CN112768697A - Composite lithium metal negative current collector and preparation method and application thereof - Google Patents

Composite lithium metal negative current collector and preparation method and application thereof Download PDF

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Publication number
CN112768697A
CN112768697A CN202011615425.5A CN202011615425A CN112768697A CN 112768697 A CN112768697 A CN 112768697A CN 202011615425 A CN202011615425 A CN 202011615425A CN 112768697 A CN112768697 A CN 112768697A
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metal
current collector
carbon
dimensional
lithium
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程春
牛树章
陈小梅
王信
黄润青
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Southwest University of Science and Technology
Southern University of Science and Technology
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 composite lithium metal negative current collector and a preparation method and application thereof, wherein the current collector comprises a three-dimensional foam metal framework and a carbon-metal hybrid interface layer on the surface of the three-dimensional foam metal framework; wherein the carbon-metal hybrid interface layer comprises a carbon-based material and a metal-based material. The composite lithium metal negative current collector directly deposits carbon-lithium-philic metal on a three-dimensional foam metal framework through a physical vapor deposition method to form a protective interface, so that the three-dimensional structure current collector modified by a carbon-lithium-philic metal hybrid structure is obtained, and the performance of metal lithium is improved.

Description

Composite lithium metal negative current collector and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium metal batteries, and relates to a composite lithium metal negative current collector and a preparation method and application thereof.
Background
Along with the rapid development of economic society, people depend on energy sources more and more closely, and the people are eager for energy storage equipment with high energy density, so that the research and the development of the next generation of secondary energy storage batteries are promoted. Metallic lithium negative electrode due to its extremely high theoretical specific capacity (3860 mAhg)-1) Lowest electrochemical potential (-3.04Vvs standard hydrogen electrode) and low weight density (0.534 gcm)-3) It is considered to be a holy cup material of the negative electrode of the next generation lithium battery.
However, lithium metal as a negative electrode material has its own problems: (1) lithium metal with high electrochemical activity reacts with electrolyte to form a layer of solid electrolyte interface film (SEI film), and the SEI film is easy to crack and form a new SEI film in the charge-discharge process, so that the lithium metal and the electrolyte are continuously consumed; (2) due to the host-free nature of the lithium metal negative electrode, serious problems of volume expansion and the like can be caused in the repeated charge and discharge process, so that the SEI film is continuously reconstructed; (3) structural and compositional non-uniformity of the SEI film can lead to non-uniform deposition/peeling of lithium, resulting in dendrite formation and growth.
The problems can cause the lithium metal battery to show low coulombic efficiency, poor cycle stability and fast capacity attenuation in charge-discharge cycles, and finally cause potential safety hazards such as short circuit, thermal runaway and the like in the battery.
In order to solve the above problems, researchers have made a lot of efforts to surface-modify a lithium metal negative electrode in consideration of poor mechanical properties and chemical instability of the original SEI film, to regulate the formation of the SEI film and to suppress dendrite growth by adjusting an electrolyte. Such as the addition of electrolyte additives, the use of solid electrolytes, and the construction of artificial SEI films. However, due to the host-free nature of lithium metal anodes, none of these approaches can fundamentally alleviate the problem of volume expansion of lithium metal anodes during cycling, which ultimately leads to SEI film cracking. In order to stabilize the lithium metal negative electrode/electrolyte interface, a 3D framework is introduced into a lithium metal bulk phase to provide enough space for lithium metal electrodeposition, and a new lithium-philic material is searched for modifying the 3D framework to regulate the nucleation growth behavior of lithium, such as Qiang-Zhang et al[Joule,2018,2,1-14]A layer of coral reef-shaped silver particles is modified on carbon fibers to serve as a lithium metal negative current collector, the problem of volume expansion in a circulation process can be buffered due to the large space volume of a three-dimensional framework structure of the carbon fibers, and the composite current collector is endowed with excellent lithium affinity due to the fact that silver and lithium can form an alloy. The two synergistic effects promote the uniform deposition and stripping of lithium, and inhibit the uncontrollable growth of lithium dendrites. In addition, the construction of an artificial Solid Electrolyte (SEI) film on a 3D skeleton can also effectively control the lithium deposition behavior, such as Yong-YaoXia [ Angew.chem.Int.Ed.2019,58,2093-]Anchoring Li on 3D copper foam6.4La3Zr1.4Ta0.6O12(LLZTO) as an artificial SEI film can effectively reduce local current density, reduce contact of an electrolyte and lithium metal, and simultaneously accommodate volume change caused by lithium deposition.
Therefore, it is necessary to develop a negative electrode current collector having lithium affinity, electrolyte wettability, guiding uniform nucleation and deposition growth of lithium, forming an SEI layer having excellent mechanical properties, and stabilizing the long cycle of the battery.
Disclosure of Invention
The invention aims to provide a composite lithium metal negative current collector and a preparation method and application thereof, wherein the current collector comprises a three-dimensional foam metal framework and a carbon-metal hybrid interface layer, and the interface has a hydrophilic-hydrophobic lithium gradient; wherein the carbon-metal hybrid interface layer comprises a carbon-based material and a metal-based material. The three-dimensional current collector is a three-dimensional structure current collector with a carbon-lithium-philic metal hybrid structure modification, which is obtained by directly depositing carbon-lithium-philic metal on three-dimensional foam metal to form a protective interface through a physical evaporation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite lithium metal negative current collector, which comprises a three-dimensional foam metal framework and a carbon-metal hybrid interface layer on the surface of the three-dimensional foam metal framework; wherein the carbon-metal hybrid interface layer comprises a carbon-based material and a metal-based material.
The composite lithium metal negative current collector obtains the three-dimensional structure current collector with the carbon-lithium-philic metal hybrid structure modification by forming the carbon-metal hybrid interface layer on the surface of the three-dimensional foam metal framework, has the advantages of lithium-philic property, electrolyte wettability, guiding uniform nucleation, deposition and growth of lithium, forming an SEI layer with excellent mechanical property, stabilizing long cycle of a battery and the like, and has important significance for the development of the lithium metal battery.
Preferably, the pore diameter of the current collector is 0.5-1 μm, for example: 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, or the like.
Preferably, the three-dimensional foam metal skeleton comprises any one of a three-dimensional foam copper skeleton, a three-dimensional foam nickel skeleton or a three-dimensional foam aluminum skeleton or a combination of at least two of the three-dimensional foam copper skeleton, the three-dimensional foam nickel skeleton or the three-dimensional foam aluminum skeleton.
Preferably, the thickness of the carbon-metal hybrid interface layer is 0.05-3 μm, for example: 0.05 μm, 0.1 μm, 0.3 μm, 0.5 μm, 1 μm, 2 μm, or 3 μm, etc., which has a lithium-philic gradient.
Preferably, the carbon-based material includes any one of carbon nanotube, graphene, carbon fiber, acetylene black, fullerene, or activated carbon, or a combination of at least two thereof.
According to the invention, the carbon layer deposited by the carbon-based material can disperse an electric field, reduce the average current density, make lithium ions distributed more uniformly and promote the uniform deposition of lithium. From the point of nucleation and deposition, the synergistic effect of the two can effectively inhibit the growth of lithium dendrites.
Preferably, the metal-based material comprises any one of gold, silver, aluminium, magnesium, calcium, tin or zinc or a combination of at least two thereof.
The invention uses lithium-philic metal as initial lithium nucleation sites to induce uniform nucleation of lithium and reduce polarization of lithium deposition.
Preferably, the thickness of the three-dimensional foam metal framework is 0.1-3 mm, for example: 0.1mm, 0.5mm, 0.8mm, 1mm, 2mm, 3mm, or the like.
Preferably, the three-dimensional foam metal skeleton has a size of 0.5-5 μm, such as: 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or the like.
Preferably, the pore diameter of the three-dimensional foam metal skeleton is 0.2-8 μm, such as: 0.2 μm, 0.8 μm, 1 μm, 3 μm, 5 μm, 6 μm, 8 μm, or the like.
In a second aspect, the present invention also provides a method for preparing the composite lithium metal negative electrode current collector according to the first aspect, the method comprising the steps of:
(1) respectively soaking the foam metal in absolute ethyl alcohol, dilute hydrochloric acid and deionized water, and ultrasonically treating to remove surface stains and an oxide layer to obtain a three-dimensional foam metal framework;
(2) and (2) carrying out vacuum evaporation treatment on the carbon-based material, the metal-based material and the three-dimensional foam metal framework obtained in the step (1) to obtain the composite lithium metal negative current collector.
According to the invention, by utilizing the unevenness and the lithium-phobicity of the surface of the three-dimensional foam metal current collector, when the carbon-metal protective layer is used for evaporating the carbon-based and metal materials on the surface of the three-dimensional foam metal in a vacuum evaporation mode, the carbon-metal protective layer has a lithium-philic-lithium-phobic gradient, can induce uniform lithium nucleation and deposition, can be used as an artificial SEI (solid electrolyte interphase) film, and can effectively prevent lithium dendrites from being formed in the charging and discharging process.
Preferably, the vacuum evaporation treatment device in the step (2) comprises a vacuum coater.
In the present invention, the vacuum deposition is performed by a vacuum deposition machine by a conventional method in the art, and the present invention is not particularly limited.
In a third aspect, the present invention provides a three-dimensional composite lithium metal anode comprising a composite lithium metal anode current collector as described in the first aspect.
The lithium metal cathode has the advantages of excellent performance, safe use and simple manufacture, and can be used for actual production.
In a fourth aspect, the invention also provides a lithium ion battery, which comprises the three-dimensional composite metal lithium negative electrode as described in the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite lithium metal negative electrode current collector provided by the invention has the advantages of lithium affinity, electrolyte wettability, guidance of uniform nucleation, deposition and growth of lithium, formation of an SEI (solid electrolyte interphase) layer with excellent mechanical properties, stability of long cycle of a battery and the like, and has important significance for development of lithium metal batteries.
(2) According to the invention, the foam metal current collector is modified through a simple and environment-friendly physical evaporation process, an artificial carbon-metal hybrid interface with a protection effect is constructed, and the performance of metal lithium can be improved.
(3) The cycle number of the current collector can reach more than 260 circles, the coulombic efficiency can reach more than 98.9, the nucleation overpotential is only below 23mV, and the cycle time of the symmetrical battery is greatly improved compared with that of the conventional three-dimensional foam copper current collector and reaches more than 2000 hours.
Drawings
Fig. 1 is a cross-sectional scanning electron microscope image of a composite lithium metal negative electrode current collector provided in example 1 of the present invention.
Fig. 2a is a scanning electron microscope image of a copper foam current collector described in comparative example 1 of the present invention, fig. 2b is a scanning electron microscope image of a silver modified copper foam current collector described in comparative example 2, and fig. 2c is a scanning electron microscope image of a composite lithium metal negative current collector described in example 1.
FIG. 3 shows the current collectors at 2mA/cm for the current collectors of example 1, comparative example 1 and comparative example 2 of the present invention2Coulombic efficiency at current density is plotted versus time.
Fig. 4 is a graph comparing the cycle stability of electrodes made using the current collector of example 1 in accordance with the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a composite lithium metal negative current collector, which is prepared by the following specific steps:
(1) respectively putting the foamy copper current collector into absolute ethyl alcohol, dilute hydrochloric acid and deionized water for soaking, and performing ultrasonic treatment to remove surface stains and oxide layers to obtain a three-dimensional foamy copper framework;
(2) putting the three-dimensional foamy copper skeleton (5cm multiplied by 5cm), the fullerene (100mg) and the silver simple substance (200mg) obtained in the step (1) into a vacuum chamber of a vacuum coating machine, and carrying out vacuum coating (5 multiplied by 10)-4Pa), evaporating silver simple substance and fullerene, depositing gas ionized atoms on the surface of the foam copper current collector to form a fullerene-silver-based protective layer with the thickness of 500nm, and obtaining the composite lithium metal negative current collector.
The cross-sectional scanning electron microscope image of the composite lithium metal negative electrode current collector is shown in fig. 1, and it can be seen from fig. 1 that the silver @ fullerene interface layer is tightly anchored on the foam copper skeleton, and the thickness of the silver @ fullerene interface layer is about 500 nm.
The scanning electron microscope image of the composite lithium metal negative current collector is shown in fig. 2c, and as can be seen from fig. 2c, the negative current collector prepared by the invention deposits carbon-silver on three-dimensional foam copper to form a protective interface, so that the current collector with a three-dimensional structure modified by a carbon-silver hybrid structure is obtained.
Example 2
The embodiment provides a composite lithium metal negative current collector, which is prepared by the following specific steps:
(1) respectively putting the foamy copper current collector into absolute ethyl alcohol, dilute hydrochloric acid and deionized water for soaking, and performing ultrasonic treatment to remove surface stains and oxide layers to obtain a three-dimensional foamy copper framework;
(2) and (2) putting the three-dimensional foam nickel skeleton (5cm multiplied by 5cm), the carbon nano tube (100mg) and the magnesium simple substance (200mg) obtained in the step (1) into a vacuum chamber of a vacuum coating machine, evaporating the magnesium simple substance and the carbon nano tube under a vacuum condition, and depositing gas ionized atoms on the surface of the foam copper current collector to form a carbon nano tube-magnesium-based protective layer with the thickness of 500nm to obtain the composite lithium metal negative current collector.
Comparative example 1
The three-dimensional copper foam skeleton described in step (1) of example 1 was used directly as a negative current collector.
The scanning electron microscope image of the three-dimensional foam copper skeleton is shown in fig. 2a, and as can be seen from fig. 2a, the surface of the three-dimensional foam copper skeleton is smooth and has no surface stains or oxidation layers.
Comparative example 2
The comparative example is different from example 1 only in that no fullerene is added in the step (2), and other conditions and parameters are completely the same as those of example 1, so that the silver modified copper foam current collector is obtained.
The scanning electron microscope image of the silver modified copper foam current collector is shown in fig. 2b, and as can be seen from fig. 2b, the method can uniformly disperse the silver simple substance on the surface of the copper foam.
And (3) performance testing:
lithium foil is used as a negative electrode, 1M LiTFSI DO L/DME (volume ratio of 1:1) +1 wt% LiNO3Is an electrolyte, Celgard2400 is a separator, and modified foam copper current collectors prepared on the basis of example 1, example 2, comparative example 1 and comparative example 2 are anodes and are arranged at 1mAcm-2Lithium plating/stripping tests were performed at current densities and the results are shown in table 1 and fig. 3-4:
TABLE 1
Figure BDA0002876505400000071
As can be seen from Table 1, the number of cycles of the current collector can reach more than 260 cycles, the coulombic efficiency reaches more than 98.9, the nucleation overpotential is only below 23mV, and the cycle time of the symmetrical battery is greatly improved to more than 2000 hours compared with the conventional three-dimensional foam copper current collector.
As can be seen from fig. 3, the composite lithium metal negative electrode current collector prepared by the present invention has high coulombic efficiency, and is stable when the cycle number reaches 80 times.
As can be seen from FIG. 4, the cycle time of the symmetrical battery with the composite lithium metal negative electrode current collector prepared by the invention can reach more than 2500 h.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The composite lithium metal negative current collector is characterized by comprising a three-dimensional foam metal framework and a carbon-metal hybrid interface layer on the surface of the three-dimensional foam metal framework;
wherein the carbon-metal hybrid interface layer comprises a carbon-based material and a metal-based material.
2. The composite lithium metal negative electrode current collector of claim 1, wherein the current collector has a pore size of 0.5 to 1 μm.
3. The composite lithium metal negative electrode current collector of claim 1 or 2, wherein the three-dimensional foamed metal skeleton comprises any one of a three-dimensional foamed copper skeleton, a three-dimensional foamed nickel skeleton, or a three-dimensional foamed aluminum skeleton, or a combination of at least two thereof.
4. The composite lithium metal negative electrode current collector of any one of claims 1 to 3, wherein the carbon-metal hybrid interface layer has a thickness of 0.05 to 3 μm with a lithium-philic gradient.
5. The composite lithium metal negative electrode current collector of any one of claims 1 to 4, wherein the carbon-based material comprises any one of or a combination of at least two of carbon nanotubes, graphene, carbon fibers, acetylene black, fullerene, or activated carbon;
preferably, the metal-based material comprises any one of gold, silver, aluminium, magnesium, calcium, tin or zinc or a combination of at least two thereof.
6. The composite lithium metal negative electrode current collector of any one of claims 1 to 5, wherein the thickness of the three-dimensional foam metal skeleton is 0.1 to 3 mm;
preferably, the size of the three-dimensional foam metal framework is 0.5-5 μm;
preferably, the aperture of the three-dimensional foam metal framework is 0.2-8 μm.
7. A method of preparing a composite lithium metal negative electrode current collector according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) respectively soaking the foam metal in absolute ethyl alcohol, dilute hydrochloric acid and deionized water, and ultrasonically treating to remove surface stains and an oxide layer to obtain a three-dimensional foam metal framework;
(2) and (2) carrying out vacuum evaporation treatment on the carbon-based material, the metal-based material and the three-dimensional foam metal framework obtained in the step (1) to obtain the composite lithium metal negative current collector.
8. The method according to claim 7, wherein the vacuum evaporation apparatus in the step (2) comprises a vacuum coater.
9. A three-dimensional composite lithium metal anode comprising the composite lithium metal anode current collector of any of claims 1-6.
10. A lithium ion battery comprising the three-dimensional composite metallic lithium negative electrode of claim 9.
CN202011615425.5A 2020-12-30 2020-12-30 Composite lithium metal negative current collector and preparation method and application thereof Pending CN112768697A (en)

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CN113564524A (en) * 2021-07-13 2021-10-29 南京邮电大学 Method for preparing carbon-coated three-dimensional porous copper current collector
CN114141984A (en) * 2021-12-01 2022-03-04 远景动力技术(江苏)有限公司 Lithium battery, negative plate thereof and preparation method of negative plate
CN114551793A (en) * 2021-09-18 2022-05-27 万向一二三股份公司 Lithium-based composite negative plate with long cycle life, preparation method thereof and solid lithium battery
CN115020657A (en) * 2022-07-27 2022-09-06 西安交通大学 Alkali metal composite cathode and integrated preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113564524A (en) * 2021-07-13 2021-10-29 南京邮电大学 Method for preparing carbon-coated three-dimensional porous copper current collector
CN114551793A (en) * 2021-09-18 2022-05-27 万向一二三股份公司 Lithium-based composite negative plate with long cycle life, preparation method thereof and solid lithium battery
CN114551793B (en) * 2021-09-18 2023-10-03 万向一二三股份公司 Lithium-based composite negative plate with long cycle life, preparation method thereof and solid lithium battery
CN114141984A (en) * 2021-12-01 2022-03-04 远景动力技术(江苏)有限公司 Lithium battery, negative plate thereof and preparation method of negative plate
CN114141984B (en) * 2021-12-01 2023-08-11 远景动力技术(湖北)有限公司 Lithium battery and negative plate thereof and preparation method of negative plate
CN115020657A (en) * 2022-07-27 2022-09-06 西安交通大学 Alkali metal composite cathode and integrated preparation method thereof
CN115020657B (en) * 2022-07-27 2024-01-30 西安交通大学 Alkali metal composite negative electrode and integrated preparation method thereof

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Application publication date: 20210507