WO2017181532A1 - Accumulateur lithium métal, et sa borne négative et son collecteur de courant en cuivre poreux - Google Patents

Accumulateur lithium métal, et sa borne négative et son collecteur de courant en cuivre poreux Download PDF

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WO2017181532A1
WO2017181532A1 PCT/CN2016/088398 CN2016088398W WO2017181532A1 WO 2017181532 A1 WO2017181532 A1 WO 2017181532A1 CN 2016088398 W CN2016088398 W CN 2016088398W WO 2017181532 A1 WO2017181532 A1 WO 2017181532A1
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current collector
copper current
porous copper
secondary battery
lithium
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PCT/CN2016/088398
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English (en)
Chinese (zh)
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杨全红
韵勤柏
贺艳兵
吕伟
游从辉
李宝华
康飞宇
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清华大学深圳研究生院
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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 belongs to the technical field of lithium secondary batteries, and particularly relates to a metal lithium secondary battery capable of suppressing lithium dendrite generation, a negative electrode thereof and a porous copper current collector.
  • the metal lithium has a low density (0.53 g/cm 3 ), a low standard electrode potential (-3.04 V), and a theoretical specific capacity (3860 mAh g -1 ), which makes it possible to significantly increase the battery when used as a negative electrode for a lithium secondary battery.
  • Energy density uneven deposition of lithium metal during charging and discharging can lead to the production of a large amount of lithium dendrites, which will pierce the battery separator, causing a short circuit in the battery and generating a large amount of heat, causing accidents such as fire or even explosion.
  • a three-dimensional conductive frame structure such as three-dimensional porous graphene has been applied to a lithium metal negative electrode to reduce the effective current density of the electrode by increasing the specific surface area of the electrode, thereby suppressing the generation of lithium dendrites.
  • these three-dimensional conductive frame structures often need to be added to the current collector through additional steps, thereby increasing the internal resistance and polarization of the battery.
  • the complicated and time-consuming preparation process of these conductive frames makes the preparation cost high and difficult to be practically applied.
  • the copper current collector is the most commonly used current collector for the negative electrode of a lithium secondary battery.
  • a lithium secondary battery capable of suppressing the generation of lithium dendrites and a negative electrode thereof and a porous copper current collector which can be used for supporting a lithium metal negative electrode and suppressing the growth of lithium dendrites.
  • the preparation step is simple, the cost is low, and the existing fluid collection application process has strong compatibility, so that it is easy to realize industrialization.
  • One of the objects of the present invention is to provide a porous lithium current collector for a lithium metal secondary battery capable of suppressing lithium dendrite generation, which can be used for supporting a lithium metal negative electrode and suppressing it against the deficiencies of the prior art.
  • the growth of lithium dendrites is simple, easy to implement, low in cost, and easy to industrialize.
  • a porous copper current collector for a negative electrode of a metal lithium secondary battery having a three-dimensionally connected porous structure and having a pore diameter ranging from 0.1 to 20 ⁇ m.
  • the present invention has the following characteristics: the three-dimensional pore structure of the porous copper current collector of the present invention can reduce the effective current density of the electrode by increasing the specific surface area of the electrode, thereby suppressing lithium dendrite generation and stabilizing the SEI film. And its three-dimensional pore structure can accommodate the deposited lithium metal, thereby slowing down the volume change of the lithium metal anode during the charge and discharge cycle. Therefore, when the three-dimensional porous copper current collector is applied to the negative electrode of the metal lithium secondary battery, the coulombic efficiency, cycle stability and safety of the battery during the cycle can be effectively improved. In addition, the pore structure of the porous copper current collector is critical for its ability to effectively inhibit the growth of lithium dendrites.
  • pore size is too small, it is difficult to have sufficient space to accommodate lithium deposition as the ordinary two-dimensional current collector; if the pore size is too large, it is difficult for the current collector to provide effective electrical contact for the metal lithium, resulting in circulation. A large amount of "dead lithium” is produced in the process, and its excessive pore structure is also difficult to provide an effective space limitation for lithium dendrite growth.
  • the porous copper current collector is prepared by a chemical de-alloying method, an electrochemical de-alloying method, an electrochemical deposition method or a metal sintering method.
  • the chemical de-alloying method has a simple preparation process and low cost, and can be prepared on a large scale.
  • the electrochemical de-alloying method and the electrochemical deposition method can precisely control the etching process, it is difficult to perform large-scale preparation.
  • the metal sintering method is expensive because it requires high-temperature heat treatment.
  • the chemical de-alloying method is preferred, and the pore structure of the porous copper current collector can be effectively adjusted by adjusting the ratio of X in the original Cu-X alloy ribbon or adjusting the de-alloying time, and the reaction conditions are mild, the cost is low, and the realization is easy. .
  • the chemical de-alloying method uses a binary or multi-element Cu-X alloy ribbon as a raw material, and uses an etching solution to remove the X element component from The Cu-X alloy ribbon is removed, and a copper current collector having a three-dimensional communication pore structure is obtained in one step, wherein the X element is at least one of Zn, Mg, Al, Ni, and Mn.
  • the mass fraction of Cu in the Cu-X alloy ribbon is controlled to be between 30% and 70% to form different porosities; Considering that the thickness of the single-sided electrode of the lithium ion battery is usually within 100 ⁇ m, the thickness of the alloy ribbon is controlled to be between 10 and 80 ⁇ m.
  • the preparation process comprises the following steps: firstly, using an etching solution at a temperature of 40 ° C to 90 ° C Or a multi-component Cu-X alloy strip is etched for 2h ⁇ 24h; after that, the etched alloy strip is taken out, washed with deoxygenated deionized water for 4-5 times, and then washed once with deoxygenated anhydrous ethanol, using deionized water and
  • the purpose of the oxygen removal treatment of anhydrous ethanol is to prevent the dissolved oxygen from oxidizing the porous copper having a large specific surface area; finally, the cleaned porous copper current collector is placed in a vacuum oven at 50 ° C to 80 ° C for drying. .
  • the etching liquid used is a mixed solution of the two components A and B;
  • the component A serves as a main etching action, and is a dilute hydrochloric acid and a dilute sulfuric acid.
  • the concentration range is 0.5mol / L ⁇ 3mol / L, the concentration is too low will make the etching rate too slow, and the too high concentration will make the reaction rate too fast, it is difficult to effectively control;
  • Component B acts as an additive to adjust the etching rate and improve the surface roughness of the etching.
  • the etching process employs one of the following methods: a dipping method, a shower method, a sputtering method, or a bubble method.
  • the impregnation method is convenient and simple, but it is not suitable for mass production; while the spray method has high etching efficiency and is easy to realize automatic control, and is suitable for production with a certain batch size.
  • the obtained porous copper current collector has a pore diameter of from 0.1 ⁇ m to 20 ⁇ m.
  • the pore structure can be regulated by adjusting the mass fraction of the X component in the Cu-X alloy ribbon, or by adjusting the etching time.
  • the invention further provides a metal lithium secondary battery anode, comprising the invention A porous copper current collector and metal lithium particles supported on the surface of the porous copper current collector and pores thereof.
  • the present invention provides a metal lithium secondary battery using the negative electrode of the present invention.
  • porous copper current collector of the present invention for suppressing the growth of lithium dendrites in a metallic lithium secondary battery is also within the scope of the present invention.
  • Example 1 is a scanning electron microscope (SEM) photograph of a porous copper current collector of Example 1 of the present invention.
  • a is a cross-sectional photograph of a porous copper current collector
  • Example 2 is a SEM photograph of a lithium negative electrode supported on a porous copper current collector of Example 1 of the present invention after 20 cycles.
  • a is a cross-sectional photograph of the negative electrode
  • b is a photograph of the upper surface of the negative electrode.
  • Fig. 3 is a SEM photograph of a lithium negative electrode supported on a porous copper current collector of Example 1 of the present invention after 100 cycles.
  • a is a cross-sectional photograph of the negative electrode
  • b is a photograph of the upper surface of the negative electrode.
  • Example 4 is a porous copper current collector of Example 1, a common copper foil current collector of Comparative Example 1, and Coulombic efficiency comparison of the lithium negative electrode supported on the commercial foamed copper current collector in Comparative Example 2 during the cycle.
  • Fig. 5 is a SEM photograph of a lithium negative electrode supported on a common copper foil of Comparative Example 1 after 20 cycles.
  • a is a cross-sectional photograph of the negative electrode
  • b is a photograph of the upper surface of the negative electrode.
  • Fig. 6 is a SEM photograph of a lithium negative electrode supported on a common copper foil of Comparative Example 1 after 100 cycles.
  • a is a cross-sectional photograph of the negative electrode
  • b is a photograph of the upper surface of the negative electrode.
  • the present embodiment provides a porous copper current collector for a negative electrode of a metal lithium secondary battery, the current collector having a three-dimensionally connected porous structure and having a pore diameter ranging from 0.1 to 20 ⁇ m.
  • a method of preparing a porous copper current collector is a chemical de-alloying method which is obtained by chemically alloying a binary Cu-Zn alloy ribbon.
  • the Cu-Zn alloy used was H62 brass with a copper content of 60.5 to 63.5%.
  • the alloy strip has a thickness of 20 ⁇ m.
  • the contaminants on the surface of the Cu-Zn alloy strip were first cleaned with absolute ethanol. Then, the alloy strip was immersed in a mixed solution of 1 mol/L dilute hydrochloric acid and 5 mol/L ammonium chloride solution by a dipping method under a water bath condition of 70 ° C for chemical de-alloying reaction for 12 h. The sample was then removed and the de-alloyed sample was washed four times with deoxygenated deionized water and then once with deoxygenated absolute ethanol. After the cleaning is completed, the sample is placed in a 60 ° C vacuum oven. After drying for 6 hours, the porous copper was punched into a disk having a diameter of 14 mm by a punching machine to be used as a three-dimensional porous current collector of a lithium metal battery.
  • the porous copper current collector prepared above was used as a cathode, and the lithium sheet was an anode, and lithium metal of 1 mAh ⁇ cm -2 was electrodeposited on the porous copper current collector.
  • the metal lithium secondary battery using the porous copper current collector prepared above and any suitable positive electrode and electrolyte are assembled into a metal lithium secondary battery.
  • the lithium metal half-cell is still assembled with the lithium sheet as the counter electrode.
  • a charge and discharge cycle of 50 ⁇ A was performed for 5 weeks in a voltage range of 0-1 V to eliminate surface contamination and stabilize the SEI film. Then, the charge/discharge cycle was performed at a current density of 1 mA ⁇ cm -2 at a capacity of 1 mAh ⁇ cm -2 , and the charge cutoff voltage was 1 V.
  • FIGS. 2 and 3 are SEM photographs of the lithium negative electrode after 20 cycles and 100 cycles of the cycle test, respectively. It can be seen that during the cycling process, the thickness of the lithium negative electrode does not change much, and the surface thereof is relatively flat, and no lithium dendrites are produced, indicating that the three-dimensional porous copper current collector can effectively inhibit the formation of lithium dendrites and the volume expansion of the electrode during the cycle.
  • Figure 4 shows the coulombic efficiency during the cycle. It can be seen that the coulombic efficiency is relatively stable and can remain above 97% after 140 weeks of cycling.
  • Example 1 The difference from Example 1 is that the process of preparing the porous copper current collector in (1) is as follows: A binary Cu-Zn alloy ribbon (H62 brass, copper content 60.5 to 63.5%) having a thickness of 30 ⁇ m was used. The alloy strip was immersed in a mixed solution of 2 mol/L dilute hydrochloric acid and 4 mol/L ammonium chloride solution under a water bath condition of 80 ° C for chemical de-alloying reaction for 9 h. The rest are the same as Embodiment 1, and will not be described again here.
  • Example 1 The difference from Example 1 is that the process of preparing the porous copper current collector in (1) is as follows: a binary Cu-Mg alloy ribbon in which the copper content is 40% and the thickness thereof is 40 ⁇ m is used. The alloy strip was immersed in a mixed solution of 2 mol/L dilute hydrochloric acid and 1 mol/L phosphoric acid under a water bath condition of 60 ° C for a chemical de-alloying reaction for 15 h. The rest are the same as Embodiment 1, and will not be described again here.
  • Example 1 The difference from Example 1 is that the process of preparing the porous copper current collector in (1) is as follows: a binary Cu-Mg alloy ribbon in which the copper content is 60% and the thickness thereof is 50 ⁇ m is used. The alloy strip was immersed in a mixed solution of 1 mol/L dilute sulfuric acid and 1 mol/L sodium sulfate solution under a water bath condition of 50 ° C for chemical de-alloying reaction for 18 h. The rest are the same as Embodiment 1, and will not be described again here.
  • Example 1 The difference from Example 1 is that the process of preparing the porous copper current collector in (1) is as follows: a binary Cu-Al alloy ribbon in which the copper content is 50% and the thickness thereof is 60 ⁇ m is used. The alloy strip was immersed in a mixed solution of 2 mol/L dilute sodium hydroxide solution and 2 mol/L sodium sulfide solution under a water bath condition of 80 ° C for chemical de-alloying reaction for 24 h. The rest are the same as Embodiment 1, and will not be described again here.
  • Example 1 The difference from Example 1 is that the process of preparing the porous copper current collector in (1) is as follows: a binary Cu-Ni alloy ribbon in which the copper content is 60% and the thickness thereof is 70 ⁇ m is used. The alloy strip was immersed in 3 mol/L dilute hydrochloric acid under a water bath condition of 80 ° C for chemical de-alloying reaction for 24 h. The rest are the same as Embodiment 1, and will not be described again here.
  • Example 1 The difference from Example 1 is that the process for preparing the porous copper current collector in (1) is as follows: a binary Cu-Mn alloy ribbon in which the copper content is 50% and the thickness thereof is 20 ⁇ m is used. The alloy strip was placed in a 70 ° C spray environment using 1 mol/L dilute hydrochloric acid by a spray method for chemical de-alloying reaction for 4 h. The rest are the same as Embodiment 1, and will not be described again here.
  • the method for preparing a porous copper current collector of the present embodiment is an electrochemical de-alloying method which is obtained by electrochemically alloying a binary Cu-Mg alloy ribbon.
  • this embodiment is an electrochemical de-alloying reaction using a three-electrode method.
  • the Ag/AgCl electrode placed in a saturated KCl solution was used as a reference electrode, and the platinum plate was a counter electrode, and a Cu-Mg alloy ribbon (thickness 20 ⁇ m, wherein the Cu mass fraction was 60%) was used as a working electrode, and the electrolyte was 0.2 mol/ L NaCl solution.
  • the de-alloying reaction was then carried out at a potential of -0.3 V for a reaction time of 1200 s. The remaining steps are the same as those in Embodiment 1, and are not described here.
  • the method for producing a porous copper current collector of the present embodiment is a metal sintering method obtained by sintering raw materials such as copper oxide and graphite powder.
  • the method comprises the steps of first mixing a copper oxide powder, a graphite powder, a polyvinyl butyral, a phosphate anion emulsifier, and a butyl phthalate phthalate (copper oxide and graphite powder)
  • the mass fractions were 60% and 30%, respectively, dissolved in ethanol.
  • the slurry was coated on a silicone-treated PET film to a thickness of 120 ⁇ m. It was then dried in an air oven at 80 ° C for 12 h, after which the PET film was removed.
  • the film was heat-treated at 1000 ° C for 1 h in air, and then reduced in a H 2 /N 2 mixed atmosphere (H 2 :N 2 volume ratio of 5:95) at 500 ° C for 2 h to obtain a porous copper foil. .
  • the remaining steps are the same as those in Embodiment 1, and are not described here.
  • Example 1 The difference from Example 1 is that the process for preparing the porous copper current collector in (1) is as follows: a ternary Cu-Zn-Mg alloy ribbon having a copper content of 60%, a zinc content of 30%, and a thickness of 20 ⁇ m is used. The alloy strip was immersed in a mixed solution of 2 mol/L dilute hydrochloric acid and 4 mol/L ammonium chloride solution and 1 mol/L sodium sulfate solution under a water bath condition of 80 ° C for 12 h. The rest are the same as Embodiment 1, and will not be described again here.
  • the difference from the first embodiment is that the metal lithium is electrodeposited on the ordinary copper foil when the metal lithium negative electrode is prepared in (2), and the rest is the same as the first embodiment, and details are not described herein again.
  • Fig. 5 and Fig. 6 are SEM photographs of the lithium negative electrode on the surface of a common copper foil, which were tested for 20 cycles and 100 cycles, respectively. It can be seen that during the circulation process, the thickness of the lithium negative electrode increases significantly, and its surface is rough. After 100 cycles, there is obvious lithium dendrite on the surface. From the Coulomb efficiency in the cycle of Figure 4, the Coulomb efficiency stability is significantly lower than that in Example 1, and the coulombic efficiency has been less than 85% after 140 cycles. This is because the uncontrolled growth of lithium dendrites makes the SEI film unstable and consumes a large amount of lithium ions, resulting in low coulombic efficiency.
  • the difference from the first embodiment is as follows: in the preparation of the metal lithium negative electrode in (2), the metal lithium is electrodeposited on the commercial foamed copper, and the commercial foamed copper has a pore size in the range of 100 ⁇ m to 400 ⁇ m, and the rest is the same as in the first embodiment, and details are not described herein again.
  • stability means that the Coulomb efficiency between adjacent loops is not large, and the variation range is less than 2%.
  • the instability means that the Coulomb efficiency varies by more than 2%.

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Abstract

La présente invention concerne le domaine technique des accumulateurs au lithium, et en particulier un collecteur de courant en cuivre poreux d'un accumulateur lithium métal, le collecteur de courant en cuivre poreux pouvant inhiber la croissance de dendrites de lithium et comportant des structures de canal de pores qui sont en communication les unes avec les autres, le diamètre des pores étant compris entre 0,1 µm et 2 µm. Par comparaison à l'état de la technique, de telles structures de pores tridimensionnelles peuvent réduire la densité de courant effective d'une électrode par augmentation de la surface spécifique de l'électrode, ce qui permet d'inhiber la croissance de dendrites de lithium et de stabiliser un film SEI. De plus, les structures de pores tridimensionnelles du collecteur de courant en cuivre poreux peuvent recevoir du lithium métallique précipité, ralentissant ainsi la variation du volume d'une borne négative en lithium métallique pendant un processus de charge/décharge cyclique. Par conséquent, lorsqu'il est appliqué à la borne négative de l'accumulateur lithium métal, le collecteur de courant en cuivre poreux tridimensionnel peut efficacement améliorer le rendement coulombien, la stabilité des cycles et la sécurité de l'accumulateur pendant un processus de cyclage.
PCT/CN2016/088398 2016-04-22 2016-07-04 Accumulateur lithium métal, et sa borne négative et son collecteur de courant en cuivre poreux WO2017181532A1 (fr)

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CN114520336B (zh) * 2022-04-21 2022-08-02 宁德时代新能源科技股份有限公司 集流体及其制造方法和设备、及集流体预制件
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102185131A (zh) * 2011-04-13 2011-09-14 长安大学 多孔集流体/锡基合金/碳纳米管一体化电极的制备方法
CN102683655A (zh) * 2012-04-26 2012-09-19 上海杉杉科技有限公司 锂离子电池三维多孔硅基复合负极材料及其制备方法
CN103326005A (zh) * 2013-06-27 2013-09-25 山东建筑大学 一种应用于锂离子电池负极的锡镍锌三元合金软体多孔材料及其制备方法
CN105489899A (zh) * 2016-01-26 2016-04-13 长安大学 一种锂离子电池负极及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1017120A1 (fr) * 1998-12-25 2000-07-05 Tokai Aluminum Foil Co., Ltd. Collecteurs de courant pour des piles
CN101590528A (zh) * 2009-06-19 2009-12-02 山东大学 一种纳米多孔铜的制备方法
CN105018776B (zh) * 2014-04-30 2017-09-29 中国科学院金属研究所 一种多孔铜箔的制备工艺及其应用
CN104716330B (zh) * 2015-03-25 2017-03-29 中国科学院化学研究所 一种三维多孔集流体及其制备方法和用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102185131A (zh) * 2011-04-13 2011-09-14 长安大学 多孔集流体/锡基合金/碳纳米管一体化电极的制备方法
CN102683655A (zh) * 2012-04-26 2012-09-19 上海杉杉科技有限公司 锂离子电池三维多孔硅基复合负极材料及其制备方法
CN103326005A (zh) * 2013-06-27 2013-09-25 山东建筑大学 一种应用于锂离子电池负极的锡镍锌三元合金软体多孔材料及其制备方法
CN105489899A (zh) * 2016-01-26 2016-04-13 长安大学 一种锂离子电池负极及其制备方法

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111063893A (zh) * 2019-12-11 2020-04-24 西北工业大学 三维导电骨架/金属氮化物复合锂金属负极集流体的制备方法
CN112133883A (zh) * 2020-09-24 2020-12-25 湖南省凯纳方科技有限公司 一种多孔结构锂电池负极电极及制备方法
CN112968174A (zh) * 2021-02-23 2021-06-15 电子科技大学 一种亲锂合金修饰层、复合锂负极材料及其制备方法和应用
CN112968174B (zh) * 2021-02-23 2022-09-13 电子科技大学 一种亲锂合金修饰层、复合锂负极材料及其制备方法和应用
CN113564524B (zh) * 2021-07-13 2023-08-01 南京邮电大学 一种制备碳包覆三维多孔铜集流体的方法
CN113564524A (zh) * 2021-07-13 2021-10-29 南京邮电大学 一种制备碳包覆三维多孔铜集流体的方法
CN114005960A (zh) * 2021-10-22 2022-02-01 长兴太湖能谷科技有限公司 一种可以抑制锂电池枝晶生长的锂金属复合带材
CN114005960B (zh) * 2021-10-22 2023-10-27 长兴太湖能谷科技有限公司 一种可以抑制锂电池枝晶生长的锂金属复合带材
CN114335559A (zh) * 2022-01-21 2022-04-12 山东大学 一种锂金属电池集流体及其制备方法和应用
CN114335559B (zh) * 2022-01-21 2023-09-01 山东大学 一种锂金属电池集流体及其制备方法和应用
CN114914454A (zh) * 2022-07-01 2022-08-16 北京理工大学重庆创新中心 一种高熵合金集流体及其制备方法和应用
CN114914454B (zh) * 2022-07-01 2023-05-26 北京理工大学重庆创新中心 一种高熵合金集流体及其制备方法和应用
CN116072884B (zh) * 2023-03-20 2023-06-13 安徽维纳物联科技有限公司 一种锂电池复合多孔集流体铜箔及其制备方法
CN116072884A (zh) * 2023-03-20 2023-05-05 安徽维纳物联科技有限公司 一种锂电池复合多孔集流体铜箔及其制备方法

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