CN114039033A - Preparation method of cuprous oxide in-situ coated foamy copper/lithium metal negative electrode material - Google Patents

Preparation method of cuprous oxide in-situ coated foamy copper/lithium metal negative electrode material Download PDF

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CN114039033A
CN114039033A CN202111306638.4A CN202111306638A CN114039033A CN 114039033 A CN114039033 A CN 114039033A CN 202111306638 A CN202111306638 A CN 202111306638A CN 114039033 A CN114039033 A CN 114039033A
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copper
lithium metal
current collector
battery
foam
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李东玮
王康
王玮杰
李勇
刘玉华
陶圆圆
谷倩倩
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New Material Institute of Shandong Academy of Sciences
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention relates to the technical field of lithium metal battery cathode materials, in particular to a preparation method of a cuprous oxide in-situ coated foamy copper/lithium metal cathode material. The surface modified foamy copper 3D current collector is provided, foamy copper is used as a framework material, and cuprous oxide is generated by in-situ oxidation of the surface of the foamy copper; and carrying out surface oxidation treatment on the cleaned and dried foamy copper by adopting a cyclic voltammetry method, and drying to obtain the surface modified foamy copper 3D current collector. The 3D current collector for the lithium metal battery, which is provided by the invention, can inhibit the growth of lithium dendrites and improve the long cycle stability and high rate performance of a lithium metal negative electrode, and has a secondary structure. The 3D current collector has a large specific surface area, a lithium ion diffusion coefficient and excellent conductivity, and shows excellent long-cycle stability and high rate performance.

Description

Preparation method of cuprous oxide in-situ coated foamy copper/lithium metal negative electrode material
Technical Field
The invention relates to the technical field of lithium metal battery cathode materials, in particular to a preparation method of a cuprous oxide in-situ coated foamy copper/lithium metal cathode material.
Background
With the rapid development of portable electronic devices and electric vehicles, urgent demands are being placed on the development of next-generation high-energy rechargeable lithium batteries. Lithium metal is due to its extremely high theoretical capacity (3860mAh g)-1) Lower standard electrochemical potential (-3.04V vs. she) and excellent intrinsic conductivity became the ultimate choice for anode materials. However, commercialization of lithium metal anodes has been hindered due to problems of uncontrolled growth of dendrites, relatively infinite volume expansion, severe side reactions, and the like. Of these challenges, dendritic growth is considered to be the most important obstacle. Dendrites easily penetrate the membrane, causing short circuits, thermal runaway, fires and even explosions. In addition, dendrites readily react with electrolytes, irreversibly consuming active substances. Dead lithium resulting from non-uniform dissolution of lithium dendrites will further reduce battery life.
Various problems of the lithium metal battery need to be solved, and research and development people nowadays usually adopt the following methods to solve the problems of the lithium metal battery: adding additives into the electrolyte, preparing an artificial SEI film, using a high-strength solid electrolyte, modifying a diaphragm and the like.
Designing functional three-dimensional (3D) framework bodies is considered a viable approach to inhibit lithium dendrite growth. The use of these three-dimensional frame bodies not only reduces the non-uniformity of the current density distribution, but also provides space for lithium metal infusion, limiting the volume change during the deposition/delithiation process. However, most 3D framework hosts exhibit lithium phobic properties. Therefore, the large-scale application of the hot infusion strategy on the three-dimensional framework body is urgently needed by modifying the surface of the framework through the lithium-philic layer.
Disclosure of Invention
The invention aims to provide a preparation method of a cuprous oxide in-situ coated foamy copper/lithium metal negative electrode material, which is characterized in that foamy copper is oxidized by adopting a cyclic voltammetry method, and a layer of lithium-philic cuprous oxide grows in situ on the surface of the foamy copper, so that a 3D current collector for a lithium metal battery, which can inhibit the growth of lithium dendrites and improve the long-cycle stability and high-rate performance of a lithium metal negative electrode, is obtained. The 3D current collector has a large specific surface area, a lithium ion diffusion coefficient and excellent conductivity, and shows excellent long-cycle stability and high rate performance.
According to one technical scheme, the surface modified foamy copper 3D current collector takes foamy copper as a framework material, and cuprous oxide is generated by in-situ oxidation of the surface of the foamy copper.
Further, the thickness of the foam copper is 0.5-1.5 mm; the porosity of the copper foam is 110-130 ppi; the cuprous oxide is in a sharp structure.
The foamy copper has the characteristics of relatively uniform three-dimensional macropores, large supporting area and high conductivity, is selected as a lithium metal negative electrode three-dimensional current collector and a copper source, and has the following characteristics: the foamy copper has a three-dimensional skeleton structure and can guide the uniform deposition of lithium; meanwhile, a large number of cavity structures can provide buffer space for the growth of lithium dendrites, and the volume expansion can be greatly delayed. However, it is worth noting that the current commercial copper foam has the problems of low specific surface area, low affinity with lithium, and the like. Based on the method, the foamed copper is used as a substrate and is modified to prepare the three-dimensional current collector meeting the requirement of the lithium metal negative electrode. The thickness and the porosity of the copper foam can influence the appearance and the performance of a final product, and tests prove that the product prepared by the copper foam with the thickness of 0.5-1.5mm and the porosity of 110-130ppi has the best performance.
In the second technical scheme of the invention, the preparation method of the surface modified copper foam 3D current collector comprises the following steps:
and carrying out surface oxidation treatment on the cleaned and dried foamy copper by adopting a cyclic voltammetry method, and drying to obtain the surface modified foamy copper 3D current collector. The method is simple and non-toxic, does not need to add a surfactant, can realize large-scale production, ensures good interface contact between the active substance and the substrate and can ensure good conductivity, and the active substance grows on the conductive substrate in situ without any binder or conductive agent.
Further, the preparation of the cleaned and dried copper foam comprises the following steps: sequentially using hydrochloric acid solution and acetone to carry out ultrasonic cleaning on the foam copper; specifically, firstly, carrying out ultrasonic cleaning on a pre-cut foam copper sheet by using a hydrochloric acid solution to remove oxides on the surface of the foam copper sheet, then taking out the foam copper which is cleaned by using hydrochloric acid, washing the foam copper with deionized water for three times, and then immersing the foam copper sheet in an acetone solution to carry out ultrasonic cleaning to remove oil stains on the surface of the foam copper sheet. And repeatedly washing the cleaned foam copper by using deionized water, and drying at 50 ℃ for later use.
The cyclic voltammetry conditions were: the voltage interval is-0.3V, the scanning speed is 1mV/s, and the number of scanning turns is 1 circle; the drying temperature is 50 ℃, and the drying time is 5-6 h. The limitation of the cyclic voltammetry condition can enable the electrochemical oxidation process to occur on the surface of the copper foam, and cuprous oxide is generated on the surface of the copper foam. The spiky shape remarkably increases the specific surface area of the foam copper, can provide larger contact area for the foam copper and the molten lithium in the subsequent process of preparing the composite lithium cathode by a melting method, and accelerates the lithium melting speed by a larger capillary effect. Meanwhile, a large number of nucleation sites and charge centers are provided for the deposition of lithium on the negative electrode, which is beneficial to reducing the area current intensity, guiding the uniform deposition of lithium and forming a flat and smooth plane to form a stable SEI film.
Further, the concentration of the hydrochloric acid solution is 0.5-1mol/L, and the ultrasonic cleaning time is 15 min; the concentration of the potassium hydroxide solution is 0.5-1 mol/L.
In alkaline solution, the concentration is related to the reaction time, the concentration is high, and the reaction time is short
According to the third technical scheme, the surface modified foamy copper 3D current collector is applied to preparation of a lithium metal battery negative electrode material.
According to the fourth technical scheme, the negative electrode material of the lithium metal battery is obtained by directly compounding the surface modified foamy copper 3D current collector serving as a framework material with lithium metal. Specifically, the lithium metal intercalation method is a high-temperature lithium metal melt-filling method.
The fifth technical scheme of the invention is that the preparation method of the lithium metal battery cathode material comprises the following steps: and under an inert environment, soaking the surface modified foamy copper 3D current collector in molten liquid lithium metal, taking out and cooling to room temperature to obtain the lithium metal battery negative electrode material.
Specifically, transferring the surface modified foam copper 3D current collector into a glove box filled with high-purity argon, firstly melting a lithium sheet into liquid lithium metal in a battery case on a heating table, immersing the surface modified foam copper 3D current collector into the liquid lithium, rapidly absorbing the liquid lithium into a porous skeleton structure of the surface modified foam copper 3D current collector, taking out the modified foam copper filled with lithium, transferring the modified foam copper into a clean crucible, and cooling to obtain the lithium metal battery cathode material.
Further, the metallic lithium sheet in the battery case was heated to 320 ℃; the water oxygen value of the high-purity argon is less than 0.1 ppm.
Because the surface modified foamy copper 3D current collector prepared by the invention loads a layer of cuprous oxide with a spine-shaped structure on the surface of the foamy copper structure in situ, the lithium affinity characteristic and the spine-shaped structure of the cuprous oxide can shorten the time for melting and filling the high-temperature lithium metal; the special structure reduces the local current density and effectively delays the growth of the lithium dendrite. Meanwhile, a large number of nucleation sites are provided for the deposition of lithium, which is beneficial to the uniform deposition of lithium, so that a flat and smooth plane is formed, and a stable SEI film is formed.
The sixth technical scheme of the invention is the application of the lithium metal battery negative electrode material in battery preparation.
Further, the battery is a symmetrical battery or a full battery;
further, when the battery is a symmetrical battery, the electrode plates of the positive electrode and the negative electrode of the symmetrical battery are all the lithium metal battery negative electrode material;
further, when the battery is a full battery, the coated LiFePO is used as the full battery anode material4The aluminum foil current collector of (1), wherein the negative electrode material is the above-mentioned negative electrode material for lithium metal batteries.
Furthermore, the two batteries are assembled in a glove box filled with argon, and the gas used by the glove box is high-purity argon; the electrolyte of the symmetrical battery is an electrolyte of 1mol of LiTFSI dissolved in 1L of DME-DOL mixed solution, the volume ratio of DME to DOL in the electrolyte of the DME-DOL mixed solution is 1:1, and LiNO with the mass percent of 2 percent is contained3And (3) an additive. The total battery electrolyte is 1mol LiPF6The electrolyte is dissolved in 1L of EC: DEC mixed solution, and the volume ratio of EC to DEC in the electrolyte of the EC: DEC mixed solution is 1: 1.
Further, the separator used in the above-described symmetric battery and full battery is a polypropylene (PP) separator.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes the frequently used foam copper current collector as the 3D framework, has good conductivity and strong toughness, can effectively control the volume change of lithium metal, reduces the current density, does not introduce too many inactive substances in the surface modification process of the foam copper current collector, and realizes the improvement of the performance of the 3D framework.
The negative 3D current collector for the lithium metal battery prepared by the method can be used as a lithium ion deposition site, can effectively reduce the local current density of the electrode through a larger specific surface area, can inhibit the volume expansion of the electrode in the internal space, effectively inhibits the growth phenomenon of lithium dendrites or the formation of dead lithium on the surface of a lithium metal battery pole piece, effectively improves the CE (coulombic efficiency) of the lithium metal battery, prolongs the cycle service life and has safety and stability in the use process.
The method for preparing the negative 3D current collector for the lithium metal battery is simple and convenient, can effectively reduce the production cost of the lithium metal battery, and promotes the commercial process of the lithium metal battery.
Drawings
Fig. 1 is an XRD pattern of the surface modified copper foam 3D current collector in example 1 of the present invention;
fig. 2 is an SEM image of a surface modified copper foam 3D current collector in example 1 of the present invention;
FIG. 3 is a diagram of the cycling stability test performance of the symmetrical cell in example 1 of the present invention;
FIG. 4 is a graph showing the cycle stability test performance of the full cell in example 1 according to the present invention;
fig. 5 is an SEM image of a surface modified copper foam 3D current collector in example 2 of the present invention;
FIG. 6 is a diagram of the cycling stability test performance of the symmetrical cell in example 2 of the present invention;
fig. 7 is an SEM image of a surface modified copper foam 3D current collector in example 3 of the present invention; wherein a is an SEM image of the material at 500 times magnification, b is an SEM image of the material at 1 ten thousand times magnification, and c is an SEM image of the material at 10 ten thousand times magnification;
fig. 8 is an SEM image of a surface modified copper foam 3D current collector in example 4 of the present invention; wherein a is an SEM image of the material at 1000 times magnification, and b is an SEM image of the material at 1 ten thousand times magnification;
fig. 9 is an SEM image of a surface modified copper foam 3D current collector in example 5 of the present invention; wherein a is an SEM image of the material at 1000 times magnification, and b is an SEM image of the material at 1 ten thousand times magnification;
fig. 10 is an SEM image of comparative example 1 surface modified copper foam 3D current collector in accordance with the present invention; wherein a is an SEM image of the material at 1000 times magnification, b is an SEM image of the material at 1 ten thousand times magnification, and c is an SEM image of the material at 2 ten thousand times magnification.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The reagents and instrumentation used in the following examples of the invention were as follows:
and (3) testing by a scanning electron microscope: the instrument model of the scanning electron microscope is JEOL JSM-7800F; x-ray powder diffraction (XRD): the model of an XRD test instrument is Bruker D8 advance, and the test range is 10-80 ℃; the charge and discharge tester comprises: the model is a Wuhan blue testing system; foam copper: shanxi Li-based Source Battery materials Ltd; lithium metal sheet: tianjin can be used in lithium industry.
The examples do not particularly indicate specific conditions, and the procedures according to the conventional procedures described in the literature in this field can be performed. The reagents used are all conventional products which are commercially available.
Example 1
(1) And (2) ultrasonically cleaning a copper foam sheet with the thickness of 0.8mm, the thickness of 130ppi and the size of 2cm multiplied by 2cm for 15min by using 1mol/L hydrochloric acid solution to remove oxides on the surface of the copper foam, taking out the copper foam cleaned by the hydrochloric acid, washing the copper foam sheet with deionized water for three times, immersing the copper foam sheet in an acetone solution for ultrasonic cleaning for 15min, and removing oil stains on the surface of the copper foam sheet. And repeatedly washing the cleaned foam copper by using deionized water, and drying at 50 ℃ for later use.
(2) Preparing 1mol/L potassium hydroxide solution, oxidizing the foamy copper in the step (1) in the potassium hydroxide solution through a cyclic voltammetry (voltage interval of-0.3-0.3V, sweep rate of 1mV/s, and 1 cycle of sweep number), drying for 5 hours at 50 ℃, and generating a layer of lithium-philic cuprous oxide on the surface layer of the foamy copper to obtain the surface modified foamy copper 3D current collector. XRD test is carried out on the surface modified copper foam 3D current collector, the result is shown in figure 1, the main components are copper and cuprous oxide, and further SEM test is carried out (figure 2), and the result shows that a layer of cuprous oxide grows on the copper foam framework, and particularly, spine-shaped oxide is generated on the smooth surface.
(3) Preparing a lithium metal battery negative electrode material: and in a glove box filled with argon gas, melting a lithium sheet on a heating table at 320 ℃ to obtain liquid lithium metal, quickly filling the liquid lithium metal into a foam copper framework after a modified foam copper current collector is contacted with the liquid lithium metal, taking out the modified foam copper filled with lithium, transferring the modified foam copper into a clean crucible, and cooling to obtain the lithium metal battery cathode material.
(4) Assembling a symmetrical battery: 1mol of LiTFSI was dissolved in 1L of a mixed solution of DME and DOL (the volume ratio of DME to DOL is 1:1), and 2% of LiNO was added in mass percentage3Adding an additive to obtain an electrolyte; using 70 mu L of the electrolyte, taking the lithium metal battery negative electrode material prepared in the step (3) as electrode plates of a positive electrode and a negative electrode of a symmetrical battery, using a polypropylene (PP) diaphragm as a diaphragm, and assembling 20 in a glove box protected by argon atmosphere25 button type symmetrical batteries. At 1 and 3mA/cm2Charging and discharging at current density of 1mAh/cm2The prepared symmetrical electrode was subjected to a cycle stability test with a commercial lithium plate as a control; the results are shown in FIG. 3. The results showed a current density of 1mA/cm2The circulation capacity is 1mAh/cm2When, Li @ Cu2The O-Cu symmetrical cell is not short-circuited in the stable cycle of overpotential of 25mV for 800 h. However, commercial lithium sheet symmetric cells exhibit an overpotential of 30mV at the beginning of cycling and increase as cycling progresses, with the overpotential exceeding 130mV after about 500h cycling due to growth of dendrites and accumulation of dead lithium on the electrode surface. When the current density is 3mA/cm2The circulation capacity is 1mAh/cm2In the meantime, the overpotential of the commercial lithium negative electrode symmetrical battery exceeds 100mV after the battery is cycled for 200h, while the initial polarization voltage of the symmetrical battery is about 50mV, and the battery has no obvious voltage fluctuation along with the cycling and has the cycle life as long as 400 h.
(5) Assembling the full cell: 1mol of LiPF6Dissolving in 1L EC: DEC mixed solution (EC and DEC volume ratio is 1:1) to obtain electrolyte, and coating LiFePO with 70 μ L of the above electrolyte4The aluminum foil current collector as a positive electrode material, the lithium metal battery negative electrode material prepared in the step (3) as a negative electrode material, and a polypropylene (PP) diaphragm as a diaphragm were used to assemble the whole battery in a glove box protected by argon atmosphere. The cycle performance of the full battery is tested under the multiplying power of 1C, and the result is shown in figure 4; fig. 4 shows that the full battery can still maintain 80% of specific capacity after 400 cycles, which effectively improves the service life of the full battery.
Example 2
The difference from example 1 is that the specification of the foam copper sheet is as follows: thickness 0.8mm, 110ppi, size 2cm x 2 cm;
SEM tests were performed on the prepared surface modified copper foam 3D current collector, and the results are shown in fig. 5; the results show that a large number of rod-like nanostructures are grown on the surface, and the length of the nanorods is about 1-2 μm, and the diameter is about 100 nm. The appearance of the growing cuprous oxide can be controlled by adjusting the porosity of the foamy copper, and the substrate with large and small porosities can induce the generation of a nanorod structure.
At 1 and 3mA/cm2Charging and discharging at current density of 1mAh/cm2The prepared symmetrical electrode is subjected to a cycle stability test, and the result is shown in figure 6; FIG. 6 shows that the current density was 1mA/cm2The circulation capacity is 1mAh/cm2When the composite electrode symmetrical battery is stably circulated for 600 hours at 30mV overpotential without short circuit, the current is increased to 3mA/cm2The composite electrode symmetrical cell stable cycle 330h, compared to example 1, is worse in cycle stability.
Example 3
(1) And (2) ultrasonically cleaning a foamed copper sheet with the thickness of 0.5mm, the thickness of 110ppi and the size of 2cm multiplied by 2cm for 15min by using 0.5mol/L hydrochloric acid solution to remove oxides on the surface of the foamed copper, taking out the foamed copper cleaned by the hydrochloric acid, washing the foamed copper with deionized water for three times, immersing the foamed copper sheet in an acetone solution for ultrasonic cleaning for 15min, and removing oil stains on the surface of the foamed copper sheet. And repeatedly washing the cleaned foam copper by using deionized water, and drying at 50 ℃ for later use.
(2) Preparing 0.5mol/L potassium hydroxide solution, oxidizing the foamy copper in the step (1) in the potassium hydroxide solution through cyclic voltammetry (voltage interval is-0.3-0.3V, sweep speed is 1mV/s, and sweep number is 1 circle), drying for 5 hours at 50 ℃, and generating a layer of lithium-philic cuprous oxide on the surface layer of the foamy copper to obtain the surface modified foamy copper 3D current collector. The surface modified copper foam 3D current collectors were SEM tested and the results are shown in figure 7. Compared with example 1, a large number of nanorods are grown on the surface, each nanorod is composed of a regular nanosheet array and has a thickness of about 10 nm.
The steps (3) and (4) are the same as in example 1.
Example 4
(1) And (2) ultrasonically cleaning a foam copper sheet with the thickness of 1.5mm, the thickness of 110ppi and the size of 2cm multiplied by 2cm for 15min by using 1mol/L hydrochloric acid solution to remove oxides on the surface of the foam copper, taking out the foam copper cleaned by the hydrochloric acid, washing the foam copper with deionized water for three times, immersing the foam copper sheet in an acetone solution for ultrasonic cleaning for 15min, and removing oil stains on the surface of the foam copper sheet. And repeatedly washing the cleaned foam copper by using deionized water, and drying at 50 ℃ for later use.
(2) Preparing 1mol/L potassium hydroxide solution, oxidizing the foamy copper in the step (1) in the potassium hydroxide solution through a cyclic voltammetry (voltage interval of-0.3-0.3V, sweep rate of 1mV/s, and 1 cycle of sweep number), drying for 5 hours at 50 ℃, and generating a layer of lithium-philic cuprous oxide on the surface layer of the foamy copper to obtain the surface modified foamy copper 3D current collector. The surface modified copper foam 3D current collectors were subjected to SEM testing and the results are shown in figure 8. Compared with the example 1, a large number of nanorods are grown on the surface, each nanorod is composed of a nanosheet array, the thickness is about 50nm, the uniformity is poor, and the thickness of the foamy copper can influence the uniformity of the shape of the generated cuprous oxide.
The steps (3) and (4) are the same as in example 1.
Example 5
(1) And ultrasonically cleaning a copper foam sheet with the thickness of 1.5mm, the thickness of 130ppi and the size of 2cm multiplied by 2cm for 15min by using 1mol/L hydrochloric acid solution, removing oxides on the surface of the copper foam sheet, taking out the copper foam sheet cleaned by the hydrochloric acid, washing the copper foam sheet with deionized water for three times, immersing the copper foam sheet in an acetone solution, and ultrasonically cleaning for 15min to remove oil stains on the surface of the copper foam sheet. And repeatedly washing the cleaned foam copper by using deionized water, and drying at 50 ℃ for later use.
(2) Preparing 1mol/L potassium hydroxide solution, oxidizing the foamy copper in the step (1) in the potassium hydroxide solution through a cyclic voltammetry (voltage interval of-0.3-0.3V, sweep rate of 1mV/s, and 1 cycle of sweep number), drying for 5 hours at 50 ℃, and generating a layer of lithium-philic cuprous oxide on the surface layer of the foamy copper to obtain the surface modified foamy copper 3D current collector. The surface modified copper foam 3D current collectors were subjected to SEM testing and the results are shown in figure 9. Compared with example 1, a large number of nanorods each composed of a nanosheet array are grown on the surface.
The steps (3) and (4) are the same as in example 1.
The assembled symmetric cells of examples 3-5 were subjected to the cycling stability test and the results are shown in table 1.
TABLE 1
Figure BDA0003340372030000091
Comparing the results of examples 1 to 5, it can be seen that 130ppi copper foam with a thickness of 0.8mm is the optimum substrate.
Comparative example 1
The difference from example 1 is that the voltage interval is-0.3-0.3V, the scanning speed is 1mV/s, and the number of scanning turns is 2. SEM analysis of the prepared current collector shows in FIG. 10, and compared with example 1, a large number of flower-rod-like nanostructures are grown on the surface, the length of the nanorods is about 300nm, and the nanorods are gathered together like flower petals, and each 'petal' is about 3-5 μm in size. The cycle stability test was performed on the assembled symmetrical cell and the full cell, and the results showed that the current density was 1mA/cm2The circulation capacity is 1mAh/cm2When the composite electrode symmetrical battery is stably circulated for 500 hours at 30mV overpotential without short circuit, the current is increased to 3mA/cm2And the composite electrode is symmetrical to the battery and is stably circulated for 200 h.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The surface modified foamy copper 3D current collector is characterized in that foamy copper is used as a framework material, and cuprous oxide is generated by in-situ oxidation of the surface of the foamy copper.
2. The surface modified copper foam 3D current collector of claim 1, wherein the copper foam thickness is 0.5-1.5 m; the porosity of the copper foam is 110-130 ppi; the cuprous oxide is in a sharp structure.
3. A method for preparing a surface modified copper foam 3D current collector according to any of claims 1-2, characterized in that it comprises the following steps:
and carrying out surface oxidation treatment on the cleaned and dried foamy copper by adopting a cyclic voltammetry method, and drying to obtain the surface modified foamy copper 3D current collector.
4. The method for preparing the surface modified copper foam 3D current collector according to claim 3, wherein the preparation of the cleaned and dried copper foam comprises: sequentially using hydrochloric acid solution and acetone to carry out ultrasonic cleaning on the foam copper;
the surface oxidation treatment is carried out in a potassium hydroxide solution;
the cyclic voltammetry conditions were: the voltage interval is-0.3V, the scanning speed is 1mV/s, and the number of scanning turns is 1 circle; the drying temperature is 50 ℃, and the drying time is 5-6 h.
5. The method for preparing the surface modified copper foam 3D current collector according to claim 4, wherein the concentration of the hydrochloric acid solution is 0.5-1mol/L, and the ultrasonic cleaning time is 15 min; the concentration of the potassium hydroxide solution is 0.5-1 mol/L.
6. Use of the surface modified copper foam 3D current collector according to any one of claims 1-2 for the preparation of negative electrode materials for lithium metal batteries.
7. The negative electrode material of the lithium metal battery is characterized by being obtained by directly compounding the surface modified foam copper 3D current collector of any one of claims 1-2 with lithium metal as a framework material.
8. The preparation method of the negative electrode material for the lithium metal battery as claimed in claim 7, which comprises the following steps: under an inert environment, the surface modified copper foam 3D current collector of any one of claims 1 to 2 is placed in molten liquid lithium metal for dipping, and then taken out and cooled to room temperature to obtain the lithium metal battery negative electrode material.
9. Use of the lithium metal battery anode material according to claim 7 in the preparation of a battery.
10. Use according to claim 9, wherein the battery is a symmetrical battery orA full cell; when the battery is a symmetrical battery, the electrode plates of the positive electrode and the negative electrode of the symmetrical battery are the negative electrode material of the lithium metal battery in claim 7; when the battery is a full battery, the positive electrode material of the full battery is coated with LiFePO4The aluminum foil current collector of (1), wherein the negative electrode material comprises the negative electrode material for lithium metal batteries according to claim 7.
CN202111306638.4A 2021-11-05 2021-11-05 Preparation method of cuprous oxide in-situ coated foamy copper/lithium metal negative electrode material Pending CN114039033A (en)

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NL2030456A NL2030456B1 (en) 2021-11-05 2022-01-07 Cathode Material Coated In situ by Copper Foam/lithium Metal Battery

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Citations (1)

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CN108598489A (en) * 2018-01-29 2018-09-28 东莞市航盛新能源材料有限公司 A kind of 3D complex coppers and preparation method thereof and a kind of collector and its application

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CN110880595B (en) * 2019-11-08 2022-11-08 重庆市加鼎盛科技有限公司 Cu 3 Preparation method of P-CuO composite flexible lithium ion battery cathode material

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CN108598489A (en) * 2018-01-29 2018-09-28 东莞市航盛新能源材料有限公司 A kind of 3D complex coppers and preparation method thereof and a kind of collector and its application

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