WO2024060417A1 - 一种锂电池用三维多孔集流体及其制备方法和应用 - Google Patents

一种锂电池用三维多孔集流体及其制备方法和应用 Download PDF

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WO2024060417A1
WO2024060417A1 PCT/CN2022/137794 CN2022137794W WO2024060417A1 WO 2024060417 A1 WO2024060417 A1 WO 2024060417A1 CN 2022137794 W CN2022137794 W CN 2022137794W WO 2024060417 A1 WO2024060417 A1 WO 2024060417A1
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current collector
foil
dimensional porous
copper
aluminum
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French (fr)
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吴唯
孙传奎
姚海迪
陈曦
杨春雷
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Shenzhen Institute of Advanced Technology 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
    • H01M4/64—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/662—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Definitions

  • the invention relates to the technical field of lithium batteries, and in particular to a three-dimensional porous current collector for lithium batteries and its preparation method and application.
  • Lithium metal is considered the Holy Grail of high-energy-density battery anode materials because of its ultra-high theoretical specific capacity density (3680mAh/g) and low reduction potential (-3.04V, relative to standard hydrogen electrodes).
  • ultra-high theoretical specific capacity density 3680mAh/g
  • low reduction potential 3.04V, relative to standard hydrogen electrodes.
  • a series of problems such as low Coulombic efficiency, short cycle life, and internal short circuit caused by lithium dendrite growth and high reactivity to the electrolyte seriously restrict the practical progress of metallic lithium anodes.
  • the current collector serves as the main substrate for the deposition/extraction of metallic lithium anodes, and its surface properties play a crucial role in the cycle stability of metallic lithium anodes.
  • the local current density on the surface of the current collector has an important influence on the electrodeposition morphology of metallic lithium. Reducing the local current density or optimizing the electric field distribution is conducive to inhibiting the formation of metallic lithium dendrites.
  • a large number of researchers have structurally designed the current collector of lithium anodes to increase its specific surface area, thereby effectively reducing the local current density on the current collector surface.
  • Most people try to use porous structures as current collectors for metallic lithium anodes, thereby compounding metallic lithium with porous current collector materials.
  • porous materials include a variety of metal foams, dealloyed porous materials, metal meshes, carbon cloths, and carbon skeletons with multi-level structures. Although their performance has been improved, such materials are still difficult to prepare, cost, and volume energy. In terms of density or mass energy density, they all have obvious shortcomings and deficiencies. Therefore, rapid porous three-dimensional transformation based on mature current collectors in the current lithium-ion battery industry system such as copper or aluminum is extremely important to improve the performance of lithium metal anodes and achieve low-cost, high-performance applications of lithium metal batteries.
  • Patent CN112216811A describes a three-dimensional copper-based current collector that uses electrospinning to spin a layer of electrochemically stable hybrid lithiophilic fibers on the surface of copper foil to achieve stable and uniform lithium deposition, strengthen the lithium anode, and suppress lithium dendrites. crystal growth.
  • additional electrospinning is cumbersome and complicated, and the spinning layer (10 ⁇ 100 ⁇ m) will significantly increase the thickness of the copper-based current collector, which is not conducive to the improvement of volume energy density.
  • Patent CN112054212A discloses a porous aluminum foil used in traditional lithium-ion batteries for the positive electrode.
  • the surface of the three-dimensional porous aluminum foil is more hydrophilic, which facilitates the coating of positive electrode materials. It can also thin the aluminum foil and increase the battery volume energy density.
  • this modification plan only focuses on the coating of aluminum foil and corresponding cathode materials, and does not consider other types of current collectors, nor the modification needs of the lithium metal anode side.
  • Patent CN108110258A discloses a method for constructing a three-dimensional structure on the surface of copper foil. Taking copper foil as the processing object, a copper foil with a three-dimensional structure on the surface is obtained through a series of steps of electrochemical polishing, chemical oxidation, drying, eutectic reduction with metallic lithium and ethanol treatment. This method has many steps and is cumbersome. It requires electrochemical acid polishing, alkaline etching, lithium melting and heating reduction, organic solvent cleaning and other steps. In addition, the surface morphology of the copper current collector treated by this method is three-dimensional nanoflowers or Nanorod-shaped, unable to achieve porous current collector.
  • the purpose of the present invention is to overcome the above technical problems and provide a preparation method and application of a three-dimensional porous current collector that is efficient, fast, and has a simple process, which can not only realize three-dimensional current collectors but also construct nanopores on the surface of the current collector.
  • the present invention provides a method for preparing a three-dimensional porous current collector for lithium batteries.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is as follows: a metal current collector foil is immersed in an oxidation etching solution, and the metal foil after etching for 1 to 50 minutes is rinsed with excess pure water and dried, that is, A metal current collector foil whose surface is made three-dimensionally porous by etching can be obtained.
  • the preparation method also includes heating and/or microwave assistance.
  • the heating and/or microwave assistance is performed after the metal current collector foil is immersed in the oxidation etching solution; the etching time is 5 to 20 minutes.
  • the etching solution is an aqueous solution of any one of potassium permanganate, silver nitrate, sodium thiosulfate, sodium persulfate, sodium hypochlorite, and ferric salt.
  • the concentration of the etching solution is 0.01 ⁇ 3mol/L.
  • the metal current collector foil includes but is not limited to copper-based current collector and aluminum-based current collector.
  • the copper-based current collector is ordinary copper foil, carbon-coated copper foil, perforated copper foil, phosphor copper Cu-Sn-P foil, brass Cu-Zn foil, copper-aluminum double-sided composite foil and other copper-based foils. Any kind of alloy foil.
  • the aluminum-based current collector is any one of ordinary aluminum foil, carbon-coated aluminum foil, perforated aluminum foil, copper-aluminum double-sided composite foil, silicon-aluminum alloy foil, aluminum-zinc alloy foil and other aluminum-based alloy foils.
  • the present invention provides a lithium secondary battery.
  • a lithium secondary battery characterized in that: the battery includes the three-dimensional lithium negative electrode according to claim 9.
  • the preparation method of the three-dimensional porous current collector provided by the invention oxidizes the copper or aluminum in the metal foil current collector through a redox reaction, ionizes and etches it away from the surface of the foil, and then oxidizes the current collector foil.
  • Three-dimensional porosification the oxidizing property of the oxidant itself, the concentration of the oxidant solution, the length of the etching treatment, heating or microwaves and other auxiliary means can effectively accelerate and regulate the degree and reaction intensity of three-dimensional porous etching, and thus the etching process can be accurately adjusted.
  • the preparation method of the three-dimensional porous current collector provided by the invention can use a variety of oxidants to etch the metal current collector foil, including: potassium permanganate, silver nitrate, sodium thiosulfate, sodium persulfate, sodium hypochlorite, trivalent Iron salts (ferric nitrate, ferric chloride).
  • Metal current collector foils include: copper-based current collectors (ordinary copper foil, carbon-coated copper foil, perforated copper foil, phosphor copper Cu-Sn-P foil, brass Cu-Zn foil, copper-aluminum double-sided composite foil and other copper foils).
  • Oxidation etching auxiliary means include: heating treatment and microwave treatment.
  • the preparation method of the three-dimensional porous current collector provided by the present invention adopts oxidative etching by oxidant, and the process is simple. There is no need to polish the current collector, lithium melting and heating reduction, organic solvent cleaning and other steps.
  • the original copper foil (or other foil materials) is directly soaked After being treated in an oxidizing etching solution, washed and dried with clean water, the current collector can be made three-dimensional and nanopores can be constructed on the surface of the current collector.
  • the three-dimensional porous current collector prepared using the preparation method of the three-dimensional porous current collector provided by the present invention can not only be used for lithium metal deposition, but can also be expanded to transform the positive and negative electrode current collectors of existing lithium-ion batteries to bring about internal resistance. reduction, magnification increase, energy density increase and many other improvements.
  • the preparation method of the three-dimensional porous current collector provided by the present invention can be used for a variety of current collectors, such as copper foil/aluminum foil and their alloyed metal foils.
  • the prepared three-dimensional porous current collector has a good three-dimensional structure and can still be accurately controlled and optimized; while creating holes on the surface of the current collector, the foil can be thinned, reducing the mass/volume ratio of the current collector, and increasing the energy density of the battery.
  • the three-dimensional porous structure can not only increase the contact area during lithium deposition and reduce the local current density to suppress lithium dendrites, but also provide enough space to facilitate volume expansion during the lithium insertion and detachment process and inhibit the generation of dead lithium.
  • the advantages of the preparation method and application of the three-dimensional porous current collector provided by the present invention are:
  • the current collector can be thinned and weighted to reduce the proportion of inactive materials and increase energy density.
  • the three-dimensional porous morphology can effectively reduce the local current density and promote uniform deposition of lithium metal to inhibit the formation and growth of lithium dendrites.
  • the three-dimensional porous morphology can effectively increase the contact area between the electrode layer and the current collector and reduce the internal resistance, which is beneficial to long-term cycle stability and rate performance improvement.
  • Figure 1 is an SEM image of a three-dimensional porous copper foil current collector in Example 1 of the present invention (potassium permanganate oxidation treatment for 1 minute, without heating and microwave assistance).
  • Figure 2 is an SEM image of a three-dimensional porous copper foil current collector in Example 2 of the present invention (potassium permanganate oxidation treatment for 3 minutes, without heating and microwave assistance).
  • Figure 3 is an SEM image of a three-dimensional porous copper foil current collector in Example 3 of the present invention (potassium permanganate oxidation treatment for 5 minutes, without heating and microwave assistance).
  • Figure 4 is an SEM image of a three-dimensional porous copper foil current collector in Example 4 of the present invention (potassium permanganate oxidation treatment for 10 minutes, without heating and microwave assistance).
  • Figure 5 is an SEM image of a three-dimensional porous copper foil current collector in Example 5 of the present invention (silver nitrate oxidation treatment for 10 minutes, assisted by heating at 50°C).
  • Figure 6 is an SEM image of a three-dimensional porous copper foil current collector in Example 6 of the present invention (sodium thiosulfate oxidation treatment for 10 minutes, microwave-assisted).
  • Figure 7 is an SEM image of a three-dimensional porous copper foil current collector in Example 7 of the present invention (sodium persulfate oxidation treatment for 10 minutes, microwave-assisted).
  • Figure 8 is an SEM image of a three-dimensional porous copper foil current collector in Example 8 of the present invention (sodium hypochlorite oxidation treatment for 10 minutes, microwave-assisted).
  • FIG9 is a SEM image of the three-dimensional porous copper foil current collector of Example 9 of the present invention (ferric chloride oxidation treatment for 10 min, microwave assisted).
  • Figure 10 is an SEM image of a three-dimensional porous brass foil current collector in Example 10 of the present invention (iron nitrate oxidation treatment for 10 minutes, microwave-assisted).
  • Figure 11 is an SEM image of the copper side of the current collector of the three-dimensional porous copper-aluminum double-sided composite foil in Example 11 of the present invention (iron nitrate oxidation treatment for 10 minutes, microwave-assisted).
  • Figure 12 is an SEM image of a three-dimensional porous phosphor copper foil current collector in Example 12 of the present invention (iron nitrate oxidation treatment for 10 minutes, microwave-assisted).
  • FIG13 is a SEM image of the three-dimensional porous aluminum foil current collector of Example 13 of the present invention (oxidation treatment with potassium permanganate for 5 min, without heating and microwave assistance).
  • Figure 14 is an SEM image of a three-dimensional porous aluminum foil current collector in Example 14 of the present invention (silver nitrate oxidation treatment for 10 minutes, assisted by heating at 50°C).
  • Figure 15 is an SEM image of the three-dimensional porous aluminum foil current collector in Example 15 of the present invention (iron chloride oxidation treatment for 10 minutes, microwave-assisted);
  • FIG16 is a SEM image of the three-dimensional porous aluminum-zinc alloy foil current collector of Example 16 of the present invention (oxidation treatment with iron nitrate for 10 min, microwave assisted).
  • Figure 17 is a SEM image of the aluminum side of the current collector of the three-dimensional porous copper-aluminum double-sided composite foil in Example 17 of the present invention (iron nitrate oxidation treatment for 10 minutes, microwave-assisted);
  • Figure 18 is an SEM image of the three-dimensional porous silicon-aluminum alloy foil current collector in Example 18 of the present invention (iron nitrate oxidation treatment for 10 minutes, microwave-assisted).
  • Figure 19 is a comparison of the Coulombic efficiency of lithium deposition in the asymmetric battery form of the three-dimensional porous copper foil current collector (potassium permanganate oxidation treatment for 5 minutes, without heating and microwave) and the untreated copper foil in Example 3 of the present invention (three-dimensional porous Afterwards, the Coulombic efficiency is significantly improved, and the deposition life is significantly improved), showing its good electrochemical performance.
  • Figure 20 is a comparison of the Coulombic efficiency of lithium deposition in the asymmetric battery form of the three-dimensional porous aluminum foil current collector (iron chloride oxidation treatment for 10 minutes, microwave-assisted) and the untreated aluminum foil in Example 15 of the present invention (after three-dimensional porousization, the Coulombic efficiency is obvious Improvement, the deposition life is significantly improved), showing its good electrochemical performance.
  • Figure 21 is a half-cell assembled with a negative electrode sheet prepared by coating the graphite negative electrode slurry on the three-dimensional porous copper foil current collector (potassium permanganate oxidation treatment for 5 minutes without heating and microwave) and the untreated copper foil in Example 3 of the present invention.
  • the impedance comparison shows that after three-dimensional porosification, the internal resistance of the battery drops significantly, showing the significant improvement in electrochemical performance brought about by three-dimensional porosification.
  • the present invention provides a method for preparing a three-dimensional porous current collector for a lithium battery.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is as follows: a metal current collector foil is immersed in an oxidation etching solution, and the metal foil after etching for 1 to 50 minutes is rinsed with excess pure water and dried, that is, A metal current collector foil whose surface is made three-dimensionally porous by etching can be obtained.
  • the preparation method also includes heating and/or microwave assistance.
  • the heating and/or microwave assistance is performed after the metal current collector foil is immersed in the oxidation etching solution; the etching time is 5 to 20 minutes.
  • the etching solution is an aqueous solution of any one of potassium permanganate, silver nitrate, sodium thiosulfate, sodium persulfate, sodium hypochlorite, and ferric salt.
  • the concentration of the etching solution is 0.01 ⁇ 3 mol/L.
  • the metal current collector foil includes but is not limited to copper-based current collector and aluminum-based current collector.
  • the copper-based current collector is any one of ordinary copper foil, carbon-coated copper foil, perforated copper foil, phosphor copper Cu-Sn-P foil, brass Cu-Zn foil, and copper-aluminum double-sided composite foil. kind.
  • the aluminum-based current collector is any one of ordinary aluminum foil, carbon-coated aluminum foil, perforated aluminum foil, copper-aluminum double-sided composite foil, silicon-aluminum alloy foil, and aluminum-zinc alloy foil.
  • the present invention provides a lithium secondary battery.
  • a lithium secondary battery characterized in that: the battery includes the three-dimensional lithium negative electrode according to claim 9.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing copper foil in a potassium permanganate aqueous solution with a concentration of 0.05 mol/L, and etching the metal foil for 1 minute. Rinse with excess pure water and dry to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing copper foil in a potassium permanganate aqueous solution with a concentration of 0.05 mol/L, and etching the metal foil for 3 minutes. Rinse with excess pure water and dry to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing copper foil in a potassium permanganate aqueous solution with a concentration of 0.05 mol/L, and etching the metal foil for 5 minutes. Rinse with excess pure water and dry to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing copper foil in a potassium permanganate aqueous solution with a concentration of 0.05 mol/L, and etching the metal foil for 10 minutes. Rinse with excess pure water and dry to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is described.
  • the method is as follows: immersing copper foil in a silver nitrate aqueous solution with a concentration of 0.02 mol/L, and etching for 10 minutes with the assistance of heating at 50°C.
  • the metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing copper foil in a sodium thiosulfate aqueous solution with a concentration of 0.02 mol/L, and etching for 10 minutes with the assistance of 800W power microwave.
  • the final metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: the copper foil is immersed in a sodium persulfate aqueous solution with a concentration of 0.02 mol/L, and etched for 10 minutes under the assistance of 800W power microwave.
  • the metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is described.
  • the method is as follows: immersing copper foil in a sodium hypochlorite aqueous solution with a concentration of 0.02 mol/L, and etching the metal for 10 minutes with the assistance of 800W power microwaves.
  • the foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is as follows: the copper foil is immersed in a ferric chloride aqueous solution with a concentration of 0.02 mol/L, and etched for 10 minutes under the assistance of 800W power microwave. The metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: the brass foil is immersed in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, and etched for 10 minutes with the assistance of 800W power microwave.
  • the final metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: a copper-aluminum double-sided composite foil is immersed in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, and is engraved under the assistance of 800W power microwave. After etching for 10 minutes, the metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is described.
  • the method is as follows: immersing the phosphorus copper foil in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, etching for 10 minutes with the assistance of 800W power microwave.
  • the metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing aluminum foil in a potassium permanganate aqueous solution with a concentration of 0.05 mol/L, and etching the metal foil for 5 minutes. After rinsing with excess pure water and drying, a metal current collector foil whose surface is three-dimensionally porous through etching can be obtained.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is described.
  • the method is as follows: immersing aluminum foil in a silver nitrate aqueous solution with a concentration of 0.02 mol/L, and etching the metal for 10 minutes with the assistance of heating at 50°C.
  • the foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for a lithium battery is provided, wherein the method is as follows: an aluminum foil is immersed in an aqueous solution of ferric chloride with a concentration of 0.02 mol/L, and the metal foil is etched for 10 minutes under the assistance of a microwave at a power of 800 W, and then rinsed and dried with an excess of pure water to obtain a metal current collector foil with a three-dimensional porous surface made by etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: the aluminum-zinc alloy foil is immersed in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, and etched for 10 minutes with the assistance of 800W power microwave.
  • the final metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: a copper-aluminum double-sided composite foil is immersed in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, and is engraved under the assistance of 800W power microwave. After etching for 10 minutes, the metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • a method for preparing a three-dimensional porous current collector for lithium batteries is shown.
  • the method is as follows: immersing a silicon aluminum alloy foil in an iron nitrate aqueous solution with a concentration of 0.02 mol/L, and etching for 10 minutes with the assistance of 800W power microwave.
  • the final metal foil is rinsed with excess pure water and dried to obtain a metal current collector foil whose surface is three-dimensionally porous through etching.
  • the three-dimensional porous copper foil current collector prepared in Example 3 (potassium permanganate oxidation treatment, without heating and microwave) and the untreated copper foil were respectively coated with graphite negative electrode slurry to prepare the semi-assembled negative electrode sheet. Battery impedance comparison.
  • any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

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Abstract

本发明涉及锂电池技术领域，尤其涉及一种锂电池用三维多孔集流体及其制备方法和应用。一种锂电池用三维多孔集流体的制备方法，所述的方法为：金属集流体箔材浸入氧化刻蚀液，刻蚀10~50min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。本发明的优点：(1) 工艺简单、高效快速；(2) 实现集流体三维和多孔化；(3) 适用于多种金属集流体；(4) 三维构造好且可精准调控；(5) 实现集流体减薄和减重。

Description

一种锂电池用三维多孔集流体及其制备方法和应用 技术领域
本发明涉及锂电池技术领域，尤其涉及一种锂电池用三维多孔集流体及其制备方法和应用。
 背景技术
金属锂因其具有超高理论比容量密度（3680mAh/g）和低还原电位（-3.04V，相对标准氢电极）而被认为是高能量密度电池负极材料的圣杯。然而，由锂枝晶生长和对电解质高反应性所造成的库伦效率低、循环寿命短、内短路等一系列问题严重制约着金属锂负极的实用化进展。
在实际的电化学体系中，集流体作为金属锂负极沉积/脱出的主要基底，其表面性质对金属锂负极的循环稳定性起着至关重要的作用。其中，集流体表面的局部电流密度对金属锂的电沉积形貌具有重要影响，降低局部电流密度或者优化电场分布有利于抑制金属锂枝晶的形成。大量研究者对锂负极的集流体进行结构化设计以提高其比表面积，从而有效降低集流体表面的局部电流密度。大家大多尝试使用多孔结构作为金属锂负极的集流体，从而将金属锂与多孔集流体材料复合。这些多孔材料包括多种金属泡沫、脱合金多孔材料、金属网、碳布和具有多级结构的碳骨架等，虽然性能有提升，但是此类材料不管是从制备难易程度、成本、体积能量密度或质量能量密度等方面而言，都具有明显缺点和不足。因此，基于铜或者铝等当前锂离子电池产业体系的成熟集流体，进行快速的多孔三维化改造，对提升锂金属负极性能，实现锂金属电池的低成本、高性能应用极为重要。
 技术问题
专利CN112216811A开了一种三维铜基集流体，通过在铜箔表面利用静电纺丝纺织一层电化学稳定的杂化亲锂纤维来实现稳定、均匀的锂沉积，坚固锂负极，并且抑制锂枝晶的生长。但是额外的静电纺丝繁琐复杂，且纺丝层（10~100μm）会明显增加铜基集流体的厚度，不利于体积能量密度的提高。
专利CN112054212A公开了一种传统锂离子电池用的多孔铝箔用于正极，三维多孔铝箔表面更加亲水，利于正极材料的涂布，同时可以减薄铝箔，提高电池体积能量密度。但是该改性方案仅仅关注于铝箔和相应的正极材料涂布，并未考虑其他种类的集流体，也未考虑锂金属负极侧的改性需求。
专利CN108110258A公开了一种铜箔表面三维结构的构造方法。以铜箔为处理对象，经电化学抛光、化学氧化、烘干、与金属锂共熔还原用乙醇处理一系列步骤得到表面具有三维结构的铜箔。此方法步骤多且过程繁琐，先后需要电化学酸性抛光、碱性刻蚀、锂熔融加热还原、有机溶剂清洗等步骤；另外，此方法处理后的铜集流体，表面形貌为三维纳米花或者纳米棒状，无法实现集流体的多孔化。
 技术解决方案
本发明的目的在于克服上述技术问题，提供一种高效快速、工艺简单，既可以实现集流体三维化还可以在集流体表面构建纳米孔洞的三维多孔集流体的制备方法及其应用。
为实现上述目的，本发明采用的技术方案如下。
第一方面，本发明提供锂电池用三维多孔集流体的制备方法。
一种锂电池用三维多孔集流体的制备方法，所述的方法为：金属集流体箔材浸入氧化刻蚀液，刻蚀1~50min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
进一步的，所述的制备方法还包括加热和/或微波辅助。
进一步的，所述的加热和/或微波辅助在金属集流体箔材浸入氧化刻蚀液后进行；刻蚀时间为5~20min。
进一步的，所述的刻蚀液为高锰酸钾、硝酸银、硫代硫酸钠、过硫酸钠、次氯酸钠、三价铁盐中任意一种的水溶液。
进一步的，所述的刻蚀液浓度为0.01~3mol/L。
进一步的，所述的金属集流体箔材包括但不限于铜基集流体和铝基集流体。
进一步的，所述的铜基集流体为普通铜箔、涂炭铜箔、打孔铜箔、磷铜Cu-Sn-P箔、黄铜Cu-Zn箔、铜铝双面复合箔及其他铜基合金箔中的任意一种。
进一步的，所述的铝基集流体为普通铝箔、涂炭铝箔、打孔铝箔、铜铝双面复合箔、硅铝合金箔、铝锌合金箔及其他铝基合金箔中的任意一种。
第二方面，本发明提供一种锂二次电池。
一种锂二次电池，其特征在于：所述的电池包含权利要求9所述的三维锂负极。
本发明提供的三维多孔集流体的制备方法，通过氧化还原反应，对金属箔材集流体中的铜或者铝进行氧化，将其离子化刻蚀而脱离箔材表面，进而对集流体箔材进行三维多孔化。其中，氧化剂本身的氧化性、氧化剂溶液浓度、刻蚀处理时长、加热或微波等辅助手段均可以有效加速和调控三维多孔刻蚀的程度和反应烈度，进而可以对刻蚀过程进行精确调节。
本发明提供的三维多孔集流体的制备方法，可使用多种氧化剂对金属集流体箔材进行刻蚀，包括：高锰酸钾，硝酸银，硫代硫酸钠，过硫酸钠，次氯酸钠，三价铁盐（硝酸铁，氯化铁）。金属集流体箔材包括：铜基集流体（普通铜箔、涂炭铜箔、打孔铜箔、磷铜Cu-Sn-P箔、黄铜Cu-Zn箔、铜铝双面复合箔及其他铜基合金箔）和铝基集流体（普通铝箔、涂炭铝箔、打孔铝箔、铜铝双面复合箔、硅铝合金箔、铝锌合金箔及其他铝基合金箔）等。氧化刻蚀辅助手段包括：加热处理和微波处理等。
本发明提供的三维多孔集流体的制备方法，采取氧化剂氧化刻蚀，工艺简单，无需对集流体进行抛光、锂熔融加热还原、有机溶剂清洗等步骤，原始铜箔（或其他箔材）直接浸泡在氧化刻蚀液中处理后，清水清洗干燥即可实现集流体三维化还可以在集流体表面构建纳米孔洞。
利用本发明提供的三维多孔集流体的制备方法制备的三维多孔集流体，不仅仅可以用于锂金属沉积，还可以拓展用于改造现有锂离子电池的正负极集流体，带来内阻降低，倍率提升，能量密度提升等诸多改善。
本发明提供的三维多孔集流体的制备方法，可以用于多种集流体，如铜箔/铝箔及其合金化的金属箔皆可行。制备的三维多孔集流体三维构造好，且仍可精准调控优化；在集流体表面造孔的同时，可将箔减薄，降低集流体质量/体积占比，提高电池能量密度。三维多孔构造，既可以提高锂沉积时的接触面积降低局部电流密度以抑制锂枝晶，又可以提供足够的空间有利于嵌锂脱离过程中的体积膨胀，抑制死锂的生成。
 有益效果
与现有技术相比，本发明提供的三维多孔集流体的制备方法及其应用的优点在于：
(1)工艺简单、高效快速。
(2) 实现集流体三维和多孔化。
(3) 适用于多种金属集流体。
(4) 三维构造好且可精准调控。
(5) 可对集流体进行减薄减重以降低非活性物质占比提高能量密度。
(6) 用于锂金属电池，三维多孔形貌可有效降低局部电流密度促进锂金属均匀沉积抑制锂枝晶形成和生长。
(7) 用于锂离子电池，三维多孔形貌可有效增加电极层与集流体的接触面积而降低内阻有利于长循环稳定和倍率性能的提高。
 附图说明
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：
图1为本发明实施例1三维多孔铜箔集流体SEM图（高锰酸钾氧化处理1 min，无加热和微波辅助）。
图2为本发明实施例2三维多孔铜箔集流体SEM图（高锰酸钾氧化处理3 min，无加热和微波辅助）。
图3为本发明实施例3三维多孔铜箔集流体SEM图（高锰酸钾氧化处理5 min，无加热和微波辅助）。
图4为本发明实施例4三维多孔铜箔集流体SEM图（高锰酸钾氧化处理10 min，无加热和微波辅助）。
图5为本发明实施例5三维多孔铜箔集流体SEM图（硝酸银氧化处理10 min，50℃加热辅助）。
图6为本发明实施例6三维多孔铜箔集流体SEM图（硫代硫酸钠氧化处理10 min，微波辅助）。
图7为本发明实施例7三维多孔铜箔集流体SEM图（过硫酸钠氧化处理10 min，微波辅助）。
图8为本发明实施例8三维多孔铜箔集流体SEM图（次氯酸钠氧化处理10 min，微波辅助）。
图9为本发明实施例9三维多孔铜箔集流体SEM图（氯化铁氧化处理10 min，微波辅助）。
图10为本发明实施例10三维多孔黄铜箔集流体SEM图（硝酸铁氧化处理10 min，微波辅助）。
图11为本发明实施例11三维多孔铜铝双面复合箔集流体铜侧SEM图（硝酸铁氧化处理10 min，微波辅助）。
图12为本发明实施例12三维多孔磷铜箔集流体SEM图（硝酸铁氧化处理10 min，微波辅助）。
图13为本发明实施例13 三维多孔铝箔集流体SEM图（高锰酸钾氧化处理5 min，无加热和微波辅助）。
图14为本发明实施例14三维多孔铝箔集流体SEM图（硝酸银氧化处理10 min，50℃加热辅助）。
图15为本发明实施例15 三维多孔铝箔集流体SEM图（氯化铁氧化处理10 min，微波辅助）；
图16为本发明实施例16 三维多孔铝锌合金箔集流体SEM图（硝酸铁氧化处理10 min，微波辅助）。
图17为本发明实施例17三维多孔铜铝双面复合箔集流体铝侧SEM图（硝酸铁氧化处理10 min，微波辅助）；
图18为本发明实施例18 三维多孔硅铝合金箔集流体SEM图（硝酸铁氧化处理10 min，微波辅助）。
图19为本发明实施例3三维多孔铜箔集流体（高锰酸钾氧化处理5 min，无加热和微波）和未处理铜箔在非对称电池形态下锂沉积库伦效率的对比（三维多孔化后，库伦效率明显提升，沉积寿命明显提升），显示其良好的电化学性能。
图20为本发明实施例15三维多孔铝箔集流体（氯化铁氧化处理10 min，微波辅助）和未处理铝箔在非对称电池形态下锂沉积库伦效率的对比（三维多孔化后，库伦效率明显提升，沉积寿命明显提升），显示其良好的电化学性能。
图21为本发明实施例3三维多孔铜箔集流体（高锰酸钾氧化处理5 min，无加热和微波）和未处理铜箔分别涂覆石墨负极浆料后制备负极极片所组装半电池的阻抗对比，三维多孔化后，电池内阻下降明显，显示三维多孔化所带来的显著电化学性能提升。
 本发明的实施方式
为使本领域的技术人员更好地理解本发明的技术方案，以下实施例对本发明的作进一步详细描述，以下实施例仅用于说明发明，但不用来限制本发明的范围。
第一方面，本发明提供锂电池用三维多孔集流体的制备方法。
一种锂电池用三维多孔集流体的制备方法，所述的方法为：金属集流体箔材浸入氧化刻蚀液，刻蚀1~50min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
进一步的，所述的制备方法还包括加热和/或微波辅助。
进一步的，所述的加热和/或微波辅助在金属集流体箔材浸入氧化刻蚀液后进行；刻蚀时间为5~20min。
进一步的，所述的刻蚀液为高锰酸钾、硝酸银、硫代硫酸钠、过硫酸钠、次氯酸钠、三价铁盐中任意一种的水溶液。
进一步的，所述的刻蚀液浓度为0.01~3mol/L。
进一步的，所述的金属集流体箔材包括但不限于铜基集流体和铝基集流体。
进一步的，所述的铜基集流体为普通铜箔、涂炭铜箔、打孔铜箔、磷铜Cu-Sn-P箔、黄铜Cu-Zn箔、铜铝双面复合箔中的任意一种。
进一步的，所述的铝基集流体为普通铝箔、涂炭铝箔、打孔铝箔、铜铝双面复合箔、硅铝合金箔、铝锌合金箔的任意一种。
第二方面，本发明提供一种锂二次电池。
一种锂二次电池，其特征在于：所述的电池包含权利要求9所述的三维锂负极。
实施例1
结合图1所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.05mol/L的高锰酸钾水溶液中，刻蚀1min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图1所示，铜箔表面开始糙化，显示出明显的刻蚀痕迹。
实施例2
结合图2所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.05mol/L的高锰酸钾水溶液中，刻蚀3min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图2所示，铜箔表面糙化加剧，显示出明显的刻蚀痕迹。
实施例3
结合图3所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.05mol/L的高锰酸钾水溶液中，刻蚀5min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图3所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例4
结合图4所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.05mol/L的高锰酸钾水溶液中，刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图4所示，铜箔表面随着刻蚀程度的加剧，出现开放式的沟壑结构。
实施例5
结合图5所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.02mol/L的硝酸银水溶液中，50℃加热辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图5所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例6
结合图6所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.02mol/L的硫代硫酸钠水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图6所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例7
结合图7所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.02mol/L的过硫酸钠水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图7所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例8
结合图8所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.02mol/L的次氯酸钠水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图8所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例9
结合图9所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜箔浸入浓度为0.02mol/L的氯化铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图9所示，铜箔表面出现明显的三维多孔结构，铜晶粒内部出现明显孔洞结构。
实施例10
结合图10所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：黄铜箔箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图10所示，黄铜箔表面开始糙化，显示出明显的三维多孔形貌。
实施例11
结合图11所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜铝双面复合箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图11所示，铜铝双面复合箔铜侧表面开始糙化，显示出明显的三维多孔形貌。
实施例12
结合图12所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：磷铜箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图12所示，磷铜箔表面开始糙化，显示出明显的三维多孔形貌。
实施例13
结合图13所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铝箔浸入浓度为0.05mol/L的高锰酸钾水溶液中，刻蚀5min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图13所示，铝箔表面出现丰富的三维多孔结构。
实施例14
结合图14所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铝箔浸入浓度为0.02mol/L的硝酸银水溶液中，50℃加热辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图14所示，铝箔表面出现丰富的三维多孔结构。
实施例15
结合图15所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铝箔浸入浓度为0.02mol/L的氯化铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图15所示，铝箔表面出现丰富的三维多孔结构。
实施例16
结合图16所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铝锌合金箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图16所示，铝锌合金箔表面出现丰富的三维多孔结构。
实施例17
结合图17所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：铜铝双面复合箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图17所示，铜铝双面复合箔铝侧表面出现丰富的三维多孔结构。
实施例18
结合图18所示，一种锂电池用三维多孔集流体的制备方法，所述的方法为：硅铝合金箔浸入浓度为0.02mol/L的硝酸铁水溶液中，800W功率微波辅助下刻蚀10min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
结果如图18所示，硅铝合金箔表面出现丰富的三维多孔结构。
实施例19
结合图19所示，实施例3制备所得三维多孔铜箔集流体（高锰酸钾氧化处理，无加热和微波）和未处理铜箔在非对称电池形态下锂沉积库伦效率的对比。
由图19可知，铜箔集流体三维多孔化后，库伦效率明显提升，沉积寿命明显提升，显示三维多孔集流体所带来的更大的表面沉积位点与更小的局部电流密度，有助于锂金属的稳定均匀沉积，有力证明了三维多孔集流体良好的电化学性能。
实施例20
结合图20所示，实施例15制备所得三维多孔铝箔集流体（氯化铁氧化处理10min，微波辅助）和未处理铝箔在非对称电池形态下锂沉积库伦效率的对比。
由图20可知，铝箔集流体三维多孔化后，库伦效率明显提升，沉积寿命明显提升，显示三维多孔集流体所带来的更大的表面沉积位点与更小的局部电流密度，有助于锂金属的稳定均匀沉积，有力证明了三维多孔集流体良好的电化学性能。
实施例21
结合图21所示，实施例3制备所得三维多孔铜箔集流体（高锰酸钾氧化处理，无加热和微波）和未处理铜箔分别涂覆石墨负极浆料后制备负极极片所组装半电池的阻抗对比。
由图21可知，三维多孔化后，电池内阻下降明显，显示三维多孔化所带来更大的集流体-电极接触面积，显著地提高了界面导电性并因此降低了电池的欧姆电阻，有利于电池倍率和充放电循环稳定性等关键性能的提升。
实施例22
实施例1~4三维多孔铜箔集流体（高锰酸钾氧化处理1~10 min，无加热和微波）和未处理铜箔的厚度与面密度对比结果如表1所示。
表1 实施例1~4三维多孔铜箔集流体和未处理铜箔的厚度与面密度对比
  高锰酸钾溶液处理时长(min) 厚度（μm） 减薄率（%） 面密度（mg/cm2） 减重率（%）
未处理铜箔 0 13.10 — 8.70 —
实施例1 1 11.08 15.4 7.29 16.2
实施例2 3 9.00 31.3 7.08 18.6
实施例3 5 8.65 34.0 6.98 19.8
实施例4 10 8.22 38.0 7.88 21.0
由表1可知，随着三维多孔化程度的加深，铜箔整体厚度和面密度明显下降，显示三维多孔化对集流体减薄减重上的显著效果，有利于在电池层面降低非活性物质成分的体积/质量占比，从而有效提高电池整体的体积能量密度和质量能量密度。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种变换，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征和步骤，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (9)

  1. 一种锂电池用三维多孔集流体的制备方法，其特征在于，所述的方法为：金属集流体箔材浸入氧化刻蚀液，刻蚀1~50min后的金属箔材用过量的纯净水漂洗、干燥，即可得到通过刻蚀而表面三维多孔化的金属集流体箔材。
  2. 根据权利要求1所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的制备方法还包括加热和/或微波辅助。
  3. 根据权利要求2所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的加热和/或微波辅助在金属集流体箔材浸入氧化刻蚀液后进行；刻蚀时间为5~20min。
  4. 根据权利要求1或2所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的刻蚀液为高锰酸钾、硝酸银、硫代硫酸钠、过硫酸钠、次氯酸钠、三价铁盐中任意一种的水溶液。
  5. 根据权利要求1或2所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的刻蚀液浓度为0.01~3mol/L。
  6. 根据权利要求1或2所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的金属集流体箔材包括但不限于铜基集流体和铝基集流体。
  7. 根据权利要求6所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的铜基集流体为普通铜箔、涂炭铜箔、打孔铜箔、磷铜Cu-Sn-P箔、黄铜Cu-Zn箔、铜铝双面复合箔及其他铜基合金箔中的任意一种。
  8. 根据权利要求6所述的一种锂电池用三维多孔集流体的制备方法，其特征在于：所述的铝基集流体为普通铝箔、涂炭铝箔、打孔铝箔、铜铝双面复合箔、硅铝合金箔、铝锌合金箔及其他铝基合金箔中的任意一种。
  9. 一种锂二次电池，其特征在于：所述的电池包含权利要求9所述的三维锂负极。
PCT/CN2022/137794 2022-09-22 2022-12-09 一种锂电池用三维多孔集流体及其制备方法和应用 Ceased WO2024060417A1 (zh)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005294168A (ja) * 2004-04-02 2005-10-20 Nissan Motor Co Ltd 電極およびこれを用いてなる電池
CN105932295A (zh) * 2016-04-22 2016-09-07 清华大学深圳研究生院 金属锂二次电池及其负极和多孔铜集流体
CN111600036A (zh) * 2020-06-01 2020-08-28 南开大学 一种用于锂金属电池集流体的三维多孔氧化铜改性铜箔及其制备方法和应用
CN112054212A (zh) * 2019-10-24 2020-12-08 南京工业大学 一种锂离子电池集流体用的多孔铝箔及其制备方法和应用
CN112708884A (zh) * 2019-10-24 2021-04-27 南京工业大学 一种锂离子电池集流体用的多孔铝箔及其简易制方法和应用
CN115347196A (zh) * 2022-09-22 2022-11-15 深圳先进技术研究院 一种锂电池用三维多孔集流体及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005294168A (ja) * 2004-04-02 2005-10-20 Nissan Motor Co Ltd 電極およびこれを用いてなる電池
CN105932295A (zh) * 2016-04-22 2016-09-07 清华大学深圳研究生院 金属锂二次电池及其负极和多孔铜集流体
CN112054212A (zh) * 2019-10-24 2020-12-08 南京工业大学 一种锂离子电池集流体用的多孔铝箔及其制备方法和应用
CN112708884A (zh) * 2019-10-24 2021-04-27 南京工业大学 一种锂离子电池集流体用的多孔铝箔及其简易制方法和应用
CN111600036A (zh) * 2020-06-01 2020-08-28 南开大学 一种用于锂金属电池集流体的三维多孔氧化铜改性铜箔及其制备方法和应用
CN115347196A (zh) * 2022-09-22 2022-11-15 深圳先进技术研究院 一种锂电池用三维多孔集流体及其制备方法和应用

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