CN110690420A - Composite material cathode, battery and preparation method thereof - Google Patents

Composite material cathode, battery and preparation method thereof Download PDF

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CN110690420A
CN110690420A CN201910860031.7A CN201910860031A CN110690420A CN 110690420 A CN110690420 A CN 110690420A CN 201910860031 A CN201910860031 A CN 201910860031A CN 110690420 A CN110690420 A CN 110690420A
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metal
layer
porous
framework
dielectric
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CN110690420B (en
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杨诚
湛厚超
邹培超
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Shenzhen International Graduate School of Tsinghua University
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Shenzhen International Graduate School of Tsinghua University
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
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    • 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
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • H—ELECTRICITY
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The composite material negative electrode comprises a three-dimensional framework and active metal, wherein the three-dimensional framework comprises a non-conductive porous dielectric layer prepared by taking a high molecular material or an inorganic oxide as a raw material and a porous conducting layer prepared by taking a carbon material or a metal material as a raw material, the porous dielectric layer and the porous conducting layer are periodically assembled together to form the three-dimensional framework with alternately arranged conductive/dielectric periods, and the active metal is embedded into the three-dimensional framework to form the composite material negative electrode. Due to the regulation and control of the periodic conductive framework on an electron transmission path and ion concentration distribution, the composite material cathode can effectively improve the stability of the metal cathode in a circulation process, inhibit dendritic crystal growth and improve the safety of the metal cathode.

Description

Composite material cathode, battery and preparation method thereof
Technical Field
The invention relates to the field of batteries, in particular to a composite material cathode, a battery and a preparation method thereof.
Background
Excessive exploitation and use of traditional fossil fuels lead to resource exhaustion and environmental pollution; however, the clean energy developed in the new era has the challenge of difficult storage, so that the electrochemical energy storage becomes the focus of attention in the new era. Meanwhile, the development of new fields such as electric vehicles, intelligent robots, national power grids, aerospace and the like also puts higher requirements on electrochemical power supplies. The traditional lithium ion battery has the advantages of stable cycle and good safety performance, but the traditional lithium ion battery cannot meet the requirements of future society on high power and large capacity of the battery.
Active metals (lithium, sodium, potassium, zinc, aluminum, etc.) are one class of ideal battery negative electrode materials. Taking lithium metal as an example, lithium metal has a high theoretical capacity density (3860mAh g)-1) And low reduction potential (-3.04V vs. standard hydrogen electrode), which can increase the battery capacity to several times that of lithium ion battery when used as the negative electrode of the battery. However, when lithium metal is used as a battery negative electrode, there are still problems of large volume change of the electrode, uncontrollable dendrite formation, poor battery safety performance, and the like; among them, the dendritic crystal disorderly growth under large current and large capacity cycling conditions and the low coulombic efficiency due to lithium loss become the main limitation of the large-scale application of the lithium metal negative electrode. How to maintain the long cycle life and high lithium utilization rate of the battery under the working conditions of large current and large capacity becomes the key research point in the field. At present, the traditional modification method comprises: using an electrolyte additive, constructing an artificial protective film of a negative electrode, modifying a diaphragm, and constructing a composite negative electrode by utilizing a three-dimensional framework; wherein the composite material negative electrode can be constructedIt is desirable to relieve the stress caused by the volume change during the metal deposition/dissolution process and to retard/suppress the occurrence of dendrites. The traditional three-dimensional frameworks are mainly divided into two main categories, namely completely conductive frameworks and completely dielectric frameworks. However, the deposition of active metals within a fully conductive framework is mainly concentrated on the electrode surface, and dendrite growth is easily induced under a large capacity condition. The dielectric framework can realize the technical effect of depositing the active metal from bottom to top, however, because the framework can not conduct electrons, the electrochemical active sites in the framework electrode are very limited, and the improvement of the rate capability of the electrode is not facilitated.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide a composite material cathode, a battery and a preparation method thereof, which can improve the stability of a metal cathode in a circulating process, inhibit the growth of dendrites and improve the safety of the metal cathode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a composite material negative electrode comprises the following steps:
s1, preparing a non-conductive porous dielectric layer by using a high polymer material or an inorganic oxide as a raw material;
s2, preparing a porous conducting layer by taking a carbon material or a metal material as a raw material;
s3, periodically assembling the porous dielectric layer and the porous conducting layer together to prepare a three-dimensional framework with alternately arranged conducting/dielectric periods, and preferably performing periodic assembly in a layer-by-layer stacking or layer-by-layer suction filtration or magnetron sputtering mode;
and S4, compounding the active metal with the three-dimensional framework, and embedding the active metal into the three-dimensional framework to obtain the composite material cathode.
Further:
the polymer material comprises one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyester, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer and polyamide thermoplastic elastomer, and the inorganic oxide comprises one or more of aluminum oxide, zinc oxide and titanium oxide; preferably, the porous dielectric layer is prepared by 3D printing, electrospinning, a templating method, or a thermally induced phase separation method.
The diameter of the polymer fibers obtained through electrostatic spinning is within the range of 100-500 nanometers, and the fibers are in a mutually overlapped state; preferably, polyacrylonitrile is used as a high polymer raw material for electrospinning, the diameter of the obtained dielectric high polymer fiber bundle is 200-300 nanometers, and the fiber bundles are mutually interwoven and overlapped to form a framework with a large number of micron-sized void spaces.
The porous dielectric layer is prepared by etching a silicon dioxide pellet template method, and a high molecular solution dispersed by the silicon dioxide pellets is formed into a film by using a blade coating or spin coating mode.
The porous conducting layer is a complete conducting layer or a gradient conducting layer combining dielectric and conduction, and the gradient conducting layer is realized by covering a conducting layer on the surface of a dielectric material in a gradient manner;
the fully conductive layer material comprises one or more of a porous carbon material and a porous metal; the porous carbon material is one or more of graphene, carbon nano tubes, conductive carbon black, graphite alkyne, carbon nano fibers and activated carbon; the porous metal is one or more of metal copper, metal nickel, metal aluminum, metal silver and metal; preferably, Polyacrylonitrile (PAN) obtained by electrospinning is carbonized at high temperature in an inert atmosphere to prepare a complete conductive layer interwoven by Carbon Nanofibers (CNF);
the gradient conducting layer is realized by covering a conducting layer on the surface of a dielectric material in a gradient manner, the dielectric material is one or more of high polymer and inorganic oxide layer ceramics, the surface conducting layer material is one or more of carbon material and metal, and the gradient conducting layer is prepared in one or more of magnetron sputtering, atomic layer deposition, suction filtration, chemical vapor deposition and 3D printing; preferably, for the magnetron sputtering method, the sputtering metal layer is controlled to leave a part of the dielectric framework not to be deposited to the metal, and the metal deposition depth is controlled to be two thirds of the whole thickness of the framework, wherein the metal content presents gradient change, so that the conductivity of the framework presents gradient change.
The three-dimensional framework simultaneously comprises 1-20 conducting layers and 1-20 dielectric layers, the thicknesses of the porous conducting layers and the porous dielectric layers are controlled to be 2-50 micrometers, and the total thickness of the three-dimensional framework is 5-1000 micrometers.
The active metal is one or more of lithium, sodium, potassium, zinc and aluminum, and is filled in the three-dimensional framework by means of electrodeposition, heating melting or rolling.
A composite material negative electrode comprises a three-dimensional framework and active metal, wherein the three-dimensional framework comprises a non-conductive porous dielectric layer prepared by taking a high molecular material or an inorganic oxide as a raw material and a porous conducting layer prepared by taking a carbon material or a metal material as a raw material, the porous dielectric layer and the porous conducting layer are periodically assembled together to form the three-dimensional framework with alternately arranged conducting/dielectric periods, and the active metal is embedded into the three-dimensional framework to form the composite material negative electrode.
A preparation method of a battery is characterized in that the composite material negative electrode, a battery positive electrode, a diaphragm and electrolyte are assembled into the battery.
A battery is provided with the composite negative electrode.
The invention has the following beneficial effects:
the invention provides a novel three-dimensional skeleton composite material cathode formed by periodically stacking conducting layers and dielectric layers, wherein the conducting layers are periodically spaced by the dielectric layers, which is different from a functional three-dimensional skeleton adopted by a metal composite cathode in the prior art, wherein the functional three-dimensional skeleton is completely conductive or completely dielectric. Compared with a completely conductive three-dimensional framework and a constructed composite material cathode, the deposition mode of the active metal in the periodic conductive framework is a bottom-up mode, the problem of concentrated growth of the metal on the surface of the completely conductive framework is avoided, the space utilization rate of the three-dimensional framework is improved, and stable circulation under the condition of larger capacity is realized. Compared with a completely dielectric three-dimensional framework and a constructed composite material cathode, the conducting layer in the periodic framework can provide more abundant metal nucleation sites, and is favorable for stable nucleation and growth of lithium metal under the condition of high rate circulation. In addition, the surface of the dielectric layer has abundant polar functional groups, so that the lithium ion concentration distribution in the framework can be adjusted, the lithium ion concentration distribution is uniformly dispersed in the whole electrode, and the stable cathode metal deposition is facilitated. When metal is disorderly deposited and dendritic crystal grows, an equipotential body can be formed when the raised metal dendritic crystal is contacted with the conductive layer on the top layer, and the conductive layer has a large surface area and a plurality of nucleation sites, so that an electric field gathered on the surface of the dendritic crystal can be dispersed, further metal deposition is promoted to tend to be flattened, self-amplification parasitic growth of the dendritic crystal is inhibited, and a self-error correction function is shown. Therefore, on the basis of the advantages of the three-dimensional framework, the framework can realize that the negative metal can be stably and highly reversibly deposited/dissolved in the framework under the conditions of high current density and large capacity due to the double regulation and control of electron and ion distribution and transmission and the self-correcting function of the periodic conductive framework.
In a word, compared with a metal composite cathode constructed by a pure conductive framework or a dielectric framework, the novel composite cathode provided by the invention can effectively improve the cycling stability of a battery, and particularly improves the performance of the battery cycling under the conditions of high capacity and high current density. The preparation method is simple, high in feasibility and high in industrial production possibility; the metal battery prepared based on the framework can stably circulate under the conditions of high capacity and high density, and the development requirements of future energy storage devices are met.
Drawings
FIG. 1 is an SEM image of a polyacrylonitrile dielectric layer prepared in an embodiment of the present invention;
fig. 2 is an SEM image of a carbon nanofiber conductive layer prepared in an embodiment of the present invention;
FIG. 3 is an SEM image of a cross-section of a stack of dielectric and conductive layers in accordance with an embodiment of the present invention;
FIG. 4 is a graph showing the relationship between the cycle coulombic efficiency and the cycle number of a half-cell composed of a lithium intercalation framework and a lithium metal plate in example 1, comparative example 1.1 and comparative example 1.2 according to the embodiment of the present invention;
FIG. 5 is a graph showing the relationship between the full cell specific capacity and the number of cycles in example 1, comparative example 1.1 and comparative example 1.2 in accordance with the embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
According to one embodiment of the invention, the composite material negative electrode comprises a three-dimensional framework and an active metal, wherein the three-dimensional framework comprises a non-conductive porous dielectric layer prepared by taking a high molecular material or an inorganic oxide as a raw material and a porous conductive layer prepared by taking a carbon material or a metal material as a raw material, the porous dielectric layer and the porous conductive layer are periodically assembled together to form the three-dimensional framework with conductive/dielectric periods alternately arranged, and the active metal is embedded into the three-dimensional framework to form the composite material negative electrode.
According to another embodiment of the present invention, a method for preparing a composite anode includes the steps of:
s1, preparing a non-conductive porous dielectric layer by using a high polymer material or an inorganic oxide as a raw material;
s2, preparing a porous conducting layer by taking a carbon material or a metal material as a raw material;
s3, periodically assembling the porous dielectric layer and the porous conducting layer together to prepare a three-dimensional framework with alternately arranged conducting/dielectric periods, and preferably performing periodic assembly in a layer-by-layer stacking or layer-by-layer suction filtration or magnetron sputtering mode;
and S4, compounding the active metal with the three-dimensional framework, and embedding the active metal into the three-dimensional framework to obtain the composite material cathode.
The sequence of steps S1 and S2 in the above preparation method is not limited.
In the preparation method, the porous conducting layer and the porous dielectric layer are prepared, and the conducting layer and the dielectric layer are assembled and combined in a periodic alternating arrangement mode to form the three-dimensional negative electrode framework with periodic conducting characteristics. The composite material cathode is prepared by combining the framework with an active metal. Due to the regulation and control of the periodic conductive framework on an electron transmission path and ion concentration distribution, the composite material cathode can effectively improve the stability of the metal cathode in a circulation process, inhibit dendritic crystal growth and improve the safety of the metal cathode.
The conception of the invention is as follows: the metal secondary battery has a phenomenon that the deposition is not uniform during the cycle, resulting in the growth of dendrites. Taking lithium metal as an example, on one hand, the growth of dendrites can cause the instability of SEI and cause the formation of 'dead lithium', so that the coulombic efficiency is reduced, and the utilization rate of the lithium metal is reduced; on the other hand, sharp dendrites can pierce through the membrane, causing a short circuit of the battery, even causing explosion of the battery, resulting in potential safety hazards. Currently, researchers have controlled lithium metal deposition by means of using a three-dimensional framework. The three-dimensional skeleton of the existing battery cathode can be divided into a conductive skeleton and a dielectric skeleton, wherein the conductive skeleton is mainly made of metal materials (copper, nickel and the like) and carbon materials, and the dielectric skeleton is mainly made of high polymer materials. The conductive framework has good conductivity, and can reduce the local current density and inhibit the growth of dendrites when being used as a current collector; however, metal ions can be reduced and deposited by electrochemical reaction on the outermost surface of the framework, rather than being uniformly deposited on the inner surface of the whole framework, resulting in the phenomena of non-uniform deposition and ineffective utilization of the internal lithium storage space. The dielectric framework has poor conductivity, metal ions are reduced from the bottom of the framework to start to deposit, and when the phenomenon of uneven lithium deposition occurs, the internal electric field starts to be unevenly distributed, so that dendritic crystals grow rapidly. The invention adopts a three-dimensional skeleton structure with periodically and alternately arranged dielectric layers and conductive layers to control electron transportation and ion distribution, thereby realizing uniform deposition of the metal cathode. Because the electron transmission path in the framework is separated by the dielectric layer, electrons cannot be directly transmitted to the surface layer of the framework to generate metal deposition behavior, and therefore active metal is deposited at the bottom of the framework firstly. When the deposited metal has uneven behavior to induce the growth of metal dendrite, once the dendrite grows to the conductive layer region and forms a conductive path with the conductive layer, the dendrite and the conductive layer with a multi-nucleation site form an equipotential body; thus, the strong local electric field at the surface of the dendrite will be weakened and its further growth will be relatively planar, exhibiting a tuning capability for "self-correction" of the metal deposition. The preparation method of the three-dimensional framework is simple, can realize batch production, can obviously improve the cycle stability and safety performance of metal cathode deposition, and has good industrial application prospect.
In some embodiments, a method of making a composite anode includes the steps of:
s1, preparing the non-conductive porous dielectric layer by using high polymer or inorganic oxide as a precursor.
In the step, the polymer material for preparing the dielectric layer may be one or more selected from polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyester, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer and polyamide thermoplastic elastomer, and the inorganic oxide material for preparing the dielectric layer may be one or more selected from alumina, zinc oxide and titanium oxide.
The preparation method of the dielectric layer comprises one or more of 3D printing, electrostatic spinning, a template method and a heat-induced phase separation method.
When the porous dielectric layer is prepared by the electrostatic spinning method, the thickness of the dielectric skeleton film is controlled by adjusting parameters such as the electrospinning push injection speed, the solid content of the electrospinning liquid, the electrospinning time and the like. Specifically, the diameter of the polymer fiber obtained by electrostatic spinning is within the range of 100-500 nanometers, the fibers are in a mutually overlapped state, and the polymer fiber has a good property of releasing tensile stress.
As shown in figure 1, when polyacrylonitrile is selected as a high polymer raw material for electrospinning, the diameter of the obtained dielectric high polymer fiber bundle is 200-300 nanometers, and the fiber bundles are mutually interwoven and overlapped to form a framework with a large number of micron-sized void spaces.
When the porous dielectric layer is prepared by utilizing the silicon dioxide bead template etching method. Specifically, a polymer solution in which silica beads are dispersed is formed into a film by using a doctor blade coating or spin coating method, wherein the thickness of the film can be controlled by adjusting the solid content of the polymer solution, the spin coating speed and time, and the doctor blade coating thickness. The thickness of the dielectric polymer film for preparing the periodically arranged skeleton is controlled within the range of 2-50 microns.
The role of the dielectric layer in this functional skeleton mainly includes two aspects: firstly, isolating electron transmission between adjacent conductive layers and controlling active metal to deposit only from bottom to top; secondly, a surface polar functional group is provided, and the surface polar functional group has strong attraction force on lithium ions so as to enable the ion distribution to be more uniform, and further enable the deposition process of the active metal to be more uniform.
And S2, preparing the porous conducting layer by taking a carbon material or a metal material as a raw material.
The conductive material in the conductive layer can be a metal material with a microstructure of nano wires, nano sheets or nano particles, or a mixture of one or more carbon materials of graphene, conductive carbon black and carbon nano tubes. The density of the carbon material is less compared to the metal material; when active metals of the same capacity are compounded, the energy density of the composite negative electrode obtained using the carbon material skeleton is higher, and therefore, a carbon material is preferable as a raw material of the conductive layer.
Specifically, the thickness of the conductive layer is controlled to be 2-50 microns thick.
The conductive layer may include a fully conductive layer and a graded conductive layer. The conductive layer can provide more metal deposition active sites in the functional framework, and the local current density is reduced to a certain extent, so that the deposition/stripping process of the active metal can be more uniform. When metal dendrite deposition occurs, the equipotential conducting layer can inhibit the further self-amplification malignant evolution phenomenon of dendrite, and certain self-error correction capability is embodied.
The fully conductive layer material may include one or more of a porous carbon material and a porous metal. The porous carbon material is one or more of graphene, carbon nano tubes, conductive carbon black, graphite alkyne, carbon nano fibers and activated carbon. The porous metal is one or more of metal copper, metal nickel, metal aluminum, metal silver and metal.
The gradient conducting layer is realized by covering the conducting layer on the surface of the dielectric material in a gradient way. The dielectric material is one or more of polymer and inorganic oxide layer ceramics, and the surface conducting layer material is one or more of carbon material and metal. The gradient conducting layer is prepared in one or more of magnetron sputtering, atomic layer deposition, suction filtration, chemical vapor deposition and 3D printing.
As shown in fig. 2, Polyacrylonitrile (PAN) obtained by electrospinning was carbonized at high temperature in an inert atmosphere to prepare a complete conductive layer interwoven with Carbon Nanofibers (CNF). The carbon nanofiber frameworks are mutually lapped, so that the structure can be maintained stable, and certain stress can be released. The carbon nano fiber has a relatively large specific surface, so that the local current density can be reduced, and the uniform deposition of lithium metal can be realized.
The gradient conductive framework combining dielectric and conductive can also achieve the electronic ion regulation and control effect and can further induce the metal to deposit from bottom to top. The preparation method of the gradient conductive framework comprises one or more of magnetron sputtering, atomic layer deposition, suction filtration, chemical vapor deposition and 3D printing.
When the gradient conductive framework is prepared by taking a magnetron sputtering method as an example, the sputtered metal can be nickel, copper and gold. Among them, copper is preferred because of its high electrical conductivity and wide commercial use. The thickness and the depth of the deposited metal are regulated and controlled by regulating the power and the working time of a magnetron sputtering instrument. In order to ensure the adjusting function of the dielectric framework, the sputtered metal layer cannot be too deep, and a part of the dielectric framework needs to be reserved and is not deposited to the metal; if the deposition depth is too shallow, the conductive portion has too poor performance to exert the function of conducting electrons. Preferably, the metal deposition depth is controlled to be two-thirds of the overall thickness of the framework. Wherein the metal content is in gradient change, so that the conductivity of the framework is in gradient change.
S3, assembling the porous dielectric layer and the porous conducting layer obtained in the steps S1 and S2 together in a layer-by-layer stacking or layer-by-layer suction filtration mode to prepare a three-dimensional framework with alternately arranged conducting/dielectric periods,
and S4, compounding the active metal with the prepared three-dimensional framework to obtain the composite material cathode.
Fig. 3 is a cross-sectional scanning electron microscope image of the dielectric polyacrylonitrile film and the conductive carbon nanofiber film after being periodically stacked, which shows that the interface between the dielectric layer and the conductive layer is well combined, no obvious fault phenomenon occurs, and a large active metal storage space is arranged in the three-dimensional framework.
In the present embodiment, the functional three-dimensional skeleton in which the dielectric layer and the conductive layer are periodically arranged is manufactured in the above manner. The preparation process of the dielectric layer is mature, and the internal pore diameter, porosity and thickness of the dielectric layer can be adjusted by adjusting parameters such as solid content of the high-molecular solution, electrospinning time and blade coating thickness. The preparation of the micro-nano conducting layer can be realized by the technical means of preparing carbon nano fibers by carbonization, sputtering and coating metal on the surface of a framework, filtering metal nanowires and the like. The preparation method of the whole functional framework is simple, the technical means for preparation is mature, and the industrial production feasibility is high.
When the battery is assembled and applied, the active metal and the functional framework are compounded by means of electrochemical embedding, melting embedding or rolling embedding, and the like, so as to prepare the composite negative electrode for the battery. The active metal used may be lithium metal, sodium metal, potassium metal, zinc metal and aluminium metal, so that a lithium metal negative electrode, a sodium metal negative electrode, a potassium metal negative electrode, a zinc metal negative electrode and an aluminium metal negative electrode may be obtained, respectively.
When the battery is charged, electrons cannot be directly transmitted to the top layer of the framework due to the existence of the dielectric layer, and only the electrons are gathered at the bottom part close to the conductive layer of the current collector, so that the electrochemical metal deposition process preferentially occurs at the conductive layer at the bottom part, and the electrons are continuously filled upwards along with the increase of the deposition amount. When the deposited metal has uneven behavior to induce the growth of metal dendrite, once the dendrite grows to the conductive layer region and forms a conductive path with the conductive layer, the dendrite and the conductive layer with a multi-nucleation site form an equipotential body; the strong local electric field at the surface of the dendrite will then be weakened and its further growth will be relatively flattened, thereby achieving a uniform growth of a relatively pure conductive skeleton versus a pure dielectric skeleton. In the negative electrode framework of the invention, metal can realize uniform bottom-up deposition and reversible bottom-up separation effects, and has obvious effects on prolonging the cycle life of the whole battery and improving the safety performance.
The structure and performance of the negative electrode skeleton manufactured in this embodiment are verified by the following specific examples.
Example 1
Dissolving PAN powder in a DMF solvent, stirring for 0.5-72 hours, and preparing a high polymer liquid with the solid content of 2-50%. Then, injecting by a syringe, and electrospinning the prepared precursor solution on an aluminum foil; and peeling the electrospun PAN from the surface of the aluminum foil to obtain the dielectric fiber membrane skeleton. By controlling the electrospinning time, a PAN film with the thickness of 2-50 microns is obtained and used for the dielectric skeleton.
And carbonizing the PAN obtained by electrospinning to obtain the conductive CNF framework material. The carbonization process comprises the following steps: firstly, placing a PAN film in a furnace at the temperature of 100-500 ℃ in an air atmosphere, preserving heat for 0.5-5 h for pre-oxidation, and then cooling the PAN film to room temperature along with the furnace; and secondly, preserving the heat of the pre-oxidized PAN film at 800-1500 ℃ for 0.5-5 h in an argon atmosphere, and then cooling to room temperature at a heating and cooling rate of 1-10 ℃/min. And obtaining the CNF film with the thickness of 2-50 microns for the conductive framework.
The preparation of the periodic PAN/CNF framework is formed by alternately stacking the obtained PAN and CNF fiber membranes for 2-10 periods, and the total thickness is 5-1000 microns.
And punching the stacked periodic negative electrode framework into a circular sheet with the diameter of 12mm by a die pressing and punching process. The wafer is used as a positive electrode, the metal lithium sheet is used as a negative electrode, the wafer is assembled into a CR2032 button half-cell in a glove box, the button half-cell is used for testing, and the button half-cell is used for testing the button half-cell to be 1-5 mA cm-2，1～5mAh cm-2Coulombic efficiency versus cycle number under the conditions. Meanwhile, after the half cell is kept still for 12 hours, the half cell is tested by 0.05-2.0 mA cm in a blue light test system-2The discharge current density of (1-10 mAh cm) is embedded in the negative electrode framework-2The lithium metal of (1). Then the battery is disassembled in a glove box, the negative electrode framework embedded with lithium metal is taken out,and (3) washing the mixture for 2-3 times by using a DMC solvent, and drying the mixture for 3 hours at room temperature. After drying, the wafer deposited with the lithium metal active substance is taken as a battery cathode, a commercial nickel cobalt lithium manganate ternary material (NCM) wafer electrode with the diameter of 12mm is taken as a battery anode, a CR2032 type full battery is assembled in a glove box, and the cycling stability of the CR2032 type full battery under the condition of 1C is tested.
Comparative example 1.1
Similar to the process described above. Dissolving PAN powder in a DMF solvent, stirring for 0.5-72 hours, and preparing a high polymer liquid with the solid content of 2-50%. Then, injecting by a syringe, and electrospinning the prepared precursor solution on an aluminum foil; and peeling the electrospun PAN from the surface of the aluminum foil to obtain the dielectric fiber membrane skeleton. By controlling the electrospinning time, the PAN membrane with adjustable thickness can be obtained. The thickness of the PAN dielectric framework material for comparative sample analysis is consistent with that of the periodic framework in the embodiment 1, and is controlled to be 5-1000 micrometers.
And punching the obtained dielectric framework into a wafer with the diameter of 12mm by a die pressing and punching process. The wafer is used as a positive electrode, the metal lithium sheet is used as a negative electrode, the wafer is assembled into a CR2032 button half-cell in a glove box, the button half-cell is used for testing, and the button half-cell is used for testing the button half-cell to be 1-5 mA cm-2，1～5mAh cm-2Coulombic efficiency versus cycle number under the conditions. Meanwhile, after the half cell is kept still for 12 hours, the half cell is tested by 0.05-2.0 mA cm in a blue light test system-2The discharge current density of (1-10 mAh cm) is embedded in the negative electrode framework-2The lithium metal of (1). And then, the battery is disassembled in a glove box, the negative electrode framework embedded with the lithium metal is taken out, and the negative electrode framework is cleaned for 2-3 times by using a DMC solvent and dried for 3 hours at room temperature. After drying, the wafer deposited with the lithium metal active substance is taken as a battery cathode, a commercial nickel cobalt lithium manganate ternary material (NCM) wafer electrode with the diameter of 12mm is taken as a battery anode, a CR2032 type full battery is assembled in a glove box, and the cycling stability of the CR2032 type full battery under the condition of 1C is tested.
Comparative example 1.2
Similar to the process described above. Dissolving PAN powder in a DMF solvent, stirring for 0.5-72 hours, and preparing a high polymer liquid with the solid content of 2-50%. Then, injecting by a syringe, and electrospinning the prepared precursor solution on an aluminum foil; and peeling the electrospun PAN from the surface of the aluminum foil to obtain the dielectric fiber membrane skeleton.
And carbonizing the PAN obtained by electrospinning to obtain the conductive CNF framework material. The carbonization process comprises the following steps: firstly, placing a PAN film in a furnace at the temperature of 100-500 ℃ in an air atmosphere, preserving heat for 0.5-5 h for pre-oxidation, and then cooling the PAN film to room temperature along with the furnace; and secondly, preserving the heat of the pre-oxidized PAN film at 800-1500 ℃ for 0.5-5 h in an argon atmosphere, and then cooling to room temperature at a heating and cooling rate of 1-10 ℃/min. The thickness of the CNF conductive framework material for comparison analysis is consistent with that of the periodic framework in the embodiment 1 by regulating and controlling the thickness of the carbonization PAN, and is controlled to be 5-1000 microns.
And punching the obtained dielectric framework into a wafer with the diameter of 12mm by a die pressing and punching process. The wafer is used as a positive electrode, the metal lithium sheet is used as a negative electrode, the wafer is assembled into a CR2032 button half-cell in a glove box, the button half-cell is used for testing, and the button half-cell is used for testing the button half-cell to be 1-5 mA cm-2，1～5mAh cm-2Coulombic efficiency versus cycle number under the conditions. Meanwhile, after the half cell is kept still for 12 hours, the half cell is tested by 0.05-2.0 mA cm in a blue light test system-2The discharge current density of (1-10 mAh cm) is embedded in the negative electrode framework-2The lithium metal of (1). And then, the battery is disassembled in a glove box, the negative electrode framework embedded with the lithium metal is taken out, and the negative electrode framework is cleaned for 2-3 times by using a DMC solvent and dried for 3 hours at room temperature. After drying, the wafer deposited with the lithium metal active substance is taken as a battery cathode, a commercial nickel cobalt lithium manganate ternary material (NCM) wafer electrode with the diameter of 12mm is taken as a battery anode, a CR2032 type full battery is assembled in a glove box, and the cycling stability of the CR2032 type full battery under the condition of 1C is tested.
As shown in fig. 4, from the half-cell performance in example 1 and the comparative example, it can be seen that the composite anode prepared based on the periodic framework has more stable coulombic efficiency and longer cycle life when cycled at large capacity and large current density. Fig. 5 is a graph of the full battery specific capacity versus cycle number based on different framework preparations, which clearly shows that the full battery obtained based on the periodic framework composite negative electrode in example 1 has better specific capacity performance and better cycle stability. These data indicate that there is a more uniform process of lithium metal deposition and exfoliation within the periodic framework, and that the periodic framework composite negative electrode exhibits a longer cycle life and has better commercial application prospects.
Example 2
SiO with the diameter of 1-20 microns2The small ball particles are dispersed in N, N-Dimethylformamide (DMF) solution of polyamide acid (PAA), and the solid content of the solution is kept within the range of 2-50 percent; PAA films of different thicknesses were prepared by adjusting the height of the doctor blade for blade coating. The silica spheres are uniformly dispersed in the PAA film. And then, preserving heat at the temperature of 60-500 ℃ for 0.5-720 min at the temperature rising speed of 1-10 ℃/min to remove the solution, preserving heat at the temperature of 60-500 ℃ for 0.5-720 min to carry out thermal imidization on PAA to obtain a Polyimide (PI) film, wherein the thickness of the dielectric PI film is controlled within the range of 2-50 microns.
And soaking the prepared PI film in hydrofluoric acid for 12h, reacting the hydrofluoric acid with the silicon dioxide pellets, and etching to obtain the dielectric PI film with porous inside. The thickness of the etched porous PI film is maintained within the range of 2-50 microns; the pore diameter and porosity inside the porous PI film are controlled by the added silica spheres, the pore diameter is controlled within the range of 1-20 microns, and the porosity is controlled within the range of 30% -95%.
And sputtering a layer of metal copper on one side of the prepared porous PI film by using a magnetron sputtering method. The sputtering depth of the metal in the porous PI film can be adjusted by adjusting the power of a magnetron sputtering machine and the aperture and porosity of the porous film. Preferably, the sputtering depth is controlled to be two thirds of the thickness of the whole porous membrane, so that the hydrophilic metal ion sites in a larger range are available, and part of the dielectric layer can be left to realize the regulation and control of the electron transmission in the framework. This gradient conductive structure itself facilitates uniform deposition of the metal cathode.
The periodic framework is formed by stacking the prepared gradient frameworks, the number of stacked layers is controlled to be 2-10 periods, and the total thickness is 5-1000 microns.
And punching the obtained periodic framework into a circular sheet with the diameter of 12mm by a die pressing and punching process. The wafer is used as a positive electrode, the metal lithium sheet is used as a negative electrode, the wafer is assembled into a CR2032 button half-cell in a glove box, the button half-cell is used for testing, and the button half-cell is used for testing the button half-cell to be 1-5 mA cm-2，1～5mAh cm-2Coulombic efficiency versus cycle number under the conditions. Meanwhile, after the half cell is kept still for 12 hours, the half cell is tested by 0.05-2.0 mA cm in a blue light test system-2The discharge current density of (1-10 mAh cm) is embedded in the negative electrode framework-2The lithium metal of (1). And then, the battery is disassembled in a glove box, the negative electrode framework embedded with the lithium metal is taken out, and the negative electrode framework is cleaned for 2-3 times by using a DMC solvent and dried for 3 hours at room temperature. After drying, the wafer deposited with the lithium metal active substance is taken as a battery cathode, a commercial nickel cobalt lithium manganate ternary material (NCM) wafer electrode with the diameter of 12mm is taken as a battery anode, a CR2032 type full battery is assembled in a glove box, and the cycling stability of the CR2032 type full battery under the condition of 1C is tested.
Comparative example 2
Similar to example 2, the non-periodically stacked gradient conductive framework prepared in comparative example 2 has the same thickness as the periodic conductive framework prepared in example 2, and is controlled to be 5-1000 micrometers. Subsequently, a battery negative electrode, an assembled battery, and a performance test comparison of the fabricated battery with the battery obtained in example 2 were performed. The specific process is as follows:
SiO with the diameter of 1-20 microns2The small ball particles are dispersed in N, N-Dimethylformamide (DMF) solution of polyamide acid (PAA), and the solid content of the solution is kept within the range of 2-50 percent; PAA films of different thicknesses were prepared by adjusting the height of the doctor blade for blade coating. The silica spheres are uniformly dispersed in the PAA film. And then, preserving heat at the temperature of 60-500 ℃ for 0.5-720 min at the temperature rising speed of 1-10 ℃/min to remove the solution, preserving heat at the temperature of 60-500 ℃ for 0.5-720 min to carry out thermal imidization on PAA to obtain a Polyimide (PI) film, wherein the thickness of the PI film is controlled within the range of 5-1000 microns.
And soaking the prepared PI film in hydrofluoric acid for 12h, reacting the hydrofluoric acid with the silicon dioxide pellets, and etching to obtain the dielectric PI film with porous inside. The thickness of the etched porous PI film is maintained within the range of 2-50 microns; the pore diameter and porosity inside the porous PI film are controlled by the added silica spheres, the pore diameter is controlled within the range of 1-20 microns, and the porosity is controlled within the range of 30% -95%.
And punching the obtained non-periodically stacked gradient conductive framework into a circular sheet with the diameter of 12mm by a die pressing and punching process. The wafer is used as a positive electrode, the metal sodium sheet is used as a negative electrode, a CR2032 button half-cell is assembled in a glove box, the button half-cell is used for testing, and the button half-cell is used for testing the button half-cell to be 1-5 mA cm-2，1～5mAh cm-2Coulombic efficiency versus cycle number under the conditions. Meanwhile, after the half cell is kept still for 12 hours, the half cell is tested by 0.05-2.0 mA cm in a blue light test system-2The discharge current density of (1-10 mAh cm) is embedded in the negative electrode framework-2Sodium metal (iii). And then, the battery is disassembled in a glove box, the negative electrode framework embedded with sodium metal is taken out, and the negative electrode framework is cleaned for 2-3 times by using DMC solvent and dried for 3 hours at room temperature. After the drying, the wafer deposited with the sodium metal active material is used as a battery cathode, a commercial sodium vanadium phosphate electrode with the diameter of 12mm is used as a battery anode, and the wafer is assembled into a CR2032 type full battery in a glove box, and the cycling stability of the full battery under the condition of 1C is tested. The performance plots obtained from the tests are similar to those in example 1 and are not provided here. The test result shows that the periodic gradient structure has better specific capacity exertion and cycling stability compared with a simple gradient structure.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention.

Claims (10)

1. The preparation method of the composite material negative electrode is characterized by comprising the following steps of:
s1, preparing a non-conductive porous dielectric layer by using a high polymer material or an inorganic oxide as a raw material;
s2, preparing a porous conducting layer by taking a carbon material or a metal material as a raw material;
s3, periodically assembling the porous dielectric layer and the porous conducting layer together to prepare a three-dimensional framework with alternately arranged conducting/dielectric periods, and preferably performing periodic assembly in a layer-by-layer stacking or layer-by-layer suction filtration or magnetron sputtering mode;
and S4, compounding the active metal with the three-dimensional framework, and embedding the active metal into the three-dimensional framework to obtain the composite material cathode.
2. The preparation method according to claim 1, wherein the polymer material comprises one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyester, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer and polyamide thermoplastic elastomer, and the inorganic oxide comprises one or more of alumina, zinc oxide and titanium oxide; preferably, the porous dielectric layer is prepared by 3D printing, electrospinning, a templating method, or a thermally induced phase separation method.
3. The preparation method according to claim 2, wherein the diameter of the polymer fiber obtained by the electrostatic spinning is within the range of 100 to 500 nm, and the fibers are in a mutually overlapped state; preferably, polyacrylonitrile is used as a high polymer raw material for electrospinning, the diameter of the obtained dielectric high polymer fiber bundle is 200-300 nanometers, and the fiber bundles are mutually interwoven and overlapped to form a framework with a large number of micron-sized void spaces.
4. The method according to claim 2, wherein the porous dielectric layer is prepared by etching a template of silica beads, and the polymer solution in which the silica beads are dispersed is formed into a film by means of doctor blading or spin coating.
5. The method according to any one of claims 1 to 4, wherein the porous conductive layer is a complete conductive layer or a gradient conductive layer combining dielectric and conductive, the gradient conductive layer is realized by covering a conductive layer on the surface of a dielectric material in a gradient manner;
the fully conductive layer material comprises one or more of a porous carbon material and a porous metal; the porous carbon material is one or more of graphene, carbon nano tubes, conductive carbon black, graphite alkyne, carbon nano fibers and activated carbon; the porous metal is one or more of metal copper, metal nickel, metal aluminum, metal silver and metal; preferably, Polyacrylonitrile (PAN) obtained by electrospinning is carbonized at high temperature in an inert atmosphere to prepare a complete conductive layer interwoven by Carbon Nanofibers (CNF);
the gradient conducting layer is realized by covering a conducting layer on the surface of a dielectric material in a gradient manner, the dielectric material is one or more of high polymer and inorganic oxide layer ceramics, the surface conducting layer material is one or more of carbon material and metal, and the gradient conducting layer is prepared in one or more of magnetron sputtering, atomic layer deposition, suction filtration, chemical vapor deposition and 3D printing; preferably, for the magnetron sputtering method, the sputtering metal layer is controlled to leave a part of the dielectric framework not to be deposited to the metal, and the metal deposition depth is controlled to be two thirds of the whole thickness of the framework, wherein the metal content presents gradient change, so that the conductivity of the framework presents gradient change.
6. The method according to any one of claims 1 to 5, wherein the three-dimensional skeleton comprises 1 to 20 conductive layers and 1 to 20 dielectric layers, the thickness of each of the porous conductive layers and the porous dielectric layers is controlled to be 2 to 50 micrometers, and the total thickness of the three-dimensional skeleton is 5 to 1000 micrometers.
7. The production method according to any one of claims 1 to 6, wherein the active metal is one or more of metals lithium, sodium, potassium, zinc and aluminum, and is filled in the three-dimensional skeleton by means of electrodeposition, heat melting or rolling.
8. The composite material negative electrode is characterized by comprising a three-dimensional framework and active metal, wherein the three-dimensional framework comprises a non-conductive porous dielectric layer prepared by taking a high molecular material or an inorganic oxide as a raw material and a porous conductive layer prepared by taking a carbon material or a metal material as a raw material, the porous dielectric layer and the porous conductive layer are periodically assembled together to form the three-dimensional framework with conductive/dielectric periods alternately arranged, and the active metal is embedded into the three-dimensional framework to form the composite material negative electrode.
9. A method for producing a battery, characterized in that the composite negative electrode according to any one of claims 1 to 8 is assembled with a battery positive electrode, a separator and an electrolyte to form a battery.
10. A battery comprising the composite negative electrode according to any one of claims 1 to 8.
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