CN111403715A - Semi-solid metal lithium negative electrode and lithium battery - Google Patents
Semi-solid metal lithium negative electrode and lithium battery Download PDFInfo
- Publication number
- CN111403715A CN111403715A CN202010228934.6A CN202010228934A CN111403715A CN 111403715 A CN111403715 A CN 111403715A CN 202010228934 A CN202010228934 A CN 202010228934A CN 111403715 A CN111403715 A CN 111403715A
- Authority
- CN
- China
- Prior art keywords
- lithium
- negative electrode
- solid
- semi
- lithium metal
- 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
Links
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A semi-solid state metal lithium negative electrode comprising a negative electrode slurry and a current collector, said negative electrode slurry being supported in or on said current collector; the negative electrode slurry includes a solid component and a liquid component; the solid component includes lithium metal particles, a conductive agent, and a thickener, and the liquid component is an electrolyte solution. The invention also relates to a lithium battery. The semi-solid metal lithium negative electrode and the lithium battery provided by the invention can prevent the growth of dendritic crystals and the piercing of a diaphragm, and can improve the electrochemical performance and the safety performance of the metal lithium electrode.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a semi-solid metal lithium negative electrode and a lithium battery with the semi-solid metal lithium negative electrode.
Background
Lithium metal is expected to be a negative electrode material for next-generation high energy density secondary electrochemical cells because of its extremely high theoretical specific mass capacity (3800mAh g)-1) And a very low counter-lithium potential (0Vvs. L i/L i)+). However, the surface of the lithium metal also reacts strongly with the current commercial electrolyte to generate lithium dendrite growth, and the active lithium metal and the electrolyte are consumed, and simultaneously, the separator is easily pierced, which causes short circuit, thermal runaway and explosion of the battery. Meanwhile, metal lithium as an electrode can generate huge volume change in the charging and discharging processes, and serious hidden danger is formed on the interface stability of the electrode, the overall mechanical stability and the packaging material of the battery. Thus, these characteristics of metallic lithium greatly restrict its commercial application.
Disclosure of Invention
In view of the above, the present invention provides a semi-solid lithium metal negative electrode capable of preventing the growth of dendrites and the piercing of a separator and improving the electrochemical performance and safety performance of the lithium metal electrode.
It is also necessary to provide a lithium battery employing the semi-solid metallic lithium negative electrode as described above.
A semi-solid state metal lithium negative electrode comprising a negative electrode slurry and a current collector, said negative electrode slurry being supported in or on said current collector; the negative electrode slurry includes a solid component and a liquid component; the solid component includes lithium metal particles, a conductive agent, and a thickener, and the liquid component is an electrolyte solution.
Further, the mass ratio of the solid component and the liquid component is in the range of 1:1 to 1: 6.
Further, the lithium metal particles are at least one of lithium powder, composite particles of lithium metal and a carbon material, and lithium metal particles having a protective layer coated on the surface thereof.
Further, the carbon material in the composite particles of lithium metal and carbon material comprises at least one of graphene, carbon nanotubes, porous activated carbon and carbon-nitrogen-III; the protective layer in the lithium metal particles coated with the protective layer on the surface comprises at least one of paraffin, solid electrolyte, titanium oxide, aluminum oxide, lithium phosphate, lithium nitride and polyvinylidene fluoride.
Further, the conductive agent comprises at least one of a carbon black conductive agent, a porous activated carbon conductive agent, a graphene conductive agent and a carbon nano tube conductive agent; the thickening agent comprises at least one of polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride-hexafluoropropylene, carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate and sodium polyacrylate.
Further, the electrolyte solution is a solution in which at least one of lithium bistrifluoromethanesulfonylimide, lithium bistrifluorosulfonylimide, lithium hexafluorophosphate, and lithium perchlorate is used as a solute, and at least one of 1, 3-dioxolane, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, sulfolane, N-dimethylacetamide, ethylene carbonate, dimethyl carbonate, ethylene carbonate, and polycarbonate is used as a solvent.
Further, the mass ratio of the lithium metal particles in the solid component is 50% -99%, the mass ratio of the conductive agent in the solid component is 1% -50%, and the mass ratio of the thickening agent in the solid component is 0.1% -20%.
Further, the current collector has a concave conductive groove or a three-dimensional conductive structure, wherein the three-dimensional conductive structure comprises at least one of a nickel foam, a copper foam, a stainless steel mesh, a nickel mesh, a graphene macroscopic body, a carbon nanotube foam, a carbon nanotube film, a carbon cloth, a carbon paper and a carbon felt three-dimensional conductive structure.
A lithium battery comprising a semi-solid lithium metal negative electrode as described above.
A method of preparing a semi-solid lithium metal negative electrode, comprising: preparing anode slurry: uniformly mixing lithium metal particles, a conductive agent, a thickening agent and an electrolyte solution to form stable cathode slurry; and loading the negative electrode slurry in or on a current collector to obtain the semi-solid metal lithium negative electrode.
According to the semi-solid metal lithium negative electrode and the lithium battery provided by the invention, micron lithium metal particles, a conductive agent and a thickening agent (solid component) are stirred in an electrolyte solution (liquid component) according to a certain mass ratio and a solid-liquid ratio to prepare high-viscosity fluid negative slurry (suspension), and the negative slurry is loaded in or on a current collector to obtain the semi-solid metal lithium negative electrode; in the semi-solid lithium metal negative electrode, the high-concentration solid component enables the negative electrode slurry to have certain fluidity and conductivity at the same time, the fluidity of the negative electrode slurry can eliminate stress generated in the lithium metal deposition process, can eliminate growth of lithium dendrites from the angle of mechanical design, and can relieve pressure caused by volume change of lithium metal on the interior of the battery, so that the integrity of an electrode structure and the electrochemical performance of the battery are ensured.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to specific embodiments, structures, characteristics and effects of the semi-solid lithium metal negative electrode and the lithium battery provided by the present invention in combination with the preferred embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a lithium battery, which comprises a semi-solid metal lithium negative electrode, wherein the semi-solid metal lithium negative electrode comprises a negative electrode slurry and a current collector, and the negative electrode slurry is loaded in or on the current collector.
The negative electrode slurry comprises a solid component and a liquid component, and the solid component and the liquid component are uniformly mixed to form a stable suspension.
Wherein the mass ratio of the solid component to the liquid component is in the range of 1:1 to 1: 6.
Preferably, the mass ratio of the solid component and the liquid component is in the range of 1:2.5 to 1: 4.
Wherein the solid component includes lithium metal particles, a conductive agent, and a thickener. Wherein the mass ratio of the lithium metal particles in the solid component is 50-99%, the mass ratio of the conductive agent in the solid component is 1-50%, and the mass ratio of the thickening agent in the solid component is 0.1-20%.
Preferably, the mass ratio of the lithium metal particles in the solid component is 75% to 95%, the mass ratio of the conductive agent in the solid component is 2% to 25%, and the mass ratio of the thickener in the solid component is 1% to 6%.
Wherein the particle size of the lithium metal particles is 10nm-500 μm. Preferably, the lithium metal particles have a particle size of 1 μm to 100 μm. In the present embodiment, the lithium metal particles have a particle size of 10 μm.
Wherein the lithium metal particles are at least one of lithium powder, composite particles of lithium metal and a carbon material, lithium metal particles coated with a protective layer on the surface, and the like.
The carbon material in the lithium metal and carbon material composite particles comprises at least one of graphene, carbon nano tubes, porous activated carbon and carbon-nitrogen-III.
Wherein the protective layer in the lithium metal particles coated with the protective layer on the surface comprises at least one of paraffin, solid electrolyte, titanium oxide, aluminum oxide, lithium phosphate, lithium nitride, polyvinylidene fluoride and the like.
Wherein the conductive agent comprises at least one of carbon black conductive agent (Super P), porous activated carbon conductive agent, graphene conductive agent, carbon nanotube conductive agent and the like. In this embodiment, the conductive agent is a carbon nanotube conductive agent.
Wherein the thickening agent comprises at least one of polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride-hexafluoropropylene, carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate and the like.
The electrolyte solution is a solution with at least one of lithium bistrifluoromethanesulfonylimide, lithium bistrifluorosulfonylimide, lithium hexafluorophosphate and lithium perchlorate as a solute and at least one of 1, 3-dioxolane, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, sulfolane, N-dimethylacetamide, ethylene carbonate, dimethyl carbonate, ethylene carbonate, polycarbonate and the like as a solvent.
Wherein the current collector has a concave conductive groove or a three-dimensional conductive structure. The three-dimensional conductive structure comprises at least one of three-dimensional conductive structures such as foamed nickel, foamed copper, a stainless steel mesh, a nickel mesh, a graphene macroscopic body, carbon nanotube foam, a carbon nanotube film, carbon cloth, carbon paper and a carbon felt.
The invention also provides a preparation method of the semi-solid metal lithium negative electrode, which comprises the following steps:
step S1, preparing anode slurry: uniformly mixing lithium metal particles, a conductive agent, a thickening agent and an electrolyte solution to form stable cathode slurry; and
step S2, loading the negative electrode slurry in or on a current collector to obtain the semi-solid lithium metal negative electrode.
Wherein the negative electrode slurry is supported in or on the current collector by doctor blade coating, extrusion coating, dip coating, roll coating, spin coating, pouring, injection, or the like.
The present invention will be specifically described below with reference to examples and comparative examples.
Example 1:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of polyethylene oxide into 3M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on a copper foil provided with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
The semi-solid lithium metal cathode is assembled into a button cell to test the electrochemical capacity. The electrolyte is a solution with 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents. The CR2032 button cell was assembled in a glove box filled with argon. The positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrodes. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 1 was able to be stably cycled for 1000 h.
Example 2:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of polyethylene oxide into 3M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on a copper foil provided with a polytetrafluoroethylene O ring by a scraper coating method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
Electrochemical capacity was tested using semi-solid metal lithium negative electrodes as described above assembled into button cells. The electrolyte is a solution with 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents. In the glove filled with argonAnd assembling into a CR2032 button cell. Wherein the positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrode. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 2 was able to be stably cycled for 1000 h.
Example 3:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of polyethylene oxide into 3M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4 hours to form stable negative electrode slurry, and loading the negative electrode slurry in a graphene macroscopic body by an injection method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
Electrochemical capacity was tested using semi-solid metal lithium negative electrodes as described above assembled into button cells. The electrolyte is a solution with 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents. The CR2032 button cell was assembled in a glove box filled with argon. The positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrodes. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 3 allowed stable cycling for 1000 h.
Example 4:
adding 900mg of lithium powder, 90mg of graphene and 10mg of polyethylene oxide into 3M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on a copper foil provided with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
Electrochemical capacity was tested using semi-solid metal lithium negative electrodes as described above assembled into button cells. The electrolyte is a solution with 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents. The CR2032 button cell was assembled in a glove box filled with argon. The positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrodes. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 4 was able to be stably cycled for 1000 h.
Example 5:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of sodium carboxymethylcellulose into 3M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4 hours to form stable negative electrode slurry, and loading the negative electrode slurry on a copper foil provided with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
Electrochemical capacity was tested using semi-solid metal lithium negative electrodes as described above assembled into button cells. The electrolyte is a solution with 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents. The CR2032 button cell was assembled in a glove box filled with argon. The positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrodes. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 5 was able to be stably cycled for 1000 h.
Example 6:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of sodium carboxymethylcellulose into 3M L electrolyte solution which takes 1M lithium hexafluorophosphate as solute and ethylene carbonate and diethyl carbonate as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on copper foil with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
The semi-solid lithium metal negative electrode was left standing for one week, and no delamination was observed.
Electrochemical capacity was tested using semi-solid metal lithium negative electrodes as described above assembled into button cells. Wherein the electrolyte is an electrolyte solution with 1M lithium hexafluorophosphate as solute and ethylene carbonate and diethyl carbonate as solvents. The CR2032 button cell was assembled in a glove box filled with argon. The positive electrode and the negative electrode of the button cell are the semi-solid metal lithium negative electrodes. The test temperature was 25 ℃. The battery has a power of 2mA cm-2The current density of the capacitor is charged and discharged, and the capacity of each charging and discharging process reaches 4mAh cm-1Until now.
Among them, the semi-solid lithium metal negative electrode fabricated in example 6 was able to be stably cycled for 400 hours.
Comparative example 1:
adding 900mg of lithium powder and 90mg of carbon nano tubes into 3M L electrolyte solution which takes 1M bistrifluoromethanesulfonylimide as solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on copper foil with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
And standing the semi-solid metal lithium negative electrode for a circle to ensure that the electrode is layered.
Comparative example 2:
600mg of lithium powder, 390mg of carbon nano tube and 10mg of polyethylene oxide are added into 3M L electrolyte solution which takes 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents to be stirred for 4 h.
Comparative example 3:
adding 900mg of lithium powder, 90mg of carbon nano tube and 10mg of polyethylene oxide into 5M L electrolyte solution which takes 1M bis (trifluoromethane sulfonyl) imide lithium as a solute and 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents, stirring for 4h to form stable negative electrode slurry, and loading the negative electrode slurry on a copper foil provided with a polytetrafluoroethylene O ring by an injection method to prepare the semi-solid metal lithium negative electrode.
And standing the semi-solid metal lithium negative electrode for one week to generate a layering phenomenon.
Comparative example 4:
900mg of lithium powder, 90mg of carbon nano tube and 10mg of polyethylene oxide are added into an electrolyte solution of 2M L with 1M lithium bistrifluoromethanesulfonylimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents and stirred for 4 hours, and the solid-liquid two phases in the proportion cannot form slurry with fluidity, but are moist solid powder.
Comparative example 5:
adding 900mg of lithium powder, 90mg of carbon nano tube and 300mg of polyethylene oxide into 3M L electrolyte solution which takes 1M lithium bistrifluoromethanesulfonimide as a solute and 1, 3-dioxolane and glycol dimethyl ether as solvents, and stirring for 4 h.
As can be seen from examples 1 to 6 and comparative examples 1 to 5, the negative electrode slurry is composed of lithium metal particles, a conductive agent, a thickener (solid component), and an electrolyte solution (liquid component), and a stable dispersion can be formed only when the mass ratio of the solid component to the liquid component is in the range of 1:1 to 1:6, and the battery assembled by using the semi-solid metal lithium negative electrode has a good cycle performance only when the semi-solid metal lithium negative electrode formed by loading the negative electrode slurry on a current collector. The batteries obtained in comparative examples 1 to 5, which lack any one of the lithium metal particles, the conductive agent and the thickener or the mass ratio of the solid component and the liquid component is out of the range of 1:1 to 1:6, have cycle performance weaker than that of the batteries of examples 1 to 6.
According to the semi-solid metal lithium negative electrode and the lithium battery provided by the invention, micron lithium metal particles, a conductive agent and a thickening agent (solid component) are stirred in an electrolyte solution (liquid component) according to a certain mass ratio and a solid-liquid ratio to prepare high-viscosity fluid negative slurry (suspension), and the negative slurry is loaded in or on a current collector to obtain the semi-solid metal lithium negative electrode; in the semi-solid lithium metal negative electrode, the high-concentration solid component enables the negative electrode slurry to have certain fluidity and conductivity at the same time, the fluidity of the negative electrode slurry can eliminate stress generated in the lithium metal deposition process, can eliminate growth of lithium dendrites from the angle of mechanical design, and can relieve pressure caused by volume change of lithium metal on the interior of the battery, so that the integrity of an electrode structure and the electrochemical performance of the battery are ensured.
Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A semi-solid state metal lithium negative electrode comprising a negative electrode slurry and a current collector, said negative electrode slurry being supported in or on said current collector; the negative electrode slurry is characterized by comprising a solid component and a liquid component, wherein the solid component comprises lithium metal particles, a conductive agent and a thickening agent, and the liquid component is an electrolyte solution.
2. The semi-solid lithium metal negative electrode of claim 1, wherein the mass ratio of the solid component to the liquid component is in the range of 1:1 to 1: 6.
3. The semi-solid lithium metal negative electrode of claim 1, wherein the lithium metal particles are at least one of lithium powder, composite particles of lithium metal and a carbon material, and lithium metal particles having a protective layer coated on a surface thereof.
4. The semi-solid metal lithium negative electrode of claim 3, wherein the carbon material comprises at least one of graphene, carbon nanotubes, porous activated carbon, carbon trinitrogen; the protective layer comprises at least one of paraffin, solid electrolyte, titanium oxide, aluminum oxide, lithium phosphate, lithium nitride and polyvinylidene fluoride.
5. The semi-solid metal lithium negative electrode of claim 1, wherein the conductive agent comprises at least one of a carbon black conductive agent, a porous activated carbon conductive agent, a graphene conductive agent, a carbon nanotube conductive agent; the thickening agent comprises at least one of polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride-hexafluoropropylene, carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate and sodium polyacrylate.
6. The semi-solid lithium metal negative electrode of claim 1, wherein the electrolyte solution is a solution having at least one of lithium bistrifluoromethanesulfonimide, lithium hexafluorophosphate, lithium perchlorate as a solute and at least one of 1, 3-dioxolane, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, sulfolane, N-dimethylacetamide, ethylene carbonate, dimethyl carbonate, ethylene carbonate, polycarbonate as a solvent.
7. The semi-solid lithium metal negative electrode of claim 1, wherein the lithium metal particles are present in the solid component in a proportion of 50% to 99% by mass, the conductive agent is present in the solid component in a proportion of 1% to 50% by mass, and the thickener is present in the solid component in a proportion of 0.1% to 20% by mass.
8. The semi-solid lithium metal negative electrode of claim 1, wherein the current collector has a concave conductive trough or a three-dimensional conductive structure, wherein the three-dimensional conductive structure comprises at least one of nickel foam, copper foam, stainless steel mesh, nickel mesh, graphene macrostructure, carbon nanotube foam, carbon nanotube film, carbon cloth, carbon paper, carbon felt three-dimensional conductive structure.
9. A lithium battery comprising a semi-solid lithium metal negative electrode according to any one of claims 1 to 8.
10. A method of preparing a semi-solid lithium metal negative electrode, comprising:
preparing anode slurry: uniformly mixing lithium metal particles, a conductive agent, a thickening agent and an electrolyte solution to form stable cathode slurry; and
and loading the negative electrode slurry in or on a current collector to obtain the semi-solid lithium metal negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228934.6A CN111403715A (en) | 2020-03-27 | 2020-03-27 | Semi-solid metal lithium negative electrode and lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228934.6A CN111403715A (en) | 2020-03-27 | 2020-03-27 | Semi-solid metal lithium negative electrode and lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111403715A true CN111403715A (en) | 2020-07-10 |
Family
ID=71433217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010228934.6A Pending CN111403715A (en) | 2020-03-27 | 2020-03-27 | Semi-solid metal lithium negative electrode and lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403715A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114927649A (en) * | 2022-05-16 | 2022-08-19 | 河北工业大学 | Preparation method of environment-compatible metal sodium cathode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522343A (en) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | Stabilized lithium metal powder for Li-ion application, composition and process |
| CN110098379A (en) * | 2019-04-25 | 2019-08-06 | 浙江锋锂新能源科技有限公司 | A kind of lithium an- ode and preparation method thereof and lithium battery using the cathode |
| CN110120542A (en) * | 2018-02-07 | 2019-08-13 | 北京好风光储能技术有限公司 | A kind of high-energy density lithium slurry battery and its working method |
| CN110137577A (en) * | 2019-06-04 | 2019-08-16 | 广东省飞驰新能源科技有限公司 | It is a kind of can high current charge-discharge iron phosphate polymer lithium lithium battery |
| CN110459810A (en) * | 2019-08-15 | 2019-11-15 | 萨姆蒂萨（天津）数据信息技术有限公司 | A kind of preparation method of lithium battery |
-
2020
- 2020-03-27 CN CN202010228934.6A patent/CN111403715A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522343A (en) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | Stabilized lithium metal powder for Li-ion application, composition and process |
| CN110120542A (en) * | 2018-02-07 | 2019-08-13 | 北京好风光储能技术有限公司 | A kind of high-energy density lithium slurry battery and its working method |
| CN110098379A (en) * | 2019-04-25 | 2019-08-06 | 浙江锋锂新能源科技有限公司 | A kind of lithium an- ode and preparation method thereof and lithium battery using the cathode |
| CN110137577A (en) * | 2019-06-04 | 2019-08-16 | 广东省飞驰新能源科技有限公司 | It is a kind of can high current charge-discharge iron phosphate polymer lithium lithium battery |
| CN110459810A (en) * | 2019-08-15 | 2019-11-15 | 萨姆蒂萨（天津）数据信息技术有限公司 | A kind of preparation method of lithium battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114927649A (en) * | 2022-05-16 | 2022-08-19 | 河北工业大学 | Preparation method of environment-compatible metal sodium cathode |
| CN114927649B (en) * | 2022-05-16 | 2023-08-22 | 河北工业大学 | Preparation method of environment-compatible metal sodium negative electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mckerracher et al. | Comparison of carbon materials as cathodes for the aluminium-ion battery | |
| Pan et al. | Enhanced electrochemical performance of sulfur cathodes with a water-soluble binder | |
| WO2020006788A1 (en) | Method for preparing composite material of metal-organic frameworks and carbon nanotubes | |
| Zhang et al. | High sulfur loading lithium–sulfur batteries based on a upper current collector electrode with lithium-ion conductive polymers | |
| EP2717366A1 (en) | High capacitance lithium ion battery containing metallic conducting materials | |
| CN106450102A (en) | Modified graphite separator for lithium-sulfur battery, preparation method of modified graphite separator and lithium-sulfur battery | |
| Huang et al. | Flexible free-standing sulfurized polyacrylonitrile electrode for stable Li/Na storage | |
| CN108808092B (en) | Active electrolyte, preparation method and application | |
| CN111490252A (en) | Lithium metal protective layer, preparation method thereof and battery with same | |
| CN108630889A (en) | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer | |
| CN110611084B (en) | Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency | |
| Dai et al. | A solid state energy storage device with supercapacitor–battery hybrid design | |
| WO2018059180A1 (en) | High-power, high-energy chemical power supply and preparation method therefor | |
| CN105074975A (en) | Negative electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery | |
| CN113540413A (en) | Positive electrode material, positive plate, lithium ion battery and preparation method thereof | |
| GB2565070A (en) | Alkali polysulphide flow battery | |
| CN107910568B (en) | Lithium primary battery | |
| CN111029579B (en) | Calcium ion battery positive electrode material, positive electrode and calcium ion battery | |
| CN111403715A (en) | Semi-solid metal lithium negative electrode and lithium battery | |
| CN116454283A (en) | Potassium ion battery positive electrode additive and preparation method and application thereof | |
| WO2023042262A1 (en) | Lithium secondary battery | |
| Hu et al. | Fabrication of SiO2 nanofiber-integrated all-inorganic electrodes for safer Li-ion batteries | |
| JP2014187383A (en) | Capacitor arranged by use of metal porous body | |
| CN108666582B (en) | Positive electrode material for flow battery and preparation method thereof | |
| JP5565112B2 (en) | Capacitor using porous metal |
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 |
Application publication date: 20200710 |
|
| RJ01 | Rejection of invention patent application after publication |