CN109037591B - Electrode, all-solid-state battery, preparation method of all-solid-state battery and lithium ion battery - Google Patents

Electrode, all-solid-state battery, preparation method of all-solid-state battery and lithium ion battery Download PDF

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CN109037591B
CN109037591B CN201810869788.8A CN201810869788A CN109037591B CN 109037591 B CN109037591 B CN 109037591B CN 201810869788 A CN201810869788 A CN 201810869788A CN 109037591 B CN109037591 B CN 109037591B
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foam
solid
carbon
negative electrode
positive electrode
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CN109037591A (en
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倪海芳
陈渊
周美丽
刘茜
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Sander New Energy Technology Development Co ltd
Soundon New Energy Technology Co Ltd
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Sander New Energy Technology Development Co ltd
Soundon New Energy Technology 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention provides an electrode, an all-solid-state battery, a preparation method of the all-solid-state battery and a lithium ion battery, and relates to the technical field of batteries. The all-solid-state battery comprises a negative electrode, a positive electrode and an electrolyte; the positive electrode comprises a conductive foam material and a positive active material filled in pores of the conductive foam material; the negative electrode is foam carbon, or comprises a conductive foam material and a negative active material filled in pores of the conductive foam material; the solid electrolyte is coated on the surface of the positive electrode and/or the surface of the negative electrode. The electrode and the all-solid-state battery can solve the problem of low energy density of the existing rechargeable battery, and achieve the technical effect of improving the energy density of the battery.

Description

Electrode, all-solid-state battery, preparation method of all-solid-state battery and lithium ion battery
Technical Field
The invention relates to the technical field of batteries, in particular to an electrode, an all-solid-state battery, a preparation method of the all-solid-state battery and a lithium ion battery.
Background
With the continuous updating and development of rechargeable battery technology, rechargeable batteries are widely used in various fields in life, especially in the fields of new energy vehicles, power grid energy storage, special vehicles, communication base stations, and the like.
The structure of a rechargeable battery composed of a liquid electrolyte generally includes a positive electrode, an electrolyte, a separator, and a negative electrode, which are sequentially stacked. The structure of an all-solid rechargeable battery generally includes a positive electrode, a solid-state electrolyte, and a negative electrode, which are sequentially stacked. The positive electrode and the negative electrode respectively comprise a current collector and a positive electrode active material or a negative electrode active material coated on the surface of the current collector, the current collector is generally an aluminum foil or a copper foil, the current collector is an inactive component of the battery, and the current collector is mainly used for transmitting carriers. There are two current collectors (positive electrode current collector and negative electrode current collector, respectively) in each cell unit of the rechargeable battery, and the weight of the current collectors accounts for more than 10% of the total weight of the rechargeable battery, and the weight of the current collectors increases as the number of layers of the positive electrode and the negative electrode in the rechargeable battery increases.
In evaluating the electrical performance index of a rechargeable battery, energy density is an important reference index. For example, in an electric vehicle, a battery with light weight and large capacity can meet the requirement of the electric vehicle, and the vehicle can run farther when the battery with the same weight is loaded. Therefore, how to increase the energy density of the secondary battery is a research focus of the secondary battery at present.
Disclosure of Invention
The first purpose of the present invention is to provide an electrode and a method for preparing the same, by which a rechargeable battery can be assembled to solve the technical problem of low energy density of the rechargeable battery in the prior art.
A second object of the present invention is to provide an all-solid battery and a method for manufacturing the same, which can alleviate the problem of low energy density of the all-solid battery in the prior art.
A third object of the present invention is to provide a lithium ion battery comprising a liquid electrolyte to alleviate the problem of low energy density of the prior art lithium ion batteries.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
an electrode comprising a conductive foam as a frame support and an electrode active material filled in pores of the conductive foam; wherein the electrode active material is a positive electrode active material or a negative electrode active material.
Further, the conductive foam material is foam carbon or foam metal;
preferably, the open-cell rate of the conductive foam material is more than or equal to 95 percent.
A preparation method of an electrode comprises the steps of soaking a conductive foam material used as a frame support body in a solution containing an electrode active material, and drying to obtain the electrode; wherein the electrode active material is a positive electrode active material or a negative electrode active material.
Further, the foam conductive material is foam carbon or foam metal.
Further, the foam carbon is obtained by carbonizing a polymer with a foam structure;
preferably, the polymer is melamine or a melamine derivative; wherein the carbonization temperature is 600-900 ℃, and the carbonization time is 1-6 h.
An all-solid-state battery includes a negative electrode, a positive electrode, and an electrolyte; wherein the content of the first and second substances,
the positive electrode comprises a conductive foam material and a positive electrode active material filled in pores of the conductive foam material;
the negative electrode is foam carbon, or comprises a conductive foam material and a negative electrode active material filled in pores of the conductive foam material.
Further, the solid electrolyte is coated on the surface of the positive electrode and/or the surface of the negative electrode.
Further, the conductive foam material is foam carbon or foam metal;
preferably, the open-cell rate of the conductive foam material is more than or equal to 95 percent.
A preparation method of an all-solid-state battery comprises the following steps:
step S1: soaking the conductive foam material in a solution containing a negative electrode active material, and drying to obtain a negative electrode, or directly taking the foam carbon as the negative electrode;
step S2: soaking the conductive foam material in a solution containing a positive active material, and drying to obtain a positive electrode;
step S3: soaking the positive electrode and/or the negative electrode in a solution containing a solid electrolyte and a binder, and drying to complete the electrolyte coating of the electrode;
step S4: and overlapping the anode and the cathode, and assembling by using a hot pressing mode, wherein the temperature is 240-290 ℃, the pressure is 5-20 MPa, and the time is 0.5-2 h.
Further, the conductive foam material is foam carbon or foam metal;
preferably, the open-cell rate of the conductive foam material is more than or equal to 95 percent.
A lithium ion battery comprising: a negative electrode, a positive electrode, an electrolyte and a separator; wherein the content of the first and second substances,
the positive electrode comprises a conductive foam material and a positive electrode active material filled in pores of the conductive foam material;
the negative electrode is foam carbon, or comprises a conductive foam material and a negative electrode active material filled in the conductive foam material;
preferably, the conductive foam material is carbon foam or metal foam;
preferably, the open-cell rate of the conductive foam material is more than or equal to 95 percent.
Compared with the prior art, the invention has the following beneficial effects:
the electrode provided by the invention adopts the conductive foam material as a frame support body as a matrix, and then the electrode active material is filled in the conductive foam material. The original current collector is replaced by the conductive foam material in the structure, the volume density of the conductive foam material is very low due to the fact that the conductive foam material is of a porous structure, and compared with an electrode of a traditional current collector structure, the weight of needed inactive substances is remarkably reduced when the electrode with the same thickness is prepared, so that the weight of the electrode can be remarkably reduced by using the conductive foam material as a carrier of an electrode active material, and the energy density of a rechargeable battery is improved.
In the all-solid-state battery provided by the invention, the positive electrode and/or the negative electrode can adopt the electrode structure, wherein the positive electrode comprises a conductive foam material used as a frame support body and a positive electrode active material filled in pores of the conductive foam material; the negative electrode is foam carbon, or the negative electrode comprises a conductive foam material serving as a frame support body and a negative electrode active material filled in pores of the conductive foam material. In the all-solid-state battery, the original current collector is replaced by the conductive foam material to be directly used as a conductive electrode or a carrier of an electrode active material, and the volume density of the conductive foam material is far lower than that of the metal foil, so that the weight of the whole all-solid-state battery can be effectively reduced by directly using the conductive foam material as the electrode or the carrier of the electrode active material, and the energy density of the all-solid-state battery is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic SEM structure of a conductive foam material according to one embodiment of the present invention;
fig. 2 is a schematic structural diagram of a lithium ion battery according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of an all-solid-state battery according to an embodiment of the present invention.
Wherein, 10-aluminum plastic film; 20-negative electrode; 30-positive electrode; 40-an electrolyte; 50-a membrane; 60-solid electrolyte.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. 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 invention.
In one aspect, the present invention provides an electrode comprising a conductive foam as a frame support and an electrode active material filled in pores of the conductive foam, wherein the electrode active material is a positive electrode active material or a negative electrode active material.
The electrode provided by the invention adopts the conductive foam material as a frame support body as a matrix, and then the electrode active material is filled in the pores of the conductive foam material. The original current collector is replaced by the conductive foam material in the structure, the volume density of the conductive foam material is very low due to the fact that the conductive foam material is of a porous structure, and compared with an electrode of a traditional current collector structure, the weight of needed inactive substances is remarkably reduced when the electrode with the same thickness is prepared, so that the weight of the electrode can be remarkably reduced by using the conductive foam material as a carrier of an electrode active material, and the energy density of a rechargeable battery is improved.
In the present invention, the conductive foam has a three-dimensional frame structure, for example, the structure of the conductive foam may be as shown in fig. 1, a large number of pores exist in the interior and on the surface of the three-dimensional frame structure, the open porosity may be, for example, 90% or more, and the three-dimensional frame structure has a certain rigidity, and can support the electrode active material without collapsing its own structure.
The electrode in the invention can be a positive electrode or a negative electrode, when the electrode is the positive electrode, the positive electrode is a conductive foam material and a positive electrode active material filled in pores of the conductive foam material, for example, the positive electrode active material can be lithium salt, sodium salt, zinc salt, sulfur or metal sulfide, etc.; when the electrode is a negative electrode, the negative electrode is a conductive foam material and a negative electrode active material filled in pores of the conductive foam material, and can be, for example, an alkali metal and an alloy thereof, a silicon negative electrode material, a silicon carbon negative electrode material, or the like. The positive electrode active material or the negative electrode active material may be selected according to a specific type of the battery, and is not particularly limited herein.
In the present invention, the conductive foam material may be, for example, carbon foam or metal foam, preferably carbon foam. The foam carbon and the foam metal both have conductivity and certain rigidity, and the electrode active material can be filled in the pores of the foam as a foam structure. The weight of the conductive foam can be further reduced due to the lower density of the carbon foam, and therefore, in the present invention, the conductive foam is preferably carbon foam.
In some embodiments of the present invention, the open cell content of the conductive foam is 95% or more, preferably 98%. The higher the open cell content of the conductive foam, the more the amount of electrode active material that can be loaded, and the further increase in the energy density of the battery can be achieved.
On the other hand, the invention provides a preparation method of the electrode, which comprises the steps of soaking a conductive foam material used as a frame support body in a solution containing an electrode active material, and drying to obtain the electrode; wherein the electrode active material is a positive electrode active material or a negative electrode active material.
In the invention, some binders can be added when preparing the solution of the electrode active material, and the binders can be polycarbonate binders, such as one or more of polyethylene carbonate, polyethylene carbonate or polypropylene carbonate. The polymer is green, environment-friendly and biodegradable. The solvent can be one of anhydrous acetonitrile, benzene, anisole or anhydrous ethanol, etc.
The method of preparing the solution containing the electrode active material may be, for example: dissolving a binder in a solvent, adding an electrode active material, uniformly stirring to obtain a homogeneous solution with certain viscosity, and then soaking a conductive foam material into the solution to dry at normal temperature; and then repeating the above steps several times to maximize the loading amount of the electrode active material. Wherein the mass ratio of the binder to the electrode active material is 3-6: 100.
In some embodiments of the present invention, the conductive foam material may be, for example, carbon foam or metal foam, both of which are conductive and have a certain rigidity, and the pores of the foam may be filled with an electrode active material as a foam structure. The weight of the conductive foam can be further reduced due to the lower density of the carbon foam, and therefore, in the present invention, the conductive foam is preferably carbon foam.
In some embodiments of the present invention, the carbon foam is obtained by carbonizing a polymer having a foam structure. Further, a polymer having a sponge-like structure may be subjected to carbonization treatment to obtain a conductive foam material. Among them, the polymer may be melamine, melamine derivatives, polyethylene, polyurethane, polystyrene, or the like, and is preferably melamine or melamine derivatives. Because melamine foam and melamine derivative foam have higher open cell content, when melamine foam and melamine derivative foam are selected as the polymer, the obtained conductive foam material has higher open cell content. The foam frame structure of the polymer with the foam structure can not collapse and deform after carbonization treatment, namely, the polymer still has a large number of cavities after carbonization and has enough strong electrical conductivity. And the polymer which is in a spongy structure is used for carbonization treatment, and the obtained holes are distributed more uniformly. The carbonization treatment can be carried out, for example, by carbonizing melamine or melamine derivatives with a foam structure under a protective atmosphere to obtain a conductive foam material, namely, carbon foam; wherein the carbonization temperature is 600-900 ℃, preferably 700-800 ℃, and the carbonization time is 1-6 h, preferably 2-4 h. The open-cell rate of the conductive foam material obtained by the method is up to more than 99%, and an SEM image is shown in figure 1. As can be seen from figure 1, the open-cell rate of the foam carbon is very high, the holes are uniformly distributed, and a three-dimensional net-shaped connecting structure is formed between the carbon materials, so that the carbon materials still have higher conductivity.
In a third aspect, the present invention provides an all-solid-state battery including a negative electrode, a positive electrode, and an electrolyte; wherein the content of the first and second substances,
the positive electrode comprises a conductive foam material and a positive electrode active material filled in pores of the conductive foam material;
the negative electrode is foam carbon, or comprises a conductive foam material and a negative active material filled in pores of the conductive foam material;
the solid electrolyte is coated on the surface of the positive electrode and/or the surface of the negative electrode.
In the all-solid-state battery provided by the invention, the positive electrode and/or the negative electrode can adopt the electrode structure, wherein the positive electrode comprises a conductive foam material used as a frame support body and a positive electrode active material filled in pores of the conductive foam material; the negative electrode is foam carbon, or the negative electrode comprises a conductive foam material serving as a frame support body and a negative electrode active material filled in pores of the conductive foam material. In the all-solid-state battery, the original current collector is replaced by the conductive foam material to be directly used as a conductive electrode or a carrier of an electrode active material, and the volume density of the conductive foam material is far lower than that of the metal foil, so that the weight of the whole all-solid-state battery can be effectively reduced by directly using the conductive foam material as the electrode or the carrier of the electrode active material, and the energy density of the all-solid-state battery is further improved.
In a traditional all-solid-state battery, a large number of gaps exist among a positive electrode, a negative electrode and a solid electrolyte, so that the short circuit phenomenon between the positive electrode and the negative electrode is avoided, the width of the solid electrolyte is a few millimeters wider than that of the positive electrode and the negative electrode, and meanwhile, a certain space is reserved on the side, led out by a tab, for welding the tab, so that a large amount of space is wasted, and the volume energy density of the battery is reduced.
In order to solve the above problems, in the present invention, a solid electrolyte is coated on the surface of the positive electrode and/or the surface of the negative electrode.
The solid electrolyte is arranged on the surface of the cathode or the anode in a coating mode, so that the distance between the cathode and the electrolyte or between the anode and the electrolyte can be reduced, and the contact tightness of the cathode and the electrolyte is improved. The structure is completely different from the design structure among the anode, the cathode and the electrolyte in the traditional sense, and replaces the anode, the cathode and the electrolyte to be crossed together, so that the space waste inside the battery is greatly reduced, and the mass energy density and the volume energy density of the battery are improved.
For example, in some embodiments of the present invention, the negative electrode is a conductive foam material, and the positive electrode is a conductive foam material and a positive active material filled in the conductive foam material; the solid electrolyte is coated on the surface of the negative electrode.
The surface of the negative electrode is uniformly coated with a layer of solid electrolyte, so that the distance between the positive electrode and the negative electrode is very short, and at the moment, the coating of the solid electrolyte is required to be free from any flaw, otherwise, the short circuit of the battery is easily caused; meanwhile, the coated electrolyte layer cannot be too thick, so that the original open pore structure of the cathode is maintained.
In the present invention, the conductive foam material may be, for example, carbon foam or metal foam, preferably carbon foam. The foam carbon and the foam metal both have conductivity and certain rigidity, and can be filled with electrode active materials in the pores of the foam after being used as a foam structure. The weight of the conductive foam can be further reduced due to the lower density of the carbon foam, and therefore, in the present invention, the conductive foam is preferably carbon foam.
The conductive foam material, especially the foam carbon, has high opening rate and large filling amount, and when the foam carbon is used for manufacturing the all-solid-state battery, the anode and the cathode are easy to intersect, thereby being beneficial to the contact of the anode and the cathode and reducing the interface resistance.
In some embodiments of the present invention, the open cell content of the conductive foam is 95% or more, preferably 98%. The higher the open-cell content of the conductive foam material, the more the amount of electrode active material that can be loaded, and the energy density of the all-solid battery can be further increased.
In a fourth aspect, the present invention provides a method for manufacturing an all-solid battery, including the steps of:
step S1: soaking the conductive foam material in a solution containing a negative electrode active material, and drying to obtain a negative electrode, or directly taking the foam carbon as the negative electrode;
step S2: soaking the conductive foam material in a solution containing a positive active material, and drying to obtain a positive electrode;
step S3: soaking the positive electrode and/or the negative electrode in a solution containing a solid electrolyte and a binder, and drying to complete the electrolyte coating of the electrode;
step S4: and overlapping the anode and the cathode, and assembling by using a hot pressing mode, wherein the temperature is 240-290 ℃, the pressure is 5-20 MPa, and the time is 0.5-2 h.
The conductive foam material may be, for example, carbon foam or metal foam. The open-cell rate of the conductive foam material is more than or equal to 95 percent.
In the preparation method of the all-solid-state battery, when the negative electrode is the conductive foam material and the negative electrode active material filled in the conductive foam material, the conductive foam material is soaked in the solution containing the negative electrode active material, and then the negative electrode is obtained after drying; or directly using the foam carbon as the negative electrode.
When the positive electrode is made of the conductive foam material and the positive electrode active material filled in the pores of the conductive foam material, the conductive foam material is soaked in a solution containing the positive electrode active material, and then the positive electrode is obtained after drying.
The preparation method can be used for obtaining the negative electrode filled with the negative electrode active material and the positive electrode filled with the positive electrode active material, and the preparation can be carried out according to specific requirements.
The preparation method of the conductive foam material can be, for example: carbonizing a polymer with a foam structure to obtain a conductive foam material; further, the preparation method of the conductive foam material comprises the following steps: and carbonizing the polymer with the sponge structure to obtain the conductive foam material. Among them, the polymer may be melamine, melamine derivatives, polyethylene, polyurethane, polystyrene, or the like, and is preferably melamine or melamine derivatives. Because melamine foam and melamine derivative foam have higher open cell content, when melamine foam and melamine derivative foam are selected as the polymer, the obtained conductive foam material has higher open cell content. The foam frame structure of the polymer with the foam structure can not collapse and deform after carbonization treatment, namely, the polymer still has a large number of cavities after carbonization and has enough strong electrical conductivity. And the polymer which is in a spongy structure is used for carbonization treatment, and the obtained holes are distributed more uniformly. For example, under a protective atmosphere, melamine or a melamine derivative having a sponge-like structure is carbonized to obtain a conductive foam material, i.e., carbon foam; wherein the carbonization temperature is 600-900 ℃, preferably 700-800 ℃, and the carbonization time is 1-6 h, preferably 2-4 h. The open-cell rate of the conductive foam material obtained by the method is up to more than 99%, and an SEM image is shown in figure 1. As can be seen from figure 1, the open-cell rate of the foam carbon is very high, the holes are uniformly distributed, and a three-dimensional net-shaped connecting structure is formed between the carbon materials, so that the carbon materials still have higher conductivity.
In the present invention, the positive electrode and/or the negative electrode is immersed in a solution containing a solid electrolyte and a binder, and dried to complete the electrolyte coating of the electrode. Wherein, some binders can be added when preparing the solution of the solid electrolyte, and the binders can be selected from polycarbonate binders, such as one or more of polyethylene carbonate, polyethylene carbonate or polypropylene carbonate. The polymer is green, environment-friendly and biodegradable. The solvent can be one of anhydrous acetonitrile, benzene, anisole or anhydrous ethanol, etc.
The solution containing the solid electrolyte may be prepared, for example, by: dissolving a binder in a solvent, adding a solid electrolyte, uniformly stirring to obtain a homogeneous solution with certain viscosity, and then soaking a conductive foam material serving as a negative electrode into the solution, and drying at normal temperature to finish coating of the negative electrode. Wherein the mass ratio of the binder to the electrode active material is 3-6: 100.
Taking an all-solid-state lithium ion type battery as an example, in some embodiments of the present invention, the negative electrode is a conductive foam material, the positive electrode is a conductive foam material and a positive active material filled in the conductive foam material, a solid electrolyte is coated on the surface of the negative electrode, and then the negative electrode, the positive electrode and the electrolyte are assembled to obtain an all-solid-state battery. The positive electrode active material is, for example, any one of or a combination of at least two of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, and lithium nickel cobalt manganate. In order to reduce the interfacial resistance between the positive electrode active material and the solid electrolyte, the positive electrode active material may be modified by coating, for example, with LiNbO3Coated LiCoO2。
In the above embodiment, the coating method in which the solid electrolyte is coated on the surface of the anode includes the steps of: and soaking the negative electrode in a solution containing a solid electrolyte and a binder, and taking out and drying to finish the electrolyte coating of the negative electrode. The uniform solid electrolyte coating layer can be obtained by adopting a coating method of soaking in solution and then drying.
In the invention, the assembly process is to assemble the anode and the cathode coated with the solid electrolyte or to stack the anode and the anode coated with the solid electrolyte by a hot pressing mode. The hot pressing parameters may be, for example: the hot pressing temperature is 240-290 ℃, the hot pressing pressure is 5-20 MPa, and the hot pressing time is 0.5-2 h.
In the hot pressing process, a certain pressure is applied, so that the anode and the cathode can be tightly attached, and the gaps between the anode and the cathode and between the anode and the solid electrolyte are reduced. Meanwhile, the conductive foam material can be extruded through hot pressing, the occupied volume of the conductive foam material is reduced, the volume of the all-solid-state battery is further reduced, and the volume energy density of the all-solid-state battery is improved. In addition, the solid electrolyte is converted from a glass state to a glass-ceramic state by hot pressing, so that the conductivity of the solid electrolyte is improved. In addition, the binder may be decomposed into more adhesive small molecules by hot pressing, thereby making the contact between the solid electrolyte and the positive electrode active material more tight.
In a fifth aspect, the present invention provides a lithium ion battery, comprising a negative electrode, a positive electrode, an electrolyte and a separator; wherein the content of the first and second substances,
the positive electrode comprises a conductive foam material and a positive electrode active material filled in pores of the conductive foam material;
the negative electrode is foam carbon, or comprises a conductive foam material and a negative active material filled in the conductive foam material.
The conductive foam material may be, for example, carbon foam or metal foam. The open-cell rate of the conductive foam material is more than or equal to 95 percent.
The lithium ion battery has the same beneficial effects as the all-solid-state battery, and the description is omitted here.
The structure of the soft package lithium ion battery of one embodiment of the invention is shown in fig. 2, and comprises an aluminum-plastic film 10, and a negative electrode 20, a positive electrode 30, an electrolyte 40 and a diaphragm 50 which are packaged in the aluminum-plastic film 10; the positive electrode comprises a conductive foam material and a positive electrode active material filled in pores of the conductive foam material; the negative electrode is foam carbon.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
This example is a positive electrode comprising a carrier as the positive electrode active materialA bulk carbon foam and a positive electrode active material filled in the carbon foam. Wherein the open-cell ratio of the foam carbon is 99 percent, and the positive active material is LiNbO3Coated LiCoO2。
Example 2
This embodiment is a method for preparing the positive electrode provided in embodiment 1, including the steps of:
a) cutting commercial melamine foam into a shape of 5cm × 5cm × 1cm, placing in a tube furnace, N2Carbonizing at 800 ℃ for 2h under a protective atmosphere, cooling, cleaning with absolute ethyl alcohol, drying at 60 ℃ to obtain the foam carbon with a self-supporting three-dimensional structure, and cutting the obtained foam carbon according to the required size to obtain the foam carbon with the size of 5cm multiplied by 0.1 cm;
b) providing LiNbO3Coated LiCoO2Dissolving the positive active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6h at 50 ℃ to obtain a positive solution, soaking the cut carbon foam in the positive solution, taking out, drying at 60 ℃, and repeating the soaking and drying process for 3 times to obtain the positive electrode.
Example 3
This example is a negative electrode including copper foam as a negative electrode active material carrier and a negative electrode active material filled in the copper foam. Wherein the open-cell ratio of the foamy copper is 95 percent, and the negative active material is graphite.
Example 4
This example is a positive electrode including aluminum foam as a positive electrode active material carrier and a positive electrode active material filled in the aluminum foam. Wherein the open-cell ratio of the foamed aluminum is 85%, and the positive electrode active material is LiNbO3Coated LiCoO2。
Example 5
In this embodiment, as shown in fig. 3, the all-solid-state lithium ion battery includes a negative electrode 20, a positive electrode 30, and a solid electrolyte 60, where the negative electrode 20 is carbon foam, the open-cell ratio of the carbon foam is 99%, the positive electrode 30 is the positive electrode provided in embodiment 1, and the solid electrolyte 60 is coated on the surface of the negative electrode 20.
Example 6
This embodiment is a method for manufacturing the all-solid-state lithium ion battery provided in embodiment 5, and includes the following steps:
a) cutting commercial melamine foam into a shape of 5cm × 5cm × 1cm, placing in a tube furnace, N2Carbonizing at 800 ℃ for 2h under a protective atmosphere, cooling, cleaning with absolute ethyl alcohol, drying at 60 ℃ to obtain the foam carbon with a self-supporting three-dimensional structure, and cutting the obtained foam carbon according to the required size to obtain the foam carbon with the size of 5cm multiplied by 0.1 cm;
b) in an argon gas filled glove box with oxygen and water content less than 0.1ppm, Li is weighed according to a molar ratio of 7:32S and P2S5As solid electrolyte raw material, dissolved in anhydrous acetonitrile solution, followed by addition of 3 wt% (as Li)2S and P2S5Taking the total weight of the carbon as a measurement reference), stirring the binder polypropylene carbonate at 60 ℃ for 24 hours to obtain a homogeneous solution, soaking the foam carbon obtained in the step a) into the homogeneous solution for 10 mm, taking out the foam carbon and putting the foam carbon into a clean glass ware, and drying the foam carbon at normal temperature to obtain a solid electrolyte coated cathode;
c) providing LiNbO3Coated LiCoO2Dissolving the positive active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6h at 50 ℃ to obtain a positive solution, soaking the cut carbon foam in the positive solution, taking out the carbon foam, drying at normal temperature, and repeating the soaking and drying process for 3 times to obtain a positive electrode;
d) and filling an argon gas containing less than 0.1ppm of oxygen and water into a glove box, superposing the obtained negative electrode coated by the solid electrolyte and the positive electrode together, hot-pressing at the pressure of 10MPa and the temperature of 250 ℃ for 1h, leading out tabs at the edges of the positive electrode plate and the negative electrode plate, and finally packaging by using an aluminum plastic film to obtain the solid lithium ion battery.
Example 7
This example is an all-solid-state lithium ion battery, which includes a negative electrode, a positive electrode, and an electrolyte, where the negative electrode is the negative electrode in example 3, the open-cell ratio of the copper foam is 95%, the positive electrode is the positive electrode provided in example 1, and the solid electrolyte is coated on the surface of the negative electrode.
The preparation method of the solid-state lithium ion battery in the embodiment comprises the following steps:
a) taking commercial graphite as a negative electrode active material, dissolving the negative electrode active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6 hours at 50 ℃ to obtain a negative electrode solution, soaking 5cm × 5cm × 0.1cm of copper foam in the negative electrode solution, taking out the solution, drying at normal temperature, and repeating the soaking and drying process for 3 times to obtain a negative electrode sheet;
b) in an argon gas filled glove box with oxygen and water content less than 0.1ppm, Li is weighed according to a molar ratio of 7:32S and P2S5As solid electrolyte raw material, dissolved in anhydrous acetonitrile solution, followed by addition of 3 wt% (as Li)2S and P2S5Taking the total weight of the anode plate as a measurement reference), stirring the binder polypropylene carbonate at 60 ℃ for 24 hours to obtain a homogeneous solution, then soaking the anode plate into the homogeneous solution for 10 mm, taking out the anode plate and putting the anode plate into a clean glass ware, and drying the anode plate at normal temperature to obtain a solid electrolyte coated anode;
c) providing LiNbO3Coated LiCoO2Dissolving the positive active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6h at 50 ℃ to obtain a positive solution, soaking foam carbon of 5cm multiplied by 0.1cm in the positive solution, taking out the foam carbon, drying at normal temperature, and repeating the soaking and drying process for 3 times to obtain a positive electrode;
d) and filling an argon filled glove box with oxygen and water contents less than 1ppm, superposing the obtained negative electrode coated by the solid electrolyte and the positive electrode together, hot-pressing at 250 ℃ for 1h under the pressure of 10MPa, then leading out tabs at the edges of the positive electrode plate and the negative electrode plate, and finally packaging by using an aluminum plastic film to obtain the solid lithium ion battery.
Example 8
The present embodiment is an all-solid-state lithium ion battery, including a negative electrode, a positive electrode, and an electrolyte, where the negative electrode is carbon foam, the open-cell ratio of the carbon foam is 99%, the positive electrode is the positive electrode provided in embodiment 4, and the surface of the negative electrode is coated with the solid electrolyte.
The preparation method of the solid-state lithium ion battery in the embodiment comprises the following steps:
a) providing 5cm × 5cm × 0.1cm of carbon foam as negative electrode, filling the glove box with argon gas containing oxygen and water less than 0.1ppm, and weighing Li at molar ratio of 7:32S and P2S5As solid electrolyte raw material, dissolved in anhydrous acetonitrile solution, followed by addition of 3 wt% (as Li)2S and P2S5Taking the total weight of the electrolyte as a measurement reference), stirring the binder polypropylene carbonate for 24 hours at 60 ℃ to obtain a homogeneous solution, then soaking foamed aluminum into the homogeneous solution for 10 mm, taking out the foamed aluminum and putting the foamed aluminum into a clean glass ware, and drying the foamed aluminum at normal temperature to obtain a solid electrolyte coated cathode;
b) providing LiNbO3Coated LiCoO2Dissolving the positive active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6h at 50 ℃ to obtain a positive solution, soaking foamed aluminum of 5cm multiplied by 0.1cm in the positive solution, taking out the positive solution, drying at normal temperature, and repeating the soaking and drying process for 3 times to obtain a positive electrode;
c) and filling an argon gas containing less than 0.1ppm of oxygen and water into a glove box, superposing the obtained negative electrode coated by the solid electrolyte and the positive electrode together, hot-pressing at the pressure of 10MPa and the temperature of 250 ℃ for 1h, leading out tabs at the edges of the positive electrode plate and the negative electrode plate, and finally packaging by using an aluminum plastic film to obtain the solid lithium ion battery.
Comparative example 1
The present comparative example is a lithium ion solid-state battery including a negative electrode, a solid electrolyte, and a positive electrode, which are arranged in this order, wherein the negative electrode is a copper foil and a graphite layer coated on the surface of the copper foil, and the positive electrode is an aluminum foil and a positive electrode material layer coated on the surface of the aluminum foil (the positive electrode material layer includes a positive electrode active material and a binder in the same ratio as in example 6), and the material composition in the positive electrode material layer is the same as that in example 6. Meanwhile, the positive and negative electrode dimensions of the lithium ion solid state battery in this comparative example were also the same as those in example 6 (wherein the total thickness of the copper foil and the graphite layer in this comparative example was the same as that of the carbon foam in example 6, and the total thickness of the copper foil and the positive electrode material layer was the same as that of the positive electrode in example 6). The assembly method of the lithium ion solid-state battery in this comparative example was a conventional coating, drying, lamination, and plastic packaging process.
The lithium ion solid-state batteries provided in examples 6 to 8 and comparative example 1 were respectively tested for mass energy density and volumetric energy density, and the test results are shown in table 1.
TABLE 1 test results
Figure BDA0001752329820000161
Figure BDA0001752329820000171
As can be seen from the data in table 1, the present invention provides a lithium ion solid state battery having both a mass energy density and a volume energy density greater than those of the lithium ion solid state battery in comparative example 1.
In summary, the lithium ion solid-state battery provided by the invention has the following advantages:
1) the secondary battery provided by the invention is improved in the prior battery structure, and after the improvement, the use of a current collector is omitted, the space waste in the battery is reduced, and the volume energy density of the battery is improved;
2) compared with the traditional solid-state battery, the battery structure provided by the invention saves the use of copper foil, aluminum foil and binder, thereby improving the mass energy density of the battery;
3) compared with the traditional structural battery, the concept of the conductive foam material with the three-dimensional network structure provided by the invention has incomparable advantages, and is expected to lead the trend of the structural design of the next generation rechargeable battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (2)

1. A preparation method of an all-solid-state lithium ion battery is characterized by comprising the following steps:
a) cutting the melamine foam into a shape of 5cm × 5cm × 1cm, placing in a tube furnace, N2Carbonizing at 800 ℃ for 2h under a protective atmosphere, cooling, cleaning with absolute ethyl alcohol, drying at 60 ℃ to obtain the foam carbon with a self-supporting three-dimensional structure, and cutting the obtained foam carbon according to the required size to obtain the foam carbon with the size of 5cm multiplied by 0.1 cm;
b) in an argon gas filled glove box with oxygen and water content less than 0.1ppm, Li is weighed according to a molar ratio of 7:32S and P2S5Dissolving the solid electrolyte raw material in anhydrous acetonitrile solution, and adding Li2S and P2S5Stirring the binder polypropylene carbonate with the total weight of 3 wt% at 60 ℃ for 24 hours to obtain a homogeneous solution, soaking the foam carbon obtained in the step a) into the homogeneous solution for 10min, taking out the foam carbon, putting the foam carbon into a clean glass ware, and drying the foam carbon at normal temperature to obtain a solid electrolyte coated cathode;
c) providing LiNbO3Coated LiCoO2Dissolving the positive active material and a polypropylene carbonate binder in an acetonitrile solution according to a mass ratio of 97:3, stirring for 6h at 50 ℃ to obtain a positive solution, soaking cut carbon foam in the positive solution, taking out the carbon foam, drying at normal temperature, and repeating the soaking and drying process for 3 times to obtain a positive electrode, wherein the open cell ratio of the carbon foam is 99%;
d) and filling an argon gas containing less than 0.1ppm of oxygen and water into a glove box, superposing the obtained negative electrode coated by the solid electrolyte and the positive electrode together, hot-pressing at the pressure of 10MPa and the temperature of 250 ℃ for 1h, leading out tabs at the edges of the positive electrode plate and the negative electrode plate, and finally packaging by using an aluminum plastic film to obtain the solid lithium ion battery.
2. An all-solid-state lithium ion battery prepared by the preparation method of claim 1.
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