CN116364931A - Three-dimensional composite carbon material with gradient lithium affinity, preparation method thereof, composite lithium anode material containing three-dimensional composite carbon material and application of composite lithium anode material - Google Patents

Three-dimensional composite carbon material with gradient lithium affinity, preparation method thereof, composite lithium anode material containing three-dimensional composite carbon material and application of composite lithium anode material Download PDF

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CN116364931A
CN116364931A CN202310386843.9A CN202310386843A CN116364931A CN 116364931 A CN116364931 A CN 116364931A CN 202310386843 A CN202310386843 A CN 202310386843A CN 116364931 A CN116364931 A CN 116364931A
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lithium
composite
carbon material
composite carbon
philic
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彭工厂
李天慧
周含笑
刘文静
郭志豪
苏子豪
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Chengdu Organic Chemicals Co Ltd of CAS
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Chengdu Organic Chemicals Co Ltd of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

The invention provides a three-dimensional composite carbon material with gradient lithium-philic property, which is a three-dimensional carbon fiber containing carbon nano tubes, wherein one surface of the composite carbon material is plated with a lithium-philic material; the carbon nano tube uniformly grown by the composite carbon material increases the specific surface area of the whole skeleton, and can reduce the local current density in the charge and discharge process; the conductivity of the whole framework is improved to promote the transmission of lithium ions; zinc oxide distributed in a gradient manner from the bottom to the top can reduce the nucleation barrier of lithium, guide lithium ions to be deposited preferentially at the bottom of the framework, and prevent metal lithium from being deposited at the uppermost surface of the framework; the invention also provides a preparation method of the composite carbon material, application of the composite carbon material in a composite lithium negative electrode material, and application of the composite lithium negative electrode material in preparation of a lithium battery.

Description

Three-dimensional composite carbon material with gradient lithium affinity, preparation method thereof, composite lithium anode material containing three-dimensional composite carbon material and application of composite lithium anode material
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a three-dimensional composite carbon material with gradient lithium affinity, a preparation method thereof, a composite lithium anode material containing the same and application thereof.
Background
The market for portable electronics and electric vehicles, which is actively developed, has stimulated the need for high density Lithium Ion Batteries (LIBs), which are limited by graphite cathodes and lithium transition metal oxide anodes, with theoretical energy densities of 250wh kg -1 . While lithium metal anodes are considered to be "ceilings" of anode materials due to their advantages of highest theoretical specific capacity, lowest reduction potential, and low density. The lithium metal is used for replacing the graphite cathode in the lithium ion battery, and the energy density of the lithium metal is expected to reach 400Wh kg -1 And the lithium negative electrode can also be matched with some non-lithium positive electrode materials, such as lithium sulfur batteries, lithium air batteries and the like. However, lithium anodes have not been commercialized at present, and mainly suffer from the following problems. Firstly, lithium has higher chemical/electrochemical activity, and side reaction can continuously occur between the lithium and electrolyte, so that the utilization rate of the lithium is lower, and the polarization is larger; secondly, uneven lithium ion flow can lead to the generation of small dendrites, and lithium ions tend to deposit on the small dendrites due to the low overpotential of the dendrite tips, so that dendrites grow rapidly, and finally safety accidents such as short circuit and the like occur when the dendrites penetrate through a diaphragm; third, the infinite volume expansion of metallic lithium during the deposition stripping process can lead to the fragmentation of SEI film, destroy the integrity of SEI film, and the exposure of fresh lithium can further cause non-uniformityLithium ion flow, resulting in non-uniform deposition of lithium. Uneven lithium deposition can lead to lithium dendrites breaking away from the current collector, creating "dead lithium" without electrical activity, resulting in severe loss of battery capacity and reduced coulombic efficiency.
Based on the above problems, there are also many limitations to the application of lithium negative electrodes, and thus, it is important to protect lithium negative electrodes and apply them to batteries.
Disclosure of Invention
Based on the above problems, the inventor's conception is mainly to stabilize a lithium anode by constructing a three-dimensional skeleton for a strategy of lithium anode protection.
The three-dimensional current collector with higher specific surface area is used as a framework of the lithium negative electrode, so that infinite change of the volume of the metal lithium in the circulation process can be effectively restrained, local current density is slowed down, and stable electrode/electrolyte interface is promoted.
However, the inventors have studied to find that: most of the carbon-based frameworks have poor affinity with metallic lithium, which can initiate uneven nucleation of lithium ions and increase nucleation overpotential. In addition, since the whole framework is conductive, lithium deposition also requires additional overpotential, and metal lithium is mainly deposited on the top of the framework under high current density to form blocky lithium, so that the utilization rate of the whole framework is greatly reduced. If the process of lithium deposition stripping is to occur in the bulk region, more lithium ions are required, inducing uneven lithium ion flow, resulting in less stable lithium deposition/stripping behavior. Under long-term cycling, the top growth mode can cause the surface lithium dendrites to pierce the separator, resulting in a short circuit of the cell.
Based on the above research findings of the inventors, the present invention aims to provide a three-dimensional composite carbon material with gradient lithium-philic property, a preparation method thereof, a composite lithium anode material containing the same and application thereof.
The embodiment of the invention is realized by the following technical scheme:
the three-dimensional composite carbon material with gradient lithium-philic property is a three-dimensional carbon fiber with carbon nano tubes grown, one surface of the composite carbon material is plated with the lithium-philic material, and the other surface of the composite carbon material is the carbon fiber with the carbon nano tubes grown.
Further, the three-dimensional carbon fiber is a fiber which has poor affinity with metal lithium and can conduct electricity; for example, the three-dimensional carbon fibers may be carbon fibers or carbon nanofibers.
Further, the lithium-philic material is a material that can undergo an alloying reaction with lithium.
Further, the content of the lithium-philic material accounts for 6-15wt% of the mass of the whole composite material.
The preparation method of the three-dimensional composite carbon material with gradient lithium-philic property comprises the steps of growing uniform carbon nanotubes on a three-dimensional carbon fiber mat to obtain a lithium-phobic composite carbon material; and covering one surface of the composite carbon material with an insulating material, soaking the composite carbon material into electrolyte, and electroplating the other surface of the composite carbon material opposite to the insulating material with a lithium-philic material to obtain the composite carbon material.
Specifically, the method comprises the following steps:
s1, catalyst impregnation: immersing the clean carbon fiber felt in a metal salt solution (such as one or more of iron, nickel and cobalt salt solutions) for about 12 hours to obtain the carbon fiber loaded with the catalyst;
s2, growing carbon nanotubes: heating the carbon fiber loaded with the catalyst to about 700 ℃ at a speed of 3-8 ℃/min under a protective gas atmosphere (such as argon, nitrogen and the like), then introducing a carbon source (such as acetylene, ethanol, methane, methanol and other gases), and preserving the heat for 10-20 minutes, wherein the gas flow ratio of the protective gas atmosphere to the carbon source is 10:1, and then cooling to room temperature under the protective gas atmosphere to obtain the CNT@CF;
s3, acid washing: soaking the CNT@CF material in an acid solution for a period of time, heating to 50-70 ℃ in a water bath, preserving heat for 1-3 hours, and washing off residual catalyst in the material; then washing with water until the pH is neutral;
s4, deposition: one surface of the CNT@CF material after pickling is covered by an insulating material, the other surface opposite to the CNT@CF material is used as a cathode, a lithium-philic material is used as an anode, and a composite carbon material with gradient lithium-philic property is obtained by depositing for a period of time through an electrodeposition method. (in addition, atomic layer deposition can be used to directly modify one surface of the material)
A composite lithium negative electrode material comprising metallic lithium, further comprising: the composite carbon material described above or a composite carbon material comprising the composite carbon material produced by the above production method.
The application of the composite lithium anode material in preparing lithium batteries.
The invention provides a preparation method for preparing a three-dimensional composite carbon skeleton with gradient lithium-philic property. And uniformly growing carbon nanotubes on the surface of the carbon fiber mat by adopting a chemical vapor deposition method to obtain a composite of the carbon nanotubes and the carbon fibers, wherein the composite is lithium-repellent. Then, the carbon fiber felt with the grown carbon nano tubes is used as a cathode, and an insulating silica gel with micro-viscosity is used for adhering to one surface of the composite material, and then an electrodeposition method is adopted: zinc foil is used as anode, zinc nitrate hexahydrate solution (or other zinc salt solution) is adopted as electrolyte, zinc oxide is electroplated locally (opposite to the surface of insulating silica gel, which is adhered to the composite material) on the composite of the carbon nano tube/carbon fiber by a constant voltage electric deposition method, and the three-dimensional composite carbon skeleton with gradient lithium-philic property is obtained after drying.
The chemical vapor deposition method is adopted to grow the uniform carbon nanotubes on the carbon fiber skeleton, so that the overall conductivity can be improved, the transmission of lithium ions is promoted, the overall specific surface area is increased, and the local current density is reduced; the lithium-philic zinc oxide is mainly concentrated at the bottom of the composite carbon skeleton, has stronger affinity with lithium, reduces nucleation barriers, and induces metallic lithium to deposit in a bottom-top manner. Meanwhile, the carbon fiber framework has certain mechanical strength and flexibility, can relieve the volume expansion in the lithium deposition stripping process, and limits dead lithium in the framework; the prepared composite lithium metal negative electrode can inhibit the growth of lithium dendrites, and remarkably improves the cycle stability and cycle life of the lithium metal negative electrode.
The invention also provides a preparation method of the composite metal lithium anode, wherein the metal lithium is taken as the anode, the composite carbon skeleton with gradient lithium-philicity is taken as the anode, and one side of the zinc oxide rich in lithium is opposite to the diaphragm. And assembling the lithium metal anode into a battery under the argon atmosphere, and depositing a certain capacity of lithium metal on the gradient lithium-philic composite carbon skeleton by an electrodeposition method to obtain the composite lithium metal anode.
A lithium metal secondary battery comprises the composite lithium metal negative electrode.
The technical scheme of the embodiment of the invention has at least the following advantages and beneficial effects:
(1) The three-dimensional self-supporting carbon fiber felt is taken as a framework, has good flexibility/mechanical strength, and can adapt to the volume change of lithium in the circulation process;
(2) The uniformly grown carbon nano tube increases the specific surface area of the whole skeleton, and can reduce the local current density in the charge and discharge process; the conductivity of the whole framework is improved to promote the transmission of lithium ions;
(3) Zinc oxide distributed in a gradient manner from bottom to top can reduce the nucleation barrier of lithium, guide lithium ions to be deposited preferentially at the bottom of the framework, and prevent metal lithium from being deposited at the uppermost surface of the framework;
(4) The prepared composite lithium metal negative electrode can inhibit the growth of lithium dendrites, and the cycle stability and the cycle life of the lithium metal negative electrode are obviously improved;
(5) The carbon nano tube uniformly grows on the carbon fiber by adopting a chemical vapor deposition method, the prepared composite carbon skeleton has light weight and higher porosity, and the energy density of the battery adopting the metal lithium composite anode can be improved to a certain extent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the top surface of a gradient lithium-philic three-dimensional framework prepared in example 1 of the present invention;
FIG. 2 is a bottom surface scanning electron microscope image of a gradient lithium-philic three-dimensional framework prepared in example 1 of the present invention;
FIG. 3 is a bottom surface SEM image of a composite lithium anode prepared according to example 2 of the invention;
FIG. 4 is a scanning electron microscope image of the composite lithium anode prepared in example 2 of the present invention after assembly into a nominal battery cycle;
FIG. 5 shows a current density of 1mAcm for a composite lithium anode prepared in example 2 of the present invention and a symmetrical battery assembled in comparative example 1 -2 Electrochemical performance graphs below.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation process comprises the following steps:
1. after the carbon fiber felt is cleaned by alcohol and deionized water, acetone is used for ultrasonic treatment for ten minutes to remove impurities and organic matters on the surface, and the carbon fiber felt is cleaned by alcohol and deionized water and dried for standby.
2. Preparing 200mL of 0.2mol/L nickel nitrate hexahydrate solution, immersing the treated carbon fiber felt into the catalyst solution, standing for 12 hours, taking out the material, and drying the material in a blast oven at 60 ℃ to obtain the carbon fiber loaded with the catalyst;
3. and (3) placing the carbon fiber loaded with the catalyst into a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under an argon atmosphere, and then introducing acetylene as a carbon source, wherein the ratio of the argon flow to the acetylene flow is 10:1, and the argon flow is 160mL/min and the acetylene flow is 16mL/min. And (3) ventilation time is ten minutes, and then cooling is carried out in an argon atmosphere to obtain the composite material of the carbon nano tube and the carbon fiber.
4. Preparing a 2mol/L hydrochloric acid solution, putting the carbon nanotube/carbon fiber composite material into the hydrochloric acid solution, and preserving heat in a water bath kettle at 60 ℃ for two hours to remove residual catalyst and carbon impurities in the composite material. Washing with deionized water after acid washing until the pH value of the material is neutral.
5. Preparing 0.1mol/L zinc nitrate hexahydrate solution as electrolyte, taking carbon nano tube/carbon fiber as cathode, 99% pure zinc foil as anode, and cutting the cathode and anode into 3 x 2cm size. To avoid that the whole structure of the carbon nanotubes/carbon fibers is electroplated, one side of the carbon nanotubes/carbon fibers composite is glued (3 x 2 x 0.03 cm) with insulating silica gel having a slight adhesion. And (3) performing constant-voltage electrodeposition (voltage is 1.0V) at room temperature, wherein the electrodeposition time is 60min, and obtaining the lithium-philic ZnO composite carbon fiber/carbon nanotube material with gradient distribution after the electrodeposition is finished.
6. Cutting the material into a wafer electrode with the diameter of 16mm, transferring the wafer electrode into a glove box under high-purity argon atmosphere, and taking a metal lithium sheet (with the diameter of 16 mm) as a negative electrode; the composite material is used as an anode, and one surface plated with zinc oxide is close to the diaphragm; the LiTFSI-DOL/DME (v/v=1:1) contained 0.1M LiNO with CR2032 type coin cell 3 Is assembled into a battery under the liquid electrolyte of the additive of (a).
7. The half cell was used at a current density of 1mA cm -2 Discharge at constant current of 5mAh cm -2 Then, the button cell is transferred into a glove box under argon atmosphere for disassembly, the lithium-plated metal lithium composite anode is taken out from the cell and assembled into a pair of cells for electrochemical test, and the following steps are needed: the lithium-plated composite negative electrode has a lithium-plated surface that is remote from the separator when the symmetrical battery is assembled.
The results are shown in fig. 1 and fig. 2, wherein fig. 1 shows the top surface of the gradient lithium-philic three-dimensional skeleton prepared in this example, and it can be seen that the surface is composed of carbon fibers with a large number of grown carbon nanotubes; fig. 2 shows the bottom surface of the gradient lithium-philic three-dimensional skeleton prepared in this example, and it can be seen that the surface of the fiber is wrapped by a zinc oxide film, so as to obtain a composite structure with lithium-philic bottom and lithium-philic top.
Example 2
The preparation process comprises the following steps:
1. after the carbon fiber felt is cleaned by alcohol and deionized water, acetone is used for ultrasonic treatment for ten minutes to remove impurities and organic matters on the surface, and the carbon fiber felt is cleaned by alcohol and deionized water and dried for standby.
2. 200mL of 0.2mol/L nickel nitrate hexahydrate solution is prepared, the treated carbon fiber felt is immersed into the catalyst solution for standing for 12 hours, and then the material is taken out and dried in a blast oven at 60 ℃.
3. And (3) placing the carbon felt loaded with the catalyst into a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under an argon atmosphere, and then introducing acetylene as a carbon source, wherein the ratio of argon to acetylene gas flow is 10:1, and the argon gas flow is 160mL/min and the acetylene gas flow is 16mL/min. And (3) ventilation time is ten minutes, and then cooling is carried out in an argon atmosphere to obtain the composite material of the carbon nano tube and the carbon fiber.
4. Preparing 2mol/L hydrochloric acid solution, putting the carbon nanotube/carbon fiber composite material into the hydrochloric acid solution, preserving heat for two hours in a water bath kettle at 60 ℃, washing with deionized water after acid washing until the pH value of the material is neutral.
5. Preparing 0.1mol/L zinc nitrate hexahydrate as electrolyte, carbon nano tube/carbon fiber as cathode, 99% pure zinc foil as anode, and cutting the cathode and anode to 3 x 2cm size. In order to avoid electrochemical reaction of the whole material of the carbon nano tube/carbon fiber, one surface of the carbon nano tube/carbon fiber composite is stuck by insulating silica gel with micro-viscosity (3 x 2 x 0.03 cm). And (3) performing constant-voltage electrodeposition (voltage is 1.0V) at room temperature, wherein the electrodeposition time is 60min, and obtaining the lithium-philic ZnO composite carbon fiber/carbon nanotube material with gradient distribution after the electrodeposition is finished.
6. Cutting the material into a wafer electrode with the diameter of 16mm, transferring the wafer electrode into a glove box under high-purity argon atmosphere, and taking a metal lithium sheet (with the diameter of 16 mm) as a negative electrode; the composite material is used as an anode, and one surface plated with zinc oxide is close to the diaphragm; the LiTFSI-DOL/DME (v/v=1:1) contained 0.1M LiNO with CR2032 type coin cell 3 The battery is assembled under the liquid electrolyte of the additive.
7. The half cell was used at a current density of 1mA cm -2 Discharge at constant current 30mAh cm -2 Then, the button cell is transferred into a glove box under argon atmosphere for disassembly, the lithium-plated metal lithium composite anode is taken out from the cell and assembled into a pair of cells for electrochemical test, and the following steps are needed: the lithium-plated composite negative electrode has a lithium-plated surface that is remote from the separator when the symmetrical battery is assembled.
The results are shown in fig. 3 to 4, wherein fig. 3 is a bottom surface SEM of the composite lithium anode prepared in example 2, and it can be seen that metallic lithium is uniformly deposited in a lump manner; FIG. 4 is a schematic diagram showing a current density of 1mA cm for a composite lithium anode assembly prepared in example 2 and a paired battery -2 The SEM image of the cross section after 20 cycles of the lower cycle shows that the metallic lithium is deposited almost at the bottom of the framework and is not found substantially at the upper layer of the framework where it is thinned.
Comparative example 1
1. After the carbon fiber felt is cleaned by alcohol and deionized water, acetone is used for ultrasonic treatment for ten minutes to remove impurities and organic matters on the surface, and the carbon fiber felt is cleaned by alcohol and deionized water and dried for standby.
2. 200mL of 0.2mol/L nickel nitrate hexahydrate solution is prepared, the treated carbon fiber felt is immersed into the catalyst solution for standing for 12 hours, and then the material is taken out and dried in a blast oven at 60 ℃.
3. And (3) placing the carbon felt loaded with the catalyst into a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under an argon atmosphere, and then introducing acetylene as a carbon source, wherein the ratio of argon to acetylene gas flow is 10:1, and the argon gas flow is 160mL/min and the acetylene gas flow is 16mL/min. And (3) ventilation time is ten minutes, and then cooling is carried out in an argon atmosphere to obtain the composite material of the carbon nano tube and the carbon fiber.
4. Preparing 2mol/L hydrochloric acid solution, putting the carbon nanotube/carbon fiber composite material into the hydrochloric acid solution, preserving heat for two hours in a water bath kettle at 60 ℃, washing with deionized water after acid washing until the pH value of the material is neutral.
5. Cutting the above materials into 16mm diameter wafer electrode, transferring into glove box under high purity argon atmosphere, taking metal lithium sheet (diameter 16 mm) as negative electrode, taking the composite material as positive electrode, and using CR2032 button typeThe cell contained 0.1M LiNO in LiTFSI-DOL/DME (v/v=1:1) 3 The battery is assembled under the liquid electrolyte of the additive.
6. The half cell was used at a current density of 1mA cm -2 Discharge at constant current 30mAh cm -2 Then, the button cell is transferred into a glove box under argon atmosphere for disassembly, the lithium-plated metal lithium composite electrode is taken out from the cell and assembled into a pair of cells for electrochemical testing, and the following steps are needed: the lithium-plated face is remote from the separator. The results are shown in FIG. 5.
This comparative example did not have a lithium-philic material plated on one side of the composite. FIG. 5 shows a current density of 1mAcm for a composite lithium anode prepared in example 2 and a symmetrical battery assembled in comparative example 1 -2 From the electrochemical performance graph below, it can be seen from fig. 5 that example 2 exhibited better electrochemical performance and was able to stably circulate for 1400 hours.
Comparative example at a current density of 1mA cm -2 ，1mAh cm -2 The polarization voltage starts to increase gradually after 600 hours of the lower stabilization cycle, because the lithium metal electrode compounded in the comparative example has pre-deposited metal lithium at the bottom of the framework, but the lithium ion nucleation cannot be guided due to the absence of the lithium-philic zinc oxide, and the nucleation overpotential of lithium cannot be effectively reduced. During long cycles, large amounts of lithium ions still tend to deposit on the top surface of the composite electrode, enriching large amounts of lithium ion flow, so that a "top growth" mode is still formed, resulting in the formation of lithium dendrites, eventually leading to increased polarization and short circuiting of the cell.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A three-dimensional composite carbon material with gradient lithium-philic property is characterized in that: the composite carbon material is a three-dimensional carbon fiber containing carbon nanotubes, and one surface of the composite carbon material is plated with a lithium-philic material.
2. The three-dimensional composite carbon material with gradient lithium-philic properties of claim 1, wherein the three-dimensional carbon fibers are conductive fibers having poor affinity for metallic lithium.
3. The three-dimensional composite carbon material having gradient lithium-philic properties according to claim 1, wherein the lithium-philic material is a material that can undergo an alloying reaction with lithium.
4. A three-dimensional composite carbon material with gradient lithiasis according to claim 3, wherein the lithiated material content is 6-15wt% of the mass of the entire composite material.
5. A method for preparing the three-dimensional composite carbon material with gradient lithium-philic property according to any one of claims 1-4, which is characterized in that uniform carbon nanotubes are grown on a three-dimensional carbon fiber mat to obtain a lithium-philic composite carbon material; and covering one surface of the composite carbon material with an insulating material, soaking the composite carbon material into electrolyte, and electroplating the other surface of the composite carbon material opposite to the insulating material with a lithium-philic material to obtain the composite carbon material.
6. The method for preparing a three-dimensional composite carbon material with gradient lithium-philic property according to claim 5, comprising the steps of:
s1, catalyst impregnation: immersing the clean carbon fiber felt in a metal salt solution for a period of time to obtain the carbon fiber loaded with the catalyst;
s2, growing carbon nanotubes: heating the carbon fiber loaded with the catalyst in a protective gas atmosphere, then introducing a carbon source, and then cooling to room temperature in the protective gas atmosphere to obtain CNT@CF;
s3, acid washing: soaking the CNT@CF material in an acid solution for a period of time, and washing off residual catalyst in the material; then washing with water until the pH is neutral;
s4, deposition: one surface of the CNT@CF material after pickling is covered by an insulating material, the other surface opposite to the CNT@CF material is used as a cathode, a lithium-philic material is used as an anode, and a deposition method is used for depositing for a period of time to obtain the composite carbon material with gradient lithium-philic property.
7. The method for preparing a three-dimensional composite carbon material with gradient lithium-philic properties according to claim 4, wherein in S4, the deposition method is an electrodeposition method.
8. The method for preparing a three-dimensional composite carbon material having gradient lithium-philic properties according to claim 4, wherein the ratio of the flow rates of the shielding gas and the carbon source is 10:1.
9. A composite lithium negative electrode material comprising metallic lithium, characterized by further comprising: the composite carbon material of any one of claims 1 to 4 or comprising a composite carbon material produced by the production method of any one of claims 5 to 8.
10. Use of the negative electrode material of claim 9 in the preparation of a lithium battery.
CN202310386843.9A 2023-04-12 2023-04-12 Three-dimensional composite carbon material with gradient lithium affinity, preparation method thereof, composite lithium anode material containing three-dimensional composite carbon material and application of composite lithium anode material Pending CN116364931A (en)

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