CN110600794A - Solid-state lithium battery and preparation method thereof - Google Patents

Solid-state lithium battery and preparation method thereof Download PDF

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CN110600794A
CN110600794A CN201910828414.6A CN201910828414A CN110600794A CN 110600794 A CN110600794 A CN 110600794A CN 201910828414 A CN201910828414 A CN 201910828414A CN 110600794 A CN110600794 A CN 110600794A
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solid
oxide
positive electrode
solid electrolyte
lithium battery
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CN110600794B (en
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邓永红
吴唯
王曼
张田
王军
魏振耀
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Southwest University of Science and Technology
Southern University of Science and 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
    • H01M10/052—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
    • H01M10/05—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

The invention belongs to the technical field of batteries, and particularly relates to a solid-state lithium battery, which comprises: the anode comprises an anode active material, wherein the anode active material comprises transition metal oxide with the particle size of 100 nanometers-1 micron. The positive active material in the solid lithium battery adopts transition metal oxide with the grain diameter of 100 nanometers to 1 micron, has higher reversible specific capacity and higher potential platform, the reversible specific capacity is more than 674mAh/g, the specific energy is more than 1014Wh/kg, and the positive active material can be matched with different types of solid electrolytes to realize stable circulation.

Description

Solid-state lithium battery and preparation method thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a solid-state lithium battery and a preparation method thereof.
Background
In the current chemical battery system, a lithium battery is considered as an energy storage device with the most prospect due to the characteristics of high energy density, long cycle life, no memory effect and the like. The electrolyte used in the traditional lithium ion battery is generally an organic liquid electrolyte, and although the liquid electrolyte can provide higher ionic conductivity and good interface contact, the organic liquid electrolyte has the problems of low lithium ion transport number, easy leakage, easy volatilization, flammability, poor safety and the like, so that the further development of the lithium battery is hindered. In view of the pursuit of higher energy density and higher safety, lithium ion batteries are gradually entering the trend of transition from conventional liquid batteries to solid batteries. Compared with the liquid electrolyte of the traditional lithium battery, the solid-state battery has the advantages that the electrolyte is a solid substance with high conductivity, the solid-state battery has good safety performance and flexibility, is easy to process into a film, has excellent interface contact and the like, can well inhibit the problem of lithium dendrite, and is widely concerned at present.
At present, the selection of the anode material of the solid-state battery is also an important factor influencing the performance of the solid-state lithium battery. The traditional solid-state battery positive electrode material adopts Lithium Cobaltate (LCO), lithium nickelate, lithium manganate, lithium iron phosphate (LFP), lithium nickel manganese Nickelate (NCM) and the like, and although the positive electrode material has a higher potential (>3.2V), the general specific capacity is lower (usually <200mAh/g), so that the specific energy of the solid-state battery is lower (500-900 Wh/kg). In addition, the conventional positive electrode material is also prone to have poor matching with a solid electrolyte, such as: conventional positive electrode materials other than lithium iron phosphate LFP strongly react with all phosphorothioate electrolytes. In addition, garnet-type oxide electrolytes (such as lithium lanthanum zirconium oxide solid electrolyte LLZO) are prone to react with lithium hemilithiated positive electrode lithium manganate (NCM) and Lithium Cobaltate (LCO) during charging, and thus the overall cycle performance is poor. Therefore, the lower specific energy and the poor matching stability with the solid electrolyte of the conventional positive electrode material become important obstacles for limiting the development of the existing solid battery system.
Disclosure of Invention
The invention aims to provide a solid-state lithium battery, which aims to solve the technical problems of low specific energy, poor matching with a solid electrolyte, incompatibility of an interface and the like of the conventional solid-state lithium battery anode material.
The invention also aims to provide a preparation method of the solid-state lithium battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a solid state lithium battery comprising: the anode comprises an anode active material, wherein the anode active material comprises transition metal oxide with the particle size of 100 nanometers-1 micron.
Preferably, the transition metal oxide is selected from: at least one of iron oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide.
Preferably, the solid electrolyte is selected from: at least one of organic solid electrolyte, inorganic solid electrolyte and organic-inorganic composite solid electrolyte.
Preferably, the solid electrolyte is selected from: at least one of lithium lanthanum zirconium oxygen solid electrolyte, lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte, polycarbonate-based solid electrolyte, polysiloxane-based solid electrolyte, composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen, and sulfide solid electrolyte.
Preferably, the anode includes an anode active material selected from the group consisting of: metallic lithium and/or lithium alloys.
Preferably, the lithium alloy is selected from: lixSi、LixAl、LixAt least one of Pb.
Preferably, the positive electrode further comprises a positive electrode conductive agent and a positive electrode binder, and the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (65-80): 15-25): 5-15.
Preferably, the method comprises the following steps: the anode comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises at least one transition metal oxide of ferric oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide with the particle size of 100 nanometers-1 micrometer; the negative electrode includes metallic lithium; the solid electrolyte is selected from: at least one of lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte and composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen.
Correspondingly, the preparation method of the solid-state lithium battery comprises the following steps:
obtaining transition metal oxide with the particle size of 100 nanometers to 1 micrometer, preparing the transition metal oxide, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, and depositing the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
and obtaining a negative electrode and a solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
Preferably, the step of obtaining the transition metal oxide having a particle size of 100 nm to 1 μm comprises: obtaining a transition metal precursor, and heating the transition metal precursor to 500-700 ℃ in an air atmosphere to react for 2-5 hours to obtain the transition metal oxide with the particle size of 100 nanometers-1 micron.
The solid lithium battery provided by the invention comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises a positive active material, and the positive active material comprises a transition metal oxide with the particle size of 100 nanometers-1 micron. The positive active material in the solid lithium battery adopts transition metal oxide with the particle size of 100 nanometers to 1 micron, on one hand, the transition metal oxide positive active material has higher reversible specific capacity and higher potential platform, and the reversible specific capacity is more than 674mAh/g, so that the solid lithium battery has higher specific energy, and the specific energy is more than 1014 Wh/kg; on the other hand, the particle size of the transition metal oxide is 100 nanometers-1 micron, and the nano-structured transition metal oxide positive active material can greatly reduce the problems of particle pulverization and the like caused by volume expansion in the circulation process of the solid-state lithium battery, so that the battery has better circulation performance. In addition, the transition metal oxide positive electrode active material has higher matching property with different types of solid electrolytes, so that the problem of interface compatibility between the positive electrode and the solid electrolytes is avoided, and the cycle stability of the solid lithium battery is further enhanced.
The invention provides a preparation method of a solid lithium battery, which comprises the following steps: preparing transition metal oxide with the particle size of 100 nanometers to 1 micrometer, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, depositing the positive electrode slurry on a positive electrode current collector to obtain a positive electrode, and then preparing the positive electrode, a negative electrode and a solid electrolyte into a solid lithium battery. According to the preparation method of the solid-state lithium battery, the anode slurry containing the transition metal oxide with the particle size of 100 nanometers to 1 micrometer can be directly deposited on the anode current collector through the modes of coating and the like to prepare the anode, the operation is simple, and the preparation method is suitable for industrial production and application.
Drawings
Fig. 1 is a scanning electron microscope image of an iron oxide positive active material used in a solid-state lithium battery provided in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a copper oxide positive active material used in a solid-state lithium battery provided in example 7 of the present invention.
Fig. 3 is a scanning electron microscope image of a manganese sesquioxide positive active material used in a solid-state lithium battery provided in embodiment 10 of the present invention.
Fig. 4 is a comparative test chart of the cycle stability of the solid lithium battery using the iron oxide positive electrode provided in example 1 of the present invention and the conventional liquid battery.
Fig. 5 is a test chart of cycle stability of the solid-state lithium battery provided in example 2 of the present invention.
Fig. 6 is a test chart of cycle stability of the solid-state lithium battery provided in embodiment 3 of the present invention.
Fig. 7 is a test chart of cycle stability of the solid-state lithium battery provided in embodiment 4 of the present invention.
Fig. 8 is a test chart of cycle stability of the solid-state lithium battery provided in example 7 of the present invention.
Fig. 9 is a test chart of cycle stability of the solid-state lithium battery provided in example 10 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
An embodiment of the present invention provides a solid-state lithium battery, including: the anode comprises an anode active material, wherein the anode active material comprises transition metal oxide with the particle size of 100 nanometers-1 micron.
The solid-state lithium battery provided by the embodiment of the invention comprises a positive electrode, a negative electrode and a solid-state electrolyte, wherein the positive electrode comprises a positive active material, and the positive active material comprises a transition metal oxide with the particle size of 100 nanometers-1 micrometer. The positive active material in the solid-state lithium battery provided by the embodiment of the invention adopts the transition metal oxide with the particle size of 100 nanometers-1 micron, on one hand, the transition metal oxide positive active material has higher reversible specific capacity and higher potential platform, and the reversible specific capacity is more than 674mAh/g, so that the solid-state lithium battery has higher specific energy, and the specific energy is more than 1014 Wh/kg; on the other hand, the particle size of the transition metal oxide is 100 nanometers-1 micron, and the nano-structured transition metal oxide positive active material can greatly reduce the problems of particle pulverization and the like caused by volume expansion in the circulation process of the solid-state lithium battery, so that the battery has better circulation performance. In addition, the transition metal oxide positive electrode active material and different types of solid electrolytes have higher matching performance, so that the problem of interface compatibility between the positive electrode and the solid electrolytes is solved, and the cycle stability of the solid lithium battery is further enhanced.
As a preferred embodiment, the transition metal oxide is selected from: at least one of iron oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide. The positive active material of the solid-state lithium battery provided by the embodiment of the invention is at least one transition metal oxide selected from iron oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide with the particle size of 100 nanometers-1 micrometer, the transition metal oxides have higher reversible specific capacity and higher potential platform, the reversible capacity can reach 1014mAh/g, the solid-state lithium battery has higher specific energy, and the specific energy can reach 1641 Wh/kg. Meanwhile, the transition metal oxide with the nano structure can reduce the problems of particle pulverization and the like caused by volume expansion in the circulation process of the solid-state lithium battery, so that the battery has better circulation performance.
In some embodiments, the transition metal oxide is selected from iron oxide having a particle size of 100 nanometers or 500 nanometers. In some embodiments, the transition metal oxide is selected from copper oxide having a particle size of 100 nm. In some embodiments, the transition metal oxide is selected from manganese oxide having a particle size of 300 nm. In some embodiments, the nanostructured transition metal oxide employed by the solid-state ion battery may also be a derivative of a nanoscale transition metal oxide that has been further carbon-coated or doped.
As a preferred embodiment, the solid electrolyte is selected from: at least one of organic solid electrolyte, inorganic solid electrolyte and organic-inorganic composite solid electrolyte. The nano-structure transition metal oxide adopted by the solid-state lithium battery in the embodiment of the invention has better matching property with the main solid-state electrolytes such as the current organic solid-state electrolyte, inorganic solid-state electrolyte, organic-inorganic composite solid-state electrolyte and the like, thereby avoiding the problem of poor interface compatibility between the traditional anode material and the solid-state electrolyte and ensuring that the battery has good cycling stability.
As a preferred embodiment, the solid electrolyte is selected from: at least one of lithium lanthanum zirconium oxygen solid electrolyte, lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte, polycarbonate-based solid electrolyte, polysiloxane-based solid electrolyte, composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen, and sulfide solid electrolyte. The nano-structure transition metal oxide adopted by the solid-state lithium battery in the embodiment of the invention has better interface compatibility with solid-state electrolytes such as lithium lanthanum zirconium oxygen solid-state electrolyte, lithium lanthanum zirconium tantalum oxygen solid-state electrolyte, lithium aluminum germanium phosphorus solid-state electrolyte, polyethylene oxide solid-state electrolyte, polycarbonate-based solid-state electrolyte, polysiloxane-based solid-state electrolyte, composite solid-state electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen, sulfide solid-state electrolyte and the like, and has the advantages of high conductivity, high transference number, excellent mechanical property, wide electrochemical stability window, good thermal stability, good chemical stability and the like, so that the battery has good cycle stability and excellent electrochemical property.
As a preferred embodiment, the anode includes an anode active material selected from the group consisting of: metallic lithium and/or lithium alloys. The negative active material of the solid-state lithium battery with the nano-structure transition metal oxide as the positive active material provided by the embodiment of the invention can be metal lithium and/or lithium alloy. In some embodiments, the lithium alloy is selected from: lixSi、LixAl、LixIn PbAt least one of them.
In a preferred embodiment, the positive electrode further comprises a positive electrode conductive agent and a positive electrode binder, and the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (65-80): 15-25): 5-15. The positive electrode of the solid-state lithium battery in the embodiment of the invention further comprises a positive electrode conductive agent and a positive electrode binder, wherein the positive electrode conductive agent comprises but is not limited to at least one of a carbon black conductive agent, an acetylene black conductive agent, a graphite conductive agent and a graphene conductive agent, and the positive electrode binder comprises but is not limited to at least one of polyacrylic acid, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyvinylidene fluoride. In addition, the mass ratio of the active substance, the conductive agent and the binder in the cathode material is (65-80): (15-25): (5-15), and the specific proportion enables the components in the cathode material to play the best synergistic effect, so that the active substance in the cathode material provides higher reversible specific capacity and potential, and the solid-state lithium battery shows higher specific energy which is more than 1014 Wh/kg. As a more preferable example, the mass ratio of the positive electrode active material to the positive electrode conductive agent and the positive electrode binder is 70:20: 10.
In some embodiments, a solid state lithium battery includes: the anode comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises at least one transition metal oxide of ferric oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide with the particle size of 100 nanometers-1 micrometer; the negative electrode includes metallic lithium; the solid electrolyte is selected from: at least one of lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte and composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen. The solid-state lithium battery provided by the embodiment of the invention has higher specific energy and cycle stability.
The solid-state lithium battery provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the solid-state lithium battery, which comprises the following steps:
s10, obtaining a transition metal oxide with the particle size of 100 nanometers to 1 micrometer, preparing the transition metal oxide, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, and depositing the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
s20, obtaining a negative electrode and a solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
The preparation method of the solid-state lithium battery provided by the embodiment of the invention comprises the following steps: preparing transition metal oxide with the particle size of 100 nanometers to 1 micrometer, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, depositing the positive electrode slurry on a positive electrode current collector to obtain a positive electrode, and then preparing the positive electrode, a negative electrode and a solid electrolyte into a solid lithium battery. According to the preparation method of the solid-state lithium battery provided by the embodiment of the invention, the anode slurry containing the transition metal oxide with the particle size of 100 nanometers-1 micrometer can be directly deposited on the anode current collector by coating and other modes to prepare the anode, the operation is simple, and the preparation method is suitable for industrial production and application.
Specifically, in step S10, a transition metal oxide with a particle size of 100 nm to 1 μm is obtained, the transition metal oxide, a positive electrode conductive agent and a positive electrode binder are made into a positive electrode slurry, and the positive electrode slurry is deposited on a positive electrode current collector to obtain a positive electrode. In the embodiment of the invention, transition metal oxide with the particle size of 100 nanometers to 1 micrometer, a positive electrode conductive agent and a positive electrode binder are prepared into positive electrode slurry, wherein the transition metal oxide comprises but is not limited to at least one of ferric oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide; the positive electrode conductive agent includes but is not limited to at least one of carbon black conductive agent, acetylene black conductive agent, graphite conductive agent and graphene conductive agent, and the positive electrode binder includes but is not limited to at least one of polyacrylic acid, sodium carboxymethyl cellulose, styrene butadiene rubber and polyvinylidene fluoride. The transition metal oxide, the positive electrode conductive agent and the positive electrode binder are mixed according to the mass ratio of (65-80): (15-25): (5-15) to obtain positive electrode slurry, and then the positive electrode slurry is deposited on a positive electrode current collector through coating and other modes to obtain the positive electrode.
In some embodiments, the transition metal oxide is mixed with a positive electrode conductive agent and a positive electrode binder according to a mass ratio of 70:20:10, and then coated on any one current collector of aluminum, platinum, gold, copper, silver, molybdenum, nickel and stainless steel metal materials to obtain the positive electrode.
As a preferred embodiment, the step of obtaining the transition metal oxide having a particle size of 100 nm to 1 μm includes: obtaining a transition metal precursor, and heating the transition metal precursor to 500-700 ℃ in an air atmosphere to react for 2-5 hours to obtain the transition metal oxide with the particle size of 100 nanometers-1 micron. The transition metal oxide with the particle size of 100 nanometers to 1 micrometer in the embodiment of the invention can be prepared by heating transition metal precursors such as iron, cobalt, manganese, nickel, copper, vanadium, chromium and the like to 500 to 700 ℃ in an air atmosphere to react for 2 to 5 hours, so as to generate the transition metal oxide with the nano structure with the particle size of 100 nanometers to 1 micrometer. The transition metal precursor may be any form of chloride, salt, etc. of transition metal, as long as it can grow into transition metal oxide with a particle size of 100 nm to 1 μm in the reaction system.
Specifically, in step S20, the negative electrode and the solid electrolyte are obtained, and the positive electrode, the negative electrode, and the solid electrolyte are formed into the solid lithium battery. The solid electrolyte of the embodiment of the present invention includes, but is not limited to, at least one of an organic solid electrolyte, an inorganic solid electrolyte, and an organic-inorganic composite solid electrolyte, and is more preferably selected from at least one of a lithium lanthanum zirconium oxygen solid electrolyte, a lithium lanthanum zirconium tantalum oxygen solid electrolyte, a lithium aluminum germanium phosphorus solid electrolyte, a polyethylene oxide solid electrolyte, a polycarbonate-based solid electrolyte, a polysiloxane-based solid electrolyte, a composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen, and a sulfide solid electrolyte; the negative electrode active material in the negative electrode is selected from metallic lithium and/or a lithium alloy. According to the embodiment of the invention, the solid-state lithium battery is prepared by assembling the anode, the cathode and the solid-state electrolyte, so that the operation is simple and convenient, and the method is suitable for industrial production and application.
In order to clearly understand the details of the above-mentioned implementation and operation of the present invention by those skilled in the art and to obviously show the advanced performance of the solid-state lithium battery according to the embodiment of the present invention, the technical solution is illustrated by a plurality of examples below.
Example 1
A solid state lithium battery comprising the following preparation steps:
obtaining Fe with grain size of 500 nm2O3Introducing said Fe2O3Preparing positive electrode slurry with conductive carbon black and polyacrylic acid, and coating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
and secondly, obtaining a lithium metal negative electrode and a lithium lanthanum zirconium tantalum oxygen solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
Example 2
A solid state lithium battery comprising the following preparation steps:
firstly, obtaining Fe with the grain diameter of about 500 nanometers2O3Introducing said Fe2O3Preparing positive electrode slurry with conductive carbon black and polyacrylic acid, and coating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
and secondly, obtaining a lithium metal negative electrode and a lithium aluminum germanium phosphorus solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
Example 3
A solid state lithium battery comprising the following preparation steps:
firstly, obtaining Fe with the grain diameter of about 500 nanometers2O3Introducing said Fe2O3Preparing positive electrode slurry with conductive carbon black and polyacrylic acid, and coating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
obtaining a lithium metal negative electrode and a polyoxyethylene solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
Example 4
A solid state lithium battery comprising the following preparation steps:
firstly, obtaining Fe with the grain diameter of about 500 nanometers2O3Introducing said Fe2O3Preparing positive electrode slurry with conductive carbon black and polyacrylic acid, and mixing the above-mentioned materialsCoating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
and secondly, obtaining a lithium metal negative electrode and polyoxyethylene plus 5 wt% of lithium lanthanum zirconium tantalum oxygen organic-inorganic composite solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
Examples 5 to 11
Examples 5 to 11 provide solid-state lithium batteries, which have the same materials and preparation methods as those in example 1 except that the positive active material oxides are different, and are not described herein again, wherein the positive active material oxides are respectively shown in table 1 below.
Comparative examples 1 to 8
The conventional positive active material, negative electrode, solid electrolyte and preparation method used in comparative examples 1 to 8 are the same as those in example 1, and are not repeated herein, wherein the lithium potential, theoretical specific capacity and theoretical specific energy of the positive active material in comparative examples 1 to 8 are shown in table 1 below.
TABLE 1
Further, in order to verify the advancement of the solid-state lithium batteries provided in the examples of the present invention and the comparative examples, the examples of the present invention were subjected to relevant electrochemical experimental tests.
Test example 1
In the embodiment of the invention, the shapes of the iron oxide positive active material (shown in the figure 1) adopted in the embodiment 1, the copper oxide positive active material (shown in the figure 2) adopted in the embodiment 7 and the manganese oxide positive active material (shown in the figure 3) adopted in the embodiment 10 are tested by a scanning electron microscope.
The test results are shown in fig. 1 to 3, and the transition metal oxide positive electrode active materials adopted in the embodiment of the present invention are all of a nano structure, wherein the particle size of the iron oxide adopted in the embodiment 1 is about 500 nm, the particle size of the copper oxide adopted in the embodiment 7 is about 100 nm, and the particle size of the manganese sesquioxide adopted in the embodiment 10 is about 300 nm.
Test example 2
The embodiment of the invention tests the cycle stability of the solid-state lithium batteries of the embodiments 1 to 4, and explores the matching property of the transition metal oxide positive active material and the currently commonly used solid-state electrolyte.
As shown in fig. 4, in example 1, the solid-state lithium battery using nano iron oxide as the positive electrode active material and the lithium lanthanum zirconium tantalum oxygen inorganic solid electrolyte as the electrolyte has almost the same specific capacity performance (850 mAh/g) as that of iron oxide in the conventional liquid battery, and has the same excellent cycle performance, which indicates that the solid-state battery has good electrochemical performance in the solid-state battery system.
As shown in fig. 5, example 2 is a solid lithium battery using nano iron oxide as a positive electrode active material and a lithium aluminum germanium phosphorus inorganic solid electrolyte as an electrolyte, and shows a higher specific capacity and a better cycling stability.
As shown in fig. 6, example 3 is a solid lithium battery using nano iron oxide as a positive electrode active material and a polyethylene oxide organic solid electrolyte as an electrolyte, and shows a higher specific capacity and a better cycling stability.
As shown in fig. 7, example 4 is a solid lithium battery using nano iron oxide as a positive electrode active material and polyoxyethylene +5 wt% lithium lanthanum zirconium tantalum oxygen organic-inorganic composite solid electrolyte as an electrolyte, and shows a higher specific capacity and a better cycling stability.
According to the test results, the nano iron oxide provided by the embodiment of the invention is a positive electrode active material, has higher specific capacity and cycling stability with different types of solid electrolytes, can be adapted to different types of solid electrolytes, has high matching performance with the solid electrolytes, and does not have the problem of interface compatibility.
Test example 3
The lithium potential, the theoretical specific capacity and the theoretical specific mass energy of the different positive active materials adopted in examples 1 and 5 to 11 and comparative examples 1 to 8 were calculated respectively, and the calculation results are shown in table 1 above.From the above results, it can be seen that the theoretical specific capacity and specific energy, V, of the transition metal oxide positive active materials used in examples 1 and 5 to 11 of the present invention are significantly higher than those of the conventional positive active materials used in comparative examples 1 to 82O3The theoretical specific capacity of the embodiment 8 as the positive active material can reach 1074 mAh/g; fe2O3The theoretical specific energy of the positive active material in the embodiment 1 can reach 1641Wh/kg, and the specific capacity is 1007 mAh/g.
In addition, the cycle performance of the solid-state lithium battery (shown in fig. 8) adopting the copper oxide cathode active material in example 7 and the solid-state lithium battery (shown in fig. 9) adopting the manganese sesquioxide cathode active material in example 10 were tested, and as shown in fig. 8 to 9, the solid-state lithium batteries provided in examples 7 and 10 of the present invention both have the advantages of high specific capacity and excellent cycle stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A solid state lithium battery, comprising: the anode comprises an anode active material, wherein the anode active material comprises transition metal oxide with the particle size of 100 nanometers-1 micron.
2. The solid state lithium battery of claim 1, wherein the transition metal oxide is selected from the group consisting of: at least one of iron oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide.
3. A solid state lithium battery as claimed in claim 1 or 2, characterized in that the solid state electrolyte is selected from: at least one of organic solid electrolyte, inorganic solid electrolyte and organic-inorganic composite solid electrolyte.
4. A solid state lithium battery as claimed in claim 3, characterized in that the solid state electrolyte is selected from: at least one of lithium lanthanum zirconium oxygen solid electrolyte, lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte, polycarbonate-based solid electrolyte, polysiloxane-based solid electrolyte, composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen, and sulfide solid electrolyte.
5. The solid state lithium battery of any one of claims 1, 2 or 4, wherein the negative electrode includes a negative active material selected from the group consisting of: metallic lithium and/or lithium alloys.
6. The solid state lithium battery of claim 5, wherein the lithium alloy is selected from the group consisting of: lixSi、LixAl、LixAt least one of Pb.
7. The solid-state lithium battery according to any one of claims 1, 2, 4, or 6, wherein the positive electrode further comprises a positive electrode conductive agent and a positive electrode binder, and a mass ratio of the positive electrode active material to the positive electrode conductive agent and the positive electrode binder is (65-80): (15-25): (5-15).
8. The solid state lithium battery of claim 7, comprising: the anode comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises at least one transition metal oxide of ferric oxide, ferrous oxide, cobalt oxide, manganese oxide, nickel oxide, copper oxide, vanadium oxide and chromium oxide with the particle size of 100 nanometers-1 micrometer; the negative electrode includes metallic lithium; the solid electrolyte is selected from: at least one of lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, polyethylene oxide solid electrolyte and composite solid electrolyte of polyethylene oxide and lithium lanthanum zirconium tantalum oxygen.
9. A method for preparing a solid-state lithium battery is characterized by comprising the following steps:
obtaining transition metal oxide with the particle size of 100 nanometers to 1 micrometer, preparing the transition metal oxide, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, and depositing the positive electrode slurry on a positive electrode current collector to obtain a positive electrode;
and obtaining a negative electrode and a solid electrolyte, and preparing the positive electrode, the negative electrode and the solid electrolyte into a solid lithium battery.
10. The method of manufacturing a solid state lithium battery as claimed in claim 9, wherein the step of obtaining the transition metal oxide having a particle size of 100 nm to 1 μm comprises: obtaining a transition metal precursor, and heating the transition metal precursor to 500-700 ℃ in an air atmosphere to react for 2-5 hours to obtain the transition metal oxide with the particle size of 100 nanometers-1 micron.
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