CN112838217A - Composite structure containing lithium cathode, preparation method thereof and solid-state battery - Google Patents

Composite structure containing lithium cathode, preparation method thereof and solid-state battery Download PDF

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CN112838217A
CN112838217A CN202011618878.3A CN202011618878A CN112838217A CN 112838217 A CN112838217 A CN 112838217A CN 202011618878 A CN202011618878 A CN 202011618878A CN 112838217 A CN112838217 A CN 112838217A
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lithium
solid electrolyte
negative electrode
solid
composite structure
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高欣
耿振
李斯剑
苏青
廖文俊
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Shanghai Electric Group Corp
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Shanghai Electric Group Corp
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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 relates to the field of batteries, and discloses a composite structure containing a lithium cathode, a preparation method of the composite structure and a solid-state battery. The preparation method of the lithium-containing negative electrode composite structure comprises the following steps: and (3) placing the lithium-containing negative pole piece, the metal oxide layer and the solid electrolyte layer which are sequentially arranged at the temperature of 150-300 ℃ for sintering treatment for 10-30min to obtain the composite structure. The preparation method can improve the interface stability of the lithium solid-state battery and reduce the production cost of the lithium solid-state battery.

Description

Composite structure containing lithium cathode, preparation method thereof and solid-state battery
Technical Field
The application relates to the field of batteries, in particular to a composite structure containing a lithium cathode, a preparation method of the composite structure and a solid-state battery.
Background
Lithium ion batteries have the advantages of high energy density, long cycle life, and the like, and are widely used in portable electronic devices and electric vehicles. In recent years, lithium batteries have been developed rapidly, and high energy density and high safety are two important indicators. However, the currently commercialized negative electrode materials of lithium ion batteries are mainly carbon-based materials such as graphite, and have low specific capacity, and cannot meet the requirement of high energy density. And the organic electrolyte used in the traditional lithium ion battery has the characteristics of low boiling point, flammability and volatility, and greatly influences the safety of the battery.
Lithium-containing negative electrodes are the most promising negative electrode materials in the next generation of lithium batteries due to the fact that the lithium-containing negative electrodes are far higher than the theoretical specific capacity and lower potential of the traditional graphite negative electrodes. The solid electrolyte is matched to replace the organic liquid electrolyte, so that the safety problem of lithium ions can be better improved. Among solid electrolytes, oxide solid electrolytes having high room temperature conductivity and a wide electrochemical window have been attracting attention. However, the above-mentioned lithium-containing negative electrode and oxide solid electrolyte have two inevitable problems, one is that the oxide solid electrolyte sheet cannot achieve high density, and on the other hand, the electrolyte sheet and the lithium-containing negative electrode cannot be in close contact to hinder lithium ion conduction, thereby resulting in high interface impedance between the lithium-containing negative electrode and the oxide solid electrolyte sheet.
The density of the oxide solid electrolyte sheet can be improved by hot-pressing sintering, electric field assisted sintering, spark plasma sintering and other techniques. The interface resistance can also be improved by introducing a metal intermediate layer that can form an alloy with the lithium-containing negative electrode. In the preparation of the solid electrolyte, a special sintering mode is used, so that the compactness of the solid electrolyte sheet can be increased, and the number of grain boundaries can be reduced. Meanwhile, a metal intermediate layer is introduced to match with the lithium-containing cathode to form a lithium alloy intermediate layer, so that the interface impedance of the lithium-containing cathode and the solid electrolyte sheet can be improved. However, the above method has the following problems: on the one hand, the equipment requirements and production costs are high, and on the other hand, the lithium-containing negative electrode can generate uncontrollable volume changes in the reaction for generating the lithium alloy, thereby causing the interfacial bonding failure of the lithium-containing negative electrode and the metal intermediate layer.
Disclosure of Invention
The application discloses a composite structure containing a lithium cathode, a preparation method thereof and a solid-state battery, so as to improve the interface stability of the lithium solid-state battery and reduce the production cost of the lithium solid-state battery.
In order to achieve the purpose, the application provides the following technical scheme:
the embodiment of the application provides a preparation method of a composite structure containing a lithium cathode, which comprises the following steps: and (3) placing the lithium-containing negative pole piece, the metal oxide layer and the solid electrolyte layer which are sequentially arranged at the temperature of 150-300 ℃ for sintering treatment for 10-30min to obtain the composite structure.
Further, firstly coating the metal oxide layer on one side surface of the solid electrolyte layer, and then placing the lithium-containing negative pole piece and the solid electrolyte layer coated with the metal oxide layer on one side surface at the temperature of 150-300 ℃ for sintering treatment for 10-30 min; wherein the lithium-containing negative electrode piece is in contact with the metal oxide layer.
Further, the composition of the lithium-containing negative electrode piece comprises at least one of lithium metal, lithium metal transition nitride or lithium metal layered oxide.
Further, the composition of the metal oxide layer includes at least one of indium tin oxide, indium oxide, or aluminum oxide.
Further, the indium tin oxide includes 90 wt% In2O3And 10 wt% SnO2。
Further, the thickness of the metal oxide layer is 10-1000nm, and the thickness of the solid electrolyte layer is 10-1000 μm.
Further, the solid electrolyte layer includes at least one of a garnet-type, NASICON-type, LISICON-type, perovskite-type, or anti-perovskite-type solid electrolyte.
Further, the metal oxide layer is formed on one side surface of the solid electrolyte layer by a sputtering method or a chemical vapor deposition method.
A composite structure comprising a lithium-containing negative electrode, prepared according to the preparation method of the present application.
A solid-state battery includes a composite structure of a positive electrode and a lithium-containing negative electrode of an embodiment of the present application disposed in lamination with the positive electrode.
By adopting the technical scheme of the application, the beneficial effects are as follows:
according to the preparation method of the composite structure of the lithium-containing negative electrode, the metal oxide layer is introduced between the lithium-containing negative electrode and the solid electrolyte layer, and sintering treatment is carried out within the range of 150-300 ℃, so that the metal oxide layer and the lithium-containing negative electrode are subjected to replacement reaction, and the composite intermediate layer containing the metal oxide and the lithium alloy is formed. The formed composite intermediate layer faces to one side of the lithium-containing negative electrode, and the formed lithium oxide and lithium alloy form a firm connection relation with the lithium-containing negative electrode, so that the failure of an interface at the position caused by the expansion of the lithium-containing negative electrode is avoided. In addition, the preparation method can enable the composite intermediate layer to form lithium oxide and lithium alloy, the generated lithium oxide and lithium alloy can be used as a transmission channel of lithium ions in the charging and discharging processes of the battery, and the interface between the composite intermediate layer and the solid electrolyte layer can be well fused to reduce the transmission resistance of the lithium ions. Therefore, the preparation method can improve the interface impedance between the lithium-containing cathode and the solid electrolyte through low-temperature sintering treatment, and avoids the use of a special sintering process to improve the density of the solid electrolyte layer, so that the preparation method has the advantages of simple production process and low production cost.
Drawings
Fig. 1 is a schematic flow chart of a method for manufacturing a solid-state battery according to an embodiment of the present disclosure.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. 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.
It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein as well as preferred features may be combined with each other to form new technical solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percent by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values. The "ranges" disclosed herein may be in the form of lower limits and upper limits, and may be one or more lower limits and one or more upper limits, respectively. In the present application, the individual reactions or process steps may be performed sequentially or in sequence, unless otherwise indicated. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present application.
In a first aspect, embodiments of the present application provide a method for preparing a composite structure including a lithium negative electrode, the method including the steps of: and (3) placing the lithium-containing negative pole piece, the metal oxide layer and the solid electrolyte layer which are sequentially arranged at the temperature of 150-300 ℃ for sintering treatment for 10-30min to obtain the composite structure.
In the embodiment of the present application, the temperature of the sintering process may be, for example, typically but not limited to, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃; the time of the sintering treatment may typically, but not restrictively, be, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30 min.
According to the preparation method of the composite structure of the lithium-containing negative electrode, the metal oxide layer is introduced between the lithium-containing negative electrode and the solid electrolyte layer, and sintering treatment is carried out within the range of 150-300 ℃, so that the metal oxide layer and the lithium-containing negative electrode are subjected to replacement reaction, and the composite intermediate layer containing the metal oxide and the lithium alloy is formed. The formed composite intermediate layer faces to one side of the lithium-containing negative electrode, and the formed lithium oxide and lithium alloy form a firm connection relation with the lithium-containing negative electrode, so that the failure of an interface at the position caused by the expansion of the lithium-containing negative electrode is avoided. In addition, the preparation method can enable the composite intermediate layer to form lithium oxide and lithium alloy, the generated lithium oxide and lithium alloy can be used as a transmission channel of lithium ions in the charging and discharging processes of the battery, and the interface between the composite intermediate layer and the solid electrolyte layer can be well fused to reduce the transmission resistance of the lithium ions. Therefore, the preparation method can improve the interface impedance between the lithium-containing cathode and the solid electrolyte through low-temperature sintering treatment, and avoids the use of a special sintering process to improve the density of the solid electrolyte layer, so that the preparation method has the advantages of simple production process and low production cost.
In addition, by using the preparation method provided by the embodiment of the application, the interface between the lithium-containing negative electrode and the formed composite intermediate layer can be kept in high integrity, and at the moment, even if the solid electrolyte layer with poor compactness prepared by using the traditional sintering process is used, the lithium-containing negative electrode and the solid electrolyte layer can be ensured to be tightly combined. In addition, the formed composite intermediate layer can also effectively limit the reaction of the lithium-containing negative electrode, avoid the volume expansion of the lithium-containing negative electrode and keep the integrity and the uniformity of the interface between the lithium-containing negative electrode and the solid electrolyte layer. The integrality and the homogeneity of interface can make current distribution more even, reduce the polarization, also can reduce to a certain extent the circulation and the puncture risk that produces lithium dendrite in the heavy current charging process, promote lithium ion battery's cycle performance, multiplying power performance and security performance.
In the preparation method of the composite structure of one embodiment of the application, the metal oxide layer is coated on one side surface of the solid electrolyte layer, and then the lithium-containing negative electrode piece and the solid electrolyte layer coated with the metal oxide layer on one side surface are placed at the temperature of 150-300 ℃ for sintering treatment for 10-30 min; wherein the lithium-containing negative electrode piece is in contact with the metal oxide layer.
The metal oxide layer is formed on the surface of the solid electrolyte layer first, so that stable interfacial contact can be formed between the metal oxide layer and the solid electrolyte layer. Then, the lithium-containing cathode and the lithium-containing cathode are sintered and compounded to form a composite interlayer, so that the lithium-containing cathode and the solid electrolyte are tightly combined.
Wherein, a metal oxide layer can be formed on the surface of the solid electrolyte layer by a magnetron sputtering method or a chemical vapor deposition method. The metal oxide layer is formed on the surface of the solid electrolyte layer by utilizing a magnetron sputtering method or a chemical vapor deposition method, so that the connection between the metal oxide layer and the solid electrolyte layer is tighter, the gap of a contact surface can be reduced, and the connection tightness between the metal oxide layer and the solid electrolyte layer is improved.
When the metal oxide layer is prepared by adopting a magnetron sputtering method, the target material uses the metal oxide to be deposited, the sputtering process is carried out under the protection of argon, and parameters such as the sputtering cavity pressure, the sputtering time and the like are determined according to the set thickness of the metal oxide layer.
The composition of the lithium-containing negative electrode piece includes but is not limited to at least one of lithium metal, lithium metal transition nitride or lithium metal layered oxide. The composition of the metal oxide layer includes, but is not limited to, at least one of indium tin oxide, indium oxide, or aluminum oxide.
In one embodiment of the present application, indium tin oxide includes 90 wt% In2O3And 10 wt% SnO2Indium tin oxide is used as a metal oxide layer, and after sintering treatment, the indium tin oxide can perform a replacement reaction with a lithium-containing negative electrode to generate lithium oxide, a lithium indium alloy, a lithium tin alloy and the like.
Indium Tin Oxide (ITO) is a typical N-type oxide semiconductor, is widely applied to transparent conductive films of organic light emitting diodes and solar cells, and generally adopts electron beam evaporation, physical vapor deposition or sputtering deposition technology, and the preparation method and parameters are stable and mature, and the operability is strong. And also can be used as a conductive additive in some researches due to higher conductivity, so the lithium-containing negative electrode sheet is suitable for being used as a metal oxide layer between the lithium-containing negative electrode sheet and the solid electrolyte layer.
By generating the lithium alloy intermediate layer such as lithium indium alloy, lithium tin alloy and the like, the lithium-containing negative pole piece and the solid electrolyte layer are further tightly compounded, and the conduction of lithium ions in the interface layer is enhanced, so that the solid-solid interface which is in forced contact before is improved, and the interface impedance is reduced. In addition, the generated lithium alloy interlayer can also more effectively ensure the integrity and the uniformity of an interface in the battery cycle process, and further improve the cycle performance, the rate capability and the safety performance of the lithium ion battery.
In the production method of the embodiment of the present application, the solid electrolyte layer includes, but is not limited to, at least one of garnet-type, NASICON (sodium super ion conductor) type, LISICON (lithium super ion conductor) type, perovskite-type, or anti-perovskite-type solid electrolytes.
The preparation method of the solid electrolyte layer includes, but is not limited to, the following methods: the solid electrolyte powder is prepared by high-temperature sintering after cold press molding, or by a high-temperature high-pressure sintering method, or by an electric field auxiliary sintering method, or by a discharge plasma sintering method, and the like. The solid electrolyte layer used in the preparation method of the embodiment of the application can be prepared and formed by using a traditional powder tabletting and sintering method, and further the production process and the production cost of the solid electrolyte layer can be effectively reduced.
In one embodiment of the present application, the metal oxide layer has a thickness of 10-1000 nm. The metal oxide layer with the thickness can effectively enable the metal oxide layer to be tightly combined with the lithium-containing cathode so as to form a composite intermediate layer, and also can enable the metal oxide layer to be fully contacted with the solid electrolyte layer so as to form stable interface contact. The thickness of the metal oxide layer may be, for example, 10nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1000 nm.
The thickness of the solid electrolyte layer is 10-1000 μm. After the solid electrolyte layer with the thickness is pressed with the metal oxide layer, an effective and stable interface can be formed with the metal oxide layer, and the problem of interface separation is prevented. The thickness of the metal oxide layer may be, for example, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, 500 μm, 700 μm, 800 μm, 900 μm, or 1000 μm.
In a second aspect, embodiments of the present application provide a composite structure of a lithium-containing negative electrode, which is obtained by using the preparation method of the first aspect of the present application.
The composite structure of the lithium-containing cathode comprises the lithium-containing cathode, a composite intermediate layer and a solid electrolyte layer which are sequentially arranged, wherein the composite intermediate layer comprises metal oxide and lithium alloy. Among them, a lithium alloy is used to enhance the performance of transporting lithium ions, and a metal oxide is used to restrict the volume expansion of a lithium-containing metal and the volume expansion when forming a lithium alloy, thereby providing the composite structure with excellent interface stability and integrity. The solid-state battery assembled by the composite structure has better safety and cycling stability.
In a third aspect, embodiments of the present application provide a solid-state battery comprising a composite structure comprising a lithium-containing negative electrode of the second aspect of the present application. In addition, the solid-state battery of the embodiment of the present application further includes a positive electrode. Since the solid-state battery includes the composite structure including the lithium-containing negative electrode of the second aspect of the present application, the solid-state battery of the embodiment of the present application has all the advantages of the composite structure of the embodiment of the present application, and details thereof are not described herein again.
The positive electrode comprises a positive electrode piece and a positive electrode material arranged on the surface of the positive electrode piece, wherein the positive electrode material comprises but is not limited to at least one of lithium cobaltate, lithium manganate, lithium iron phosphate and lithium nickel cobalt manganese.
The composite structure of the lithium-containing negative electrode of the present application will be described in further detail with reference to examples.
Example 1
This embodiment is a method for manufacturing a solid-state battery, as shown in fig. 1, including the steps of:
s1) preparation of LLZTO solid electrolyte layer:
preparing a precursor of LLZTO by conventional solid phase reaction method, sintering the precursor at 950 deg.C for 12h, and adding Al2O3The powder was nodular to give the final desired LLZTO powder. The powder is pressed into a sheet shape and then sintered in a muffle furnace at 1140 ℃ for 12 hours. And grinding and polishing the sintered electrolyte sheet, and storing the electrolyte sheet in a glove box in an Ar atmosphere for later use.
Wherein LLZTO is Ta-doped LLZO (cubic garnet type Li)7La3Zr2O12)。
S2) preparing a metal oxide layer:
depositing an Indium Tin Oxide (ITO) thin film layer on the surface of the milled and polished LLZTO solid electrolyte layer by a magnetron sputtering method; wherein the target material is ITO (90 wt% In)2O3，10wt％SnO2) The sputtering process is carried out in the Ar gas protective atmosphere, the sputtering time is about 2min, and the thickness of the obtained Indium Tin Oxide (ITO) layer is about 40 nm.
S3) preparation of a lithium-containing negative electrode composite structure:
and (3) placing the LLZTO solid electrolyte layer coated with the Indium Tin Oxide (ITO) thin film layer and a metal lithium sheet together, sintering at 200 ℃ for 15min, and naturally cooling to obtain the composite structure of the cathode metal lithium and the solid electrolyte layer.
S4) preparation of solid-state battery
Lithium iron phosphate (LiFePO) coated with graphite4) The anode used as the anode material and the prepared composite structure are stacked, wherein the lithium iron phosphate of the anode is arranged in contact with the solid electrolyte layer; the stack was then placed on a punch and punched to obtain a solid-state battery.
Example 2
This example is a method for manufacturing a solid-state battery, and the method for manufacturing this example is different from example 1 in that the temperature in the sintering treatment in step S3) of this example is 160 ℃, and is otherwise the same as example 1.
Example 3
This example is a method for manufacturing a solid-state battery, and the method for manufacturing this example is different from example 1 in that the temperature in the sintering treatment in step S3) of this example is 270 ℃, and is otherwise the same as example 1.
Comparative example 1
This comparative example is a method for manufacturing a solid-state battery, and the method for manufacturing this example is different from example 1 in that the temperature in the sintering process in step S3) of this comparative example is 100 ℃, and is otherwise the same as example 1.
Comparative example 2
This comparative example is a method for manufacturing a solid-state battery, and the manufacturing method of this example is different from that of example 1 in that the temperature in the sintering process in step S3) of this comparative example is 350 ℃, and is otherwise the same as example 1.
Comparative example 3
The comparative example is a method of manufacturing a solid-state battery, comprising the steps of:
s1) preparation of LLZTO solid electrolyte layer:
preparing a precursor of LLZTO by a traditional solid phase reaction method, sintering the precursor at 950 ℃ for 12h, and adding Al2O3The powder was nodular to give the final desired LLZTO powder. The powder is pressed into a sheet shape and then sintered in a muffle furnace at 1140 ℃ for 12 hours. And grinding and polishing the sintered electrolyte sheet, and storing the electrolyte sheet in a glove box in an Ar atmosphere for later use.
Wherein LLZTO is Ta-doped LLZO (cubic garnet type Li)7La3Zr2O12)。
S2) preparation of metal layer:
depositing a metal tin film layer on the surface of the milled and polished LLZTO solid electrolyte layer by a magnetron sputtering method; the target material is made of metal Sn, the sputtering process is carried out in an Ar gas protection atmosphere, the sputtering time is about 2min, and the thickness of the obtained metal Sn layer is about 40 nm.
S3) preparation of a lithium-containing negative electrode composite structure:
and (3) placing the LLZTO solid electrolyte layer coated with the metal Sn film layer and a metal lithium sheet together, sintering at 200 ℃ for 15min, and naturally cooling to obtain the composite structure of the negative electrode metal lithium and the solid electrolyte layer.
S4) preparation of solid-state battery
Lithium iron phosphate (LiFePO) coated with graphite4) The anode used as the anode material and the prepared composite structure are stacked, wherein the lithium iron phosphate of the anode is arranged in contact with the solid electrolyte layer; the stack was then placed on a punch and punched to obtain a solid-state battery.
Example 4
The embodiment of the application relates to a preparation method of a solid-state battery, which comprises the following steps:
s1) preparation of LLZTO solid electrolyte layer:
preparing a precursor of LLZTO by a traditional solid phase reaction method, sintering the precursor at 950 ℃ for 12h, and adding Al2O3The powder was nodular to give the final desired LLZTO powder. The powder is pressed into a sheet shape and then sintered in a muffle furnace at 1140 ℃ for 12 hours. And grinding and polishing the sintered electrolyte sheet, and storing the electrolyte sheet in a glove box in an Ar atmosphere for later use.
Wherein LLZTO is Ta-doped LLZO (cubic garnet type Li)7La3Zr2O12)。
S2) preparing a metal oxide layer:
depositing an Indium Tin Oxide (ITO) thin film layer on the surface of the milled and polished LLZTO solid electrolyte layer by a magnetron sputtering method; wherein the target material is ITO (90 wt% In)2O3，10wt％SnO2) The sputtering process is carried out in the Ar gas protective atmosphere, the sputtering time is about 2min, and the thickness of the obtained Indium Tin Oxide (ITO) layer is about 40 nm.
S3) preparation of a lithium-containing negative electrode composite structure:
and (3) placing the LLZTO solid electrolyte layer coated with the Indium Tin Oxide (ITO) thin film layer and a metal lithium sheet together, sintering at 200 ℃ for 15min, and naturally cooling to obtain the composite structure of the cathode metal lithium and the solid electrolyte layer.
S4) preparation of solid-state battery
Stacking and placing a ternary material (NCM523) containing lithium, nickel and manganese cobalt as a positive electrode of a positive electrode material, wherein the ternary material (NCM523) containing lithium, nickel and manganese cobalt of the positive electrode is in contact with the solid electrolyte layer; the stack was then placed on a punch and punched to obtain a solid-state battery.
Comparative example 4
This comparative example is a method of manufacturing a solid-state battery, and the manufacturing method of this example is different from that of comparative example 3 in that the cathode material used in this comparative example is a ternary material of lithium nickel cobalt manganese (NCM523), and the others are the same as those of comparative example 3.
The solid-state battery rate performance and the cycle stability of examples 1 to 4 and comparative examples 1 to 4 were respectively tested, and the results are shown in table 1. The test method of the multiplying power performance comprises the steps of charging to 4.0V of upper limit voltage by using a 0.2C constant current and discharging to 2.5V of lower limit voltage by using 0.2C and 1C constant current. The testing method of the cycling stability comprises the following steps: the environmental temperature is 30 ℃, the circulating current is 0.2C, the circulating voltage interval is 2.5-4.0V, and the capacity retention rate is calculated.
TABLE 1
Figure BDA0002875618380000111
As can be seen from the data in table 1, when the sintering temperatures of the lithium-containing negative electrode tab, the metal oxide layer, and the solid electrolyte layer are not within the ranges defined in the present application, the rate performance and the cycle stability of the solid-state battery are significantly reduced in examples 1 to 3 as compared with the data of comparative examples 1 to 2. As can be seen from the data of examples 1 and 4 and comparative examples 3 and 4, when the metal oxide layer in the lithium-containing negative electrode composite structure is replaced with a metal layer, the rate performance and cycle stability of the resulting solid-state battery are also significantly reduced. Therefore, the solid-state battery provided by the embodiment of the application has high rate performance and good cycling stability.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.

Claims (10)

1. A method for preparing a composite structure containing a lithium negative electrode is characterized by comprising the following steps:
and (3) placing the lithium-containing negative pole piece, the metal oxide layer and the solid electrolyte layer which are sequentially arranged at the temperature of 150-300 ℃ for sintering treatment for 10-30min to obtain the composite structure.
2. The method as claimed in claim 1, wherein the metal oxide layer is coated on one side of the solid electrolyte layer, and then the lithium-containing negative electrode plate and the solid electrolyte layer coated with the metal oxide layer on one side are sintered at 300 ℃ for 10-30 min; wherein the lithium-containing negative electrode piece is in contact with the metal oxide layer.
3. The production method according to claim 1 or 2, wherein the composition of the lithium-containing negative electrode sheet includes at least one of lithium metal, lithium metal transition nitride, or lithium metal layered oxide.
4. The production method according to claim 1 or 2, wherein the composition of the metal oxide layer includes at least one of indium tin oxide, indium oxide, or aluminum oxide.
5. The method of claim 4, wherein the indium tin oxide comprises 90 wt% In2O3And 10 wt% SnO2。
6. The production method according to claim 1 or 2, wherein the thickness of the metal oxide layer is 10 to 1000nm, and the thickness of the solid electrolyte layer is 10 to 1000 μm.
7. The production method according to claim 1 or 2, wherein the solid electrolyte layer includes at least one of a garnet-type, NASICON-type, LISICON-type, perovskite-type, or anti-perovskite-type solid electrolyte.
8. The production method according to claim 1 or 2, wherein the metal oxide layer is formed on one side surface of the solid electrolyte layer by a sputtering method or a chemical vapor deposition method.
9. A lithium-containing negative electrode composite structure, characterized by being produced by the production method according to any one of claims 1 to 8.
10. A solid-state battery comprising a composite structure of a positive electrode and the lithium-containing negative electrode of claim 9 provided in a stack with the positive electrode.
CN202011618878.3A 2020-12-31 2020-12-31 Composite structure containing lithium cathode, preparation method thereof and solid-state battery Pending CN112838217A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156532A (en) * 2021-11-29 2022-03-08 北京理工大学 Multilayer composite solid electrolyte and preparation method thereof
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery
CN115513538A (en) * 2021-06-07 2022-12-23 山东大学 Flexible buffer layer for solid-state lithium metal battery and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108110217A (en) * 2017-12-19 2018-06-01 成都亦道科技合伙企业（有限合伙） A kind of solid state lithium battery composite negative pole and preparation method thereof
CN108550859A (en) * 2018-05-21 2018-09-18 珠海光宇电池有限公司 Porous current collector and preparation method thereof and lithium battery
CN109921097A (en) * 2019-03-21 2019-06-21 中国科学院上海微***与信息技术研究所 A kind of preparation method of all-solid-state battery and thus obtained all-solid-state battery
CN109935825A (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 battery structure and preparation method thereof
CN111435756A (en) * 2019-12-27 2020-07-21 蜂巢能源科技有限公司 Lithium battery and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108110217A (en) * 2017-12-19 2018-06-01 成都亦道科技合伙企业（有限合伙） A kind of solid state lithium battery composite negative pole and preparation method thereof
CN109935825A (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 battery structure and preparation method thereof
CN108550859A (en) * 2018-05-21 2018-09-18 珠海光宇电池有限公司 Porous current collector and preparation method thereof and lithium battery
CN109921097A (en) * 2019-03-21 2019-06-21 中国科学院上海微***与信息技术研究所 A kind of preparation method of all-solid-state battery and thus obtained all-solid-state battery
CN111435756A (en) * 2019-12-27 2020-07-21 蜂巢能源科技有限公司 Lithium battery and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115513538A (en) * 2021-06-07 2022-12-23 山东大学 Flexible buffer layer for solid-state lithium metal battery and preparation method and application thereof
CN115513538B (en) * 2021-06-07 2024-04-30 山东大学 Flexible buffer layer for solid lithium metal battery and preparation method and application thereof
CN114156532A (en) * 2021-11-29 2022-03-08 北京理工大学 Multilayer composite solid electrolyte and preparation method thereof
CN114156532B (en) * 2021-11-29 2024-02-06 北京理工大学 Multilayer composite solid electrolyte and preparation method thereof
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery
CN114914422B (en) * 2022-05-19 2024-03-15 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery

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