WO2017181532A1 - Lithium metal secondary battery, and negative terminal and porous copper current collector thereof - Google Patents

Lithium metal secondary battery, and negative terminal and porous copper current collector thereof 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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French (fr)
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%.

Abstract

The present invention relates to the technical field of lithium secondary batteries, and in particular to a porous copper current collector of a lithium metal secondary battery, the porous copper current capable of inhibiting the growth of lithium dendrite and having pore channel structures that are in communication with each other, the pore diameter ranging from 0.1 μm to 2 μm. Compared with the prior art, such three-dimensional pore structures can reduce the effective current density of an electrode by increasing the specific surface area of the electrode, thereby inhibiting the growth of lithium dendrite and stabilizing an SEI film. Moreover, the three-dimensional pore structures of the porous copper current collector can accommodate precipitated lithium metal, thereby slowing down the change in the volume of a lithium metal negative terminal during a cycling charging/discharging process. Therefore, when being applied to the negative terminal of the lithium metal secondary battery, the three-dimensional porous copper current collector can effectively improve the coulombic efficiency, the cycling stability, and the security of the battery during a cycling process.

Description

金属锂二次电池及其负极和多孔铜集流体Metal lithium secondary battery and its negative electrode and porous copper current collector 技术领域Technical field
本发明属于锂二次电池技术领域，尤其涉及一种可抑制锂枝晶产生的金属锂二次电池及其负极和多孔铜集流体。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.
背景技术Background technique
近年来可移动电子设备和电动汽车的快速发展使得提高锂二次电池的能量密度显得迫在眉睫。金属锂的密度低(0.53g/cm3)、标准电极电位低(-3.04V)、理论比容量高(3860mAh g-1)，这些特点使其作为锂二次电池负极使用时可显著提高电池的能量密度。但是，在充放电过程中锂金属的不均匀沉积会导致大量锂枝晶的产生，这些枝晶会刺穿电池隔膜，造成电池短路，并产生大量的热，引发着火甚至爆炸等事故。此外，锂枝晶的生长也使得电极表面难以形成稳定的固体电解质界面(SEI)膜，从而导致大量锂被消耗，造成循环过程中库伦效率低、容量衰减快。In recent years, the rapid development of mobile electronic devices and electric vehicles has made it urgent to increase the energy density of lithium secondary batteries. 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. However, 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. In addition, the growth of lithium dendrites also makes it difficult to form a stable solid electrolyte interface (SEI) film on the electrode surface, resulting in a large amount of lithium being consumed, resulting in low coulombic efficiency and fast capacity decay during the cycle.
近期，三维多孔石墨烯等三维导电框架结构被应用于锂金属负极中，以通过增加电极比表面积来降低电极的有效电流密度，从而抑制锂枝晶的产生。但是，这些三维导电框架结构往往需要通过额外的步骤添加到集流体上，从而增大了电池内阻和极化。并且，这些导电框架复杂和耗时的制备过程使其制备成本较高，难以进行实际应用。 Recently, 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. However, 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. Moreover, the complicated and time-consuming preparation process of these conductive frames makes the preparation cost high and difficult to be practically applied.
铜集流体是锂二次电池负极最常用的集流体。有鉴于此，确有必要提供一种可抑制锂枝晶产生的锂二次电池及其负极和多孔铜集流体，该多孔铜集流体可用于负载金属锂负极，并抑制锂枝晶的生长，而且其制备步骤简单，成本低，与现有集流体应用工艺契合性强，因此容易实现产业化。The copper current collector is the most commonly used current collector for the negative electrode of a lithium secondary battery. In view of the above, it is indeed necessary to provide 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. Moreover, 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.
发明内容Summary of the invention
本发明的目的之一在于：针对现有技术的不足，而提供一种可抑制锂枝晶产生的金属锂二次电池多孔铜集流体，该多孔铜集流体可用于负载金属锂负极，并抑制锂枝晶的生长，而且其制备步骤简单，易于实现，成本低，容易实现产业化。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.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种金属锂二次电池负极用多孔铜集流体，所述集流体具有三维连通的多孔结构，并且孔径范围为0.1-20μm。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 μm.
相对于现有技术，本发明具有以下特点：本发明的多孔铜集流体的三维孔结构通过增加电极的比表面积可降低电极有效电流密度，从而抑制锂枝晶产生，稳定SEI膜。并且其三维孔结构可容纳沉积的锂金属，从而减缓锂金属负极在充放电循环过程中的体积变化。因此，将该三维多孔铜集流体应用于金属锂二次电池负极中时可有效提高电池在循环过程中的库伦效率、循环稳定性和安全性。此外，该多孔铜集流体的孔结构对其能否有效抑制锂枝晶的生长至关重要。若孔径过小，则其如普通二维集流体一样难以有足够的空间容纳锂沉积；而若孔径过大，则集流体难以为金属锂提供有效的电接触，造成循环过 程中大量“死锂”产生，并且其过大的孔结构也难以为锂枝晶生长提供有效的空间限制。Compared with the prior art, 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. If the 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.
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，所述多孔铜集流体是通过化学去合金化法、电化学去合金化法、电化学沉积法或金属烧结法制备得到的。其中，化学去合金化法制备过程简单，成本低，可进行大规模制备。而尽管电化学去合金化法和电化学沉积法可对刻蚀过程进行精确调控，但其难以进行大规模制备。而金属烧结法由于需要高温热处理，因此成本较高。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, 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. of. Among them, the chemical de-alloying method has a simple preparation process and low cost, and can be prepared on a large scale. Although 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.
其中，优选为化学去合金化法，多孔铜集流体的孔结构可通过调整原始Cu-X合金带中X的比例或调整去合金化时间进行有效调节，而且反应条件温和，成本低，便于实现。Among them, 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. .
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，所述化学去合金化法是以二元或多元Cu-X合金带为原材料，使用刻蚀液将X元素组分从Cu-X合金带中脱除，一步得到具有三维连通孔道结构的铜集流体，其中，X元素为Zn、Mg、Al、Ni和Mn中的至少一种。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, 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.
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，所述Cu-X合金带中Cu的质量分数控制在30％-70％之间，以形成不同的孔隙率；此外，考虑到锂离子电池的单面电极厚度通常在100μm以内，因此将合金带厚度控制在10～80μm之间。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, 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 μm, the thickness of the alloy ribbon is controlled to be between 10 and 80 μm.
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，其制备过程包括如下步骤：首先在40℃～90℃条件下使用刻蚀液将二元 或多元Cu-X合金带刻蚀2h～24h；之后将刻蚀后的合金带取出，用除氧去离子水清洗4～5次，再用除氧无水乙醇清洗一次，所用去离子水和无水乙醇进行除氧处理的目的在于防止其中溶解的氧将具有较大比表面积的多孔铜氧化；最后将清洗干净的多孔铜集流体置于50℃～80℃的真空烘箱中烘干待用。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, 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. .
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，所用刻蚀液为A、B两种组分的混合溶液；组分A起主要刻蚀作用，为稀盐酸、稀硫酸和稀氢氧化钠溶液中的一种，浓度范围为0.5mol/L～3mol/L，浓度过低将使刻蚀速率过慢，而浓度过高则使反应速率过快，难以进行有效控制；组分B作为添加剂起调节刻蚀速率、改善刻蚀表面粗糙度等作用，为稀硝酸、磷酸、过氧化氢、氯化铵溶液、硫酸钠溶液、硫代硫酸钠溶液、硫化钠、硝酸钠溶液中的至少一种，浓度范围为0～6mol/L。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, 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. And one of the dilute sodium hydroxide solutions, 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. It is dilute nitric acid, phosphoric acid, hydrogen peroxide, ammonium chloride solution, sodium sulfate solution, sodium thiosulfate solution, sodium sulfide, and sodium nitrate. At least one of the solutions has a concentration ranging from 0 to 6 mol/L.
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，刻蚀过程采用以下方法：浸渍法、喷淋法、溅射法或鼓泡法中的一种。其中，浸渍法方便简单，但不适合于大批量生产；而喷淋法刻蚀效率较高，容易实现自动化控制，适合于有一定批量的生产。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, the etching process employs one of the following methods: a dipping method, a shower method, a sputtering method, or a bubble method. Among them, 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.
作为本发明金属锂二次电池负极用多孔铜集流体的一种改进，所得多孔铜集流体的孔径在0.1μm-20μm之间。其孔结构既可通过调整Cu-X合金带中X组分的质量分数进行调控，也可通过调整刻蚀时间进行调控。As an improvement of the porous copper current collector for the negative electrode of the metal lithium secondary battery of the present invention, the obtained porous copper current collector has a pore diameter of from 0.1 μm to 20 μm. 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.
本发明进一步提供了一种金属锂二次电池负极，包括本发明所述 的多孔铜集流体和负载于所述多孔铜集流体的表面及其孔内的金属锂颗粒。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.
此外，本发明还提供了一种金属锂二次电池，其使用的负极为本发明所述的负极。Further, the present invention provides a metal lithium secondary battery using the negative electrode of the present invention.
本发明的多孔铜集流体在金属锂二次电池中抑制锂枝晶生长的用途也属于本发明的保护范围。The use of the 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.
附图说明DRAWINGS
下面结合附图和具体实施方式，对本发明及其有益技术效果进行详细说明。The present invention and its beneficial technical effects will be described in detail below with reference to the accompanying drawings and specific embodiments.
图1为本发明的实施例1的多孔铜集流体的扫描电子显微镜(SEM)照片。1 is a scanning electron microscope (SEM) photograph of a porous copper current collector of Example 1 of the present invention.
其中：a为多孔铜集流体的横截面照片；Where: a is a cross-sectional photograph of a porous copper current collector;
b为多孔铜集流体的上表面照片。b is a photograph of the upper surface of the porous copper current collector.
图2为本发明的实施例1的多孔铜集流体上负载的锂负极在循环20圈后的SEM照片。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.
其中：a为所述负极的横截面照片；Wherein: a is a cross-sectional photograph of the negative electrode;
b为所述负极的上表面照片。b is a photograph of the upper surface of the negative electrode.
图3为本发明的实施例1的多孔铜集流体上负载的锂负极在循环100圈后的SEM照片。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.
其中：a为所述负极的横截面照片；Wherein: a is a cross-sectional photograph of the negative electrode;
b为所述负极的上表面照片。b is a photograph of the upper surface of the negative electrode.
图4为实施例1中多孔铜集流体、对比例1中普通铜箔集流体和 对比例2中商用泡沫铜集流体上负载的锂负极在循环过程中的库伦效率对比。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.
图5为本发明的对比例1的普通铜箔上负载的锂负极在循环20圈后的SEM照片。Fig. 5 is a SEM photograph of a lithium negative electrode supported on a common copper foil of Comparative Example 1 after 20 cycles.
其中：a为所述负极的横截面照片；Wherein: a is a cross-sectional photograph of the negative electrode;
b为所述负极的上表面照片。b is a photograph of the upper surface of the negative electrode.
图6为本发明的对比例1的普通铜箔上负载的锂负极在循环100圈后的SEM照片。Fig. 6 is a SEM photograph of a lithium negative electrode supported on a common copper foil of Comparative Example 1 after 100 cycles.
其中：a为所述负极的横截面照片；Wherein: a is a cross-sectional photograph of the negative electrode;
b为所述负极的上表面照片。b is a photograph of the upper surface of the negative electrode.
具体实施方式detailed description
实施例1Example 1
本实施例提供了一种金属锂二次电池负极用多孔铜集流体，该集流体具有三维连通的多孔结构，并且孔径范围为0.1-20μm。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 μm.
(1)本实施例中，制备多孔铜集流体的方法为化学去合金化法，其是通过将二元Cu-Zn合金带进行化学去合金化得到。所用Cu-Zn合金为H62黄铜，铜含量60.5～63.5％。合金带厚度为20μm。(1) In the present embodiment, 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 μm.
首先用无水乙醇将Cu-Zn合金带表面的污染物清洗干净。然后采用浸渍法在70℃水浴条件下将合金带浸泡在1mol/L稀盐酸和5mol/L氯化铵溶液的混合溶液中进行化学去合金化法反应12h。之后将样品取出，用脱氧去离子水对去合金化后的样品清洗四次，然后用脱氧无水乙醇清洗一次。清洗结束后，将样品放入60℃真空烘箱中 干燥6h，然后用冲片机将多孔铜冲成直径14mm的圆片，以作为锂金属电池三维多孔集流体使用。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.
从图1所示的SEM照片可见多孔铜集流体的内部存在三维连通的孔结构，其孔径在0.2-2μm范围内。From the SEM photograph shown in Fig. 1, it is found that there is a three-dimensionally connected pore structure inside the porous copper current collector, and the pore diameter is in the range of 0.2 to 2 μm.
(2)使用多孔铜集流体的金属锂负极的制备：(2) Preparation of a metal lithium negative electrode using a porous copper current collector:
以上述制备的多孔铜集流体为阴极，锂片为阳极，在多孔铜集流体上电沉积1mAh·cm-2的金属锂。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.
(3)金属锂二次电池的组装：(3) Assembly of metal lithium secondary battery:
将上述制备的使用多孔铜集流体的金属锂负极与任意合适的正极、电解液组装金属锂二次电池。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.
在本实施例中，仍以锂片为对电极组装金属锂半电池。In this embodiment, the lithium metal half-cell is still assembled with the lithium sheet as the counter electrode.
(4)金属锂二次电池电化学性能测试：(4) Electrochemical performance test of metallic lithium secondary battery:
先在0-1V的电压区间以50μA的电流充放电循环5周，以消除表面污染和稳定SEI膜。然后按1mAh·cm-2的容量以1mA·cm-2的电流密度进行充放电循环，充电截止电压为1V。First, a charge and discharge cycle of 50 μA 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.
图2和图3分别为所述锂负极在循环测试20圈和100圈后的SEM照片。可见在循环过程中，锂负极的厚度变化不大，并且其表面较平整，无锂枝晶产生，说明三维多孔铜集流体可有效抑制循环过程中锂枝晶的生成和电极体积膨胀。图4为其循环过程中的库伦效率，可见其库伦效率较稳定，在循环140周后仍可保持在97％以上。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.
实施例2Example 2
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使 用二元Cu-Zn合金带(H62黄铜，铜含量60.5～63.5％)，其厚度为30μm。在80℃水浴条件下将合金带浸泡在2mol/L稀盐酸和4mol/L氯化铵溶液的混合溶液中进行化学去合金化法反应9h。其余同实施例1，这里不再赘述。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 μm 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.
实施例3Example 3
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用二元Cu-Mg合金带，其中铜含量为40％，其厚度为40μm。在60℃水浴条件下将合金带浸泡在2mol/L稀盐酸和1mol/L磷酸的混合溶液中进行化学去合金化法反应15h。其余同实施例1，这里不再赘述。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 μm 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.
实施例4Example 4
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用二元Cu-Mg合金带，其中铜含量为60％，其厚度为50μm。在50℃水浴条件下将合金带浸泡在1mol/L稀硫酸和1mol/L硫酸钠溶液的混合溶液中进行化学去合金化法反应18h。其余同实施例1，这里不再赘述。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 μm 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.
实施例5Example 5
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用二元Cu-Al合金带，其中铜含量为50％，其厚度为60μm。在80℃水浴条件下将合金带浸泡在2mol/L稀氢氧化钠溶液和2mol/L硫化钠溶液的混合溶液中进行化学去合金化法反应24h。其余同实施例1，这里不再赘述。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 μm 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.
实施例6 Example 6
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用二元Cu-Ni合金带，其中铜含量为60％，其厚度为70μm。在80℃水浴条件下将合金带浸泡在3mol/L稀盐酸中进行化学去合金化法反应24h。其余同实施例1，这里不再赘述。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 μm 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.
实施例7Example 7
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用二元Cu-Mn合金带，其中铜含量为50％，其厚度为20μm。采用喷淋法，将合金带置于使用1mol/L稀盐酸的70℃喷淋环境下进行化学去合金化法反应4h。其余同实施例1，这里不再赘述。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 μm 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.
实施例8Example 8
与实施例1不同的是，本实施例制备多孔铜集流体的方法为电化学去合金化法，其是通过将二元Cu-Mg合金带进行电化学去合金化法得到。Different from Embodiment 1, 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.
具体而言，本实施例是利用三电极法进行电化学去合金化反应。以置于饱和KCl溶液中的Ag/AgCl电极为参比电极，铂片为对电极、Cu-Mg合金带(厚度20μm，其中Cu质量分数为60％)为工作电极，电解液为0.2mol/L NaCl溶液。然后在-0.3V电位下进行去合金化反应，反应时间为1200s。其余步骤同实施例1，这里不再赘述。Specifically, 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 μm, 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.
实施例9Example 9
与实施例1不同的是，本实施例制备多孔铜集流体的方法为金属烧结法，其是通过将氧化铜和石墨粉末等原料进行烧结得到。Unlike the first embodiment, 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.
具体而言，该方法包括以下步骤：首先将氧化铜粉末、石墨粉末、 聚乙烯醇缩丁醛、磷酸酯阴离子乳化剂和邻苯二甲酸丁酯苯甲酯的混合物(氧化铜和石墨粉末的质量分数分别为60％和30％)溶于乙醇中，搅拌6h后将浆料涂布于硅树脂处理过的PET薄膜上，涂布厚度为120μm。然后将其置于80℃鼓风烘箱中干燥12h，之后可将PET膜除去。接下来，先将该薄膜在空气中1000℃下热处理1h，再在500℃下H2/N2混合气氛(H2:N2体积比为5:95)中还原2h，从而得到多孔铜箔。其余步骤同实施例1，这里不再赘述。Specifically, 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. After stirring for 6 hours, the slurry was coated on a silicone-treated PET film to a thickness of 120 μm. It was then dried in an air oven at 80 ° C for 12 h, after which the PET film was removed. Next, 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.
实施例10Example 10
与实施例1不同的是：(1)中制备多孔铜集流体的过程如下：使用三元Cu-Zn-Mg合金带，其中铜含量为60％，锌含量为30％，其厚度为20μm。在80℃水浴条件下将合金带浸泡在2mol/L稀盐酸和4mol/L氯化铵溶液及1mol/L硫酸钠溶液的混合溶液中进行化学去合金化法反应12h。其余同实施例1，这里不再赘述。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 μm 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.
对比例1Comparative example 1
与实施例1不同的是：(2)中制备金属锂负极时将金属锂电沉积在普通铜箔上，其余同实施例1，这里不再赘述。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.
图5和图6分别为普通铜箔表面负载的锂负极循环测试20圈和100圈后的SEM照片。可见在循环过程中，锂负极的厚度增加较明显，并且其表面较粗糙，在循环100圈后其表面有明显的锂枝晶产生。由图4的循环过程中库伦效率可见其库伦效率稳定性明显低于实施例1，在经过140圈循环后库伦效率已低于85％。这是由于锂枝晶的不可控生长使得SEI膜不稳定，消耗大量锂离子，导致库伦效率较低。 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.
对比例2Comparative example 2
与实施例1不同的是：(2)中制备金属锂负极时将金属锂电沉积在商用泡沫铜上，商用泡沫铜孔径在100μm～400μm范围内，其余同实施例1，这里不再赘述。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 μm to 400 μm, and the rest is the same as in the first embodiment, and details are not described herein again.
由图4的循环过程中库伦效率可见其库伦效率稳定性显著低于实施例1，仅在循环29圈后库伦效率就已低于90％。说明商用泡沫铜过大的孔隙难以为锂沉积提供足够的空间限域，从而无法抑制锂枝晶的生长。并且，商用泡沫铜过大的孔隙使得其难以在循环过程中为锂金属提供有效的电接触和物理支撑，从而导致大量“死锂”产生，降低了库伦效率。From the Coulomb efficiency of the cycle of Figure 4, the Coulomb efficiency stability is significantly lower than that of Example 1, and the Coulomb efficiency is less than 90% only after 29 cycles. It is indicated that the excessive pores of commercial foam copper are difficult to provide sufficient space limitation for lithium deposition, so that the growth of lithium dendrites cannot be inhibited. Moreover, the excessive pores of commercial foam copper make it difficult to provide effective electrical and physical support for lithium metal during the cycle, resulting in a large amount of "dead lithium" production, reducing coulombic efficiency.
表1实施例1-9与对比例1-2负载的锂负极在1.0mA·cm-2电流密度下以1.0mAh·cm-2的容量进行充放电循环的库伦效率稳定性对比Table 1 Comparison of Coulomb efficiency stability of the charge and discharge cycle of the lithium negative electrode supported in Examples 1-9 and Comparative Example 1-2 at a current density of 1.0 mA·cm -2 at a capacity of 1.0 mAh·cm -2
组别Group 40圈40 laps 80圈80 laps 120圈120 laps
实施例1Example 1 稳定stable 稳定stable 稳定stable
实施例2Example 2 稳定stable 稳定stable 稳定stable
实施例3Example 3 稳定stable 稳定stable 稳定stable
实施例4Example 4 稳定stable 稳定stable 不稳定Unstable
实施例5Example 5 稳定stable 稳定stable 不稳定Unstable
实施例6Example 6 稳定stable 稳定stable 不稳定Unstable
实施例7Example 7 稳定stable 稳定stable 稳定stable
实施例8Example 8 稳定stable 稳定stable 稳定stable
实施例9Example 9 稳定stable 稳定stable 稳定stable
实施例10Example 10 稳定stable 稳定stable 稳定stable
对比例1Comparative example 1 稳定stable 不稳定Unstable 不稳定Unstable
对比例2Comparative example 2 不稳定Unstable 不稳定Unstable 不稳定Unstable
其中，稳定是指相邻循环圈数间的库伦效率不大，变化幅度小于2％，不稳定是指库伦效率变化幅度大于2％。Among them, 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%.
根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。 Variations and modifications of the above-described embodiments may also be made by those skilled in the art in light of the above disclosure. Therefore, the invention is not limited to the specific embodiments disclosed and described herein, and the modifications and variations of the invention are intended to fall within the scope of the appended claims. In addition, although specific terms are used in the specification, these terms are merely for convenience of description and do not limit the invention.

Claims (10)

  1. 一种金属锂二次电池负极用多孔铜集流体，其特征在于：所述集流体具有三维连通的多孔结构，并且孔径范围为0.1-20μm。A porous copper current collector for a negative electrode of a lithium metal secondary battery, characterized in that the current collector has a three-dimensionally connected porous structure and has a pore diameter ranging from 0.1 to 20 μm.
  2. 根据权利要求1所述的金属锂二次电池负极用多孔铜集流体，其特征在于：所述多孔铜集流体是通过化学去合金化法、电化学去合金化法、电化学沉积法或金属烧结法制备得到的。The porous copper current collector for a negative electrode of a lithium metal secondary battery according to claim 1, wherein the porous copper current collector is a chemical de-alloying method, an electrochemical de-alloying method, an electrochemical deposition method, or a metal Prepared by sintering.
  3. 根据权利要求2所述的金属锂二次电池负极用多孔铜集流体，其特征在于：所述化学去合金化法是以二元或多元Cu-X合金带为原材料，使用刻蚀液将X元素组分从Cu-X合金带中脱除，一步得到具有三维连通孔道结构的铜集流体，其中，X元素为Zn、Mg、Al、Ni和Mn中的至少一种。The porous copper current collector for a negative electrode of a lithium metal secondary battery according to claim 2, wherein 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 X The elemental component is removed from the Cu-X alloy ribbon, and a copper current collector having a three-dimensional interconnected pore structure is obtained in one step, wherein the X element is at least one of Zn, Mg, Al, Ni, and Mn.
  4. 根据权利要求3所述的金属锂二次电池负极用多孔铜集流体，其特征在于：所述Cu-X合金带中Cu的质量分数控制在30％-70％之间；所述Cu-X合金带的厚度为10～80μm。The porous copper current collector for a negative electrode of a lithium metal secondary battery according to claim 3, wherein a mass fraction of Cu in said Cu-X alloy ribbon is controlled to be between 30% and 70%; said Cu-X The thickness of the alloy ribbon is 10 to 80 μm.
  5. 根据权利要求3所述的金属锂二次电池负极用多孔铜集流体，其特征在于，其制备过程包括如下步骤：首先在40℃～90℃条件下使用刻蚀液将二元或多元Cu-X合金带刻蚀2h～24h；之后将刻蚀后的合金带取出，用除氧去离子水清洗4～5次，再用除氧无水乙醇清洗一次；最后将清洗干净的多孔铜集流体置于50℃～80℃的真空烘箱中烘干待用。The porous copper current collector for a negative electrode of a lithium metal secondary battery according to claim 3, wherein the preparation process comprises the following steps: first, using an etching solution to treat binary or multi-component Cu- at 40 ° C to 90 ° C; X alloy strip is etched for 2h~24h; then the etched alloy strip is taken out, washed 4~5 times with deionized deionized water, then washed once with deoxygenated anhydrous ethanol; finally cleaned porous copper current collector It is placed in a vacuum oven at 50 ° C ~ 80 ° C for drying.
  6. 根据权利要求3所述的金属锂二次电池负极用多孔铜集流体， 其特征在于，刻蚀过程采用以下方法：浸渍法、喷淋法、溅射法或鼓泡法中的一种。The porous copper current collector for a negative electrode of a metal lithium secondary battery according to claim 3, It is characterized in that the etching process employs one of the following methods: a dipping method, a shower method, a sputtering method, or a bubble method.
  7. 根据权利要求3所述的金属锂二次电池负极用多孔铜集流体，其特征在于，所用刻蚀液为A、B两种组分的混合溶液；组分A为稀盐酸、稀硫酸和稀氢氧化钠溶液中的一种，浓度范围为0.5mol/L～3mol/L；组分B为稀硝酸、磷酸、过氧化氢、氯化铵溶液、硫酸钠溶液、硫代硫酸钠溶液、硫化钠、硝酸钠溶液中的至少一种，浓度范围为0～6mol/L。The porous copper current collector for a negative electrode of a lithium metal secondary battery according to claim 3, wherein the etching liquid used is a mixed solution of two components A and B; and the component A is dilute hydrochloric acid, dilute sulfuric acid and rare One of sodium hydroxide solution, the concentration range is 0.5mol / L ~ 3mol / L; component B is dilute nitric acid, phosphoric acid, hydrogen peroxide, ammonium chloride solution, sodium sulfate solution, sodium thiosulfate solution, vulcanization At least one of sodium and sodium nitrate solution has a concentration ranging from 0 to 6 mol/L.
  8. 一种金属锂二次电池负极，其特征在于：包括权利要求1-7任一项所述的多孔铜集流体和负载于所述多孔铜集流体的表面及其孔内的金属锂颗粒。A negative electrode for a lithium metal secondary battery, comprising the porous copper current collector according to any one of claims 1 to 7 and metallic lithium particles supported on a surface of the porous copper current collector and pores thereof.
  9. 一种金属锂二次电池，其特征在于使用权利要求8所述的负极。A metal lithium secondary battery characterized by using the negative electrode according to claim 8.
  10. 权利要求1-7所述的多孔铜集流体在金属锂二次电池中抑制锂枝晶生长的用途。 The use of the porous copper current collector according to any of claims 1 to 7 to inhibit lithium dendrite growth in a metallic lithium secondary battery.
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