CN111725561A - Solid electrolyte, preparation method thereof and all-solid-state battery - Google Patents

Solid electrolyte, preparation method thereof and all-solid-state battery Download PDF

Info

Publication number
CN111725561A
CN111725561A CN202010765945.8A CN202010765945A CN111725561A CN 111725561 A CN111725561 A CN 111725561A CN 202010765945 A CN202010765945 A CN 202010765945A CN 111725561 A CN111725561 A CN 111725561A
Authority
CN
China
Prior art keywords
electrolyte
layer
solid
electrolyte layer
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010765945.8A
Other languages
Chinese (zh)
Other versions
CN111725561B (en
Inventor
邓志
李帅
赵予生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest University of Science and Technology
Southern University of Science and Technology
Original Assignee
Southwest University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest University of Science and Technology filed Critical Southwest University of Science and Technology
Priority to CN202010765945.8A priority Critical patent/CN111725561B/en
Publication of CN111725561A publication Critical patent/CN111725561A/en
Application granted granted Critical
Publication of CN111725561B publication Critical patent/CN111725561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2300/008—Halides
    • 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 application provides a solid electrolyte, a preparation method thereof and an all-solid-state battery, belonging to the technical field of secondary batteries. The solid electrolyte includes a first electrolyte layer for contacting with the positive electrode active layer and a second electrolyte layer for contacting with the negative electrode active layer, which are overlapped. Wherein the material of the first electrolyte layer is a halide inorganic electrolyte material; the material of the second electrolyte layer is an anti-perovskite material. The halide inorganic electrolyte is in contact with the positive active layer, so that the interface impedance is low, the chemical and electrochemical stability is good, and a good positive-electrolyte interface can be obtained; the anti-perovskite solid electrolyte is in contact with the negative active layer, the interface impedance is small, the chemical and electrochemical stability of the anti-perovskite solid electrolyte to the negative active layer is good, and the growth of dendrites can be inhibited, so that a good negative-electrolyte interface is obtained.

Description

Solid electrolyte, preparation method thereof and all-solid-state battery
Technical Field
The application relates to the technical field of secondary batteries, in particular to a solid electrolyte, a preparation method thereof and an all-solid-state battery.
Background
The secondary lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, is rapidly developed in recent decades, and is widely applied to the fields of power grid energy storage, electric automobiles, portable electronic equipment and the like; however, as the living standard of human beings is increasingly improved, the demand for developing a battery with higher energy density, longer service life and higher safety is more urgent.
In order to meet the needs of human production and living, a variety of next-generation battery technologies have been proposed in succession, including: lithium air batteries, lithium sulfur batteries, aqueous batteries, sodium/magnesium/zinc/aluminum ion batteries, flow batteries, all-solid-state batteries, and the like. Compared with the traditional liquid battery, the all-solid-state lithium battery has the advantages of good mechanical property, safety performance and the like by using the solid electrolyte to replace the organic liquid electrolyte, and meanwhile, the use of the metal lithium cathode is possible, so that the energy density of the battery is greatly improved.
Among the most critical problems faced by all-solid-state batteries in the prior art are the interface problems: the interface impedance between the electrolyte anode material and the electrolyte material is large; the interface resistance between the negative electrode metal lithium and the electrolyte is large.
Disclosure of Invention
The application aims to provide a solid electrolyte, a preparation method thereof and an all-solid-state battery, which can reduce the interface impedance of the battery.
In a first aspect, the present application provides a solid electrolyte comprising a first electrolyte layer for contacting with a positive active layer and a second electrolyte layer for contacting with a negative active layer, which are overlapped. Wherein the material of the first electrolyte layer is a halide inorganic electrolyte material; the material of the second electrolyte layer is an anti-perovskite material.
The inventor finds that the halide inorganic electrolyte material is a material with higher conductivity and better stability with the anode material, so that after the first electrolyte layer is contacted with the anode active layer, the interface impedance is lower, the chemical and electrochemical stability is better, and a better anode-electrolyte interface can be obtained; the anti-perovskite solid electrolyte is in contact with the negative active layer (the halide inorganic electrolyte layer is isolated from the negative active layer, so that the halide inorganic electrolyte layer is prevented from being in contact with the negative active layer and reacting), the interface impedance is low, the chemical and electrochemical stability of the anti-perovskite solid electrolyte to the negative active layer is good, the growth of dendritic crystals can be inhibited, and a good negative-electrolyte interface can be obtained.
In one possible embodiment, the anti-perovskite material is a halide anti-perovskite material. The anti-perovskite material and the halide inorganic electrolyte material both contain halogen elements, and even if the diffusion of the halogen elements exists in the solid electrolyte, the influence on the electrolyte structure can be reduced, and the stability of the structure is better.
In one possible embodiment, the halogen element in the anti-perovskite material is identical to the halogen element in the halide inorganic electrolyte material. The structural stability of the solid electrolyte can be further improved.
In one possible embodiment, the solid electrolyte is a lithium ion solid electrolyte and the halide inorganic electrolyte material is LixLnX3+xWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br or I, and X is more than or equal to 1 and less than or equal to 5; the halide anti-perovskite material is Li3-yOHyX is Cl, Br or I, and y is more than or equal to 0 and less than or equal to 1.
LixLnX3+xThe conductivity of the anode material is higher, and the stability with the anode material is better. Li3-yOHyThe stability between the X and the negative electrode metal lithium sheet is better, and the generation of lithium dendrites can be effectively avoided.
In one possible embodiment, the solid electrolyte is a sodium ion solid electrolyte and the halide inorganic electrolyte material is NazLnX3+zWherein Ln is Sc, Y, In, Ga or La; x is Cl, Br, I or BF4Z is more than or equal to 1 and less than or equal to 5; the halide anti-perovskite material is Na3OX or Na4OX2Wherein X is Cl, Br, I or BF4。
NazLn3+zX6The conductivity of the anode material is higher, and the stability with the anode material is better. Na (Na)3OX or Na4OX2And the stability between the anode and the cathode metal sodium sheet is better, and the generation of sodium dendrites can be effectively avoided.
In one possible embodiment, the thickness of the first electrolyte layer is greater than the thickness of the second electrolyte layer, and the mass of the first electrolyte layer accounts for 70% -95% of the mass of the solid electrolyte.
Since the halide inorganic electrolyte material has a higher conductivity and the anti-perovskite material has a lower conductivity, the amount of the first electrolyte layer is greater, and the total resistance of the solid electrolyte can be reduced.
The thickness of the second electrolyte layer is 10nm-10 μm. The relatively thin thickness of the anti-perovskite layer further reduces the overall impedance of the solid-state electrolyte and also separates the negative active layer from the halide inorganic electrolyte layer to increase chemical stability.
In a second aspect, the present application provides an all-solid battery including the above-described solid electrolyte, a positive electrode active layer, and a negative electrode active layer. The positive electrode active layer is arranged on one side of the first electrolyte layer, which is far away from the second electrolyte layer, and the negative electrode active layer is arranged on one side of the second electrolyte layer, which is far away from the first electrolyte layer. Wherein the material of the positive electrode active layer includes a halide inorganic electrolyte material.
The interfacial resistance between the solid electrolyte and the positive electrode active layer can be reduced, and the interfacial resistance between the solid electrolyte and the negative electrode active layer can be reduced. Meanwhile, the material of the positive electrode active layer includes a material identical to that of the first electrolyte layer, so that the transmission effect of ions and electrons in the active material layer can be better.
In a third aspect, the present application provides a method of preparing a solid electrolyte, comprising forming a first electrolyte layer and a second electrolyte layer that overlap. The solid electrolyte has low interface resistance and can inhibit dendritic crystal growth.
In one possible embodiment, a halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted to form a first electrolyte layer; and pouring the anti-perovskite powder on the surface of the first electrolyte layer, and compacting the anti-perovskite powder to form a second electrolyte layer.
Or pouring the anti-perovskite powder into a mould, and compacting the anti-perovskite powder to form a second electrolyte layer; a halide inorganic electrolyte powder is poured onto the surface of the second electrolyte layer, and the halide inorganic electrolyte powder is compacted to form the first electrolyte layer.
After one electrolyte layer is formed by pressing, powder is added to perform pressing on the other electrolyte layer, so that the subsequently added powder can be infiltrated into the electrolyte layer obtained by pressing, the density of the solid electrolyte is improved, the densification of the solid electrolyte is realized, the grain resistance caused by different electrolyte powders is reduced, and the overall resistance of the solid electrolyte is reduced.
In one possible embodiment, the halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted with a punch to form the first electrolyte layer. And forming a second electrolyte layer on the surface of the first electrolyte layer by film plating.
The second electrolyte layer is formed by a film plating mode, so that on one hand, the thickness of the second electrolyte layer can be smaller, and the conductivity of the solid electrolyte is higher. On the other hand, atomic layer deposition is realized during film coating, so that the second electrolyte layer can penetrate into the pores on the surface of the first electrolyte layer, the density of the solid electrolyte is improved, the densification of the solid electrolyte is realized, the grain resistance caused by different electrolyte powders is reduced, and the overall resistance of the solid electrolyte is reduced. Meanwhile, the surface of the anti-perovskite layer can be smoother through atomic layer deposition, current concentration is not easy to form on the solid electrolyte, and the current distribution is more uniform.
In one possible embodiment, the second electrolyte layer is formed with a thickness of 10nm to 10 μm during plating. The anti-perovskite layer with the thickness can be obtained more easily in a film coating mode.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
Fig. 1 is a schematic structural diagram of an all-solid-state battery provided in an embodiment of the present application;
fig. 2 is a charge-discharge cycle performance diagram of the lithium-ion all-solid-state battery provided in example 1 of the present application;
fig. 3 is a charge-discharge curve diagram of a lithium ion all-solid-state battery provided in embodiment 1 of the present application at different rates;
FIG. 4 is a graph showing the charging and discharging curves of the lithium ion all-solid-state battery provided in comparative example 1 at different turns;
FIG. 5 is a first-turn charge-discharge curve diagram of the lithium-ion all-solid-state battery provided in comparative example 2;
fig. 6 is a charge-discharge curve diagram of the lithium ion all-solid-state battery provided in comparative example 3 at different numbers of turns.
Icon: 110-a solid electrolyte; 111-a first electrolyte layer; 112-a second electrolyte layer; 120-positive active layer; 130-positive current collector; 140-negative active layer; 150-negative current collector.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.
Fig. 1 is a schematic structural diagram of an all-solid-state battery according to an embodiment of the present disclosure. Referring to fig. 1, the solid electrolyte 110 includes a first electrolyte layer 111 and a second electrolyte layer 112 overlapping each other, the first electrolyte layer 111 is used to contact with the positive electrode active layer 120, the first electrolyte layer 111 is made of a halide inorganic electrolyte material, which is a material with high conductivity and good stability with respect to the positive electrode material, so that after the first electrolyte layer 111 contacts with the positive electrode active layer 120, the interface impedance is small, the chemical and electrochemical stability is good, and a good positive electrode-electrolyte interface can be obtained.
The second electrolyte layer 112 is used to contact with the negative electrode active layer 140, the material of the second electrolyte layer 112 is an anti-perovskite material, the anti-perovskite electrolyte layer contacts with the negative electrode active layer 140 (the halide inorganic electrolyte layer is isolated from the negative electrode active layer 140, so as to prevent the halide inorganic electrolyte layer from contacting with the negative electrode active layer 140 and reacting), the interface impedance is also small, the chemical and electrochemical stability of the anti-perovskite electrolyte layer to the negative electrode active layer 140 is good, the growth of dendrites can be inhibited, and a good negative electrode-electrolyte interface can be obtained.
In an embodiment of the present application, the anti-perovskite material is a halide anti-perovskite material. The anti-perovskite material and the halide inorganic electrolyte material both contain halogen elements, and even if diffusion of the halogen elements occurs in the solid electrolyte 110, the influence on the electrolyte structure can be reduced, and the stability of the structure is better.
Optionally, the halogen element in the anti-perovskite material is identical to the halogen element in the inorganic electrolyte material. The structural stability of the solid electrolyte 110 can be further improved.
If the solid electrolyte 110 is a lithium ion solid electrolyte, the halide inorganic electrolyte material is LixLnX3+xWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br or I, and X is more than or equal to 1 and less than or equal to 5. When x is 3, the halide inorganic electrolyte material is Li3LnX6For example: the halide inorganic electrolyte material is Li3ScCl6、Li3YCl6、Li3InCl6、Li3GaCl6、Li3LaCl6、Li3ScBr6、Li3YBr6、Li3InBr6、Li3GaBr6、Li3LaBr6、Li3ScI6、Li3YI6、Li3InI6、Li3GaI6Or Li3LaI6(ii) a When x is 2, the halide inorganic electrolyte material is Li2LnX5For example: the halide inorganic electrolyte material is Li2ScCl5、Li2YCl5、Li2InCl5、Li2GaCl5、Li2LaCl5、Li2ScBr5、Li2YBr5、Li2InBr5、Li2GaBr5、Li2LaBr5、Li2ScI5、Li2YI5、Li2InI5、Li2GaI5Or Li2LaI5。
For a lithium ion solid electrolyte, the halide inorganic electrolyte material has higher conductivity, and can improve the transmission effect of ions and electrons. Selecting it as a raw material of the first electrolyte layer 111 can make the stability between the first electrolyte layer 111 and the positive electrode material better.
The halide anti-perovskite material is Li3-yOHyX is Cl, Br or I, and y is more than or equal to 0 and less than or equal to 1. When y is 0, the halide anti-perovskite material is Li3OX, for example: the halide anti-perovskite material is Li3OCl、Li3OBr or Li3OI; when y is 0.5, the halide anti-perovskite material is Li2.5OH0.5X, for example: the halide anti-perovskite material is Li2.5OH0.5Cl、Li2.5OH0.5Br or Li2.5OH0.5I; when y is 1, the halide anti-perovskite material is Li2OHX, for example: the halide anti-perovskite material is Li2OHCl、Li2OHBr or Li2OHI。
The halide anti-perovskite material is selected as the raw material of the second electrolyte layer 112, and the stability between the halide anti-perovskite material and the negative electrode metal lithium sheet is better, so that the negative electrode metal lithium sheet can be prevented from contacting the first electrolyte layer 111, and the generation of lithium dendrites can be effectively avoided.
If the solid electrolyte 110 is a sodium ion solid electrolyte, the halide inorganic electrolyte material is NazLnX3+zWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br, I or BF4And z is more than or equal to 1 and less than or equal to 5. When z is 3, the halide inorganic electrolyte material is Na3LnX6For example: the halide inorganic electrolyte material is Na3ScCl6、Na3YCl6、Na3InCl6、Na3GaCl6、Na3LaCl6、Na3ScBr6、Na3YBr6、Na3InBr6、Na3GaBr6、Na3LaBr6、Na3ScI6、Na3YI6、Na3InI6、Na3GaI6、Na3LaI6、Na3Sc(BF4)6、Na3Y(BF4)6、Na3In(BF4)6、Na3Ga(BF4)6Or Na3La(BF4)6(ii) a When z is 4, the halide inorganic electrolyte material is Na4LnX7For example: the halide inorganic electrolyte material is Na4ScCl7、Na4YCl7、Na4InCl7、Na4GaCl7、Na4LaCl7、Na4ScBr7、Na4YBr7、Na4InBr7、Na4GaBr7、Na4LaBr7、Na4ScI7、Na4YI7、Na4InI7、Na4GaI7、Na4LaI7、Na4Sc(BF4)7、Na4Y(BF4)7、Na4In(BF4)7、Na4Ga(BF4)7Or Na4La(BF4)7。
For sodium ion solid electrolytes, the halide inorganic electrolyte material has higher conductivity, and can improve the transmission effect of ions and electrons. Selecting it as a raw material of the first electrolyte layer 111 can make the stability between the first electrolyte layer 111 and the positive electrode material better.
The halide anti-perovskite material is Na3OX or Na4OX2Wherein X is Cl, Br, I or BF4. Optionally, the halide anti-perovskite material is Na3OX, for example: the halide anti-perovskite material is Na3OCl、Na3OBr、Na3OI or Na3OBF4(ii) a Optionally, the halide anti-perovskite material is Na4OX2For example: halide anti-perovskite materialIs Na4OCl2、Na4OBr2、Na4OI2Or Na4O(BF4)2。
The halide anti-perovskite material is selected as the raw material of the second electrolyte layer 112, and the stability between the halide anti-perovskite material and the negative electrode metal sodium sheet is better, so that the negative electrode metal sodium sheet can be prevented from contacting the first electrolyte layer 111, and the generation of sodium dendrite can be effectively avoided.
In the embodiment of the present application, the thickness of the first electrolyte layer 111 is greater than that of the second electrolyte layer 112, and the mass of the first electrolyte layer 111 accounts for 70% to 95% of the mass of the solid electrolyte 110. The mass of the first electrolyte layer 111 is greater, and the total resistance of the solid electrolyte 110 can be reduced.
In some possible embodiments, the first electrolyte layer 111 has a mass of 70% and the second electrolyte layer 112 has a mass of 30%; or 95% by mass of the first electrolyte layer 111 and 5% by mass of the second electrolyte layer 112; or 80% by mass of the first electrolyte layer 111 and 20% by mass of the second electrolyte layer 112; or the first electrolyte layer 111 is 90% by mass and the second electrolyte layer 112 is 10% by mass.
Alternatively, the thickness of the first electrolyte layer 111 is 150-. The thickness of the second electrolyte layer 112 is 10nm to 10 μm. The thinner thickness of the anti-perovskite layer further reduces the overall resistance of the solid electrolyte 110 and also enables the negative active layer 140 to be spaced apart from the halide inorganic electrolyte layer for increased chemical stability.
In some possible embodiments, the thickness of the first electrolyte layer 111 is 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm. The thickness of the second electrolyte layer 112 is 10nm, 50nm, 100nm, 500nm, 1 μm, or 10 μm.
The preparation method of the solid electrolyte 110 includes: the first electrolyte layer 111 and the second electrolyte layer 112 are formed to overlap. The solid electrolyte 110 having a low interface resistance and capable of suppressing the growth of dendrites is obtained.
In one embodiment, the halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted with a punch (the punch may not be used, as long as a structure capable of compacting a powdery substance is within the scope of the present application) to form the first electrolyte layer 111; the anti-perovskite powder is poured onto the surface of the first electrolyte layer 111, and the anti-perovskite powder is compacted with a punch to form the second electrolyte layer 112.
After the first electrolyte layer 111 is formed by pressing, the anti-perovskite powder is added to perform pressing of the second electrolyte layer 112, so that the anti-perovskite powder added subsequently can permeate into the first electrolyte layer 111 obtained by pressing, the density of the solid electrolyte 110 is improved, the densification of the solid electrolyte 110 is realized, the grain resistance caused by different powders is reduced, and the overall resistance of the solid electrolyte 110 is reduced.
In another embodiment, the second electrolyte layer 112 is formed by pouring the anti-perovskite powder into a mold, and compacting the anti-perovskite powder with a punch (or without a punch, provided that the structure capable of compacting the powdered substance is within the scope of the present application); the halide inorganic electrolyte powder is poured onto the surface of the second electrolyte layer 112, and the halide inorganic electrolyte powder is compacted with a punch to form the first electrolyte layer 111.
After the second electrolyte layer 112 is formed by pressing, the halide inorganic electrolyte powder is added to perform pressing on the first electrolyte layer 111, so that the halide inorganic electrolyte powder added subsequently can permeate into the second electrolyte layer 112 obtained by pressing, the density of the solid electrolyte 110 is improved, the densification of the solid electrolyte 110 is realized, the grain resistance caused by different electrolyte powders is reduced, and the overall resistance of the solid electrolyte 110 is reduced.
In the two embodiments, since the second electrolyte layer 112 (the anti-perovskite layer) is formed by powder pressing, and the position where the first electrolyte layer 111 and the second electrolyte layer 112 are in contact with each other is densely connected by pressing, in order to provide a better isolation effect to the anti-perovskite layer, the material of the anti-perovskite layer is relatively more, the mass ratio is relatively larger, but the preparation is simpler.
In other embodiments, the halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted with a punch to form the first electrolyte layer 111. The second electrolyte layer 112 is formed by plating on the surface of the first electrolyte layer 111.
The second electrolyte layer 112 is formed by plating, on one hand, the second electrolyte layer 112 can be made thinner, and the conductivity of the solid electrolyte 110 can be made higher (if it is thicker later, it is not easy to form by plating). On the other hand, atomic layer deposition is realized during film coating, so that the second electrolyte layer 112 can penetrate into the pores on the surface of the first electrolyte layer 111, the density of the solid electrolyte 110 is improved, the densification of the solid electrolyte 110 is realized, the grain resistance caused by different electrolyte powders is reduced, and the overall resistance of the solid electrolyte 110 is reduced. Meanwhile, the atomic layer deposition can enable the surface of the anti-perovskite layer to be smoother, the concentration of current is not easy to form on the solid electrolyte 110, and the distribution of the current is more uniform.
In one possible embodiment, the second electrolyte layer 112 is formed to a thickness of 10nm to 10 μm during plating. The anti-perovskite layer with the thickness can be obtained more easily in a film coating mode, the structure formed by the anti-perovskite layer is more uniformly distributed, the compactness is better, and the overall impedance of the obtained solid electrolyte 110 is lower.
The above-described solid electrolyte 110 may be used to prepare an all-solid battery including the above-described solid electrolyte 110, a positive electrode active layer 120, a positive electrode current collector 130, a negative electrode active layer 140, and a negative electrode current collector 150. The positive electrode active layer 120 is disposed on a side of the first electrolyte layer 111 facing away from the second electrolyte layer 112, and the positive electrode collector 130 is disposed on a side of the positive electrode active layer 120 facing away from the first electrolyte layer 111. The negative electrode active layer 140 is disposed on a side of the second electrolyte layer 112 facing away from the first electrolyte layer 111, and the negative electrode collector 150 is disposed on a side of the negative electrode active layer 140 facing away from the second electrolyte layer 112. The interfacial resistance between the solid electrolyte 110 and the positive electrode active layer 120 can be reduced, and the interfacial resistance between the solid electrolyte 110 and the negative electrode active layer 140 can be reduced.
Among them, the material of the positive electrode active layer 120 includes a halide inorganic electrolyte material. The material of the positive electrode active layer 120 includes a material conforming to the first electrolyte layer 111, and the transport effect of ions and electrons in the active material layer can be made better.
The following describes a method for manufacturing a lithium ion all-solid-state battery:
preparation of the positive electrode active layer 120:
positive electrode active material (LiCoO)2LiNi, Ni, Co and Mn ternary material0.6Co0.2Mn0.2O2(NCM) nickel cobalt aluminum ternary material LiNi0.8Co0.15Al0.05O2(NCA) and LiFePO4One or more of the above); a conductive agent (one or more of conductive carbon black Super-P, Ketjen black, carbon nanotubes, and graphene); electrolyte powder (Li)xLnX3+xWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br or I, and X is more than or equal to 1 and less than or equal to 5); a binder (one or more of polyvinylidene fluoride (PVDF), Poly (vinylidene fluoride-co-hexafluoropropylene)), Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and Polytetrafluoroethylene (PTFE).
Mixing the above materials, grinding or ball-milling, uniformly mixing in a solvent (one or more of N-methyl pyrrolidone (NMP), N-Dimethylformamide (DMF, N-dimethyl formamide) and isopropanol), uniformly spin-coating or blade-coating on an aluminum foil (positive current collector 130), and drying to obtain the positive electrode sheet with the positive active layer 120 formed on the positive current collector 130 for later use.
Preparing a lithium ion all-solid-state battery:
the negative current collector 150 (e.g., copper foil), the negative lithium metal sheet, the solid electrolyte 110 and the positive electrode sheet prepared above are sequentially placed into a battery mold (wherein the second electrolyte layer 112 is in contact with the negative lithium metal sheet, and the first electrolyte layer 111 is in contact with the positive active layer 120 of the positive electrode sheet), pressurized, sealed and assembled.
In other embodiments, the positive electrode material may be prepared first by: the positive electrode active material, the conductive agent and the electrolyte powder can be uniformly mixed by grinding or ball milling without adding the binder for later use.
Then, preparing the lithium ion all-solid-state battery, wherein the preparation method comprises the following steps: the solid electrolyte 110 is placed in a mold with the first electrolyte layer 111 facing upward, the previously prepared positive electrode material is poured onto the first electrolyte layer 111 and then compacted with a punch to obtain the solid electrolyte 110 with the positive electrode active layer 120, and then the positive electrode current collector 130, the solid electrolyte 110, the negative electrode metallic lithium sheet and the negative electrode current collector 150 are sequentially placed in a battery mold (wherein the second electrolyte layer 112 is in contact with the negative electrode metallic lithium sheet and the positive electrode active layer 120 is in contact with the positive electrode current collector 130), pressure-sealed and assembled.
The lithium ion solid-state battery prepared by the method can reduce the interface impedance, has better stability and can inhibit the growth of lithium dendrites.
If the all-solid-state battery is a sodium ion all-solid-state battery, the preparation method of the all-solid-state battery is basically the same as that of a lithium ion all-solid-state battery, and the difference is that: the selection of the positive active material and the electrolyte powder material is different, the electrolyte powder material is consistent with the halide inorganic electrolyte material in the sodium ion solid electrolyte, and the positive active material is the positive active material of the sodium ion battery, such as: oxide positive electrode material Na0.44MnO2Polyanionic positive electrode material Na3V2(PO4)3Prussian blue Na2CoFe(CN)6(ii) a And the negative metal lithium sheet is replaced by a negative metal sodium sheet.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the lithium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing 90% of Li by mass3InCl6Pouring the powder into a mould and compacting Li with a punch3InCl6The powder formed a first electrolyte layer having a thickness of 200 μm; mixing 10% of Li2OHCl powder is poured on the surface of the first electrolyte layer, and Li is compacted by a punch2The OHCl powder forms the second electrolyte layer.
(2) Preparing a positive pole piece: LiFePO with the mass percentage of 80 percent 410 percent of conductive carbon black Super-P and 5 percent of Li3InCl6Mixing electrolyte powder and 5% of polyvinylidene fluoride by mass percentage, grinding or ball milling, then uniformly mixing in N-methyl pyrrolidone serving as a solvent, uniformly spin-coating or blade-coating on an aluminum foil, and drying to obtain a positive pole piece for later use.
(3) Preparing a lithium ion all-solid-state battery: and (2) sequentially putting the copper foil, the negative metal lithium sheet, the solid electrolyte obtained in the step (1) and the positive pole piece obtained in the step (2) into a battery die (wherein the second electrolyte layer is in contact with the negative metal lithium sheet, and the first electrolyte layer is in contact with the positive active layer of the positive pole piece), pressurizing, sealing and assembling.
Example 2
The preparation method of the lithium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing Li3InCl6Pouring the powder into a mould and compacting Li with a punch3InCl6The powder formed a first electrolyte layer having a thickness of 200 μm; forming Li with a thickness of 500nm on the first electrolyte layer by means of evaporation coating2An OHCl second electrolyte layer.
The steps of the method for preparing the positive electrode plate and the lithium ion all-solid-state battery are the same as those in the embodiment 1.
Example 3
The preparation method of the sodium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing 90% of Na by mass3InCl6Pouring the powder into a die, compacting Na with a punch3InCl6The powder formed a first electrolyte layer having a thickness of 200 μm; na accounting for 10 percent of the mass percentage3Pouring OCl powder on the surface of the first electrolyte layer, and compacting Na by a punch3The OCl powder forms the second electrolyte layer.
(2) Preparing a positive pole piece: mixing 80% of Na by mass3V2(PO4)310 percent of conductive carbon black Super-P and 5 percent of Na3InCl6Mixing electrolyte powder and 5% of polyvinylidene fluoride by mass percentage, grinding or ball milling, then uniformly mixing in N-methyl pyrrolidone serving as a solvent, uniformly spin-coating or blade-coating on an aluminum foil, and drying to obtain a positive pole piece for later use.
(3) Preparing a sodium ion all-solid-state battery: and (2) sequentially putting the copper foil, the negative metal sodium sheet, the solid electrolyte obtained in the step (1) and the positive pole piece obtained in the step (2) into a battery die (wherein the second electrolyte layer is in contact with the negative metal sodium sheet, and the first electrolyte layer is in contact with the positive active layer of the positive pole piece), pressurizing, sealing and assembling.
Example 4
The preparation method of the sodium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing Na3InCl6Pouring the powder into a die, compacting Na with a punch3InCl6The powder formed a first electrolyte layer having a thickness of 200 μm; forming Na with a thickness of 500nm on the first electrolyte layer by means of evaporation coating3An OCl second electrolyte layer.
The steps of the method for preparing the positive electrode plate and the sodium ion all-solid-state battery are the same as those in example 3.
Comparative example 1
The preparation method of the lithium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing 90% of Li by mass6.4La3Zr1.4Ta0.6O12Pouring the powder into a mould and compacting Li with a punch6.4La3Zr1.4Ta0.6O12The powder formed a first electrolyte layer having a thickness of 200 μm; mixing 10% of Li2OHCl powder is poured on the surface of the first electrolyte layer, and Li is compacted by a punch2The OHCl powder forms the second electrolyte layer.
(2) Preparing a positive pole piece: LiFePO with the mass percentage of 80 percent 410 percent of conductive carbon black Super-P and 5 percent of Li6.4La3Zr1.4Ta0.6O12Mixing electrolyte powder and 5% of polyvinylidene fluoride by mass percentage, grinding or ball milling, then uniformly mixing in N-methyl pyrrolidone serving as a solvent, uniformly spin-coating or blade-coating on an aluminum foil, and drying to obtain a positive pole piece for later use.
(3) The procedure for preparing a lithium ion all-solid battery was the same as in example 1.
Comparative example 2
The preparation method of the lithium ion all-solid-state battery comprises the following steps:
(1) preparing a solid electrolyte: mixing Li3InCl6Pouring the powder into a mould and compacting Li with a punch3InCl6The powder forms a solid electrolyte layer.
(2) Preparing a positive pole piece: LiFePO with the mass percentage of 80 percent 410 percent of conductive carbon black Super-P and 5 percent of Li3InCl6Mixing electrolyte powder and 5% of polyvinylidene fluoride by mass percentage, grinding or ball milling, then uniformly mixing in N-methyl pyrrolidone serving as a solvent, uniformly spin-coating or blade-coating on an aluminum foil, and drying to obtain a positive pole piece for later use.
(3) Preparing a lithium ion all-solid-state battery: and (3) sequentially putting the copper foil, the negative metal lithium sheet, the solid electrolyte obtained in the step (1) and the positive pole piece obtained in the step (2) into a battery die, pressurizing and sealing, and completing assembly.
Comparative example 3
The preparation method of the lithium ion all-solid-state battery comprises the following steps:
(1) a system ofPreparing a solid electrolyte: mixing Li2OHCl powder is poured into a mold and Li is compacted with a punch2The OHCl powder forms a solid electrolyte layer.
(2) Preparing a positive pole piece: LiFePO with the mass percentage of 80 percent 410 percent of conductive carbon black Super-P and 5 percent of Li2And mixing the OHCL electrolyte powder and 5% of polyvinylidene fluoride by mass percentage, grinding or ball milling, then uniformly mixing in a solvent N-methyl pyrrolidone, uniformly spin-coating or blade-coating on an aluminum foil, and drying to obtain the positive pole piece for later use.
(3) Preparing a lithium ion all-solid-state battery: and (3) sequentially putting the copper foil, the negative metal lithium sheet, the solid electrolyte obtained in the step (1) and the positive pole piece obtained in the step (2) into a battery die, pressurizing and sealing, and completing assembly.
Experimental example 1
The charge-discharge cycle performance of the lithium ion all-solid-state battery provided in example 1 of the present application is shown in fig. 2, and the cycle performance graph is obtained by testing at a test temperature of 100 ℃ and a multiplying factor of 0.1C, and as can be seen from fig. 2, the charge-discharge capacity of the lithium ion all-solid-state battery provided in example 1 of the present application can reach 130mAhg-1And the charge-discharge cycle is stable. The lithium ion all-solid-state battery provided by the application has better charge and discharge performance.
Fig. 3 is a charge-discharge curve diagram of the lithium ion all-solid-state battery provided in embodiment 1 of the present application at different magnifications (0.1C, 0.5C, and 1C), and it can be seen from fig. 3 that the battery provided in embodiment 1 of the present application has better magnification performance and still maintains a specific discharge capacity of 125mAh/g at a magnification of 1C.
Fig. 4 is a charge-discharge curve diagram of the lithium ion all-solid-state battery provided in comparative example 1 at different turns, and it can be seen from comparison between fig. 3 and fig. 4 that the battery provided in comparative example 1 has large charge-discharge polarization, low capacity and fast capacity fading.
Fig. 5 is a first-turn charge-discharge curve diagram of the lithium ion all-solid-state battery provided in comparative example 2, and as can be seen from comparison between fig. 3 and fig. 5, the halide solid-state electrolyte continues to react directly after the contact with the lithium metal, the electrolyte impedance increases sharply, the polarization of the battery is severe, and the capacity is difficult to exert.
Fig. 6 is a charge-discharge curve diagram of the lithium ion all-solid-state battery provided in comparative example 3 at different cycles, and it can be seen from comparison between fig. 3 and fig. 6 that the charge-discharge efficiency at the first cycle is low, the charge-discharge polarization is large, the capacity is low, and the capacity decays quickly.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (10)

1. A solid state electrolyte, comprising: a first electrolyte layer for contacting with the positive electrode active layer and a second electrolyte layer for contacting with the negative electrode active layer, which are overlapped;
wherein the material of the first electrolyte layer is a halide inorganic electrolyte material; the material of the second electrolyte layer is an anti-perovskite material.
2. The solid state electrolyte of claim 1, wherein the anti-perovskite material is a halide anti-perovskite material;
optionally, the halogen element in the anti-perovskite material is identical to the halogen element in the halide inorganic electrolyte material.
3. The solid electrolyte of claim 2, wherein the solid electrolyte is a lithium ion solid electrolyte and the halide inorganic electrolyte material is LixLnX3+xWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br or I, and X is more than or equal to 1 and less than or equal to 5; the halide anti-perovskite material is Li3-yOHyX is Cl, Br or I, and y is more than or equal to 0 and less than or equal to 1.
4. According to the rightThe solid electrolyte of claim 2, wherein the solid electrolyte is a sodium ion solid electrolyte and the halide inorganic electrolyte material is NazLnX3+zWherein Ln is Sc, Y, In, Ga or La, X is Cl, Br, I or BF4Z is more than or equal to 1 and less than or equal to 5; the halide anti-perovskite material is Na3OX or Na4OX2Wherein X is Cl, Br, I or BF4。
5. The solid state electrolyte of any one of claims 1-4, wherein the thickness of the first electrolyte layer is greater than the thickness of the second electrolyte layer, and the mass of the first electrolyte layer is 70-95% of the mass of the solid state electrolyte;
optionally, the second electrolyte layer has a thickness of 10nm to 10 μm.
6. An all-solid-state battery comprising the solid-state electrolyte according to any one of claims 1 to 5, a positive electrode active layer, and a negative electrode active layer;
the positive electrode active layer is arranged on one side of the first electrolyte layer, which is far away from the second electrolyte layer, and the negative electrode active layer is arranged on one side of the second electrolyte layer, which is far away from the first electrolyte layer;
wherein a material of the positive electrode active layer includes the halide inorganic electrolyte material.
7. A method for producing a solid electrolyte according to any one of claims 1 to 5, comprising: and forming the first electrolyte layer and the second electrolyte layer which are overlapped.
8. The production method according to claim 7, characterized in that a halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted to form the first electrolyte layer; pouring an anti-perovskite powder on the surface of the first electrolyte layer, and compacting the anti-perovskite powder to form the second electrolyte layer;
or pouring an anti-perovskite powder into a mold, and compacting the anti-perovskite powder to form the second electrolyte layer; pouring a halide inorganic electrolyte powder on the surface of the second electrolyte layer, and compacting the halide inorganic electrolyte powder to form the first electrolyte layer.
9. The production method according to claim 7, characterized in that a halide inorganic electrolyte powder is poured into a mold, and the halide inorganic electrolyte powder is compacted with a punch to form the first electrolyte layer;
and plating a film on the surface of the first electrolyte layer to form the second electrolyte layer.
10. The production method according to claim 9, wherein the thickness of the second electrolyte layer formed at the time of plating is 10nm to 10 μm.
CN202010765945.8A 2020-07-31 2020-07-31 Solid electrolyte, preparation method thereof and all-solid-state battery Active CN111725561B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010765945.8A CN111725561B (en) 2020-07-31 2020-07-31 Solid electrolyte, preparation method thereof and all-solid-state battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010765945.8A CN111725561B (en) 2020-07-31 2020-07-31 Solid electrolyte, preparation method thereof and all-solid-state battery

Publications (2)

Publication Number Publication Date
CN111725561A true CN111725561A (en) 2020-09-29
CN111725561B CN111725561B (en) 2021-09-28

Family

ID=72574440

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010765945.8A Active CN111725561B (en) 2020-07-31 2020-07-31 Solid electrolyte, preparation method thereof and all-solid-state battery

Country Status (1)

Country Link
CN (1) CN111725561B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112670563A (en) * 2020-12-30 2021-04-16 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN113054245A (en) * 2021-03-12 2021-06-29 南方科技大学 Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery
WO2022080628A1 (en) * 2020-10-12 2022-04-21 삼성에스디아이주식회사 All-solid-state secondary battery and manufacturing method therefor
WO2023106128A1 (en) * 2021-12-07 2023-06-15 パナソニックＩｐマネジメント株式会社 Battery
WO2024008723A1 (en) * 2022-07-04 2024-01-11 Saint-Gobain Ceramics & Plastics Inc. Buffer layer for all-solid-state batteries

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014150763A1 (en) * 2013-03-15 2014-09-25 Los Alamos National Security, Llc Anti-perovskite solid electrolyte compositions
CN109786822A (en) * 2018-12-28 2019-05-21 南方科技大学 A kind of richness lithium anti-perovskite oxide composite electrolyte and its preparation method and application
CN109775744A (en) * 2019-01-11 2019-05-21 蜂巢能源科技有限公司 The preparation method of halogenation yttrium lithium and its application in solid electrolyte and battery
CN109935909A (en) * 2017-12-19 2019-06-25 成都亦道科技合伙企业（有限合伙） A kind of lithium an- ode battery structure and preparation method thereof
CN109935895A (en) * 2017-12-19 2019-06-25 成都英诺科技咨询有限公司 Solid electrolyte and its lithium battery electric core, lithium battery
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN110534802A (en) * 2019-09-11 2019-12-03 蜂巢能源科技有限公司 Solid electrolyte and its preparation method and application
CN110534796A (en) * 2019-07-23 2019-12-03 珠海冠宇电池有限公司 A kind of solid lithium battery and preparation method thereof
CN110556571A (en) * 2018-05-30 2019-12-10 郑州新世纪材料基因组工程研究院有限公司 lithium titanate lanthanum composite material, preparation method thereof and lithium ion solid-state battery
CN110635113A (en) * 2019-08-16 2019-12-31 南方科技大学 Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode
CN110970667A (en) * 2019-12-20 2020-04-07 横店集团东磁股份有限公司 Composite halide solid electrolyte, preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014150763A1 (en) * 2013-03-15 2014-09-25 Los Alamos National Security, Llc Anti-perovskite solid electrolyte compositions
CN109935909A (en) * 2017-12-19 2019-06-25 成都亦道科技合伙企业（有限合伙） A kind of lithium an- ode battery structure and preparation method thereof
CN109935895A (en) * 2017-12-19 2019-06-25 成都英诺科技咨询有限公司 Solid electrolyte and its lithium battery electric core, lithium battery
CN110556571A (en) * 2018-05-30 2019-12-10 郑州新世纪材料基因组工程研究院有限公司 lithium titanate lanthanum composite material, preparation method thereof and lithium ion solid-state battery
CN109786822A (en) * 2018-12-28 2019-05-21 南方科技大学 A kind of richness lithium anti-perovskite oxide composite electrolyte and its preparation method and application
CN109775744A (en) * 2019-01-11 2019-05-21 蜂巢能源科技有限公司 The preparation method of halogenation yttrium lithium and its application in solid electrolyte and battery
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN110534796A (en) * 2019-07-23 2019-12-03 珠海冠宇电池有限公司 A kind of solid lithium battery and preparation method thereof
CN110635113A (en) * 2019-08-16 2019-12-31 南方科技大学 Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode
CN110534802A (en) * 2019-09-11 2019-12-03 蜂巢能源科技有限公司 Solid electrolyte and its preparation method and application
CN110970667A (en) * 2019-12-20 2020-04-07 横店集团东磁股份有限公司 Composite halide solid electrolyte, preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080628A1 (en) * 2020-10-12 2022-04-21 삼성에스디아이주식회사 All-solid-state secondary battery and manufacturing method therefor
CN112670563A (en) * 2020-12-30 2021-04-16 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN112670563B (en) * 2020-12-30 2022-05-17 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN113054245A (en) * 2021-03-12 2021-06-29 南方科技大学 Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery
CN113054245B (en) * 2021-03-12 2022-08-19 南方科技大学 Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery
WO2023106128A1 (en) * 2021-12-07 2023-06-15 パナソニックＩｐマネジメント株式会社 Battery
WO2024008723A1 (en) * 2022-07-04 2024-01-11 Saint-Gobain Ceramics & Plastics Inc. Buffer layer for all-solid-state batteries

Also Published As

Publication number Publication date
CN111725561B (en) 2021-09-28

Similar Documents

Publication Publication Date Title
US11929463B2 (en) All-solid-state secondary battery and method of charging the same
CN111725561B (en) Solid electrolyte, preparation method thereof and all-solid-state battery
CN110943248B (en) Lithium secondary battery
CN108365165B (en) Solid-state lithium battery with novel electrolyte composite mode and preparation method thereof
KR101886358B1 (en) All solid state battery having LATP-containing cathode electrode composite and manufacturing method the same
CN111834662B (en) Interface functional layer, preparation method thereof and lithium ion battery
CN111758176A (en) Method for predoping negative electrode active material, method for producing negative electrode, and method for producing power storage device
CN114242942B (en) Composite buffer layer with stable anode interface and solid-state lithium metal battery thereof
CN110676433B (en) Composite lithium cathode, preparation method thereof and lithium battery
CN109088095B (en) All-solid-state lithium battery and preparation method thereof
CN113451580A (en) Interface layer and lithium ion battery comprising same
KR102407143B1 (en) All solid secondary battery and method of manufacturing the same
JP2012038597A (en) Aqueous paste for forming anode active material layer of nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery anode and manufacturing method thereof, and nonaqueous electrolyte secondary battery
CN115189014A (en) Preparation and application of composite electrolyte membrane based on sodium ion sulfide solid electrolyte
US20240113299A1 (en) Silicon-Based Composite Anodes for High Energy Density, High Cycle Life Solid-State Lithium-Ion Battery
US20220311044A1 (en) Method of making composite polymer electrolyte for all solid-state lithium-ion battery
CN113594456B (en) Positive electrode slurry, preparation method thereof, positive plate and lithium ion battery
CN113285117B (en) Composite solid electrolyte and lithium ion battery comprising same
CN112701347B (en) Electrochemical device and electronic equipment
US20210384517A1 (en) All-solid-state battery having high energy density and capable of stable operation
CN114649592A (en) All-solid-state battery including lithium storage layer having multi-layer structure and method of manufacturing the same
WO2023223581A1 (en) Battery
EP4009394B1 (en) Anti-dendrite negative electrodes, and the electrochemical cells containing them
US20230133463A1 (en) Anode for all-solid-state battery and manufacturing method thereof
KR102207523B1 (en) Lithium secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant