CN111725480A - Composite shape memory alloy cathode, preparation method thereof and lithium battery - Google Patents

Composite shape memory alloy cathode, preparation method thereof and lithium battery Download PDF

Info

Publication number
CN111725480A
CN111725480A CN202010605390.0A CN202010605390A CN111725480A CN 111725480 A CN111725480 A CN 111725480A CN 202010605390 A CN202010605390 A CN 202010605390A CN 111725480 A CN111725480 A CN 111725480A
Authority
CN
China
Prior art keywords
memory alloy
shape memory
lithium
framework
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010605390.0A
Other languages
Chinese (zh)
Inventor
陈锡龙
赵伟
李素丽
李俊义
徐延铭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhuhai Cosmx Battery Co Ltd
Original Assignee
Zhuhai Cosmx Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhuhai Cosmx Battery Co Ltd filed Critical Zhuhai Cosmx Battery Co Ltd
Priority to CN202010605390.0A priority Critical patent/CN111725480A/en
Publication of CN111725480A publication Critical patent/CN111725480A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M4/36—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
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a composite shape memory alloy cathode, a preparation method thereof and a lithium battery, wherein the composite shape memory alloy cathode is provided with a three-dimensional shape memory alloy framework, and at least part of the surface of the framework is coated with a conductive material; also includes a lithium-containing material filled in the three-dimensional pores. According to the composite shape memory alloy negative electrode, the conductive material is coated on the surface of the three-dimensional shape memory alloy, so that the volume expansion of the negative electrode can be relieved, and the problem of dendritic crystal growth induction caused by the rough surface of an alloy framework can be solved.

Description

Composite shape memory alloy cathode, preparation method thereof and lithium battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a composite shape memory alloy cathode, a preparation method thereof and a lithium battery.
Background
Since birth, lithium ion batteries (lithium batteries for short) are receiving attention from people because of their characteristics of high energy density, good cycle performance, no memory effect, environmental friendliness, and the like. In the 3C field, such as the field of small electronic products like mobile phones, notebooks, digital cameras and unmanned planes, lithium ion batteries have been indispensable key components. With the development of the times, in the field of new energy electric automobiles and even potential aviation and power grid energy storage fields, lithium ion secondary batteries play or are about to play an important role. However, most of the current commercial lithium secondary batteries use graphite carbon cathodes, the theoretical specific capacity of the graphite carbon cathodes is 372mAh/g, actual research and development are close to the theoretical limit, and the leading edge level of the whole battery core is about 300Wh/kg at present. For electric automobiles, the energy density is not enough to meet the demand of people for long-endurance and long-life batteries, so that it is necessary to develop an electrode material with higher theoretical specific capacity.
The lithium metal negative electrode has a specific capacity as high as 3860mAh/g, which is one order of magnitude higher than commercial graphite, and has the lowest standard electrode potential (-3.045V), which means that more energy can be emitted than other negative electrode materials, thus having considerable potential in high-capacity lithium battery applications. Nevertheless, the use of lithium metal as the negative electrode has several relatively troublesome problems. On one hand, because lithium metal belongs to a host-free material, the deposition/stripping process is disordered, lithium dendrite is easily generated in the process, the lithium dendrite penetrates through a diaphragm, and the short circuit of a positive electrode and a negative electrode is caused, so that potential safety hazards are generated. On the other hand, the lithium metal has high activity and reacts with the electrolyte, although at this stage, a protective SEI film (solid electrolyte interface film) is formed on the surface of the lithium metal, so as to prevent the subsequent reaction. However, the SEI film has poor mechanical properties and is easily broken after cycling to expose fresh lithium below, and the fresh lithium reacts with the electrolyte again, so that the active material of the battery is continuously consumed, and the capacity of the battery is rapidly reduced. Moreover, corrosion of the electrolyte can cause the surface of the lithium to become fluffy and porous, so that the battery expands, thereby causing potential safety hazards.
In recent years researchers have proposed a number of approaches to suppress or alleviate the above problems. With the exception of the positive electrode, several major basic structures in batteries have been studied accordingly. Such as separator modification, electrolyte modification, negative electrode lithium storage, current collector modification, and the like. The three-dimensional shape memory alloy has shape memory characteristics, and when the three-dimensional shape memory alloy is used as a negative electrode lithium storage material, the expansion of a lithium negative electrode can be inhibited to a certain extent, and the safety of the lithium negative electrode is improved. Moreover, the three-dimensional conductive network of the three-dimensional memory alloy can reduce the actual surface current density and prolong the moral time. However, the three-dimensional shape memory alloy has the problem of rough framework, and the current density at the rough and sharp part is higher, which can be used as a non-uniform nucleation site to induce the generation of lithium dendrite.
Therefore, a composite shape memory alloy negative electrode is urgently needed to be researched to solve the problem of lithium dendrite generation due to rough induction of a shape memory alloy framework and realize long cycle life of a lithium battery.
Disclosure of Invention
The invention provides a composite shape memory alloy cathode, which is characterized in that a conductive material is coated on the surface of a shape memory alloy, so that the problem of lithium dendrite growth induction caused by rough three-dimensional shape memory alloy framework is further inhibited while the volume expansion of the cathode is relieved.
The invention also provides a preparation method of the composite shape memory alloy cathode, the process is simple, the problem of lithium dendrite growth induction caused by the rough three-dimensional shape memory alloy framework is further inhibited by coating the conductive material on the surface of the three-dimensional shape memory alloy framework, and the long cycle life of a lithium battery is realized.
The invention also provides a lithium battery, and by using the composite shape memory alloy cathode, the safety and the cycle life are improved.
In order to achieve the purpose, the invention provides the technical scheme that:
in a first aspect, the invention provides a composite shape memory alloy cathode, which comprises a three-dimensional shape memory alloy framework, wherein at least part of the surface of the framework is coated with a conductive material;
also includes a lithium-containing material filled in the three-dimensional pores.
Aiming at the defects of the currently used shape memory alloy negative electrode, the improved scheme provided by the invention is that the surface of the framework is further coated with a conductive material, and the composite type memory alloy negative electrode is formed by combining the filling of a lithium-containing material. In the present invention, the memory alloy before being coated may be a material used in the prior art, and generally is a sheet with a continuously distributed three-dimensional structure and size, and three-dimensional pores are formed (a certain number of open pores and closed pores are formed according to the shape and structure of the skeleton), and the filled lithium-containing material refers to a lithium material used for preparing the negative electrode plate, and includes lithium powder, lithium blocks, or lithium alloy powder, and the like, and also includes a binder, a solvent, and the like, which are well known to those skilled in the art and are required for preparing the negative electrode material, and the present invention is not limited thereto.
Cladding conducting material at shape memory alloy surface can wrap the coarse sharp-pointed department on the skeleton, makes the surface of skeleton more smooth, consequently, can understand that conducting material's cladding area is big more, and especially when complete cladding and thickness are even, the surface of shape memory alloy skeleton also is more smooth, more does benefit to the uneven distribution who avoids the electric current.
Compared with the similar negative electrode in the prior art, the composite shape memory alloy negative electrode has the advantages that at least part of the surface of the used memory alloy framework is coated with the conductive material, so that the surface of the framework is smoother, the uneven distribution of current is favorably avoided, then the material containing lithium ions is filled in the pores of the framework, the problem of inducing the growth of lithium dendrites caused by the roughness of the three-dimensional shape memory alloy framework is inhibited, and the long cycle life of a lithium battery is realized.
The region coated with the conductive material forms a coating layer to some extent, and thus, the coating thickness of the conductive material is the thickness of the coating layer. Generally, the thickness of the conductive material coating layer is ensured to be within a certain range, which shows that the coating effect is better, and the conductivity and the coating property are better considered. Therefore, in the present invention, the cladding thickness of the conductive material is limited to about 5nm-2 μm, such as 100-500 nm.
If the porosity of the shape memory alloy framework is too low, the content of the lithium-containing material of the whole negative electrode can be influenced, so that the performance of the negative electrode can be influenced; too high porosity affects the strength of the shape memory alloy skeleton, and further affects the electrical properties of the negative electrode plate. Therefore, the porosity of the three-dimensional shape memory alloy framework is further limited, and when the porosity is about 40-98%, such as 60-75%, the filling amount of the lithium-containing material and the strength of the negative pole piece can be ensured, so that the exertion of the electrical property of the negative pole piece is further facilitated.
When the porosity is smaller, the thickness of the three-dimensional shape memory alloy framework needs to be larger to ensure that the negative electrode still has enough lithium-containing materials, and when the porosity is larger, the thickness of the three-dimensional shape memory alloy framework can be properly reduced under the condition of ensuring certain mechanical strength. In a particular embodiment of the invention, the thickness of the three-dimensional shape memory alloy skeleton is about 10 μm to 2mm, such as 200 μm to 500 μm.
The distribution of the pores in the direction perpendicular to the thickness direction is not particularly limited, and the pores may be randomly distributed or may be designed to be substantially uniformly distributed, and the present invention is within the protection scope of the present invention. It can be understood that when the pores of the shape memory alloy framework are distributed basically uniformly in the direction perpendicular to the thickness direction, the strength and the like of the negative pole piece are more stable, and the mechanical property of the negative pole piece is favorably ensured.
Further, the distribution of the lithium-containing material and the conductive material in the alloy skeleton structure can be adjusted by setting the pore density distribution of the three-dimensional shape memory alloy skeleton. For example, the density distribution of the pores may be increased stepwise or linearly in the thickness direction. Of course, in order to achieve the desired effect, the density distribution of the pores may be increased and then decreased, or decreased and then increased in the thickness direction, and the like, and the inventors do not particularly limit this.
As described above, the present invention provides a composite shape memory alloy negative electrode, in which at least a part of the surface of the three-dimensional shape memory alloy skeleton is coated with a conductive material, and it is advantageous that the surface of the alloy skeleton is coated as much as possible, and depending on the surface characteristics of the three-dimensional shape memory alloy skeleton and the process of forming the coating with the conductive material, there may be some regions where no coating is formed or there may be a difference in coating thickness. The shape memory alloy can be coated with a conductive material by means of impregnation, for example, the conductive carbon material can be selected from more than one of carbon black, charcoal, graphite, acetylene black, activated carbon, graphene or carbon nanotubes, and can also be a conductive polymer material, for example, more than one of polyacetylene, polythiophene, polyaniline or polypyrrole.
In addition, the conductive material may be an organic material that can provide a carbon source, such as glucose, sucrose, phenol resin, polytetrafluoroethylene, or the like, and is pyrolyzed and coated on at least a part of the surface of the three-dimensional shape memory alloy skeleton. Under the respective conditions for effecting pyrolysis in which carbon is attached as a conductive carbon material to the surface of the alloy skeleton, the heat treatment temperature of the pyrolysis process may be adjusted depending on the organic material selected, for example, 500-700 ℃.
In a second aspect, the invention further provides a preparation method of the composite memory alloy negative electrode, which comprises the step of forming a coating layer of a conductive material on at least part of the surface of the skeleton of the shape memory alloy, and filling pores with a lithium-containing material. The element composition and forming method of the shape memory alloy skeleton, the method of forming the conductive material coating on the surface thereof, and the basic method of filling the lithium material can be adjusted by using known techniques or according to actual requirements, for example, in the case of coating the conductive material, impregnation coating or pyrolytic carbon coating can be selected according to the properties of the material used.
The shape memory alloy material is a material which is composed of more than two metal elements and has shape memory effect through thermoelasticity and martensite phase transformation and inversion thereof, the metal elements with the shape memory function in the shape memory alloy framework material of the invention are selected from the metal elements with the shape memory function commonly used in the field, such as Ti, Cu and Fe, and can be prepared into TiNi alloy, CuAlMn alloy, CuZnAl alloy, FeMnSi alloy and the like. The preparation method of the three-dimensional shape memory alloy framework can adopt the conventional method in the field, for example, the alloy ingot can be melted firstly, poured into a pore-forming template and shaped, then the pore-forming agent is removed, cleaned and dried, and then heat treatment is carried out, so as to obtain the three-dimensional shape memory alloy framework; or preparing the alloy by adopting an electric arc melting method, then carrying out strip throwing treatment under the vacuum condition by using a copper roller rapid quenching method to obtain the ultrathin strip-shaped alloy, then corroding the ultrathin strip-shaped alloy by using a solution containing chloride ions, cleaning, drying and carrying out heat treatment to obtain the three-dimensional shape memory alloy framework.
The preparation method of the composite memory alloy cathode is simple in process, and the conductive material is coated on the surface of the shape memory alloy, so that the problem of lithium dendrite generation caused by rough shape memory alloy framework is avoided, and the long cycle life of the lithium battery is realized.
In a third aspect, the invention provides a lithium battery, which adopts the negative electrode plate. The lithium battery using the composite shape memory alloy cathode has no special requirements on the cathode material, the electrolyte and the like, and the types of the lithium battery can be, for example, a lithium ion soft package battery, a square lithium ion battery, an aqueous solution battery and the like.
The lithium battery can avoid the problem of lithium dendrite generation caused by the rough shape memory alloy framework, and realizes the long cycle life of the lithium battery.
The preparation method of the composite shape memory alloy cathode has simple process and is convenient for industrial production, and the composite shape memory alloy cathode prepared by the method has smoother skeleton surface by coating the conductive material on the surface of the three-dimensional shape memory alloy skeleton, so that the uneven distribution of current is improved while the volume expansion of the cathode is relieved, thereby avoiding the generation of lithium dendrite. The lithium battery adopts the negative pole piece, so that the problem of lithium dendrite generation caused by rough shape memory alloy framework can be avoided, and the long cycle life of the lithium battery is realized.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic structural diagram of a shape memory alloy skeleton according to an embodiment of the present invention;
FIG. 2 is an SEM image of the shape memory alloy skeleton of example 1;
FIG. 3 is a SEM image of a graphene-clad shape memory alloy skeleton of example 1;
fig. 4 is a schematic diagram of the cycle performance of the lithium batteries of example 1 and comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The present invention is described in detail below:
example 1
Embodiment 1 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a FeMnSi alloy ingot by adopting an electric arc melting method, melting the FeMnSi alloy ingot, and pouring the melted FeMnSi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Fe with the thickness of 0.5mm64Mn30Si6Three-dimensional alloy framework, and then processing the three-dimensional alloy framework at 610 ℃ under vacuum to obtain Fe64Mn30Si6The shape memory alloy skeleton has porosity of 75%. As shown in fig. 1, the pores are substantially uniformly distributed in a direction perpendicular to the thickness direction.
Dissolving a vinyltrimethoxysilane coupling agent and a graphene dispersion liquid in deionized water to form a solution, immersing a shape memory alloy framework in the solution, and performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the surface coated with the graphene, wherein the coating thickness is 50nm as shown in figures 2-3, figure 2 is an SEM image of the memory alloy framework without the coated carbon material, the surface of the memory alloy framework is rough, and figure 3 is an SEM image of the memory alloy framework coated with the graphene, and the surface of the memory alloy framework is very smooth.
Cutting the prepared three-dimensional shape memory alloy into a preset size, and then heating and melting the lithium block into the framework to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting electrolyte to prepare the lithium ion soft package battery, then carrying out electrochemical performance test, wherein the test result is shown in table 1, and testing the cycle performance of the lithium battery, and the test result is shown in figure 4.
Example 2
Embodiment 2 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a FeMnSi alloy ingot by adopting an electric arc melting method, melting the FeMnSi alloy ingot, and pouring the melted FeMnSi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Fe with the thickness of 0.3mm64Mn30Si6Processing the three-dimensional alloy framework at 600 ℃ under vacuum to obtain the memory alloy Fe with the three-dimensional framework64Mn30Si6The porosity was 70%.
Dissolving a vinyl triethoxysilane coupling agent and an acetylene black dispersion liquid in NMP (N-methyl pyrrolidone) to form a dispersion liquid, immersing the shape memory alloy skeleton into the dispersion liquid, and performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the surface coated with the acetylene black, wherein the coating thickness is 230 nm.
Cutting the prepared three-dimensional shape memory alloy into a proper size, and then rolling a commercial lithium belt into the framework by using a rolling method to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 3
Embodiment 3 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a FeMnSi alloy ingot by adopting an electric arc melting method, melting the FeMnSi alloy ingot, and pouring the melted FeMnSi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Fe with the thickness of 0.3mm65Mn30Si5Processing the three-dimensional alloy framework at 600 ℃ under vacuum to obtain the memory alloy Fe with the three-dimensional framework65Mn30Si5The porosity was 70%.
Dispersing a vinyl triethoxysilane coupling agent and carbon black in NMP to form a dispersion liquid, immersing the shape memory alloy skeleton into the dispersion liquid, performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the surface coated with the carbon black, wherein the coating thickness is 160 nm.
Mixing Fe65Mn30Si5And cutting the shape memory alloy into a proper size, heating and melting the lithium block into the framework to obtain the negative pole piece with the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 4
Embodiment 4 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a FeMnSi alloy ingot by adopting an electric arc melting method, melting the FeMnSi alloy ingot, and pouring the melted FeMnSi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Fe with the thickness of 0.3mm65Mn30Si5Processing the three-dimensional alloy framework at 600 ℃ under vacuum to obtain the memory alloy Fe with the three-dimensional framework65Mn30Si5The porosity was 70%.
Dispersing a vinyl triethoxysilane coupling agent and an active carbon dispersion liquid in NMP to form a dispersion liquid, immersing a shape memory alloy framework into the dispersion liquid, and performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the surface coated with the active carbon, wherein the coating thickness is 150 nm.
Commercial lithium-silicon alloy powder and a binder SBR (styrene butadiene rubber) are mixed in a solvent toluene to form slurry, and the slurry is filled with Fe65Mn30Si5And drying the shape memory alloy framework, and cutting the shape memory alloy framework into a proper size to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 5
Embodiment 5 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a FeMnSi alloy ingot by adopting an electric arc melting method, melting the FeMnSi alloy ingot, and pouring the melted FeMnSi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain alloy Fe with three-dimensional sheet shape65Mn30Si50.2mm in thickness and having poresThe ratio was 63%.
Using phenolic resin as a carbon source, placing the alloy above the carbon source, heating to 600 ℃ under Ar protective atmosphere to pyrolyze the phenolic resin to obtain Fe with the surface coated with carbon65Mn30Si5The three-dimensional shape memory alloy framework is coated with the thickness of 20 nm.
Mixing Fe65Mn30Si5And cutting the shape memory alloy framework into a proper size, heating and melting the lithium block into the framework to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 6
Embodiment 6 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Charging materials according to a preset proportion, preparing a TiNi alloy ingot by adopting an electric arc melting method, melting the TiNi alloy ingot, and pouring the TiNi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain a TiNi three-dimensional alloy framework with the thickness of 0.5mm, and then processing the TiNi three-dimensional alloy framework at 550 ℃ under vacuum to obtain the memory alloy TiNi with the three-dimensional framework, wherein the porosity of the TiNi is 80%.
Dissolving a vinyltriethoxysilane coupling agent and a carbon nano tube dispersion liquid in NMP to form a solution, immersing the shape memory alloy skeleton into the solution, and performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the surface coated with the carbon nano tube, wherein the coating thickness is 320 nm.
Cutting the prepared three-dimensional shape memory alloy framework into a proper size, and then rolling a commercial lithium belt into the framework by using a rolling method to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 7
Embodiment 7 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Charging according to a preset proportion, preparing a TiNi alloy ingot by arc melting, melting the TiNi alloy ingot, and pouring the TiNi alloy ingot into a sintered pore-forming agent NaAlO2And (3) shaping in the template, then removing the pore-forming agent by acid cleaning, cleaning and drying to obtain a TiNi three-dimensional alloy skeleton with the thickness of 0.5mm, wherein the porosity is 80%.
Using cane sugar as carbon source, placing alloy above the carbon source, in N2And heating to 600 ℃ under the protective atmosphere to pyrolyze the sucrose to obtain the carbon-coated TiNi three-dimensional shape memory alloy, wherein the coating thickness is 10 nm.
Cutting the prepared three-dimensional shape memory alloy framework into a proper size, and then rolling a commercial lithium belt into the framework by using a rolling method to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 8
Embodiment 8 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Charging materials according to a preset proportion, preparing a TiNi alloy ingot by adopting an electric arc melting method, melting the TiNi alloy ingot, and pouring the TiNi alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, wherein NaAlO2Gradient is formed in the pore space of the template along the thickness direction, the pore-forming agent is removed through acid cleaning, and the pore-forming agent is cleaned and dried to obtain the pore-forming agent with gradient along the thickness directionThe thickness of the porosity is 0.5mm, and the overall porosity is 85%.
Using cane sugar as carbon source, placing alloy above the carbon source, in N2And heating to 600 ℃ under the protective atmosphere to pyrolyze the sucrose to obtain the carbon-coated TiNi three-dimensional shape memory alloy, wherein the coating thickness is 15 nm.
Cutting the prepared three-dimensional shape memory alloy framework into a proper size, and then rolling a commercial lithium belt into the framework by using a rolling method to obtain the TiNi shape memory alloy framework lithium cathode with the surface of the framework coated with carbon.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 9
Embodiment 9 provides a lithium battery, and a method of manufacturing the lithium battery includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuAlMn alloy ingot by adopting electric arc melting, melting the CuAlMn alloy ingot, and pouring the melted CuAlMn alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Cu with the thickness of 0.2mm73Al17Mn10The three-dimensional alloy framework has a porosity of 75%.
Using glucose as a carbon source, placing the alloy above the carbon source, heating to 600 ℃ under Ar protective atmosphere to pyrolyze the glucose, and obtaining the Cu with the framework surface coated with carbon73Al17Mn10The coating thickness of the three-dimensional shape memory alloy is 20 nm.
Mixing Cu73Al17Mn10And cutting the shape memory alloy framework into a proper size, and heating and melting the lithium block into the framework to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 10
Embodiment 10 provides a lithium battery, and a preparation method thereof includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuAlMn alloy ingot by adopting electric arc melting, melting the CuAlMn alloy ingot, and pouring the melted CuAlMn alloy ingot into a sintered pore-forming agent NaAlO2Shaping in a template, then removing a pore-forming agent by acid cleaning, cleaning and drying to obtain Cu with the thickness of 0.2mm73Al17Mn10The alloy framework has a porosity of 75%.
Using polytetrafluoroethylene as a carbon source, placing the alloy above the carbon source, heating to 600 ℃ under Ar protective atmosphere to obtain Cu with the surface coated with carbon73Al17Mn10The three-dimensional shape memory alloy framework is coated with the thickness of 22 nm.
Mixing Cu73Al17Mn10And cutting the three-dimensional shape memory alloy framework into a proper size, and then rolling the commercial lithium belt into the framework by using a rolling method to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 11
Embodiment 11 provides a lithium battery, which includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuAlMn alloy ingot by adopting an electric arc melting method, melting the CuAlMn alloy ingot, and pouring the melted CuAlMn alloy ingot into a sintered pore-forming agent NaAlO2Shaping in template, acid washing to remove pore-forming agent, washing, and bakingObtaining Cu with a thickness of 0.2mm73Al17Mn10Treating the three-dimensional alloy framework at 600 ℃ under vacuum to obtain Cu73Al17Mn10The porosity of the three-dimensional shape memory alloy framework is 75%.
Dissolving a vinyltriethoxysilane coupling agent and polypyrrole in ethanol to form a solution, then immersing the shape memory alloy skeleton into the solution, and performing ultrasonic dispersion and drying to obtain the three-dimensional shape memory alloy with the skeleton surface coated with the polypyrrole, wherein the coating thickness is 300 nm.
Mixing Cu73Al17Mn10Cutting the shape memory alloy framework into a proper size, and then rolling a commercial lithium belt into the framework by using a rolling method to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 12
Embodiment 12 provides a lithium battery, which includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuZnAl alloy ingot by adopting an electric arc melting method, carrying out strip casting treatment on the alloy ingot under a vacuum condition by using a copper roller rapid quenching method to obtain an ultrathin strip alloy, then corroding the ultrathin strip alloy by using a solution containing chloride ions, cleaning and drying to obtain Cu with the thickness of 0.3mm63Zn27Al10Treating the three-dimensional porous alloy framework at 600 ℃ under vacuum to obtain Cu63Zn27Al10The porosity of the three-dimensional porous shape memory alloy framework is 50 percent.
And dispersing a vinyl triethoxysilane coupling agent and polythiophene into ethanol to form a dispersion liquid, then immersing the shape memory alloy framework into the dispersion liquid, and performing ultrasonic dispersion and drying to obtain the porous shape memory alloy with the framework surface coated with the polythiophene, wherein the coating thickness is 450 nm.
Commercial lithium powder and Styrene Butadiene Rubber (SBR) as a binder are mixed in toluene as a solvent to form slurry, and the slurry is filled with Cu63Zn27Al10And drying the shape memory alloy framework, and cutting the shape memory alloy framework into a proper size to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 13
Embodiment 13 provides a lithium battery, which includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuZnAl alloy ingot by adopting electric arc melting, carrying out strip throwing treatment on the alloy ingot under a vacuum condition by using a copper roller rapid quenching method to obtain an ultrathin strip alloy, then corroding the ultrathin strip alloy by using a solution containing chloride ions, cleaning and drying to obtain Cu with the thickness of 0.3mm63Zn27Al10Treating the three-dimensional porous alloy framework at 600 ℃ under vacuum to obtain Cu63Zn27Al10The porosity of the three-dimensional porous shape memory alloy framework is 50 percent.
Dissolving allyl triethoxysilane coupling agent and polyaniline in NMP to form dispersion, then immersing the shape memory alloy skeleton into the dispersion, and performing ultrasonic dispersion and drying to obtain the shape memory alloy skeleton with the surface coated with polyaniline, wherein the coating thickness is 420 nm.
Commercial lithium powder and SBR as a binder are mixed in toluene as a solvent to form slurry, and the slurry is filled with Cu63Zn27Al10And drying the memory alloy framework, and cutting the memory alloy framework into a proper size to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Example 14
Embodiment 14 provides a lithium battery, which includes the steps of:
1) preparation of composite shape memory alloy cathode
Feeding materials according to a preset proportion, preparing a CuZnAl alloy ingot by adopting electric arc melting, carrying out strip throwing treatment on the alloy ingot under a vacuum condition by using a copper roller rapid quenching method to obtain an ultrathin strip alloy, then corroding the ultrathin strip alloy by using a solution containing chloride ions, cleaning and drying to obtain Cu with the thickness of 0.3mm63Zn27Al10Treating the three-dimensional porous alloy framework at 600 ℃ under vacuum to obtain Cu63Zn27Al10The porosity of the three-dimensional porous shape memory alloy framework is 50 percent.
Dispersing an allyl triethoxysilane coupling agent and polyacetylene in NMP to form a dispersion liquid, then immersing the shape memory alloy skeleton into the dispersion liquid, and performing ultrasonic dispersion and drying to obtain the shape memory alloy skeleton with the surface coated with polyacetylene, wherein the coating thickness is 200 nm.
Commercial lithium-silicon alloy powder and a binder SBR are mixed in a solvent toluene to form slurry, and then the slurry is filled with Cu63Zn27Al10And drying the shape memory alloy framework, and cutting the shape memory alloy framework into a proper size to obtain the negative pole piece of the composite shape memory alloy negative pole.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Comparative example 1
Comparative example 1 provides a lithium battery, the preparation method of which includes the steps of:
1) preparation of negative pole piece
The method comprises the steps of using commercial foam nickel as a three-dimensional current collector framework, enabling the porosity of the commercial foam nickel to be 95% and the thickness of the commercial foam nickel to be 0.3mm, mixing commercial lithium powder and a binder SBR in a solvent toluene to form slurry, filling the slurry into the foam nickel, drying, and cutting into a proper size to obtain the nickel composite lithium cathode.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting electrolyte to prepare the lithium ion soft package battery, then carrying out electrochemical performance test, wherein the test result is shown in table 1, and testing the cycle performance of the lithium battery, and the test result is shown in figure 4.
Comparative example 2
Comparative example 2 provides a lithium battery, the preparation method of which includes the steps of:
1) preparation of negative pole piece
Commercial foam copper is used as a three-dimensional current collector framework, the porosity of the commercial foam copper is 95%, the thickness of the commercial foam copper is 0.3mm, a commercial lithium belt is directly pressed into the foam copper in a rolling manner of a roller press, and the commercial lithium belt is cut into a proper size to obtain the copper composite lithium cathode.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
Comparative example 3
Comparative example 3 provides a lithium battery, the preparation method of which includes the steps of:
1) preparation of negative pole piece
The method comprises the steps of using commercial foamed aluminum as a three-dimensional current collector framework, enabling the porosity of the current collector framework to be 95% and the thickness of the current collector framework to be 0.3mm, mixing commercial lithium silicon alloy powder and a binder SBR in a solvent toluene to form slurry, filling the slurry into the aluminum framework, drying, and cutting into a proper size to obtain the aluminum composite lithium silicon alloy cathode.
2) Preparation of lithium batteries
And (3) winding the negative pole piece, the diaphragm and the positive pole piece in sequence by using a conventional process, then injecting an electrolyte to prepare the lithium ion soft package battery, and then carrying out an electrochemical performance test, wherein the test result is shown in table 1.
The electrochemical performance test of the above examples and comparative examples was conducted by measuring the number of cycles at which the capacity was decreased to 80% of the initial value under the conditions of 25 ℃ and 0.5C/0.5C, and the results are shown in Table 1.
TABLE 1 electrochemical Performance test of lithium batteries of examples and comparative examples
Figure BDA0002560893960000151
Figure BDA0002560893960000161
As can be seen from table 1 and fig. 4, when the initial discharge capacity and the first-pass efficiency of the lithium battery prepared by using the composite shape memory alloy negative electrode of the present invention are substantially the same as those of the lithium battery prepared by using a conventional three-dimensional current collector in comparison with the lithium battery prepared by using a comparative example, the cycle number of the lithium battery of the embodiment of the present invention is significantly increased when the capacity is attenuated to 80% of the initial value, which indicates that the composite shape memory alloy negative electrode of the present invention has a good cycle performance.
In conclusion, the composite shape memory alloy negative electrode disclosed by the invention can coat the rough and sharp part on the shape memory alloy framework by coating the conductive material on the surface of the shape memory alloy, so that the problem of lithium dendrite generation caused by the rough shape memory alloy framework is solved while the volume expansion of the negative electrode is relieved. The preparation method of the composite memory alloy cathode is simple in process, and the conductive material is coated on the surface of the shape memory alloy, so that the problem of lithium dendrite generation caused by rough shape memory alloy framework is avoided, and the long cycle life of the lithium battery is realized. The lithium battery of the invention uses the composite shape memory alloy cathode, and the safety and the cycle life are both improved. In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The composite shape memory alloy cathode has a three-dimensional shape memory alloy skeleton, at least partial surface of the skeleton is coated with a conductive material, and lithium-containing materials are filled in three-dimensional pores.
2. The composite shape memory alloy negative electrode of claim 1, wherein the coating thickness of the conductive material is 5nm to 2 μm.
3. The composite shape memory alloy negative electrode of claim 1, the porosity of the three-dimensional shape memory alloy skeleton being 40-98%.
4. The composite shape memory alloy negative electrode of claim 3, the three-dimensional shape memory alloy skeleton having a thickness of 10 μ ι η -2 mm.
5. The composite shape memory alloy negative electrode of any of claims 1-4, wherein the pores are substantially uniformly distributed perpendicular to the thickness direction.
6. The composite shape memory alloy anode of claim 5, a density distribution of the pores increases stepwise or linearly in a thickness direction.
7. The composite shape memory alloy negative electrode of claim 1, wherein the conductive material coats at least a part of the surface of the three-dimensional shape memory alloy skeleton by means of impregnation;
the conductive material is a conductive carbon material and/or a conductive polymer material.
8. The composite shape memory alloy negative electrode of any one of claims 1 to 4, wherein the conductive material is pyrolytically coated onto at least a portion of the surface of the three-dimensional shape memory alloy skeleton with an organic material that can provide a carbon source.
9. The method for preparing the composite memory alloy negative electrode as claimed in any one of claims 1 to 8, comprising forming a coating layer of a conductive material on at least a part of the surface of the skeleton, and filling pores with a lithium-containing material.
10. A lithium battery using the negative electrode sheet claimed in claim 9.
CN202010605390.0A 2020-06-29 2020-06-29 Composite shape memory alloy cathode, preparation method thereof and lithium battery Pending CN111725480A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010605390.0A CN111725480A (en) 2020-06-29 2020-06-29 Composite shape memory alloy cathode, preparation method thereof and lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010605390.0A CN111725480A (en) 2020-06-29 2020-06-29 Composite shape memory alloy cathode, preparation method thereof and lithium battery

Publications (1)

Publication Number Publication Date
CN111725480A true CN111725480A (en) 2020-09-29

Family

ID=72569579

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010605390.0A Pending CN111725480A (en) 2020-06-29 2020-06-29 Composite shape memory alloy cathode, preparation method thereof and lithium battery

Country Status (1)

Country Link
CN (1) CN111725480A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112909222A (en) * 2020-12-07 2021-06-04 中国科学院宁波材料技术与工程研究所 Lithium metal negative electrode and preparation method and application thereof
CN115986087A (en) * 2023-01-09 2023-04-18 杰瑞新能源科技有限公司 Silane coupling agent modified covalent organic framework/graphene composite material, preparation method thereof, electrode and battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106935864A (en) * 2017-03-09 2017-07-07 华南理工大学 A kind of nanoporous copper-zinc-aluminum shape memory alloy and preparation method and application
CN107799736A (en) * 2017-09-22 2018-03-13 山东大学 A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof
CN108448115A (en) * 2018-03-15 2018-08-24 清华大学 A kind of asymmetric skeleton structure of lithium metal battery cathode
WO2019010476A1 (en) * 2017-07-07 2019-01-10 University Of Pittsburgh-Of The Commonwealth System Of Higher Education High capacity, air-stable, structurally isomorphous lithium alloy multilayer porous foams
CN109309203A (en) * 2017-07-26 2019-02-05 中能中科（天津）新能源科技有限公司 Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application
CN109873162A (en) * 2017-12-04 2019-06-11 中国科学院大连化学物理研究所 A kind of compound 3D collector and its preparation and application
CN110957477A (en) * 2019-10-30 2020-04-03 苏州大学 Porous ceramic composite lithium metal cathode and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106935864A (en) * 2017-03-09 2017-07-07 华南理工大学 A kind of nanoporous copper-zinc-aluminum shape memory alloy and preparation method and application
WO2019010476A1 (en) * 2017-07-07 2019-01-10 University Of Pittsburgh-Of The Commonwealth System Of Higher Education High capacity, air-stable, structurally isomorphous lithium alloy multilayer porous foams
CN109309203A (en) * 2017-07-26 2019-02-05 中能中科（天津）新能源科技有限公司 Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application
CN107799736A (en) * 2017-09-22 2018-03-13 山东大学 A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof
CN109873162A (en) * 2017-12-04 2019-06-11 中国科学院大连化学物理研究所 A kind of compound 3D collector and its preparation and application
CN108448115A (en) * 2018-03-15 2018-08-24 清华大学 A kind of asymmetric skeleton structure of lithium metal battery cathode
CN110957477A (en) * 2019-10-30 2020-04-03 苏州大学 Porous ceramic composite lithium metal cathode and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FEIHONG REN等: "Pseudocapacitance Induced Uniform Plating/Stripping of Li Metal Anode in Vertical Graphene Nanowalls", 《ADV. FUNCT. MATER.》 *
云斯宁 主编: "《新型能源材料与器件》", 31 January 2019, 中国建材工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112909222A (en) * 2020-12-07 2021-06-04 中国科学院宁波材料技术与工程研究所 Lithium metal negative electrode and preparation method and application thereof
CN115986087A (en) * 2023-01-09 2023-04-18 杰瑞新能源科技有限公司 Silane coupling agent modified covalent organic framework/graphene composite material, preparation method thereof, electrode and battery
CN115986087B (en) * 2023-01-09 2023-08-18 杰瑞新能源科技有限公司 Silane coupling agent modified covalent organic framework/graphene composite material, preparation method thereof, electrode and battery

Similar Documents

Publication Publication Date Title
JP3568052B2 (en) Porous metal body, method for producing the same, and battery electrode plate using the same
US11063264B2 (en) Porous structure Si Cu composite electrode of lithium ion battery and preparation method thereof
CN108682820B (en) Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery
CN109509877B (en) Carbon-coated porous metal coating current collector, preparation method and lithium battery
CN108963265B (en) Negative current collector for lithium metal battery and preparation method thereof
CN110707288B (en) Silicon-based negative electrode active material and preparation method and application thereof
CN109755515B (en) Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof
CN110197899B (en) Preparation method of lithium foil
CN111244394B (en) Metal lithium composite electrode and preparation method thereof
CN111725513A (en) Composite shape memory alloy cathode, preparation method thereof and lithium battery
CN106848250B (en) Carbon-sulfur material with high sulfur content and preparation method thereof
CN110571413A (en) Electrode and lithium cell with composite bed structure
CN108682830B (en) Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof
CN113851648A (en) Composite negative electrode for solid-state battery, preparation method of composite negative electrode and solid-state battery
CN111725480A (en) Composite shape memory alloy cathode, preparation method thereof and lithium battery
CN110299514B (en) Core-shell structure silicon-carbon negative electrode material, preparation method and negative electrode plate
KR20130116895A (en) An electrode for lithium ion batteries and the method for manufacturing the same
CN115411351A (en) Solid-state battery modified by ion/electron mixed conductive solid interface layer and preparation method thereof
CN108767193B (en) Positive electrode containing low-swelling graphite coating and lithium battery
CN109888173B (en) Preparation method of three-dimensional continuous porous copper/graphite electrode
CN113451547A (en) Composite metal lithium cathode and lithium ion battery comprising same
KR20130101375A (en) Preparation method of electrode for litium rechargeable battery
CN103247776B (en) The preparation method of electrode composite material
CN107658457B (en) SiO for fused salt electrolysis2-Gc/C composite electrode and preparation method thereof
CN111646472A (en) Method for in-situ preparation of porous silicon-carbon composite negative electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200929