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CN113659195A - Composite film, preparation method thereof and solid-state lithium battery - Google Patents

Composite film, preparation method thereof and solid-state lithium battery Download PDF

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Publication number
CN113659195A
CN113659195A CN202110751994.0A CN202110751994A CN113659195A CN 113659195 A CN113659195 A CN 113659195A CN 202110751994 A CN202110751994 A CN 202110751994A CN 113659195 A CN113659195 A CN 113659195A
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solid electrolyte
layer
lithium ion
composite film
solid
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胡欣超
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Evergrande New Energy Technology Shenzhen Co Ltd
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Evergrande New Energy Technology Shenzhen Co Ltd
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

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Abstract

The invention relates to the technical field of solid-state lithium batteries, and provides a composite film, a preparation method thereof and a solid-state lithium battery. The composite film comprises a main body functional layer and an interface protective layer combined on at least one side surface of the main body functional layer, wherein the main body functional layer is a solid electrolyte main body layer or a negative plate, and the interface protective layer is made of an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃. The composite film provided by the invention can effectively improve the interface stability between the solid electrolyte and the negative electrode, and protect the solid electrolyte from being reduced when the solid electrolyte is contacted with the negative electrode, particularly the negative electrode of lithium, so that the solid electrolyte can keep better lithium ion conductivity. In addition, the influence on the lithium ion conductivity of the solid electrolyte can be reduced.

Description

Composite film, preparation method thereof and solid-state lithium battery
Technical Field
The application belongs to the technical field of solid-state lithium batteries, and particularly relates to a composite film and a preparation method thereof, and a solid-state lithium battery.
Background
The lithium secondary battery is a clean and efficient energy storage device and plays a significant role in the field of energy storage. Since commercialization, lithium secondary batteries have rapidly occupied the market in the field of energy storage due to their advantages of high energy density, long cycle life, no memory effect, and the like. However, the existing commercial lithium ion battery takes toxic and flammable organic liquid electrolyte as electrolyte, and potential safety hazards such as liquid leakage, fire and the like are easily caused. The non-toxic and non-flammable inorganic solid electrolyte replaces liquid electrolyte, so that the safety problem can be effectively improved, the lithium metal cathode can be safely used, and the energy density of a lithium battery system is greatly improved. Therefore, the preparation and development of inorganic solid electrolytes are receiving extensive attention from researchers.
The solid-state lithium battery system composed of the inorganic solid electrolyte and the lithium metal negative electrode has a remarkable advantage in energy density, but many inorganic solid electrolytes are difficult to stably exist with lithium metal. Such as Li of the NASICON (sodium super ion conductor) type1+ yAlyTi2-y(PO4)3(LATP) or Li1+zAlzGe2-z(PO4)3(LAGP) with a higher total ionic conductivity at room temperature (>10- 4S/cm) and room temperature grain conductivity (>10-3S/cm) and has good stability to both water and air, but high valence state of Ti4+With Ge4+The lithium ion conductive electrolyte is easy to be reduced by a lithium metal negative electrode, so that the ionic conductivity of the electrolyte is greatly reduced, and the electrochemical performance of the battery is seriously influenced. Perovskite type electrolytes such as Li0.34La0.56TiO3The high valence Ti element in (LLTO) has a similar problem to LATP. The prior art methods of protecting solid electrolytes reduce the lithium ion conductivity of the solid electrolyte.
Disclosure of Invention
The invention aims to provide a composite film, a preparation method thereof and a solid-state lithium battery, and aims to solve the problem that the lithium ion conductivity of a solid-state electrolyte is reduced by the conventional method for protecting the solid-state electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a composite film, which comprises a main body functional layer and an interface protective layer combined on at least one side surface of the main body functional layer, wherein the main body functional layer is a solid electrolyte main body layer or a negative plate, and the material of the interface protective layer is an inorganic lithium ion conductor material with the melting point less than or equal to 700 ℃.
According to the composite film provided by the invention, the interface protective layer is arranged on at least one side surface of the solid electrolyte main body layer or the negative plate, so that the interface stability between the solid electrolyte and the negative electrode can be effectively improved, the solid electrolyte and the negative electrode are protected from being reduced particularly when being contacted with a lithium negative electrode, and the solid electrolyte can keep better lithium ion conductivity. More importantly, the inventor finds that the interface protection layer needs to be subjected to heat treatment when being applied to the surface of the solid electrolyte bulk layer, and the conventional heat treatment can cause a large number of side reactions, and researches show that the melting point of the material of the interface protection layer is less than or equal to 700 ℃, so that the inorganic lithium ion conductor material can be subjected to heat treatment under the low-temperature condition of less than or equal to 700 ℃, the risk of side reactions between the inorganic lithium ion conductor material and the solid electrolyte under the high-temperature condition is reduced, and the lithium ion conductivity of the solid electrolyte is further ensured.
In one embodiment of the composite thin film of the present invention, the inorganic lithium ion conductor material is selected from materials having a lithium ion conductivity of 1 × 10 or more-9S cm-1Preferably, the lithium ion conductivity is 1X 10 or more-7S cm-1The inorganic material of (1). In this case, the inorganic lithium ion conductor material has good lithium ion transport ability, so that the influence of the interface protective layer on the lithium ion transport ability of the solid electrolyte can be reduced, and the lithium ion transport ability of the solid electrolyte can be ensured. Meanwhile, the lithium ion can be prevented from being deposited in the electrolyte to influence the performance of the electrolyte.
In one embodiment of the composite thin film of the present invention, the melting point is 700 ℃ or lower, and the lithium ion conductivity is 1 × 10 or higher-7S cm-1The inorganic lithium ion conductor material of (b) may be selected from Li1+xBxC1-xO3Wherein x satisfies: x is more than 0.2 and less than 0.4. The inorganic lithium ion conductor material can be used as an interface protection layer material of a solid electrolyte main body layer or a negative plate and can be arranged between the solid electrolyte main body layer and the negative plateThe stability of the interface between the solid electrolyte and the negative electrode is effectively improved, and the influence on the lithium ion conductivity of the solid electrolyte is reduced.
In one embodiment of the composite film of the present invention, the thickness of the interface protection layer is 15 to 60 μm. Within this thickness range, the interface protective layer can improve the interface stability between the solid electrolyte and the negative electrode and reduce the influence on the lithium ion conductivity of the solid electrolyte. If the thickness of the interface protection layer is small, the above effect is not significant. Although the material of the interface protection layer has a certain lithium ion conductivity and can reduce the lithium ion conduction effect of the electrolyte, when the thickness of the interface protection layer is too thick, the influence of the interface protection layer on the lithium ion conduction effect is amplified, and the ion conductivity of the electrolyte layer is reduced.
As an embodiment of the composite thin film of the present invention, the material of the solid electrolyte host layer is selected from the group consisting of materials having an electron conductivity of 1X 10 or less-9S cm-1And an ionic conductivity of 1X 10 or more-4S cm-1Preferably, at least one of LATP, LAGP and LLTO is used. The solid electrolytes such as LATP, LAGP, LLTO and the like have excellent lithium ion conductivity, and after an interface protective layer is formed on the surface of the solid electrolyte, the reduction of the negative electrode, particularly a lithium negative electrode, to the electrolyte can be avoided, so that the stability of the solid electrolyte to the negative electrode, particularly lithium metal, is improved; meanwhile, the interface protection layer has small influence on the ion transmission performance of the electrolyte, so that the ion conductivity of the solid electrolyte is ensured.
In one embodiment of the composite film of the present invention, the thickness of the solid electrolyte main body layer is 100 to 300 μm. The thickness of the solid electrolyte main body layer is within the range, and the solid electrolyte main body layer has better ion transmission performance.
As an embodiment of the composite film of the present invention, the material of the solid electrolyte host layer is at least one selected from LATP, LAGP and LLTO, and the thickness of the solid electrolyte host layer is 100 to 300 μm.
As an embodiment of the composite film of the present invention, the negative electrode sheet is a lithium negative electrode. When the negative plate is a lithium negative electrode, the interface modification layer is arranged between the negative electrode of the solid-state battery and the solid-state electrolyte, and the interface modification layer on the surface of the negative plate can avoid the reduction of the lithium negative electrode to the solid-state electrolyte and improve the ion transmission performance of the solid-state electrolyte.
The second aspect of the present invention provides a method for preparing a composite film, comprising the steps of:
providing a main body function layer, wherein the main body function layer is a solid electrolyte main body layer or a negative plate; dispersing an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃ in a solvent to obtain inorganic lithium ion conductor material dispersion liquid;
and forming the inorganic lithium ion conductor material dispersion liquid on at least one side surface of the main body functional layer to obtain an inorganic lithium ion conductor material prefabricated layer, and carrying out first sintering treatment on the inorganic lithium ion conductor material prefabricated layer to obtain the interface protective layer.
According to the preparation method of the composite film, the low-melting-point lithium ion conductor material is co-sintered with the solid electrolyte or the negative plate, and the lithium ion conductor material forms a thin and tightly contacted protective layer on the surface of the solid electrolyte or the negative plate. When the composite film is used for a solid-state battery, the interface protective layer is positioned between the negative electrode and the solid-state electrolyte, and the solid-state electrolyte is protected from being reduced and losing the lithium ion conduction capability when contacting with the negative electrode, particularly a lithium negative electrode. Since the lithium ion conductor material has lithium ion conductivity and a low melting point, the influence on the lithium ion conductivity of the solid electrolyte can be reduced.
As an embodiment of the preparation method of the composite film, the temperature of the first sintering treatment is 500-700 ℃, and the heat preservation time is 1-3 h. Under the conditions of the sintering treatment, the lithium ion conductor material melts and forms a thin and closely contacted protective layer on the surface of the solid electrolyte or negative electrode sheet. If the temperature of the first sintering treatment is too low, the lithium ion conductor material is not melted enough to form an interface protective layer; if the temperature of the first sintering treatment is too high, the lithium ion conductor material itself undergoes a side reaction to generate another substance, which degrades the performance of the interface protective layer.
In one embodiment of the method for preparing the composite film of the present invention, the inorganic lithium ion conductor material has a median particle size D50 of 0.5 to 1 μm. In this case, the formed interface protection layer is dense and has high ionic conductivity.
As an embodiment of the preparation method of the composite film, the concentration of the inorganic lithium ion conductor material dispersion liquid is 0.1-1 g/mL, and the thickness of the inorganic lithium ion conductor material prefabricated layer is 50-100 μm. The interface protection layer formed in the case is compact and has a proper thickness, and when the interface protection layer is used for an interface layer between the solid electrolyte and the negative electrode of the solid-state battery, the solid electrolyte can be effectively protected from being reduced to lose lithium ion conductivity when being in contact with the negative electrode, particularly a lithium negative electrode, and the influence on the lithium ion transmission performance of the solid electrolyte is reduced.
As an embodiment of the method for producing a composite thin film of the present invention, the host functional layer is a solid electrolyte host layer, and the method for producing the solid electrolyte host layer is: and tabletting the solid electrolyte, and then carrying out second sintering treatment to obtain the solid electrolyte main body layer. By this method, a dense solid electrolyte bulk layer can be formed.
As an embodiment of the preparation method of the composite film, the tabletting is carried out under the condition of the pressure of 100-200 MPa. And tabletting is carried out under the pressure, so that a solid electrolyte main body layer with high density can be obtained.
As an embodiment of the preparation method of the composite film, the temperature of the second sintering is 800-1000 ℃, and the heat preservation time is 0.5-4 h. Performing the second sintering treatment in the above temperature range can obtain a solid electrolyte bulk layer having increased hardness and being dense, thereby improving the electrical conductivity of the solid electrolyte bulk layer. If the temperature of the second sintering treatment is too high, the solid electrolyte is easily decomposed or side reactions occur.
As an embodiment of the preparation method of the composite film of the present invention, the median particle size D50 of the solid electrolyte is 100nm to 1 μm, which is advantageous for obtaining a dense solid electrolyte bulk layer.
As an embodiment of the preparation method of the composite film, the tabletting is carried out under the condition of the pressure of 100-200 MPa, the temperature of the second sintering is 800-1000 ℃, the heat preservation time is 0.5-4 h, and the median particle size D50 of the solid electrolyte is 100 nm-1 μm.
In a third aspect, the present invention provides an all-solid-state lithium battery, including the composite film according to the first aspect or the composite film prepared by the method according to the second aspect, and an interface protection layer of the composite film is located between a negative electrode and a solid electrolyte.
According to the all-solid-state lithium battery provided by the invention, the composite film of the first aspect of the invention or the composite film prepared by the method of the second aspect of the invention is contained, and the interface protective layer is positioned between the negative electrode and the solid electrolyte, so that the solid electrolyte is protected from being reduced and losing the lithium ion conduction capability when being contacted with the negative electrode, particularly the lithium negative electrode; in addition, the lithium ion conductor material has lithium ion conductivity and low melting point, and can reduce the influence on the lithium ion conductivity of the solid electrolyte, thereby ensuring the lithium ion conductivity of the solid electrolyte to the maximum extent.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is an EIS diagram of a lithium solid state battery a3 provided in an embodiment of the present application;
fig. 2 is an EIS diagram of the solid lithium battery D1 provided in comparative example 1;
fig. 3 is a charge-discharge curve diagram of a solid-state lithium battery a3 provided in the embodiments of the present application;
fig. 4 is a charge-discharge graph of the solid lithium battery D1 provided in comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The term "EIS" is an abbreviation for "Electrochemical Impedance Spectroscopy" and refers to Electrochemical Impedance Spectroscopy.
The interface modification between the electrode and the electrolyte can effectively improve the interface stability between the solid electrolyte and the negative electrode, particularly the lithium negative electrode. In view of the above, embodiments of the present disclosure provide a composite film, which can improve the interface stability between a solid electrolyte and a negative electrode, particularly a lithium negative electrode, by forming an interface protection layer on at least one side surface of the solid electrolyte or the negative electrode.
In a first aspect, an embodiment of the present application provides a composite film, including a host functional layer, and an interface protection layer bonded to at least one side surface of the host functional layer, where the host functional layer is a solid electrolyte host layer or a negative electrode sheet, and the interface protection layer is made of an inorganic lithium ion conductor material having a melting point of less than or equal to 700 ℃.
According to the composite film provided by the embodiment of the application, the interface protection layer is arranged on at least one side surface of the solid electrolyte main body layer or the negative plate, so that the interface stability between the solid electrolyte and the negative electrode can be effectively improved, the solid electrolyte and the negative electrode are protected from being reduced particularly when being in contact with a lithium negative electrode, and the solid electrolyte can keep better lithium ion conductivity. The material of the interface protection layer has certain ionic conductivity, so that the uniform distribution of ions such as lithium ions is obviously improved, the growth of dendritic crystals is effectively inhibited, and the method has important significance for the practical application of the all-solid-state lithium metal battery; more importantly, the inventor finds that the interface protection layer needs to be subjected to heat treatment when being applied to the surface of the solid electrolyte bulk layer, and the conventional heat treatment can cause a large number of side reactions, and researches show that the melting point of the material of the interface protection layer is less than or equal to 700 ℃, so that the inorganic lithium ion conductor material can be subjected to heat treatment under the low-temperature condition of less than or equal to 700 ℃, the risk of side reactions between the inorganic lithium ion conductor material and the solid electrolyte under the high-temperature condition is reduced, and the lithium ion conductivity of the solid electrolyte is further ensured.
The composite film provided by the embodiment of the application can be divided into two implementation situations according to the type of the main body functional layer.
In the first embodiment, the composite film is a composite film formed by a solid electrolyte and an interface protective layer, and the interface protective layer is used for avoiding the direct contact between the solid electrolyte and the negative electrode, particularly the lithium negative electrode, and avoiding the reduction of the negative electrode, particularly the lithium negative electrode, on the solid electrolyte. In some embodiments, an interfacial protection layer is formed on one side surface of the solid electrolyte bulk layer for avoiding direct contact of the solid electrolyte with the negative electrode, particularly a lithium negative electrode. In some embodiments, both side surfaces of the solid electrolyte body layer form an interface protection layer.
In the embodiment of the present application, the solid electrolyte in the solid electrolyte bulk layer may be a common solid electrolyte. In some embodiments, the material of the solid electrolyte host layer is selected from the group consisting of electronic conductivities less than or equal to 1 x 10-9S cm-1And an ionic conductivity of 1X 10 or more-4S cm-1Preferably, at least one of LATP, LAGP and LLTO is used. Solid electrolytes such as LATP, LAGP, LLTO and the like have excellent lithium ion conductivity, but the materials are easily reduced by a lithium metal negative electrode to greatly reduce the ionic conductivity of the electrolyte, so that the electrochemical performance of the battery is seriously influenced. By forming an interface protective layer on the surface of the solid electrolyte, the reduction of the electrolyte by the negative electrode, particularly the lithium negative electrode, can be avoided, and the stability of the solid electrolyte to the negative electrode, particularly lithium metal, is improved. Meanwhile, the interface protection layer has little influence on the lithium ion transport performance of LATP, LAGP and LLTO, thereby ensuring the lithium ion conductivity of the solid electrolyte such as LATP, LAGP and LLTO which the negative electrode, particularly the lithium negative electrode is easily reduced.
In some embodiments, the thickness of the solid electrolyte bulk layer is 100 to 300 μm. The thickness of the solid electrolyte main body layer is within the range, and the solid electrolyte main body layer has better ion transmission performance. Illustratively, the thickness of the solid electrolyte bulk layer may be 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, 300 μm, and the like, as specific thicknesses.
In some embodiments, the material of the solid electrolyte host layer is selected from at least one of LATP, LAGP and LLTO, and the thickness of the solid electrolyte host layer is 100-300 μm, so that the solid electrolyte host layer can exert excellent lithium ion conductivity, and the electrochemical performance of the solid battery can be improved.
In the second embodiment, the composite film is formed by the negative electrode sheet and the interface protection layer, and the interface protection layer is used for preventing the solid electrolyte from being in direct contact with the negative electrode, particularly the lithium negative electrode, and preventing the negative electrode, particularly the lithium negative electrode, from reducing the solid electrolyte. In some embodiments, an interface protection layer is formed on one side surface of the negative electrode sheet for avoiding direct contact of the solid electrolyte with the negative electrode, particularly a lithium negative electrode. In some embodiments, the interface protection layer is formed on both side surfaces of the negative electrode sheet.
In the embodiment of the present application, a common negative electrode sheet may be used as the negative electrode sheet. In some embodiments, the negative electrode sheet is a lithium negative electrode. When the negative plate is a lithium negative electrode, the interface modification layer arranged on the surface of the lithium negative electrode can block the direct contact between the solid-state battery negative electrode and the solid-state electrolyte, so that the reduction of the lithium negative electrode to the solid-state electrolyte is avoided, and the ion transmission performance of the solid-state electrolyte can be ensured.
In the two implementation cases, the material for constructing the interface protection layer is an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃. On one hand, the material of the interface protection layer has certain ionic conductivity, so that the uniform distribution of ions such as lithium ions is obviously improved, the growth of dendritic crystals is effectively inhibited, and the method has important significance for the practical application of the all-solid-state lithium metal battery; on the other hand, the melting point of the material of the interface protection layer is less than or equal to 700 ℃, so that the inorganic lithium ion conductor material can be subjected to heat treatment under the low-temperature condition of less than or equal to 700 ℃, the risk of side reaction between the inorganic lithium ion conductor material and the solid electrolyte under the high-temperature condition is reduced, and the lithium ion conductivity of the solid electrolyte is further ensured.
In some embodiments, the inorganic lithium ion conductor material is selected from lithium ion conductivityGreater than or equal to 1 × 10-9S cm-1Preferably, the lithium ion conductivity is 1X 10 or more-7S cm-1The inorganic material of (1). In this case, the inorganic lithium ion conductor material has good lithium ion transport ability, so that the influence of the interface protective layer on the lithium ion transport ability of the solid electrolyte can be reduced, and the lithium ion transport ability of the solid electrolyte can be ensured. Meanwhile, the lithium ion can be prevented from being deposited in the electrolyte to influence the performance of the electrolyte.
In some embodiments, the inorganic lithium ion conductor material is selected from Li1+xBxC1-xO3Wherein x satisfies: x is more than 0.2 and less than 0.4. The inorganic lithium ion conductor material can be arranged between the solid electrolyte main body layer and the negative plate as an interface protection layer material of the solid electrolyte main body layer or the negative plate, so that the interface stability between the solid electrolyte and the negative electrode is effectively improved, and the influence on the lithium ion conductivity of the solid electrolyte is reduced.
In some embodiments, the thickness of the interface protection layer is 15 to 60 μm. Within this thickness range, the interface protective layer can improve the interface stability between the solid electrolyte and the negative electrode and reduce the influence on the lithium ion conductivity of the solid electrolyte. If the thickness of the interface protection layer is small, the above effect is not significant. Although the material of the interface protection layer has a certain lithium ion conductivity and can reduce the lithium ion conduction effect of the electrolyte, when the thickness of the interface protection layer is too thick, the influence of the interface protection layer on the lithium ion conduction effect is amplified, and the ion conductivity of the electrolyte layer is reduced. Illustratively, the thickness of the interface protection layer may be a specific thickness of 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, or the like.
The composite film provided by the embodiment of the application can be prepared by the following method.
In a second aspect, an embodiment of the present application provides a method for preparing a composite film, including the following steps:
s01, providing a main body functional layer, wherein the main body functional layer is a solid electrolyte main body layer or a negative plate; dispersing an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃ in a solvent to obtain an inorganic lithium ion conductor material dispersion liquid.
In this step, the selection of the inorganic lithium ion conductor material having a melting point of 700 ℃ or less and the effect thereof are as described above, and will not be described herein for brevity.
In the embodiment of the application, an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃ is dispersed in a solvent to obtain an inorganic lithium ion conductor material dispersion liquid, and then an interface protection layer is prepared.
In the embodiment of the present application, the inorganic lithium ion conductor material is preferably a nanoscale material. In some embodiments, the inorganic lithium ion conductor material has a median particle size D50 of 0.5 to 1 μm. The particle size of the inorganic lithium ion conductor material is in the range, the formed interface protective layer is compact, and the ion conductivity is relatively high. If the median particle size D50 of the inorganic lithium ion conductor material is too high, the obtained interface protection layer has insufficient compactness and relatively low ionic conductivity, and thus, when the inorganic lithium ion conductor material is arranged between the negative electrode of the solid-state battery and the solid-state electrolyte, the ion transmission performance is affected.
The embodiment of the application is used for dissolving the dispersed inorganic lithium ion conductor material, and a solvent with certain solubility to the inorganic lithium ion conductor material can be selected. In some embodiments, the solvent is selected from at least one of ethanol, N-methylpyrrolidone, deionized water, isopropanol. The solvent has good dispersion performance on the inorganic lithium ion conductor material.
In some embodiments, the uniformity of dispersion of the bulk inorganic lithium ion conductor material in the solvent can be improved by ultrasonic dispersion.
In some embodiments, the inorganic lithium ion conductor material dispersion has a concentration of 0.1 to 1 g/mL. The interface protection layer formed in the case is compact and has a proper thickness, and when the interface protection layer is used for an interface layer between the solid electrolyte and the negative electrode of the solid-state battery, the solid electrolyte can be effectively protected from being reduced to lose lithium ion conductivity when being in contact with the negative electrode, particularly a lithium negative electrode, and the influence on the lithium ion transmission performance of the solid electrolyte is reduced. Illustratively, the concentration of the dispersion of inorganic lithium ion conductor material can be 0.1g/mL, 0.2g/mL, 0.3g/mL, 0.4g/mL, 0.5g/mL, 0.6g/mL, 0.7g/mL, 0.8g/mL, 0.9g/mL, 1g/mL, and the like.
In the embodiment of the application, the main functional layer for forming the interface protection layer includes two implementation cases. In a first embodiment, the host functional layer is a solid electrolyte host layer. At this time, the interface protective layer is formed directly on the surface of the solid electrolyte bulk layer for isolating the negative electrode, particularly the lithium negative electrode, from the solid electrolyte bulk layer. In a second implementation case, the host functional layer is a negative plate. At this time, the interface protection layer is formed directly on the surface of the negative electrode sheet, and can also serve to isolate the influence of the negative electrode, particularly the lithium negative electrode, on the solid electrolyte bulk layer.
In some embodiments, when the host functional layer is a solid electrolyte host layer, the solid electrolyte host layer is prepared by: and tabletting the solid electrolyte, and then carrying out second sintering treatment to obtain the solid electrolyte main body layer. By subjecting the solid electrolyte powder to a method requiring post-sintering treatment, a dense solid electrolyte bulk layer can be formed.
In some embodiments, the solid electrolyte has a median particle size D50 of 100nm to 1 μm, which is advantageous for obtaining a dense solid electrolyte bulk layer. If the median particle size D50 of the solid electrolyte is too large, the density of the solid electrolyte bulk layer decreases, and the ionic conductivity of the corresponding solid electrolyte bulk layer decreases.
In the embodiment of the application, solid electrolyte powder is tabletted to form a solid electrolyte prefabricated layer. In some embodiments, tableting is performed under a pressure of 100 to 200 MPa. And tabletting is carried out under the pressure, so that the solid electrolyte main body layer with high density can be obtained after subsequent sintering treatment.
And carrying out second sintering treatment on the solid electrolyte prefabricated layer obtained after tabletting so as to improve the density of the solid electrolyte layer. In some embodiments, the temperature of the second sintering is 800-1000 ℃ and the holding time is 0.5-4 h. Performing the second sintering treatment in the above temperature range can obtain a solid electrolyte bulk layer having increased hardness and being dense, thereby improving the electrical conductivity of the solid electrolyte bulk layer. If the temperature of the second sintering treatment is too high, the solid electrolyte is easily decomposed or side reactions occur, so that the material basis of the solid electrolyte is changed, the properties of the electrolyte are changed, and the electrochemical performance of the solid battery is affected.
In some embodiments, the solid electrolyte with the median particle size D50 of 100nm to 1 μm is tabletted under the pressure of 100 to 200MPa, and the tabletted solid electrolyte is subjected to heat preservation treatment for 0.5 to 4 hours under the temperature of 800 to 1000 ℃. The density of the solid electrolyte main body layer obtained by the method is more than 90 percent, and the high lithium ion conductivity is more than 1 multiplied by 10-4S cm-1。
S02, forming inorganic lithium ion conductor material dispersion liquid on at least one side surface of a main body function layer to obtain an inorganic lithium ion conductor material prefabricated layer, and performing first sintering treatment on the inorganic lithium ion conductor material prefabricated layer to obtain an interface protection layer.
In the embodiment of the present application, the inorganic lithium ion conductor material dispersion is formed on at least one side surface of the host functional layer by a solution processing method. Illustratively, the solution processing method may be knife coating, spin coating, spray coating, and even under allowable conditions, the inorganic lithium ion conductor material dispersion may be formed on at least one side surface of the host functional layer by printing.
In some embodiments, the inorganic lithium ion conductor material dispersion liquid with the concentration of 0.1-1 g/mL is formed on at least one side surface of the main body functional layer, so as to obtain the inorganic lithium ion conductor material prefabricated layer with the thickness of 50-100 μm. The interface protection layer formed in the case is compact and has a proper thickness, and when the interface protection layer is used for an interface layer between the solid electrolyte and the negative electrode of the solid-state battery, the solid electrolyte can be effectively protected from being reduced to lose lithium ion conductivity when being in contact with the negative electrode, particularly a lithium negative electrode, and the influence on the lithium ion transmission performance of the solid electrolyte is reduced.
Further, the obtained prefabricated layer of the inorganic lithium ion conductor material is subjected to first sintering treatment, so that the density of the prefabricated layer of the inorganic lithium ion conductor material is improved. Meanwhile, the inorganic lithium ion conductor material in the prefabricated layer of the inorganic lithium ion conductor material is melted to form an interface protection layer. When the main body function layer is a solid electrolyte main body layer, in the first sintering treatment process, the inorganic lithium ion conductor material in the inorganic lithium ion conductor material prefabricated layer is melted and is in chemical contact with the solid electrolyte, a thin and closely contacted protective layer is formed on the surface of the solid electrolyte, and the solid electrolyte is protected from being reduced and losing lithium ion conduction capability when being in contact with a lithium cathode.
In some embodiments, the temperature of the first sintering treatment is 500-700 ℃ and the holding time is 1-3 h. Under the conditions of the sintering treatment, the lithium ion conductor material melts and forms a thin and closely contacted protective layer on the surface of the solid electrolyte or negative electrode sheet. If the temperature of the first sintering treatment is too low, the lithium ion conductor material is not melted enough to form an interface protective layer; if the temperature of the first sintering treatment is too high, the lithium ion conductor material itself undergoes a side reaction to generate another substance, which degrades the performance of the interface protective layer.
According to the preparation method of the composite film, the lithium ion conductor material with the low melting point is co-sintered with the solid electrolyte or the negative plate, and the lithium ion conductor material forms a thin and tightly contacted protective layer on the surface of the solid electrolyte or the negative plate. When the composite film is used for a solid-state battery, the interface protective layer is positioned between the negative electrode and the solid-state electrolyte, and the solid-state electrolyte is protected from being reduced and losing the lithium ion conduction capability when contacting with the negative electrode, particularly a lithium negative electrode. Since the lithium ion conductor material has lithium ion conductivity and a low melting point, the influence on the lithium ion conductivity of the solid electrolyte can be reduced.
In a third aspect, an embodiment of the present application provides an all-solid-state lithium battery, including the composite film according to the first aspect of the embodiment of the present application or the composite film prepared by the method according to the second aspect of the embodiment of the present application, and an interface protection layer of the composite film is located between a negative electrode and a solid electrolyte.
The all-solid-state lithium battery provided by the embodiment of the application comprises the composite film of the first aspect of the embodiment of the application or the composite film prepared by the method of the second aspect of the embodiment of the application, and the interface protective layer is positioned between the negative electrode and the solid electrolyte, so that the solid electrolyte is protected from being reduced and losing lithium ion conductivity when contacting with the negative electrode, particularly the lithium negative electrode; in addition, the lithium ion conductor material has lithium ion conductivity and low melting point, and can reduce the influence on the lithium ion conductivity of the solid electrolyte, thereby ensuring the lithium ion conductivity of the solid electrolyte to the maximum extent.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a composite film comprises the following steps:
(1) 350mg of nano LATP (chemical formula is Li)1.3Al0.3Ti1.7(PO4)3) Preparing the mother powder into a green body with the diameter of 14mm under the pressure of 150Mpa by using a dry powder tablet press, placing the green body in a muffle furnace, and carrying out heat treatment for 3h at the temperature of 950 ℃ to prepare the LATP electrolyte sheet with the thickness of 400 mu m.
(2) Taking 50g D50 as 0.5 mu m Li1.2B0.2C0.8O3Ultrasonically dispersing powder (interface protective layer material) in ethanol, uniformly coating the obtained dispersion liquid with the concentration of 0.5g/mL on the surface of a LATP electrolyte sheet to form a prefabricated layer with the thickness of 50 mu m, transferring the LATP sheet coated with the dispersion liquid to a muffle furnace, and carrying out heat treatment at the temperature of 680 ℃ for 2h to obtain LATP-Li with a chemical interface1.2B0.2C0.8O3Electrolyte, wherein the interface protective layer (Li)1.2B0.2C0.8O3Layer) had a thickness of 15 μm.
Example 2
A method for preparing a composite film, which is different from that of example 1 in that: the electrolyte mother powder is Li1.4Al0.4Ti1.6(PO4)3The interface protective layer material is Li1.3B0.3C0.7O3Powder, transferring the LATP sheet coated with the dispersion liquid to a muffle furnace, and then carrying out heat treatment for 2h at the temperature of 700 ℃ to obtain LATP-Li with a chemical interface1.3B0.3C0.7O3An electrolyte.
Example 3
A method for preparing a composite film, which is different from that of example 1 in that: the electrolyte mother powder is Li1.3Al0.3Ti1.7(PO4)3The interface protective layer material is Li1.2B0.2C0.8O3Powder, transferring the LATP sheet coated with the dispersion liquid to a muffle furnace, and then carrying out heat treatment for 2h at the temperature of 700 ℃ to obtain LATP-Li with a chemical interface1.2B0.2C0.8OO3An electrolyte.
Example 4
A preparation method of a composite film comprises the following steps:
(1) 350mg of nano LAGP (chemical formula is Li)1.3Al0.3Ge1.7(PO4)3) Preparing the mother powder into a green body with the diameter of 14mm under the pressure of 100Mpa by using a dry powder tablet press, placing the green body in a muffle furnace, and carrying out heat treatment for 4h at the temperature of 900 ℃ to prepare the LAGP electrolyte sheet with the thickness of 380 mu m.
(2) Taking 50g D50 as 1 μm Li1.2B0.2C0.8O3Ultrasonically dispersing powder (interface protective layer material) in deionized water, uniformly coating the obtained dispersion liquid with the concentration of 0.8g/mL on the surface of a LAGP electrolyte sheet to form a prefabricated layer with the thickness of 72 mu m, transferring the LAGP sheet coated with the dispersion liquid to a muffle furnace, and carrying out heat treatment for 1h at the temperature of 680 ℃ to obtain the LAGP-Li with a chemical interface1.2B0.2C0.8O3Electrolyte, wherein the interface protective layer (Li)1.2B0.2C0.8O3Layer) has a thickness of 20 μm.
Example 5
A preparation method of a composite film comprises the following steps:
(1) 350mg of nano-LLTO (chemical formula is Li)0.34La0.56TiO3) Preparing the mother powder into a green body with the diameter of 14mm under the pressure of 150Mpa by using a dry powder tablet press, placing the green body in a muffle furnace,heat-treating at 1250 deg.C for 8h to obtain LLTO electrolyte sheet with thickness of 500 μm.
(2) Taking 50g D50 as 0.8 mu m Li1.2B0.2C0.8O3(interface protective layer material) is ultrasonically dispersed in absolute ethyl alcohol, the obtained dispersion liquid with the concentration of 1g/mL is uniformly coated on the surface of a LLTO electrolyte sheet to form a prefabricated layer with the thickness of 100 mu m, the LLTO sheet coated with the dispersion liquid is transferred to a muffle furnace and is subjected to heat treatment for 0.5h at the temperature of 650 ℃, and the LLTO-Li with a chemical interface is prepared1.2B0.2C0.8O3Electrolyte, wherein, the interface Li1.2B0.2C0.8O3The thickness was 30 μm.
Comparative example 1
A method of preparing a solid electrolyte comprising the steps of:
(1) 350mg of nano LATP (Li)1.3Al0.3Ti1.7(PO4)3) The mother powder is made into a green body with the diameter of 14mm under the pressure of 150Mpa by using a dry powder tablet press, and then the green body is thermally treated for 3 hours at the high temperature of 950 ℃ in a muffle furnace to prepare the conventional LATP electrolyte sheet.
Solid lithium batteries, namely a solid lithium battery a1-5 and a solid lithium battery D1, were constructed by using the composite films obtained in examples 1-5 and the solid electrolyte obtained in comparative example 1. The solid-state battery is assembled by a positive plate, a composite film and a negative plate. The positive plate is prepared as follows: mixing the raw materials according to LiNi0.8Co0.1Mn0.1O2Dispersing the Super-P PVDF (weight ratio) in an NMP (N-methyl pyrrolidone) solvent in a ratio of 9:0.5:0.5 to obtain a pole piece with a solid content of 65%, coating to obtain the pole piece, and drying in a vacuum oven at 80 ℃ to obtain a positive pole piece; the negative plate is made of lithium metal, and the battery is assembled and packaged in a button battery case in sequence according to the sequence of the positive electrode, the electrolyte and the negative electrode to obtain the solid-state lithium battery. And (3) carrying out performance test on the obtained solid-state lithium battery, wherein the test items and the test method are as follows:
(1) electrochemical impedance testing: solid-state lithium battery testing is carried out by using Gamry electrochemical workstation, and testing frequency range is 0.1 multiplied by 10-6～10×10-6Hz。
(2) Constant current charge and discharge test: charging and discharging at 50 deg.C and 0.1C current density within 3-4.2V voltage range.
The test results are shown in table 1 below.
TABLE 1
Figure BDA0003145075610000161
As can be seen from table 1, the solid lithium batteries a1 to a5 constructed using the composite thin film provided in the examples of the present application as a solid electrolyte have good lithium ion conductivity as a whole, as compared with the solid lithium battery D1 corresponding to comparative example 1, which indicates that Li1+xBxC1-xO3The modification has little effect on the conductivity of the solid electrolyte body. The capacity retention of the second rings of the solid lithium batteries a1 to a5 is also better than that of the solid lithium battery D1 corresponding to comparative example 1 (the capacity retention of a1 to a5 is higher than that of D1), and the polarization voltage is smaller. Therefore, the composite film provided by the embodiment of the application can endow the solid-state lithium battery with more stable electrochemical performance.
Fig. 1 and 2 show EIS diagrams of the lithium solid-state battery a3 and the lithium solid-state battery D1, respectively. As can be seen, the composite film obtained in example 3 has improved contact stability between the solid electrolyte and lithium metal. On the basis, the impedance of the solid lithium battery A3 is slightly larger than that of the solid lithium battery D1, which shows that Li1+xBxC1-xO3The modification has little effect on the LATP host conductivity.
Fig. 3 and 4 show charge/discharge diagrams of lithium solid-state battery a3 and lithium solid-state battery D1, respectively. It can be seen from the figure that the capacity retention of the second circle of lithium solid state battery A3 is significantly larger than that of lithium solid state battery D1, and has smaller polarization, indicating that lithium solid state battery A3 has more stable electrochemical performance.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.

Claims (13)

1. The composite film is characterized by comprising a main body functional layer and an interface protective layer combined on at least one side surface of the main body functional layer, wherein the main body functional layer is a solid electrolyte main body layer or a negative plate, and the interface protective layer is made of an inorganic lithium ion conductor material with the melting point of less than or equal to 700 ℃.
2. The composite film of claim 1, wherein the inorganic lithium ion conductor material is selected from the group consisting of materials having an ionic conductivity of 1 x 10 or more-9S cm-1The inorganic material of (1).
3. The composite film of claim 1, wherein the inorganic lithium ion conductor material is selected from Li1+xBxC1- xO3Wherein x satisfies: x is more than 0.2 and less than 0.4.
4. The composite film according to claim 1, wherein the interface protective layer has a thickness of 15 to 60 μm.
5. The composite film according to any one of claims 1 to 4, wherein the material of the solid electrolyte host layer is selected from the group consisting of materials having an electronic conductivity of 1 x 10 or less-9S cm-1And an ionic conductivity of 1X 10 or more-4S cm-1The inorganic material of (1); and/or
The material of the solid electrolyte main body layer is selected from at least one of LATP, LAGP and LLTO; and/or
The thickness of the solid electrolyte main body layer is 100-300 mu m.
6. The composite film according to any one of claims 1 to 4, wherein the negative electrode sheet is a lithium negative electrode.
7. The preparation method of the composite film is characterized by comprising the following steps of:
providing a main body function layer, wherein the main body function layer is a solid electrolyte main body layer or a negative plate; dispersing an inorganic lithium ion conductor material with a melting point less than or equal to 700 ℃ in a solvent to obtain inorganic lithium ion conductor material dispersion liquid;
and forming the inorganic lithium ion conductor material dispersion liquid on at least one side surface of the main body functional layer to obtain an inorganic lithium ion conductor material prefabricated layer, and carrying out first sintering treatment on the inorganic lithium ion conductor material prefabricated layer to obtain the interface protective layer.
8. The method for preparing the composite film according to claim 7, wherein the temperature of the first sintering treatment is 500 to 700 ℃ and the holding time is 1 to 3 hours.
9. The method of preparing a composite film according to claim 7, wherein the inorganic lithium ion conductor material has a median particle size D50 of 0.5 to 1 μm.
10. The method for preparing a composite film according to claim 7, wherein the concentration of the dispersion liquid of the inorganic lithium ion conductor material is 0.1 to 1g/mL, and the thickness of the prefabricated layer of the inorganic lithium ion conductor material is 50 to 100 μm.
11. The method for producing a composite film according to any one of claims 7 to 10, wherein the host functional layer is a solid electrolyte host layer, and the solid electrolyte host layer is produced by: and tabletting the solid electrolyte, and then carrying out second sintering treatment to obtain the solid electrolyte main body layer.
12. The method for preparing a composite film according to claim 11, wherein the tabletting is performed under a pressure of 100 to 200 MPa; and/or
The temperature of the second sintering is 800-1000 ℃, and the heat preservation time is 0.5-4 h; and/or
The median particle size D50 of the solid electrolyte is 100 nm-1 μm.
13. A solid-state lithium battery comprising the composite film according to any one of claims 1 to 6 or the composite film produced by the method according to any one of claims 7 to 12, wherein an interface protective layer of the composite film is provided between a negative electrode and a solid-state electrolyte.
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