CN115172883A - High-energy-density lithium-rich all-solid-state lithium battery and preparation method thereof - Google Patents

High-energy-density lithium-rich all-solid-state lithium battery and preparation method thereof Download PDF

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CN115172883A
CN115172883A CN202110362800.8A CN202110362800A CN115172883A CN 115172883 A CN115172883 A CN 115172883A CN 202110362800 A CN202110362800 A CN 202110362800A CN 115172883 A CN115172883 A CN 115172883A
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lithium
positive electrode
solid electrolyte
solid
electrode layer
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郭现伟
李德阳
尉海军
王永涛
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Beijing University of Technology
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Beijing University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof belong to the field of all-solid-state lithium battery manufacturing. The all-solid-state lithium battery comprises a composite positive electrode layer, an inorganic solid electrolyte layer and a negative electrode layer, wherein the composite positive electrode layer is composed of a high-specific-energy lithium-rich manganese-based positive electrode material and an inorganic solid electrolyte. According to the invention, the aggregate of the composite positive electrode layer and the electrolyte ceramic chip is prepared by a low-temperature integrated co-sintering process, so that the energy consumption and the manufacturing cost are effectively reduced, the interface contact between the high-specific-energy lithium-rich manganese-based positive electrode material and the inorganic solid electrolyte is improved, the utilization rate of the positive electrode active material is improved, the side reaction between the positive electrode material and the solid electrolyte caused by the traditional high-temperature sintering process is inhibited, and the electrochemical performance of the all-solid-state lithium battery is improved; the low co-firing temperature of the composite anode can reduce the energy consumption of the all-solid-state battery in mass production, and an effective solution is provided for preparing the high-energy-density all-solid-state battery.

Description

High-energy-density lithium-rich all-solid-state lithium battery and preparation method thereof
Technical Field
The invention belongs to the field of all-solid-state lithium battery manufacturing, and particularly relates to a high-energy-density lithium-rich all-solid-state lithium battery and a preparation method thereof.
Background
Lithium ion batteries have the advantages of high energy density, good cycling stability and the like, and are widely applied to the fields of electronic products, automobiles, energy storage and the like. Currently, most lithium ion batteries use organic liquid electrolytes. However, the liquid electrolyte is very volatile and leaks, which affects the service life of the battery; meanwhile, the liquid electrolyte is unstable at a high temperature, and the local temperature of the lithium ion battery is too high under the conditions of overcharge and short circuit, so that the battery is ignited and exploded. Aiming at the safety problem faced by the lithium ion battery, the inorganic solid electrolyte with high thermal stability, incombustibility, no volatilization leakage and the like is adopted to replace the liquid electrolyte, so that the inorganic all-solid-state battery is constructed, and the problem can be fundamentally solved. For inorganic all-solid-state lithium batteries, the electrochemical stability window of the garnet solid electrolyte is more than 5V, which is enough to meet the voltage requirement of a high-specific-energy positive electrode material, and the garnet solid electrolyte provides inherent advantages for developing inorganic all-solid-state batteries based on the high-specific-energy lithium-rich manganese-based positive electrode material.
The solid-solid interface contact between the electrode and the electrolyte is poor, so that the overall impedance of the battery is high, the utilization rate of the anode material is low, and the discharge capacity of the battery is low. In addition, when the composite anode is prepared by adopting the traditional high-temperature co-sintering, the sintering temperature is high, and the sintering time is long, so that the interface reaction between the anode material and the solid electrolyte occurs, and the large-scale production cost of the all-solid-state battery is high. According to the invention, the sintering temperature and the sintering time are controlled, the interface reaction is limited, the interface contact is further improved by adopting the fusing auxiliary agent, the composite anode with high energy density is constructed, and the all-solid-state lithium battery is assembled, so that excellent electrochemical performance is obtained, and the production cost of the all-solid-state battery is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a composite positive electrode suitable for a high-energy-density lithium-rich all-solid-state battery, and an inorganic all-solid-state battery with high energy density and high safety is obtained by assembling the composite positive electrode. By adopting the low-temperature co-sintering preparation method of the composite anode, the energy consumption and the production cost can be greatly reduced, the side reaction of the high-specific-energy lithium-rich manganese-based anode material and the inorganic solid electrolyte in the sintering process can be effectively inhibited, the interface contact between the electrolyte material and the anode material is enhanced, the interface impedance is reduced, the discharge capacity of the inorganic all-solid-state battery is improved, and the safety is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high energy density lithium-rich all-solid-state lithium battery and a composite anode thereof, a composite anode-inorganic solid electrolyte aggregate prepared by the composite anode and an inorganic all-solid-state lithium battery comprising the aggregate are provided, wherein the composite anode-inorganic solid electrolyte aggregate is prepared by low-temperature integrated co-sintering.
The invention also provides a preparation method of the composite positive electrode layer-solid electrolyte laminated aggregate in the scheme, which comprises the following steps:
(1) Weighing a high-capacity lithium-rich manganese-based positive electrode material, an inorganic solid electrolyte powder, a sintering additive and an electronic conductor required by a composite positive electrode according to a certain mass ratio, and adding a proper amount of polyvinylidene fluoride (PVDF) and an organic solvent for full grinding to prepare slurry;
(2) Uniformly coating the slurry prepared in the step (1) on the surface of the LLZO ceramic chip, and then carrying out vacuum drying to preliminarily obtain a laminated unit of the composite anode and the solid electrolyte layer;
(3) Placing the laminated unit obtained in the step (2) in heating equipment for sintering, and then reducing the temperature to room temperature to obtain a composite positive electrode layer-solid electrolyte ceramic sheet aggregate with an interface in close contact;
(4) And (4) carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the assembly in the step (3), and polishing the gold layer on the side surface of the assembly.
The composite cathode material in the step (1) comprises the following raw materials:
70-90 wt% of high-capacity lithium-rich manganese-based positive electrode material;
5wt% -15 wt% of inorganic solid electrolyte powder;
5-10 wt% of a fusing assistant; and
0wt% -5 wt% of an electronic conductor.
The inorganic solid electrolyte powder is preferably garnet-type Lithium Lanthanum Zirconate (LLZO) electrolyte powder, the LLZO electrolyte powder comprises lithium, lanthanum, zirconium and doping elements, and the doping elements comprise one or more of aluminum, iron, gallium, yttrium, cerium, antimony, tantalum, niobium, vanadium and the like. The average particle diameter of the inorganic solid electrolyte powder is 40nm to 500nm, preferably 200nm.
The fusing auxiliary agent is one or more of lithium borate, lithium metaborate, lithium nitrate and lithium phosphate; lithium borate and lithium metaborate are preferred.
Wherein the electron conductor is one or more of nitride or oxide such as titanium nitride, vanadium nitride, antimony tin oxide, etc., preferably titanium nitride or vanadium nitride.
In the step (2), the LLZO ceramic sheet is formed by pressing and sintering the LLZO powder corresponding to the inorganic solid electrolyte powder in the step (1), and specifically comprises the following steps: the ceramic sheet is formed by pressing LLZO powder, the pressure is 8 Mpa-10 Mpa, the pressure maintaining time is 10 s-15 s, and the ceramic sheet is sintered in oxygen atmosphere at 1050 ℃ -1250 ℃.
The uniform coating method described in step (2) includes, but is not limited to, a blade coating method, a screen printing method, a casting method, and the like.
In the step (3), the calcining equipment is not particularly required, and electric furnace equipment well known to researchers in the field, such as a silicon carbide rod furnace, can be adopted. The calcination treatment process comprises calcination temperature, calcination time, heating rate, atmosphere conditions and the like. Preferably, in the embodiment, the calcination temperature is 450-650 ℃, the sintering time is 0.5-2 hours, the heating rate is 2-10 ℃/min, the cooling rate is natural cooling, and the atmosphere condition is natural air atmosphere.
The high-energy-density composite positive electrode prepared by low-temperature co-sintering can greatly reduce energy consumption, improve the interface contact between a positive electrode material and a solid electrolyte, reduce the occurrence of side reactions, and reduce interface impedance, thereby improving the performance of the battery.
The invention provides an inorganic all-solid-state lithium battery, which comprises at least one battery unit, wherein the battery unit comprises a negative electrode, and the composite positive electrode layer-solid electrolyte laminated aggregate.
The negative electrode has: metallic lithium sheets and lithium alloys, and the like, but are not limited thereto. The anode of the present invention may be one of suitable anodes or a plurality of anodes in any ratio. Preferably a sheet of metallic lithium.
According to a specific embodiment, when the all solid-state lithium battery of the present invention is assembled, the obtained composite positive electrode layer-solid electrolyte laminated assembly is assembled with a negative electrode material to obtain the battery. More specifically, the composite positive electrode layer-solid electrolyte laminated aggregate is directly laminated with a negative electrode, the negative electrode layer adopts a melting method, the surface of a negative electrode layer sheet is scraped clean to expose metal luster, then the negative electrode layer sheet is pressed to be thin and is attached to the side of the solid electrolyte laminated aggregate of the composite positive electrode layer-solid electrolyte laminated aggregate, the composite positive electrode layer sheet is placed on a heating platform to be heated to 300 ℃ and kept for 10min, so that the metal of the negative electrode layer sheet is melted on the solid electrolyte, and the obtained composite positive electrode layer, inorganic solid electrolyte layer and negative electrode layer form a laminated all-solid-state lithium battery;
the composite positive electrode layer and the negative electrode layer are also provided with current collectors. The current collector of the present invention is not particularly limited, and may be any current collector that can be used in the art. The current collector is usually a metal foil, a metal sheet, a metal foam, or the like. Common metals such as nickel, copper, aluminum, stainless steel, and the like.
According to a specific embodiment, the all-solid-state lithium battery is further assembled in a glove box filled with an argon atmosphere.
The invention has the following advantages:
(1) According to the lithium ion battery composite positive electrode layer provided by the invention, a high-specific-energy lithium-rich manganese-based positive electrode material is introduced into the composite positive electrode structure of the inorganic all-solid-state battery, and interface contact is improved by adopting a low-temperature integrated co-sintering interface engineering method, so that the production cost of the all-solid-state battery is reduced, and the discharge capacity and the energy density of the inorganic all-solid-state battery are improved;
(2) The used materials and the final product of the invention do not relate to the introduction of organic substances, so that the safety problems that the liquid substances are unstable at higher temperature and can cause the ignition and explosion of the battery and the like are completely avoided, and the assembled inorganic all-solid-state battery can be used at high temperature; and can completely avoid the potential safety hazard that the electrolyte is easy to volatilize and leak, and has wide application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a first-turn charge-discharge curve of an all-solid battery according to example 1 of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any numerical values disclosed herein are not limited to the precise range or value and should be understood to encompass data proximate to the range or value. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, lithium borate, LLZO solid electrolyte powder and titanium nitride according to a mass ratio of 70; the method comprises the steps of taking an LLZO ceramic wafer as a substrate, coating composite anode slurry on one side of the LLZO ceramic wafer by a scraper to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, spraying gold on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembling
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, pressing to be thin, attaching the lithium sheet to the negative side of the laminated unit, placing the laminated unit on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 2
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, a mixture of lithium borate and lithium nitrate, LLZO electrolyte powder and titanium nitride in a mass ratio of 70; coating the composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a scraper to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium indium alloy to expose metallic luster, pressing to be thin, attaching the thin lithium indium alloy to the negative side of an upper laminated unit, placing the thin lithium indium alloy on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting the alloy on the negative side of the laminated unit; during the battery assembly process, the battery is packaged by using aluminum alloy as a current collector.
Example 3
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, a mixture of lithium borate and lithium nitrate and LLZO electrolyte powder according to a mass ratio of 8; the method comprises the steps of taking an LLZO ceramic wafer as a substrate, coating composite anode slurry on one side of the LLZO ceramic wafer by a scraper to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, spraying gold on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side face of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, thinning, attaching to the negative side of an upper laminated unit, placing on a heating platform, heating to 300 ℃, keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 4
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, lithium borate, LLZO solid electrolyte powder and vanadium nitride according to a mass ratio of 80; the method comprises the steps of taking an LLZO ceramic chip as a substrate, coating composite anode slurry on one side of the LLZO ceramic chip by a scraper to obtain a uniform composite anode coating, placing the ceramic chip in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, spraying gold on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, pressing to be thin, attaching the lithium sheet to the negative side of the laminated unit, placing the laminated unit on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 5
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, lithium metaborate, LLZO electrolyte powder and titanium nitride according to a mass ratio of 70; coating the composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a scraper to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium indium alloy to expose metallic luster, pressing to be thin, attaching the thin lithium indium alloy to the negative side of an upper laminated unit, placing the thin lithium indium alloy on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting the alloy on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 6
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-manganese-rich positive electrode material, lithium borate and LLZO electrolyte powder according to a mass ratio of 90; the method comprises the steps of coating composite anode slurry on the anode side of an LLZO ceramic wafer serving as a substrate by a scraper to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean. (2) Assembling
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, pressing to be thin, attaching the lithium sheet to the negative side of an upper laminated unit, placing the laminated unit on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; in the battery assembling process, the aluminum alloy is used as a current collector for battery packaging
Example 7
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode material, lithium metaborate and LLZO inorganic solid electrolyte powder according to a mass ratio of 90; coating the composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a screen printing method to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing a gold layer on the side surface of the aggregate to be clean.
(2) Assembling
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, pressing to be thin, attaching the lithium sheet to the negative side of an upper laminated unit, placing the laminated unit on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, the battery is packaged by using foamed nickel as a current collector.
Example 8
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode active material, a mixture of lithium borate and lithium nitrate, LLZO electrolyte powder and vanadium nitride according to a mass ratio of 80; coating composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a screen printing method to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing a gold layer on the side surface of the aggregate to be clean.
(2) Assembling
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, pressing to be thin, attaching the lithium sheet to the negative side of an upper laminated unit, placing the laminated unit on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 9
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode active material, lithium borate and LLZO electrolyte powder according to a mass ratio of 8; coating composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a screen printing method to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, spraying gold on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium indium alloy to expose metallic luster, pressing to be thin, attaching the thin lithium indium alloy to the negative side of an upper laminated unit, placing the thin lithium indium alloy on a heating platform, heating to 300 ℃ and keeping for about 10min, and melting the alloy on the negative side of the laminated unit; during the battery assembly process, battery packaging is performed using nickel foam as a current collector.
Example 10
A high energy density lithium-rich all-solid-state lithium battery and a preparation method thereof comprise the following steps:
(1) Preparation of composite positive electrode-solid electrolyte laminated unit of lithium battery
Fully mixing a lithium-rich manganese-based positive electrode active material, a mixture of lithium metaborate and lithium nitrate, LLZO electrolyte powder and vanadium nitride according to a mass ratio of 80; coating the composite anode slurry on one side of a LLZO ceramic wafer serving as a substrate by adopting a screen printing method to obtain a uniform composite anode coating, placing the ceramic wafer in a sintering container, sintering in an air atmosphere, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, cooling to room temperature along with a furnace to obtain an aggregate of a composite anode and an inorganic solid electrolyte, carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the aggregate, and polishing the gold layer on the side surface of the aggregate to be clean.
(2) Assembly
In a glove box filled with argon atmosphere, scraping the surface of a lithium sheet to expose metallic luster, thinning, attaching to the negative side of an upper laminated unit, placing on a heating platform, heating to 300 ℃, keeping for about 10min, and melting lithium metal on the negative side of the laminated unit; during the battery assembly process, the battery is packaged by using foamed nickel as a current collector.

Claims (9)

1. A method for producing a composite positive electrode layer-solid electrolyte laminated aggregate, characterized by comprising the steps of:
(1) Weighing a high-specific-energy lithium-rich manganese-based positive electrode material, an inorganic solid electrolyte powder, a sintering additive and an electronic conductor required by a composite positive electrode according to a certain mass ratio, and adding a proper amount of polyvinylidene fluoride (PVDF) and an organic solvent for full grinding to prepare slurry;
(2) Uniformly coating the slurry prepared in the step (1) on the surface of the LLZO ceramic chip, and then carrying out vacuum drying to preliminarily obtain a laminated unit of the composite anode and the solid electrolyte layer;
(3) Placing the laminated unit obtained in the step (2) in heating equipment for sintering, and then reducing the temperature to room temperature to obtain a composite positive electrode layer-solid electrolyte ceramic sheet assembly with an interface in close contact;
(4) And (4) carrying out gold spraying treatment on the surfaces of the two sides of the anode and the cathode of the assembly in the step (3), and polishing the gold layer on the side surface of the assembly.
2. The method for producing a composite positive-electrode layer-solid electrolyte laminated assembly according to claim 1, wherein the raw material of the composite positive-electrode material of step (1) comprises the following composition:
70-90 wt% of high-capacity lithium-rich manganese-based positive electrode material;
5wt% -15 wt% of inorganic solid electrolyte powder;
5-10 wt% of a fusing assistant; and
0wt% -5 wt% of electronic conductor
The inorganic solid electrolyte powder is preferably garnet-type Lithium Lanthanum Zirconate (LLZO) electrolyte powder, the LLZO electrolyte powder comprises lithium, lanthanum, zirconium and doping elements, wherein the doping elements comprise one or more of aluminum, iron, gallium, yttrium, cerium, antimony, tantalum, niobium, vanadium and the like;
the fusing auxiliary agent is one or more of lithium borate, lithium metaborate, lithium nitrate and lithium phosphate; lithium borate and lithium metaborate are preferred.
The electronic conductor is one or more of nitride or oxide such as titanium nitride, vanadium nitride, tin antimony oxide and the like; preferably titanium nitride or vanadium nitride.
3. The method of producing a composite positive electrode layer-solid electrolyte laminate aggregate according to claim 1, wherein in the step (2), the LLZO ceramic sheet is sintered for the same inorganic solid electrolyte powder pressed sheet used in the step (1), and is subjected to polishing treatment before assembling the all-solid battery.
4. The method for producing a composite positive electrode layer-solid electrolyte laminated assembly according to claim 1, wherein the uniform coating method in the step (2) includes, but is not limited to, a doctor blade coating method, a screen printing method, a casting method, and the like.
5. The method for producing a composite positive electrode layer-solid electrolyte laminated assembly according to claim 1, wherein in the step (3), the calcination temperature is 450 ℃ to 650 ℃, the sintering time is 0.5 to 2 hours, the cooling rate is natural cooling, and the atmosphere condition is a natural air atmosphere.
6. An inorganic all-solid-state lithium battery comprising at least one battery cell, said battery cell comprising, in order, the composite positive electrode layer-solid electrolyte assembly prepared by the method according to any one of claims 1 to 5, and a negative electrode.
7. The inorganic all-solid-state lithium battery according to claim 6, wherein the negative electrode is selected from one of a metallic lithium plate, a lithium alloy or a plurality of lithium alloys in any ratio.
8. The method for preparing the inorganic all-solid-state lithium battery of claim 6 or 7, characterized in that the composite positive electrode layer-solid electrolyte laminated assembly is directly laminated with a negative electrode, the negative electrode layer adopts a melting method, firstly, the surface of a negative electrode layer sheet is scraped clean to expose metallic luster, then, the negative electrode layer sheet is pressed to be thin and is attached to the side of the solid electrolyte laminated assembly of the composite positive electrode layer-solid electrolyte laminated assembly, the composite positive electrode layer sheet is placed on a heating platform to be heated to 300 ℃ and kept for 10min, so that the metal of the negative electrode layer sheet is melted on the solid electrolyte, and the obtained composite positive electrode layer, inorganic solid electrolyte layer and negative electrode layer form the laminated all-solid-state lithium battery.
9. The method of claim 8, wherein the laminated all solid-state lithium battery is assembled in a glove box filled with argon atmosphere, an inorganic all solid-state battery of the type including but not limited to button, soft pack and steel can.
CN202110362800.8A 2021-04-02 2021-04-02 High-energy-density lithium-rich all-solid-state lithium battery and preparation method thereof Pending CN115172883A (en)

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