CN114171716A - Solid-state composite metal lithium cathode with high electron/ion transmission characteristics and preparation method and application thereof - Google Patents

Solid-state composite metal lithium cathode with high electron/ion transmission characteristics and preparation method and application thereof Download PDF

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CN114171716A
CN114171716A CN202111229315.XA CN202111229315A CN114171716A CN 114171716 A CN114171716 A CN 114171716A CN 202111229315 A CN202111229315 A CN 202111229315A CN 114171716 A CN114171716 A CN 114171716A
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lithium
metal
solid
composite
philic
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郭青鹏
韩喻
朱宇豪
郑春满
谢凯
陈宇方
李宇杰
刘双科
王丹琴
谢威
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National University of Defense Technology
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    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a solid composite metal lithium cathode with high electron/ion transmission characteristics, a preparation method and application thereof. The preparation method is to compound the raw materials by adopting a melting lithium filling or electrochemical deposition mode. According to the solid composite metal lithium cathode, the lithium-philic three-dimensional carbon skeleton material, the gel polymer electrolyte and the metal lithium are compounded together, so that the solid composite metal lithium cathode can effectively inhibit the generation of lithium dendrite and the volume change of an electrode in the circulation process on the premise of having high electron/ion transmission characteristics, and a solid battery constructed by the solid composite metal lithium cathode has high specific capacity and circulation stability, and is high in safety, high in use value and good in application prospect. The preparation method of the solid composite metal lithium cathode has the advantages of simple process, continuous production and the like, is suitable for large-scale preparation, and is convenient for industrial application.

Description

Solid-state composite metal lithium cathode with high electron/ion transmission characteristics and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium metal secondary batteries, relates to a composite metal lithium cathode for a solid-state lithium battery, and a preparation method and application thereof, and particularly relates to a solid-state composite metal lithium cathode with high electron/ion transmission characteristics, and a preparation method and application thereof.
Background
In recent years, with the continuous rise and vigorous development of the fields of portable electronics, electric automobiles, weaponry, aerospace, large-scale electricity storage and the like, higher requirements are put on the energy density and the safety performance of lithium batteries. However, the energy density increase of the conventional liquid lithium ion battery is close to the limit value, and the potential safety problem restricts the wider application of the lithium ion battery in the novel high-energy-density power battery. Therefore, battery systems with both high energy density and high safety are the subject of the eager layout of the next generation power battery technology. The solid lithium metal battery replaces organic electrolyte with solid electrolyte with outstanding electrochemical stability and thermal stability, and can be matched with a high-voltage positive electrode material and a metal lithium negative electrode so as to achieve the aim of high energy density and high safety of the battery. Therefore, solid-state lithium metal batteries are considered to be the most promising battery system to replace commercial lithium ion batteries. However, solid-state batteries still face some technical challenges in terms of their practical use.
Compared with a liquid organic electrolyte, the solid electrolyte has higher electrochemical stability, but most of the solid electrolyte can react with a metal lithium electrode to form an interface layer with poor conductivity due to the existence of a valence-variable element. Therefore, the lithium metal negative electrode in the solid-state battery also faces an interface problem of reactivity with the solid-state electrolyte. In addition, in the solid lithium battery, the problems of volume expansion and uneven lithium deposition of the metallic lithium negative electrode still exist, and particularly, huge volume change and serious lithium dendrite problems can be caused under high current density, so that the structure of the lithium battery can be damaged, and the cycle performance and the service life of the lithium battery are further reduced.
Aiming at the problem of the lithium negative electrode side in the solid-state battery, how to obtain a metal lithium negative electrode with uniform lithium metal electrode de-intercalation, accurate thickness control and high interface stability in the process of charging and discharging with high current density of the battery becomes an important challenge for expanding application of the solid-state battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a solid composite metal lithium cathode with high electron/ion transmission characteristics, which can effectively inhibit the generation of lithium dendrite and the volume change of the electrode in the circulation process, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the solid composite metal lithium negative electrode is formed by compounding metal lithium, a lithium-philic three-dimensional carbon skeleton material and a gel polymer electrolyte.
In the solid composite metal lithium negative electrode, the metal lithium and the gel polymer electrolyte are distributed on the surface and in the lithium-philic three-dimensional carbon skeleton material; or, the metallic lithium is wrapped on the surface and inside of the lithium-philic three-dimensional carbon skeleton material, and the gel polymer electrolyte is distributed on the surface and inside of the metallic lithium.
In the solid composite metal lithium cathode, the lithium-philic three-dimensional carbon skeleton material comprises a three-dimensional carbon skeleton material, and the surface of the three-dimensional carbon skeleton material is coated with metal oxide; the three-dimensional carbon skeleton material is one of carbon fiber cloth, carbon nanofiber non-woven fabric, carbon felt, a porous carbon film and foam carbon; the metal oxide is at least one of zinc oxide, aluminum oxide, iron oxide and copper oxide.
In the solid composite metal lithium negative electrode, the gel polymer electrolyte further comprises a high molecular polymer material, a lithium salt and an ionic liquid; the mass ratio of the high molecular polymer material, the lithium salt and the ionic liquid is 1: 1.4.
In the solid composite metal lithium cathode, the polymer material is at least one of polyether material, polyvinylidene fluoride, copolymerization modified polymer material based on polyvinylidene fluoride, sodium carboxymethylcellulose, polyurethane, polyacrylonitrile, polymethyl methacrylate, polyvinyl formal, perfluorosulfonic acid, polyvinyl butyral and polyvinyl chloride.
In the solid-state composite lithium metal cathode, the lithium salt is at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonate) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium dioxalate borate and lithium tetrafluoroborate.
In the solid-state composite metal lithium negative electrode, the ionic liquid is further improved, and the ionic liquid is at least one of piperidine ionic liquid, quaternary ammonium ionic liquid, imidazole ionic liquid and pyrrole ionic liquid.
In the solid composite metal lithium negative electrode, the polyether material is polyethylene oxide; the copolymerization modified polymer material based on polyvinylidene fluoride is polyvinylidene fluoride hexafluoropropylene.
In the solid composite metal lithium cathode, the piperidine ionic liquid is N-methyl-N-propyl piperidine bis (trifluoromethyl sulfonyl) imide; the quaternary ammonium ionic liquid is N-methyl-N, N-diethyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide; the imidazole ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide; the pyrrole ionic liquid is N-methyl-N-propyl pyrrole bis (trifluoromethyl sulfonyl) imine.
As a general technical concept, the invention also provides a preparation method of the solid-state composite metal lithium cathode with high electron/ion transmission characteristics, which is prepared by any one of the following methods;
the method comprises the following steps: the method for preparing the solid composite metal lithium cathode based on the melting lithium filling mode comprises the following steps:
s1, mixing molten metal lithium with the lithium-philic three-dimensional carbon framework material to enable the molten metal lithium to be diffused to the surface and the interior of the lithium-philic three-dimensional carbon framework material to form a carbon-lithium composite structure;
s2, coating the gel polymer electrolyte solution on the surface of the carbon-lithium composite structure obtained in the step S1, drying, and enabling the gel polymer electrolyte to penetrate into the carbon-lithium composite structure in the drying process to obtain the solid composite metal lithium negative electrode with high electron/ion transmission characteristics.
The second method comprises the following steps: the method for preparing the solid composite metal lithium cathode based on the electrochemical deposition mode comprises the following steps:
(1) coating the gel polymer electrolyte solution on the surface of the lithium-philic three-dimensional carbon skeleton material, drying, and penetrating the gel polymer electrolyte into the lithium-philic three-dimensional carbon skeleton material in the drying process to obtain the lithium-philic three-dimensional carbon skeleton material coated by the gel polymer electrolyte layer;
(2) assembling the lithium-philic three-dimensional carbon framework material coated by the gel polymer electrolyte layer obtained in the step (1) and a metal lithium sheet into a primary battery for electrochemical deposition, depositing metal lithium on the surface and in gaps of the lithium-philic three-dimensional carbon framework material, and cleaning to obtain the solid composite metal lithium cathode with high electron/ion transmission characteristics.
The preparation method of the solid-state composite metal lithium cathode with high electron/ion transmission characteristics is further improved, and when the preparation method is adopted, the preparation method comprises the following steps:
in step S1, the molten lithium metal is prepared by heating a lithium metal sheet to 200-900 ℃;
in step S2, the drying is performed under vacuum conditions; the drying temperature is 90-110 ℃; the drying time is 24-36 h;
the preparation method of the solid-state composite metal lithium cathode with high electron/ion transmission characteristics is further improved, and when the preparation method is adopted for preparation, the method comprises the following steps:
in the step (1), the drying is carried out under vacuum condition; the drying temperature is 90-110 ℃; the drying time is 24-36 h;
in the step (2), the electrochemical deposition is carried out under the protection of argon atmosphere; the current density in the electrochemical deposition process is 0.1mA cm-2～0.5mA cm-2(ii) a The time of the electrochemical deposition is 1-100 h; the cleaning agent adopted for cleaning is dimethyl carbonate.
In the preparation method of the solid-state composite metal lithium negative electrode with high electron/ion transmission characteristics, the lithium-philic three-dimensional carbon skeleton material is further improved, and is prepared by the following preparation method: soaking a three-dimensional carbon material in a colloidal aqueous solution of a metal oxide for 12-24 h, drying at 50-100 ℃, heating the obtained sample to 500-800 ℃ at a heating rate of 5-10 ℃/min under a nitrogen protective atmosphere, and preserving heat for 0.5-1.5 h to obtain a lithium-philic three-dimensional carbon framework material; the mass concentration of the metal oxide colloid in the metal oxide colloid aqueous solution is 5%.
In the preparation method of the solid-state composite metal lithium negative electrode with high electron/ion transmission characteristics, the gel polymer electrolyte solution is further improved by the following preparation method: dissolving a high molecular polymer material, lithium salt and ionic liquid in an organic solvent, and stirring at the temperature of 30-55 ℃ for 20-30 min to obtain a gel polymer electrolyte solution; the organic solvent is at least one of acetone, butanone and N-methyl pyrrolidone.
The invention also provides application of the solid composite lithium metal cathode or the solid composite lithium metal cathode prepared by the preparation method in a solid battery as a general technical concept.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a solid composite metal lithium cathode with high electron/ion transmission characteristics, which is compounded by metal lithium, a lithium-philic three-dimensional carbon skeleton material and a gel polymer electrolyte. In the invention, the lithium-philic three-dimensional carbon skeleton material and the gel polymer electrolyte respectively form a high-conductivity electron-conducting network and a high-conductivity ion-conducting network, so that not only is a space provided for pre-storing metallic lithium, and the gel polymer electrolyte can regulate and control the nucleation and deposition behaviors of lithium metal so as to ensure the uniform de-intercalation of lithium ions in the nucleation and growth processes, the growth of lithium dendrites is inhibited, and the volume expansion problem of the lithium metal negative electrode is relieved, so that the solid composite metal lithium negative electrode formed by compounding the lithium-philic three-dimensional carbon framework material, the gel polymer electrolyte and the metal lithium can effectively inhibit the generation of the lithium dendrites and the volume change of the electrode in the circulation process on the premise of having high electron/ion transmission characteristics, the method has very important scientific significance and practical significance for realizing the application of the safe and effective solid-state battery with high energy density.
(2) The invention also provides a preparation method of the solid composite metal lithium cathode with high electron/ion transmission characteristics, and the solid composite metal lithium cathode is formed by compounding the metal lithium, the lithium-philic three-dimensional carbon skeleton material and the gel polymer electrolyte in a melting lithium filling or electrochemical deposition mode. The preparation method has the advantages of simple process, continuous production and the like, is suitable for large-scale preparation, and is convenient for industrial application.
(3) The invention also provides an application of the solid composite metal lithium cathode in a solid battery, in particular to a solid composite metal lithium cathode which is used as the cathode of the solid battery, the solid battery constructed by the solid battery has higher specific capacity and cycling stability, shows excellent interface stability to a lithium metal electrode, further improves the safety of the battery, particularly a solid lithium secondary battery, can enable the solid battery to realize high-voltage charging and discharging, effectively inhibit the generation of lithium dendrites, reduce the interface impedance in the battery, and improve the comprehensive targets of energy density, cycle life and safety performance of the solid battery, and has wide application prospect and advantages.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a schematic view of the process and structure of a solid-state composite lithium metal anode prepared in example 1 of the present invention.
FIG. 2 shows different carbon materials coated with Al according to examples 1, 2, 3 and 4 of the present invention2O3And comparing the front and the back micro-topography.
Fig. 3 is a schematic diagram of solid-state lithium composite metal anodes prepared in examples 1 and 2 of the present invention.
Fig. 4 is a scanning electron microscope image of the surface and cross section of a solid state composite lithium metal anode prepared in example 1 of the present invention.
Fig. 5 is a surface EDS analysis chart of the solid state composite lithium metal anode prepared in example 1 of the present invention.
FIG. 6 is a graph showing the cycle performance test of the gel polymer electrolyte prepared from the gel polymer electrolyte solution in the Li/Li symmetric battery according to example 1 of the present invention.
Fig. 7 is an SEM image of the surface and cross-section of a solid lithium composite negative electrode after constant charge and discharge of the solid lithium composite metal negative electrode symmetric solid-state battery prepared in example 1 of the present invention.
Fig. 8 is an SEM image of the surface and cross-section of the electrode after constant charge and discharge of the symmetric lithium composite anode solid-state battery including only the C — Li structure without coating with the gel electrolyte in comparative example 1.
Fig. 9 is a diagram showing the overpotential effect of a symmetrical battery with a solid-state lithium composite metal negative electrode prepared in example 8 of the present invention at different current densities.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. The experimental methods in the examples, in which specific conditions are not specified, were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
A solid composite metal lithium cathode with high electron/ion transmission characteristics is formed by compounding metal lithium, a lithium-philic three-dimensional carbon skeleton material and a gel polymer electrolyte, and specifically comprises the following components: the metallic lithium and the gel polymer electrolyte are distributed on the surface and in the lithium-philic three-dimensional carbon skeleton material.
In this embodiment, the lithium-philic three-dimensional carbon skeleton material includes carbon fiber cloth, and the surface of the carbon fiber cloth is coated with alumina.
In this example, the gel polymer electrolyte was composed of polyvinylidene fluoride hexafluoropropylene [ P (VDF-HFP) ], lithium bis (trifluoromethanesulfonate) imide (LiTFSI), and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI), and the mass ratio of P (VDF-HFP), LiTFSI, and EMITFSI was 1: 1.4.
The preparation method of the solid-state composite lithium metal negative electrode with high electron/ion transport properties in the embodiment is to specifically prepare the solid-state composite lithium metal negative electrode by using carbon fiber cloth with an alumina surface modification as a carrier through a hot-melting infusion method, and includes the following steps:
(1) pretreatment of the carbon cloth: respectively carrying out ultrasonic treatment on carbon fiber cloth (Guangwei composite material carbon cloth) in ethanol and deionized water for 10min, and carrying out heat treatment for 2h at 200 ℃ in an air atmosphere. And soaking the carbon cloth after heat treatment in uniform AlOOH sol with the mass concentration of 5% for 12h, drying in a 50 ℃ oven for 24h, further placing the carbon cloth in a tubular furnace, and heating at the heating rate of 5 ℃/min to 500 ℃ for 1h under the nitrogen protection atmosphere to obtain the carbon cloth coated with the aluminum oxide.
(2) Under the protection of argon atmosphere, heating a metal lithium sheet to 300 ℃ to be completely melted into lithium metal liquid, then putting the pretreated carbon cloth into the metal lithium liquid to ensure that molten lithium is automatically and uniformly diffused on the carbon cloth, so that the molten metal lithium is diffused to the surface and the interior of the lithium-philic three-dimensional carbon skeleton material, and naturally cooling to form a lithium-carbon cloth negative electrode skeleton structure, namely a carbon-lithium composite structure.
(3) Respectively weighing the polymer matrix, the lithium salt and the ionic liquid according to the mass ratio of 1: 1.4, dissolving the polymer matrix, the lithium salt LiTFSI and the ionic liquid EMITFSI in a N-methyl pyrrolidone solvent, and magnetically stirring for 30min at 50 ℃ to obtain a clear gel polymer solution with the mass fraction of 6.7%, namely the gel polymer electrolyte solution.
(4) And uniformly coating the gel polymer solution on one surface of the lithium-carbon cloth negative electrode framework structure, drying for 24 hours in a vacuum drying oven at 100 ℃, wherein the gel polymer electrolyte permeates into the carbon-lithium composite structure in the drying process, and the gel polymer electrolyte layer is soaked in the surface and the internal structure of the carbon-lithium composite layer to obtain the solid composite metal lithium negative electrode. In this step, the gel polymer electrolyte solution may be coated on the surface of the carbon-lithium composite structure by dipping, knife coating, spin coating, spray coating, or sputtering.
Example 2
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as the embodiment 1, except that: the lithium-philic three-dimensional carbon skeleton material used in example 2 was carbon fiber cloth (taiwan carbon energy carbon cloth).
Example 3
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as the embodiment 1, except that: the lithium-philic three-dimensional carbon skeleton material used in example 3 was a carbon nanofiber nonwoven fabric.
Example 4
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as the embodiment 1, except that: the lithium-philic three-dimensional carbon skeleton material used in example 4 was a porous carbon film.
Example 5
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as the embodiment 1, except that: the lithium-philic three-dimensional carbon skeleton material used in example 5 was a carbon felt.
Example 6
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as the embodiment 1, except that: the lithium-philic three-dimensional carbon skeleton material used in example 6 was carbon foam.
Example 7
A solid composite metal lithium cathode with high electron/ion transmission characteristics is formed by compounding metal lithium, a lithium-philic three-dimensional carbon skeleton material and a gel polymer electrolyte, and specifically comprises the following components: the metallic lithium and the gel polymer electrolyte are distributed on the surface and in the lithium-philic three-dimensional carbon skeleton material.
In this embodiment, the lithium-philic three-dimensional carbon skeleton material includes carbon fiber cloth, and the surface of the carbon fiber cloth is coated with alumina.
In the present example, the gel polymer electrolyte was composed of polyvinylidene fluoride hexafluoropropylene [ P (VDF-HFP) ], lithium bis (trifluoromethanesulfonate) imide (LiTFSI), and EMITFSI, and the mass ratio of P (VDF-HFP), LiTFSI, and EMITFSI was 1: 1.4.
The preparation method of the solid-state composite lithium metal cathode with high electron/ion transmission characteristics in the embodiment, specifically, the solid-state composite lithium metal cathode is prepared by taking carbon fiber cloth modified by an alumina surface as a carrier through an electrodeposition method, and includes the following steps:
(1) pretreatment: respectively carrying out ultrasonic treatment on carbon fiber cloth (Guangwei composite material carbon cloth) in ethanol and deionized water for 10min, and carrying out heat treatment for 2h at 200 ℃ in an air atmosphere. And soaking the carbon cloth after heat treatment in uniform AlOOH sol with the mass concentration of 5% for 5h, drying in a 50 ℃ oven for 24h, further placing the carbon cloth in a tubular furnace, and heating to 500 ℃ for heat treatment for 1h at the heating rate of 5 ℃/min under the nitrogen protection atmosphere to obtain the carbon cloth coated with the aluminum oxide.
(2) Respectively weighing the polymer matrix, the lithium salt LiTFSI and the ionic liquid EMITFSI according to the mass ratio of the polymer matrix to the lithium salt to the ionic liquid of 1: 1.4, dissolving the polymer matrix, the lithium salt LiTFSI and the ionic liquid EMITFSI in a N-methyl pyrrolidone solvent, and magnetically stirring the solution at 50 ℃ for 30min to obtain a clear gel polymer solution with the mass fraction of 6.7%, namely the gel polymer electrolyte solution
(3) And uniformly coating the gel polymer solution on one surface of the carbon fiber cloth coated with the alumina, drying the carbon fiber cloth in a vacuum drying oven at 100 ℃ for 24 hours, and infiltrating the gel polymer electrolyte into the lithium-philic three-dimensional carbon skeleton material in the drying process to obtain a carbon cloth structure coated with the gel polymer electrolyte layer, namely the lithium-philic three-dimensional carbon skeleton material coated with the gel polymer electrolyte layer, and cutting the carbon cloth structure into a wafer with the diameter of 15mm on a cutting machine.
(4) Under the protection of argon atmosphere, the pretreated carbon cloth and the metal lithium sheet are assembled into a primary battery at 0.1mA cm-2Electrochemical deposition is carried out for 50h under current density, metal lithium is deposited on the surface and in the gaps of the lithium-philic three-dimensional carbon skeleton material, and the surface capacity of the deposited lithium metal is 5mAh cm-2And finally, disassembling the battery, taking out the carbon cloth deposited with the lithium metal, and cleaning the carbon cloth by using dimethyl carbonate (DMC) to obtain the composite lithium cathode, namely the solid composite lithium cathode with high electron/ion transmission characteristic.
Example 8
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 7, except that: the lithium-philic three-dimensional carbon skeleton material used in example 8 was carbon fiber cloth (taiwan carbon energy cloth).
Example 9
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 7, except that: the lithium-philic three-dimensional carbon skeleton material used in example 9 was a carbon nanofiber nonwoven fabric.
Example 10
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 7, except that: the lithium-philic three-dimensional carbon skeleton material used in example 10 was a porous carbon film.
Example 11
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 7, except that: the lithium-philic three-dimensional carbon skeleton material used in example 11 was carbon foam.
Example 12
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 8, except that: the surface capacity of the lithium metal deposited in example 12 was 10mAh cm-2。
Example 13
A method for preparing a solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics, which is substantially the same as example 8, except that: the surface capacity of the lithium metal deposited in example 13 was 15mAh cm-2。
Comparative example 1
A preparation method of a solid composite lithium negative electrode, which is a hot melting infusion method for preparing the composite lithium negative electrode by taking alumina surface modified Guangwei composite carbon cloth as a carrier, comprises the following steps:
(1) pretreatment of the carbon cloth: respectively carrying out ultrasonic treatment on carbon fiber cloth (Guangwei composite material carbon cloth) in ethanol and deionized water for 10min, and carrying out heat treatment for 2h at 200 ℃ in an air atmosphere. And soaking the carbon cloth after heat treatment in uniform AlOOH sol with the concentration of 5% for 5h, drying in a 50 ℃ oven for 24h, and further performing heat treatment on the carbon cloth at 500 ℃ to obtain the carbon cloth coated with the aluminum oxide.
(2) Under the protection of argon atmosphere, heating a metal lithium sheet to 300 ℃ to be completely melted into lithium metal liquid, then putting the pretreated carbon cloth into the metal lithium liquid to ensure that the molten lithium automatically and uniformly diffuses on the carbon cloth, and naturally cooling to form a lithium-carbon cloth negative electrode framework structure.
Fig. 1 is a schematic view of the process and structure of a solid-state composite lithium metal anode prepared in example 1 of the present invention. In the present invention, the operations involved are all carried out in a glove box or a drying room.
FIG. 2 shows different carbon materials coated with Al according to examples 1, 2, 3 and 4 of the present invention2O3And comparing the front and the back micro-topography. As can be seen from FIG. 2, Al is observed in the electron micrograph2O3The thin layer can be uniformly coated on the surface of the carbon material.
Fig. 3 is a schematic diagram of solid-state lithium composite metal anodes prepared in examples 1 and 2 of the present invention. As can be seen from fig. 3, the lithium metal can be uniformly embedded in the pore structure of the carbon cloth.
Fig. 4 is a surface and cross-sectional Scanning Electron Microscope (SEM) image of a solid state composite lithium metal anode prepared in example 1 of the present invention. As can be seen from fig. 4, in the solid-state composite lithium metal anode prepared by the hot-melt infusion method, the lithium metal uniformly wraps the carbon fibers and sufficiently fills the voids between the carbon fibers.
Fig. 5 is a surface EDS analysis chart of the solid state composite lithium metal anode prepared in example 1 of the present invention. As can be seen from fig. 5, the F element and the S element are mainly derived from the gel polymer electrolyte component, and it is further demonstrated that the gel polymer electrolyte is wrapped and filled between the surface of the lithium metal and the gap.
FIG. 6 is a graph showing the cycle performance test of the gel polymer electrolyte prepared from the gel polymer electrolyte solution in the Li/Li symmetric battery according to example 1 of the present invention. As can be seen from fig. 6, the voltage of the symmetric cell remained stable throughout the test procedure, indicating that the gel polymer electrolyte system can maintain a stable interface to the lithium metal electrode, further indicating that the ionic liquid-based gel polymer electrolyte has good interface compatibility with the lithium metal electrode.
Fig. 7 is an SEM image of the surface and cross-section of a solid lithium composite negative electrode after constant charge and discharge of the solid lithium composite metal negative electrode symmetric solid-state battery prepared in example 1 of the present invention. Fig. 8 is an SEM image of the surface and cross-section of the electrode after constant charge and discharge of the symmetric lithium composite anode solid-state battery including only the C — Li structure without coating with the gel electrolyte in comparative example 1. As can be seen from a comparison of fig. 7 and 8, in the lithium-less-side lithium composite negative electrode sample (example 1) coated with the gel electrolyte layer according to the present invention, metallic lithium can be deposited relatively uniformly in the thickness direction without any significant metallic lithium deposit on the electrolyte-facing surface, whereas in the lithium composite negative electrode (comparative example 1) not coated with the gel electrolyte, metallic lithium is deposited non-uniformly in the thickness direction and is deposited mainly on the contact surface between the lithium composite negative electrode and the electrolyte.
Fig. 9 is a diagram showing the overpotential effect of a symmetrical battery with a solid-state lithium composite metal negative electrode prepared in example 8 of the present invention at different current densities. As can be seen from FIG. 9, the current density was 0.1mA cm-2At a current density of 0.04V and 1mA cm-2Under the large current, the overpotential is 0.2V, and the symmetrical battery is 0.1mA cm-2At a current density of 1mAh cm-2The capacity of (2) shows better cycling stability.
Therefore, according to the all-solid-state composite lithium negative electrode preparation technology, the three-dimensional carbon material is the conductive network frame, the gel polymer layer is the ion conducting transmission layer, and the lithium metal is localized through the gel polymer electrolyte, a double-conductive network for conducting lithium ions and electrons can be simultaneously constructed in the lithium negative electrode, so that a stable localized lithium negative electrode structure is formed, and the generation of lithium dendrites and the volume change in the circulation process can be effectively inhibited.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (10)

1. The solid composite metal lithium negative electrode with high electron/ion transmission characteristics is characterized by being formed by compounding metal lithium, a lithium-philic three-dimensional carbon skeleton material and a gel polymer electrolyte.
2. The solid state composite lithium metal anode of claim 1, wherein the lithium metal and the gel polymer electrolyte are distributed on the surface and inside the lithium-philic three-dimensional carbon skeleton material; or, the metallic lithium is wrapped on the surface and inside of the lithium-philic three-dimensional carbon skeleton material, and the gel polymer electrolyte is distributed on the surface and inside of the metallic lithium.
3. The solid state composite metallic lithium anode of claim 2, wherein the lithium-philic three-dimensional carbon skeleton material comprises a three-dimensional carbon skeleton material, the surface of which is coated with a metal oxide; the three-dimensional carbon skeleton material is one of carbon fiber cloth, carbon nanofiber non-woven fabric, carbon felt, a porous carbon film and foam carbon; the metal oxide is at least one of zinc oxide, aluminum oxide, iron oxide and copper oxide.
4. The solid state composite lithium metal anode according to any one of claims 1 to 3, wherein the gel polymer electrolyte comprises a high molecular polymer material, a lithium salt and an ionic liquid; the mass ratio of the high molecular polymer material, the lithium salt and the ionic liquid is 1: 1.4.
5. The solid state composite lithium metal anode of claim 4, wherein the polymer material is at least one of a polyether material, polyvinylidene fluoride, a copolymer modified polymer material based on polyvinylidene fluoride, sodium carboxymethylcellulose, polyurethane, polyacrylonitrile, polymethyl methacrylate, polyvinyl formal, perfluorosulfonic acid, polyvinyl butyral, and polyvinyl chloride;
the lithium salt is at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonate) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium dioxalate borate and lithium tetrafluoroborate;
the ionic liquid is at least one of piperidine ionic liquid, quaternary ammonium ionic liquid, imidazole ionic liquid and pyrrole ionic liquid.
6. The solid state lithium metal composite anode according to claim 5, wherein the polyether material is polyethylene oxide; the copolymerization modified polymer material based on polyvinylidene fluoride is polyvinylidene fluoride hexafluoropropylene;
the piperidine ionic liquid is N-methyl-N-propyl piperidine di (trifluoromethyl sulfonyl) imine; the quaternary ammonium ionic liquid is N-methyl-N, N-diethyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide; the imidazole ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide; the pyrrole ionic liquid is N-methyl-N-propyl pyrrole bis (trifluoromethyl sulfonyl) imine.
7. The preparation method of the solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics according to any one of claims 1 to 6, characterized by comprising the following steps of;
the method comprises the following steps: the method for preparing the solid composite metal lithium cathode based on the melting lithium filling mode comprises the following steps:
s1, mixing molten metal lithium with the lithium-philic three-dimensional carbon framework material to enable the molten metal lithium to be diffused to the surface and the interior of the lithium-philic three-dimensional carbon framework material to form a carbon-lithium composite structure;
s2, coating the surface of the carbon-lithium composite structure obtained in the step S1 with a gel polymer electrolyte solution, drying, and penetrating the gel polymer electrolyte into the carbon-lithium composite structure in the drying process to obtain the solid composite metal lithium cathode with high electron/ion transmission characteristics;
the second method comprises the following steps: the method for preparing the solid composite metal lithium cathode based on the electrochemical deposition mode comprises the following steps:
(1) coating the gel polymer electrolyte solution on the surface of the lithium-philic three-dimensional carbon skeleton material, drying, and penetrating the gel polymer electrolyte into the lithium-philic three-dimensional carbon skeleton material in the drying process to obtain the lithium-philic three-dimensional carbon skeleton material coated by the gel polymer electrolyte layer;
(2) assembling the lithium-philic three-dimensional carbon framework material coated by the gel polymer electrolyte layer obtained in the step (1) and a metal lithium sheet into a primary battery for electrochemical deposition, depositing metal lithium on the surface and in gaps of the lithium-philic three-dimensional carbon framework material, and cleaning to obtain the solid composite metal lithium cathode with high electron/ion transmission characteristics.
8. The method for preparing the solid-state composite lithium metal anode with high electron/ion transport property according to claim 7, wherein the method comprises the following steps:
in step S1, the molten lithium metal is prepared by heating a lithium metal sheet to 200-900 ℃;
in step S2, the drying is performed under vacuum conditions; the drying temperature is 90-110 ℃; the drying time is 24-36 h;
when the preparation method II is adopted:
in the step (1), the drying is carried out under vacuum condition; the drying temperature is 90-110 ℃; the drying time is 24-36 h;
in the step (2), the electrochemical deposition is carried out under the protection of argon atmosphere; the current density in the electrochemical deposition process is 0.1mA cm-2～0.5mA cm-2(ii) a The time of the electrochemical deposition is 1-100 h; the cleaning agent adopted for cleaning is dimethyl carbonate.
9. The preparation method of the solid-state composite metallic lithium negative electrode with high electron/ion transmission characteristics according to claim 7 or 8, wherein the lithium-philic three-dimensional carbon skeleton material is prepared by the following preparation method: soaking a three-dimensional carbon material in a colloidal aqueous solution of a metal oxide for 12-24 h, drying at 50-100 ℃, heating the obtained sample to 500-800 ℃ at a heating rate of 5-10 ℃/min under a nitrogen protective atmosphere, and preserving heat for 0.5-1.5 h to obtain a lithium-philic three-dimensional carbon framework material; the mass concentration of the metal oxide colloid in the metal oxide colloid aqueous solution is 5 percent;
the gel polymer electrolyte solution is prepared by the following preparation method: dissolving a high molecular polymer material, lithium salt and ionic liquid in an organic solvent, and stirring at the temperature of 30-55 ℃ for 20-30 min to obtain a gel polymer electrolyte solution; the organic solvent is at least one of acetone, butanone and N-methyl pyrrolidone.
10. Use of the solid state lithium metal composite anode according to any one of claims 1 to 6 or the solid state lithium metal composite anode prepared by the preparation method according to any one of claims 7 to 9 in a solid state battery.
CN202111229315.XA 2021-10-21 2021-10-21 Solid-state composite metal lithium cathode with high electron/ion transmission characteristics and preparation method and application thereof Pending CN114171716A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114665098A (en) * 2022-04-29 2022-06-24 重庆大学 Composite lithium metal negative electrode material, preparation method thereof and metal lithium battery
WO2023216209A1 (en) * 2022-05-13 2023-11-16 宁德时代新能源科技股份有限公司 Pore-forming agent for secondary battery, preparation method for pore-forming agent, negative electrode sheet, electrode assembly, and secondary battery
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