Invention
The invention aims at a high-power all-solid-state battery and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the 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 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) or a combination of several.
Discharging the all-solid-state battery under low pressure to a position below an electrochemical stability window of a sulfide fast ion conductor, wherein the all-solid-state battery is presented; or charged at low voltage above the sulfide fast ion conductor electrochemical stability window, an all-solid state battery is presented.
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 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) 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 O 12 (x=0,1,A=Ca,Sr,Ba,M=Nb,Ta,Bi)、ϒ-Al 2 O 3 One or more of the following; 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, polydivinylsulfide and derivatives thereof; the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalato borate, lithium trifluoro (CF) 3 SO 3 Li), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) 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 sequentially stacking the anode, the solid electrolyte and the cathode to form the integrated all-solid-state lithium battery with the sandwich structure.
The negative electrode 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 below the sulfide fast ion conductor electrochemical stability window or charges the battery above the sulfide fast ion conductor electrochemical stability window, and then charges or discharges the battery for use.
The all-solid-state battery is firstly discharged below an electrochemical stability window of a sulfide fast ion conductor under a low voltage of 0-1.5V or charged (3-5V) above the electrochemical stability window of the sulfide fast ion conductor, so that the sulfide fast ion conductor at the contact part with the conductive agent is decomposed to generate battery active substances with capacity, the active substances are generated in situ through electrochemical reaction, and the active substances are contacted with the sulfide fast ion conductor and the conductive agent in an atomic level, so that the active substances have 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 electrolyte is discharged under the low voltage of 0-1.5V or charged (3-5V) to the position 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 below the electrochemical stability window of the sulfide fast ion conductor or charged above the electrochemical stability window of the sulfide fast ion conductor, and only the sulfide fast ion conductor contacted with the conductive agent in the positive electrode can be decomposed and generate Li in the process 2 S,P 2 S 5 , Li 2 S n Etc. by-products, wherein Li 2 S，Li 2 S n Is an electrochemically active material, and the generated byproducts can prevent the electrolyte from decomposing during the subsequent charge and discharge process due to the inertia of electrons and ions (the electrolyte in the positive electrode does not undergo oxidation-reduction reaction if not contacted with electrons). Li generated after discharge 2 S generates Li during charging 2 S n Or Li generated after charging 2 S n Li is generated during discharge 2 S, S. After this, the electrochemical reaction during the battery charge and discharge is as follows: .
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 a reference for developing a high-safety, high-capacity and rapid charge and discharge battery.
The method is suitable for all-solid-state batteries which take sulfide fast ion conductors and conductive agents as electrode components, utilizes the generated sulfide byproducts as active materials of the batteries so as to improve the rate performance, and the generated byproducts are tightly contacted with sulfide electrolyte on the atomic scale to realize fast ion and electron transmission.
The high-power all-solid-state battery of the present invention utilizing the above method spontaneously decomposes into Li at low voltage using sulfide electrolyte 2 By utilizing the characteristics of by-products such as S and the like and utilizing the generated Li 2 S serves as the positive electrode active material of the battery. Due to the generated Li 2 S is generated spontaneously in situ, so that the active material is in close contact with sulfide electrolyte and conductive agent on the atomic scale, thereby greatly reducing solid-solid interface impedance and facilitating rapid transmission of ions and electrons. The all-solid-state battery assembled in this way can be manufactured at 25mA cm -2 Realizes stable circulation under the current density of (1.54 mAh cm) and can reach the battery capacity -2 . And the ratio of sulfide electrolyte to conductive agent in the positive electrode material is further regulated to obtain the full-solid lithium battery with different capacities and high multiplying power and high cycle stability.
Drawings
Fig. 1a is a schematic diagram of a discharging process of a high-power all-solid-state battery according to an embodiment of the present invention in the first cycle; fig. 1b is a schematic diagram of a change of a discharge ending substance of a first cycle of a high-power all-solid-state battery according to an embodiment of the present invention.
Fig. 2 is a graph showing the relationship between capacity and voltage at different cycles of the high-power all-solid-state battery according to example 1 of the present invention.
Fig. 3 is a graph showing the relationship between capacity and voltage in the steady state of the high-power all-solid-state battery according to embodiment 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to a high-power all-solid-state battery, which comprises an anode, an electrolyte and a cathode, wherein the anode 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 cell is first discharged below the sulfide fast ion conductor electrochemical stability window or charged above the sulfide fast ion conductor electrochemical stability window, positiveOnly sulfide fast ion conductors in contact with the conductive agent in the electrode are decomposed in the process and Li is generated 2 S,P 2 S 5 ,Li 2 S n Etc. by-products, wherein Li 2 S，Li 2 S n Is an electrochemically active material, and the generated byproducts can prevent the electrolyte from decomposing during the subsequent charge and discharge process due to the inertia of electrons and ions (the electrolyte in the positive electrode does not undergo oxidation-reduction reaction if not contacted with electrons). Li generated after discharge 2 S generates Li during charging 2 S n Or Li generated after charging 2 S n Li is generated during discharge 2 S, S. After this, the electrochemical reaction during the battery charge and discharge is as follows: . The generated sulfide byproducts are used as the active materials of the battery to further improve the rate performance, and the generated byproducts are tightly contacted with sulfide electrolyte on the atomic scale to realize rapid ion and electron transmission.
Example 1
Li is mixed with 3 PS 4 Mixing the material with conductive carbon black according to the mass ratio of 7:3, and fully grinding and mixing the mixture to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold pressing methods can be used to prepare all-solid-state batteries, specifically: first, 0.1 g of Li is taken 3 PS 4 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, firstly, cross-flow discharge is carried out to 1V (vs. Li/Li) + ) After the discharge, the battery was charged to a voltage of 4V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a, 1b and 2).
The battery obtained by using the above example was subjected to a cross-flow charge-discharge test, and the active material of high capacity had been generated at the time of the first discharge to 1V, and the redox reaction occurring at the charge-discharge of the subsequent battery was all based on the generated active material.
As can be seen from the figure, the battery is first discharged to Li 3 PS 4 Below the electrochemical stability window, the reactions that occur are different following normal charge and discharge. At the first-round discharge, li 3 PS 4 Will decompose at low voltage to produce Li 2 S and other byproducts, li when the battery is charged 2 S will generate Li 2 S n And contributes to capacity. Due to Li 3 PS 4 Is irreversible and other by-products formed can also inhibit Li 3 PS 4 Further decomposition, this ensures an ion transport channel in the positive electrode. In the subsequent electrochemical reaction of the cell, only Li occurs 2 S and Li 2 S n And oxidation-reduction reaction between the two.
Example 2
Li is mixed with 7 P 3 S 11 Mixing with graphene according to a mass ratio of 5:5, and fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold pressing methods can be used to prepare all-solid-state batteries, specifically: first, 0.1 g of Li is taken 7 P 3 S 11 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, and is charged to 4.5V (vs. Li/Li) in a cross-flow manner + ) After the charge is completed, the battery is subjected to cross-current discharge to a voltage of 1V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a, 1b and 3).
The battery obtained by using the above example was subjected to a cross-flow charge-discharge test, and the active material of high capacity had been generated when the battery was charged to 4.5V for the first time, and the redox reaction occurring in the charge-discharge of the subsequent battery was all based on the generated active material.
It can be seen from the figure that the use of in situ formation of high capacity active species greatly reduces the resistance of the cell reaction kinetics, which results in reduced electrochemical polarization of the cell reaction and a cell efficiency approaching 100%.
Example 3
Li is mixed with 10 GeP 2 S 12 Mixing with super P according to a mass ratio of 4:6, and fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold-pressing methods can be used to prepare all-solid-state batteries. First, 0.1 g of Li is taken 10 GeP 2 S 12 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, firstly, cross-flow discharge is carried out to 0.5V (vs. Li/Li) + ) After the discharge, the battery was charged to a voltage of 4V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
Example 4
Li is mixed with 10 SnP 2 S 12 Mixing with super P according to a mass ratio of 4:6, and fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold-pressing methods can be used to prepare all-solid-state batteries. First, 0.1 g of Li is taken 10 SnP 2 S 12 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, and is charged to 4.5V (vs. Li/Li) in a cross-flow manner + ) After the charge is completed, the battery is subjected to cross-current discharge to a voltage of 1V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
Example 5
Will be 0.7. 0.7 Li 2 S: 0.3P 2 S 5 Mixing with conductive carbon black according to a mass ratio of 5: 5. mixing, fully grinding and mixing to obtain the composite positive electrode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold-pressing methods can be used to prepare all-solid-state batteries. First, 0.1 g of Li is taken 10 GeP 2 S 12 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, firstly, cross-flow discharge is carried out to 0.8V (vs. Li/Li) + ) After the discharge, the battery was charged to a voltage of 4V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
Example 6
Li is mixed with 10 SiP 2 S 12 Mixing with graphite according to a mass ratio of 7:3, and fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold-pressing methods can be used to prepare all-solid-state batteries. First, 0.1 g of Li is taken 10 SiP 2 S 12 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, and is charged to 4.5V (vs. Li/Li) in a cross-flow manner + ) After the charge is completed, the battery is subjected to cross-current discharge to a voltage of 0.5V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
Example 7
Li is mixed with 6 PS 5 Cl and ketjen black are mixed according to the mass ratio of 6:4, and the mixture is fully ground and mixed to be used as a composite anode. For fast separation with sulfidesAll-solid-state batteries in which the subconductors are electrolytes can be prepared by cold pressing. First, 0.1 g of Li is taken 10 GeP 2 S 12 The resulting mixture was placed in a swagelok-type battery under a pressure of 100 Mpa for 1 min, and then 10 mg of the above-mentioned composite positive electrode powder was uniformly spread on one side of the electrolyte sheet and kept under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, and is charged to 5.5V (vs. Li/Li) in a cross-flow manner + ) After the charge is completed, the battery is subjected to cross-current discharge to a voltage of 1V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
Example 8
Li is mixed with 6 PS 5 And mixing Br and KS graphite according to a mass ratio of 5:5, and fully grinding and mixing to obtain the composite anode. For all-solid-state batteries using sulfide fast ion conductors as electrolytes, cold-pressing methods can be used to prepare all-solid-state batteries. First, 0.1 g of Li is taken 6 PS 5 Cl was placed in a swagelok type cell under a pressure of 100 Mpa for 1 min, followed by uniformly spreading 10 mg of the above composite cathode powder on one side of the electrolyte sheet and under a pressure of 300 Mpa 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 for 5 min under the pressure of 50 Mpa. Finally, the battery is placed on a constant current charge-discharge instrument, firstly, cross-flow discharge is carried out to 1V (vs. Li/Li) + ) After the discharge, the battery was charged to a voltage of 4V (vs. Li/Li + ). Charge and discharge tests were then performed at voltage intervals 1-4V (see fig. 1a and 1 b).
As can be seen from the above examples, fig. 1a and fig. 1b, which show the generation of active materials in the positive electrode after the battery is discharged at low voltage after the battery is assembled, show that decomposition of sulfide fast ion conductor occurs during the first cycle of discharge at low voltage; after the first cycle discharge of the battery is finished, high-capacity electrochemical active substance Li is generated 2 S, S. The active material in the positive electrode is generated after the battery is charged under high voltage after being assembled, and sulfide fast ion conductor can also be generated in the first cycle charging processDecomposition at high voltage; after the first cycle discharge of the battery is finished, high-capacity electrochemical active substance Li is generated 2 S n /S。

Claims (7)

1. The high-power all-solid-state battery comprises a positive electrode, a solid electrolyte and a negative electrode, and is characterized in that 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 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) or a combination of several;
discharging the all-solid-state battery below an electrochemical stability window of a sulfide fast ion conductor; or charging to above the sulfide fast ion conductor electrochemical stability window; the sulfide fast ion conductor in the contact part with the conductive agent is decomposed to generate a battery active substance with capacity, and the active substance is generated in situ by electrochemical reaction, so that the active substance is in atomic-level contact with the sulfide fast ion conductor and the conductive agent, the ion and electron transmission is fast in the subsequent oxidation-reduction process, the solid-solid interface impedance is reduced, and the high multiplying power and the high cycling stability of the all-solid battery are further realized; the redox reactions occurring in the charge and discharge of the subsequent cell are all based on the active species generated in situ by the electrochemical reactions described above;
the mass ratio of the sulfide fast ion conductor to the conductive agent is 2:8-8:2.
2. a 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) 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 O 12 (x=0,1,A=Ca,Sr,Ba,M=Nb,Ta,Bi)、ϒ-Al 2 O 3 One or more of the following; the polymer solid electrolyte is composed of a polymer and a lithium salt.
3. A high power all-solid-state battery according to claim 2, wherein: the polymer is one or more of polyoxyethylene, polyoxypropylene, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl carbonate, polyvinylpyrrolidone, polymethyl methacrylate, polyvinylidene fluoride, polyethylene glycol acrylate, polydivinylsulfide and derivatives thereof; the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalato borate, lithium trifluoro (CF) 3 SO 3 Li), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI).
4. A method of making a high power all-solid-state battery according to claim 1, characterized by: a positive electrode, a solid electrolyte and a negative electrode; or sequentially stacking the anode, the solid electrolyte and the cathode to form the integrated all-solid-state lithium battery with the sandwich structure.
5. The method for manufacturing a high-power all-solid-state battery according to claim 4, wherein: the negative electrode is one of a metal lithium sheet, a metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene and silicon carbon negative electrode.
6. The method of producing a high power all-solid-state battery according to claim 4, wherein said all-solid-state battery is discharged below an electrochemical stability window of a sulfide fast ion conductor with a cutoff voltage of 0 to 1.5V; or charging to above the electrochemical stability window of the sulfide fast ion conductor, and the cut-off voltage is 3-5v; the sulfide fast ion conductor in contact with the conductive agent is decomposed to generate a battery active substance with capacity, and the active substance is generated in situ by electrochemical reaction, so that the active substance is in atomic-level contact with the sulfide fast ion conductor and the conductive agent, the ion and electron transmission is fast in the subsequent oxidation-reduction process, the solid-solid interface impedance is reduced, and the high multiplying power and the high cycling stability of the all-solid battery are further realized.
7. A method of improving the efficiency of a solid state battery, characterized by: discharging the all-solid-state battery of claim 1 below the sulfide fast ion conductor electrochemical stability window with a cutoff voltage of 0-1.5V; or charging to above the electrochemical stability window of the sulfide fast ion conductor, and the cut-off voltage is 3-5v; and further can realize high multiplying power and high cycle stability of the all-solid-state battery.
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