WO2018170976A1 - 锂离子电池多孔结构Si/Cu复合电极及其制造方法 - Google Patents

锂离子电池多孔结构Si/Cu复合电极及其制造方法 Download PDF

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WO2018170976A1
WO2018170976A1 PCT/CN2017/080802 CN2017080802W WO2018170976A1 WO 2018170976 A1 WO2018170976 A1 WO 2018170976A1 CN 2017080802 W CN2017080802 W CN 2017080802W WO 2018170976 A1 WO2018170976 A1 WO 2018170976A1
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current collector
ion battery
lithium ion
composite electrode
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French (fr)
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黄婷
崔梦雅
肖荣诗
杨武雄
武强
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Beijing University of Technology
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Beijing University of Technology
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    • H—ELECTRICITY
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    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
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    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a negative electrode structure of a lithium ion battery and a manufacturing method thereof, in particular to a Si/Cu composite electrode having a porous structure and a manufacturing method thereof, and belongs to the technical field of advanced manufacturing.
  • Lithium Ion Batteries have high capacity, no memory effect, fast reversible charge and discharge, and high coulombic efficiency. They have been widely used in mobile phones, notebook computers, and electric vehicles and energy storage. At present, lithium ion battery anode materials are mainly concentrated in graphite, which is close to the theoretical specific capacity of 372 mAh / g, and it is difficult to further meet the demand for higher energy / density applications.
  • Si has attracted extensive attention due to its high lithium insertion ability (theoretical specific capacity of 4200 mAh/g), abundant reserves, and no pollution to the environment.
  • Si mainly reacts between two phases during charge and discharge:
  • the uneven volume expansion of Si (the volume change can reach 270%) produces stress that eventually causes Si to pulverize and Si detaches from the current collector and loses electrical contact with the current collector, eventually leading to the negative electrode.
  • the structural conductivity is weakened.
  • Theoretical research and experimental results show that the performance of Si electrode can be optimized by increasing the graphite conductive coating layer on Si or reducing the load density of Si. Both methods will reduce the mass loading capacity of Si, thus limiting the increase of total capacity and practical application. .
  • the mass loading of the active material Si in the Si electrode having better stability is only 0.1-3.5 mg/cm 2 . For example, Li et al.
  • the technical solution of the present invention is as follows.
  • a porous electrode for a lithium ion battery comprising:
  • a current collector that is metallurgically bonded to the bulk porous metal.
  • the material of the bulk porous metal is Cu.
  • the material of the current collector is Cu.
  • the active material is Si particles.
  • the present invention also provides a lithium ion battery comprising the porous electrode according to any one of the above aspects.
  • the present invention also provides a method of preparing a porous electrode comprising the steps of:
  • the Si, Cu, and Al powders are thoroughly mixed and then pressed and formed;
  • the press-formed Si/Cu/Al material is pressed together with the Cu current collector into a vacuum furnace for sintering and diffusion welding to form a Si-Cu-Al precursor alloy, and metallurgical bonding of the precursor alloy and the current collector is realized. ;
  • the Al element in the Si-Cu-Al precursor alloy was removed by chemical etching to finally obtain a porous Si/Cu composite electrode which was metallurgically bonded to the current collector.
  • the weight percentage of the three powders of Si, Cu, and Al is 8 to 25% Si, 50 to 72% Cu, The rest is Al.
  • the vacuum sintering and diffusion welding temperatures are 450-550 ° C, the pressure is 0.2-1.0 MPa, and the time is 0.5-1.5 h.
  • the etchant used in the chemical etching method is selected from the group consisting of sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid.
  • the concentration of the etchant used in the chemical etching method is 1-5 mol/L, and the etching time is 4-10 h.
  • the invention has the following advantages: 1) the active material Si is embedded in the bulk porous Cu, and the porous Cu acts as a "conductive agent” and a "binder", which can alleviate the pulverization of the active material Si particles due to the volume effect. And shedding, which can improve the electron transport efficiency, and the porous structure increases the contact area between Si and the electrolyte, and accelerates the reaction efficiency of lithium intercalation. Therefore, the composite electrode can obtain excellent comprehensive performance under high-quality loading conditions of the active material Si, that is, high capacity and excellent cycle performance. 2) Combining traditional powder metallurgy, diffusion welding and de-alloying technology to realize integrated manufacturing of lithium-ion battery anode material-structure-function, the manufacturing method is mature and simple.
  • Fig. 1 is a schematic view showing a porous structure Si/Cu composite electrode of a lithium ion battery of the present invention.
  • FIG. 2 is a cross-sectional view of the SEM and EDS elements of the precursor alloy of the embodiment of FIG. 1.
  • Figure 3 is an XRD pattern of the precursor alloy after sintering and diffusion welding of the embodiment of Figure 1.
  • Figure 4 is a cross-sectional SEM image of the precursor of the embodiment of Figure 1 after dealloying.
  • porous structure refers to an electrode structure in which small particles are stacked into a pore-like structure to facilitate material reaction and transfer.
  • active material means a material having lithium intercalation ability.
  • binder means a substance which is added for the purpose of attaching an active substance and which may be removed or not removed before or during sintering.
  • the term "conductive agent” means that in order to ensure good charge and discharge performance of the electrode, a certain amount of conductive substance is usually added during the production of the pole piece, and the active substance and the current are mixed between the active materials.
  • the body functions to collect microcurrents to reduce the contact resistance of the electrodes to accelerate the rate of electron movement, and at the same time, it can effectively increase the migration rate of ions in the electrode material, thereby improving the charge and discharge efficiency of the electrodes.
  • current collector refers to a structure or a part that collects current, and its function is mainly to collect currents generated by a battery active material and output it to the outside.
  • binder means fine particles composed of dry, dispersed solid particles.
  • a porous electrode of a lithium ion battery includes a bulk porous metal having a continuous porous structure; an active material embedded in the porous structure of the bulk porous metal; a current collector, Metallurgically bonded to the bulk porous metal.
  • the material of the bulk porous metal is Cu.
  • the bulk porous metal has a pore size ranging from 10 to 20 ⁇ m.
  • the material of the current collector may be Cu, stainless steel, Ni.
  • the active material is Si particles.
  • the active material has a particle size ranging from 100 nm to 45 ⁇ m.
  • the active material Si is embedded in the bulk porous Cu, and the bulk porous Cu is combined with the current collector metallurgy to play the dual role of "conductive agent” and "binder".
  • the present invention also provides a corresponding manufacturing method, and the specific steps are as follows.
  • Step 1 A certain proportion of Si, Cu, and Al powders are thoroughly mixed and then press-formed.
  • Step 2 Press-pressing the pressed Si/Cu/Al material with the Cu current collector and placing it in a vacuum furnace for sintering and diffusion welding to form a Si-Cu-Al precursor alloy, and realizing the precursor alloy and current collector Metallurgical combination.
  • Step 3 The Al element in the Si-Cu-Al precursor alloy is removed by chemical etching, and finally a porous Si/Cu composite electrode metallurgically bonded to the current collector is obtained.
  • the weight percentage of the composite electrode precursor material is 8 to 25% Si, 50 to 72% Cu, and the balance is Al.
  • Si content is too low, the battery capacity is not high, and when the Si content is too high, the Cu or Al content is inevitably lowered.
  • the Cu content is too low, it is difficult to form a continuous porous Cu structure, and the active material Si is easily pulverized and peeled off during the battery cycle;
  • the Al content is too low, the porosity is low, the electrolyte cannot sufficiently contact the active material Si, and the lithium intercalation is lowered. And the rate of reaction for delithiation.
  • the Cu content is too high, both the Si and the Al content are reduced, and the amount of the active material is reduced, which adversely affects. The same is true when the Al content is too high.
  • the vacuum sintering and diffusion welding temperatures are 450-550 ° C, the pressure is 0.2-1.0 MPa, and the time is 0.5-1.5 h.
  • the etchant used in the chemical etching method is selected from the group consisting of sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid.
  • the concentration of the etchant used in the chemical etching method is 1-5 mol/L, and the etching time is 4-10 h.
  • the mixed Si/Cu/Al powder was press-formed using Shanghai Xinnuo SYP-30T tablet press, pressure: 0.4 MPa, time: 5 min, and a press-formed Si/Cu with a diameter of 8 mm and a thickness of about 200 ⁇ m was obtained.
  • /Al material The SEM image of the cross section of the precursor alloy of this material and the distribution of EDS elements are shown in Fig. 2.
  • the pressed Si/Cu/Al material is closely adhered to the Cu current collector, placed in a vacuum furnace and heated to 470 ° C, and pressure is applied. 0.4MPa, heat preservation and pressure for 45min, the atoms mutually diffuse to form a strong metallurgical bond.
  • the XRD pattern of the precursor alloy after sintering and diffusion welding is shown in Fig. 3.
  • the sample obtained by sintering and diffusion welding was immersed in a 3 mol/L HCl solution for 4-10 h, then washed twice with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours to dissolve the Si surface.
  • the SiO 2 which may be present is washed with deionized water and absolute ethanol several times to obtain a porous Si/Cu composite electrode.
  • the cross-sectional SEM image is shown in Fig. 4.
  • the mixed Si/Cu/Al powder was press-formed using Shanghai Xinnuo SYP-30T tablet press, pressure: 0.4 MPa, time: 5 min, and a press-formed Si/Cu with a diameter of 8 mm and a thickness of about 200 ⁇ m was obtained. /Al material.
  • the pressed Si/Cu/Al material is closely adhered to the Cu current collector, placed in a vacuum furnace and heated to 470 ° C, and pressure is applied. 0.4MPa, heat preservation and pressure for 45min, the atoms mutually diffuse to form a strong metallurgical bond.
  • the sample obtained by sintering and diffusion welding was immersed in a 3 mol/L HCl solution for 4-10 h, then washed twice with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours to dissolve the Si surface.
  • the SiO 2 which may be present is washed several times with deionized water and absolute ethanol to obtain a porous Si/Cu composite electrode.
  • Raw materials: Si, Cu, Al powder, weight percentage is Si: Cu: Al 25: 50: 25, Si powder mesh number is -325 mesh, Cu powder mesh number is -300 mesh, aluminum powder mesh number is -325 mesh .
  • the mixed Si/Cu/Al powder was press-formed using Shanghai Xinnuo SYP-30T tablet press, pressure: 0.4 MPa, time: 5 min, and a press-formed Si/Cu with a diameter of 8 mm and a thickness of about 200 ⁇ m was obtained. /Al material.
  • the pressed Si/Cu/Al material is closely adhered to the Cu current collector, placed in a vacuum furnace and heated to 470 ° C, and pressure is applied. 0.4MPa, heat preservation and pressure for 45min, the atoms mutually diffuse to form a strong metallurgical bond.
  • the sample obtained by sintering and diffusion welding was immersed in a 3 mol/L HCl solution for 4-10 h, then washed twice with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours to dissolve the Si surface.
  • the SiO 2 which may be present is washed several times with deionized water and absolute ethanol to obtain a porous Si/Cu composite electrode.
  • the performance test of the porous structure Si/Cu composite electrode prepared in Example 1 was carried out.
  • the test procedure was carried out by using the Wuhan Blue Electron CT2001D test system.
  • the current density was 100 mA/g, and the area specific capacity of the test results was 9.6 mAh/cm 2 for the first time.
  • the discharge coulombic efficiency is 76%, and the Coulomb efficiency is maintained above 93% from the second charge and discharge. It can be seen that the composite electrode of the present invention has good overall performance.

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Abstract

本发明公开了一种锂离子电池多孔结构Si/Cu复合电极及其制造方法。该复合电极包括活性物质、块体多孔Cu和集流体。其中的活性物质Si嵌入在块体多孔Cu中，块体多孔Cu与集流体冶金结合，起到"粘结剂"和"导电剂"的双重作用，既缓解活性物质Si颗粒的粉化和脱落，又提高电子传输效率，同时多孔结构增大活性物质Si与电解质的接触面积，加快嵌锂化合的反应效率。该复合电极的制造方法是：首先采用粉末冶金和扩散焊接技术，以Si、Cu、Al粉末为原材料，在Cu集流体上制备Si-Cu-Al前驱体合金，然后利用化学脱合金的方法脱去Si-Cu-Al前驱体合金中的Al元素，获得具有多孔结构的Si/Cu复合电极。

Description

锂离子电池多孔结构Si/Cu复合电极及其制造方法 技术领域
本发明涉及锂离子电池负极结构及其制造方法，具体地说，涉及一种具有多孔结构的Si/Cu复合电极及其制造方法，属于先进制造技术领域。
背景技术
锂离子电池(Lithium Ion Batteries，LIBs)具有高容量、无记忆效应、快速可逆充放电和高库伦效率等优点，已经广泛应用于手机、笔记本电脑以及电动汽车和储能领域。目前，锂离子电池负极材料主要集中在石墨，已经接近理论比容量372mAh/g，难以进一步满足对更高能量/密度应用的需求。锂离子电池的负极材料中，Si因为高的嵌锂能力(理论比容量达4200mAh/g)、储备丰富及对环境无污染而引起广泛关注。
然而，Si在充放电过程当中存在严重的粉化脱落以及导电性迅速衰减等问题，这些成为其作为负极材料的阻碍。Si在充放电过程中主要发生两种相的反应：
(1)单晶Si
Figure PCTCN2017080802-appb-000001
非晶化LiXSi(a-LiXSi)
(2)非晶化LiXSi
Figure PCTCN2017080802-appb-000002
金属间化合物Li15Si4(i-Li15Si4)
在这种相反应中，Si的不均匀的体积膨胀(体积变化可以达到270％)产生的应力最终造成了Si的粉化以及Si从集流体上脱落并与集流体失去电接触，最终导致负极结构导电性的减弱。目前理论研究和实验结果证明通过在Si上增加石墨导电包裹层或降低Si的负载密度可以优化Si电极性能，这两种方式都会降低Si的质量装载能力，因此限制了总容量的提升和实际应用。目前，具有较好稳定性的Si电极中活性材料Si的质量装载量仅为0.1-3.5mg/cm2。例如，Li等人通过电化学刻蚀的方法合成了大尺寸的海绵体介孔Si材料，材料内部的孔隙可以很好的容纳Si的体积膨胀，并通过化学气相沉积法在材料表面覆盖了C层，然后通过添加导电剂和粘结剂，将负极材料涂覆在集流体表面，活性物质的装载量不高，约为2mg/cm2，其首次充放电库伦效率为～56％，第二次开始维持在99.4％，面积比容量仅为～1.5mAh/cm2。 (Li,X.,et al.,Mesoporous silicon sponge as an anti-pulverization structure for high-performance lithium-ion battery anodes.Nat Commun,2014.5:p.4105.)Yi等人合成了由石墨烯层包裹的Si-C复合材料，将其涂覆在集流体表面，首次库伦效率为64％，第二次循环开始平均的库伦效率为99.51％，但活性物质Si的装载量(3.18mg/cm2)和面积比容量(3.2mAh/cm2)同样不高。(Yi,R.,et al.,Dual conductive network-enabled graphene/Si–C composite anode with high areal capacity for lithium-ion batteries.Nano Energy,2014.6:p.211-218.)
因此，如何提高Si的负载量并避免Si在高负载条件下体积膨胀造成的粉化和脱落问题，是提高电极容量和性能的关键。
发明内容
本发明的目的在于提供一种与集流体冶金结合具有多孔结构的Si/Cu复合电极及其制造方法。本发明的技术方案如下。
一种锂离子电池的多孔电极，包括：
块体多孔金属，其具有连续的多孔结构；
活性物质，其嵌入到所述块体多孔金属的多孔结构之中；
集流体，其与所述块体多孔金属冶金结合。
优选地，所述块体多孔金属的材料为Cu。
优选地，所述集流体的材料为Cu。
优选地，所述活性物质为Si颗粒。
本发明还提供了一种锂离子电池，包括根据以上技术方案中任一项所述的多孔电极。
本发明还提供了一种制备多孔电极的方法，其包括以下步骤：
将Si、Cu、Al三种粉末充分混合后压制成型；
将压制成型的Si/Cu/Al材料与Cu集流体压合在一起放入真空炉中进行烧结和扩散焊接，形成Si-Cu-Al前驱体合金，并实现前驱体合金与集流体的冶金结合；
采用化学腐蚀法脱去Si-Cu-Al前驱体合金中的Al元素，最终得到与集流体冶金结合的多孔Si/Cu复合电极。
优选地，所述Si、Cu、Al三种粉末的重量百分比为8～25％Si、50～72％Cu、 其余为Al。
优选地，所述真空烧结和扩散焊接温度为450-550℃，压力为0.2-1.0MPa，时间为0.5-1.5h。
优选地，所述化学腐蚀法所用的腐蚀剂选自氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、磷酸、氢氟酸。
优选地，所述化学腐蚀法所用的腐蚀剂的浓度为1-5mol/L，腐蚀时间为4-10h。
本发明的优点是：1)活性物质Si嵌入块体多孔Cu中，多孔Cu起到“导电剂”和“粘结剂”的双重作用，既可以缓解活性物质Si颗粒因为体积效应造成的粉化和脱落，又可以提高电子传输效率，同时多孔结构增大Si与电解质的接触面积，加快嵌锂化合的反应效率。因此，该复合电极可以在活性物质Si高质量装载条件下，获得优良的综合性能，即高容量及优良的循环性能。2)将传统的粉末冶金、扩散焊接和脱合金技术相结合，实现锂离子电池负极材料-结构-功能一体化制造，制造方法技术成熟，简单易行。
附图说明
图1是本发明的锂离子电池多孔结构Si/Cu复合电极示意图。
图2是图1实施例前驱体合金截面SEM图及EDS元素分布图。
图3是图1实施例烧结和扩散焊后的前驱体合金XRD图。
图4是图1实施例前驱体脱合金后截面SEM图。
具体实施方式
下面结合具体的实施例对本发明作进一步详细的描述，但本发明不限于以下实施例。
此处，术语“多孔结构”系指由小颗粒堆积成具有孔状结构的电极结构，以利于物质反应与传递。
此处，术语“活性物质”系指具有嵌锂能力的材料。
此处，术语“粘结剂”系指为了连接活性物质而添加的可在烧结前或烧结过程中除掉或不除掉的物质。
此处，术语“导电剂”系指为了保证电极具有良好的充放电性能，在极片制作时通常加入一定量的导电物质，其在活性物质之间、活性物质与集流 体之间起到收集微电流的作用，以减小电极的接触电阻加速电子的移动速率，同时也能有效地提高离子在电极材料中的迁移速率，从而提高电极的充放电效率。
此处，术语“集流体”系指汇集电流的结构或零件，其功用主要是将电池活性物质产生的电流汇集起来并对外输出。
此处，术语“粉末”系指干燥、分散的固体颗粒组成的细微粒子。
如图1所示，一种锂离子电池的多孔电极，包括块体多孔金属，其具有连续的多孔结构；活性物质，其嵌入到所述块体多孔金属的多孔结构之中；集流体，其与所述块体多孔金属冶金结合。
优选地，所述块体多孔金属的材料为Cu。在一优选的实施例中，所述块体多孔金属的孔径范围为10～20μm。
优选地，所述集流体的材料可以为Cu、不锈钢、Ni。
优选地，所述活性物质为Si颗粒。在一优选的实施例中，所述活性物质的粒径范围为100nm～45μm。
活性物质Si嵌入块体多孔Cu中，块体多孔Cu与集流体冶金结合，起到“导电剂”和“粘结剂”的双重作用。
针对这种复合电极结构特点，本发明还提供了相应的制造方法，具体步骤如下。
步骤1：将一定比例的Si、Cu、Al三种粉末充分混合后压制成型。
步骤2：将压制成型的Si/Cu/Al材料与Cu集流体压合在一起放入真空炉中进行烧结和扩散焊接，形成Si-Cu-Al前驱体合金，并实现前驱体合金与集流体的冶金结合。
步骤3：采用化学腐蚀法脱去Si-Cu-Al前驱体合金中的Al元素，最终得到与集流体冶金结合的多孔Si/Cu复合电极。
优选地，制备该复合电极前驱体材料的重量百分比为8～25％Si、50～72％Cu，其余为Al。Si含量过低时，电池容量不高，Si含量过高时，必然使Cu或Al含量降低。Cu含量过低时，难以形成连续的多孔Cu结构，电池循环过程中活性物质Si易粉化脱落；而Al含量过低时，孔隙率低，电解液不能充分与活性物质Si接触，降低嵌锂和脱锂的反应速率。Cu含量过高时，无论是减小Si还是Al的含量，均会减小活性物质的负载量，带来不利影响。Al含量过高时亦然。
优选地，所述真空烧结和扩散焊接温度为450-550℃，压力为0.2-1.0MPa，时间为0.5-1.5h。
优选地，所述化学腐蚀法所用的腐蚀剂选自氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、磷酸、氢氟酸。
优选地，所述化学腐蚀法所用的腐蚀剂的浓度为1-5mol/L，腐蚀时间为4-10h。
实施例1
原料：Si、Cu、Al粉末，重量百分比为Si:Cu:Al＝10:72:18，Si粉末目数为-325目，Cu粉末目数为-300目，铝粉末目数为-325目。
腐蚀液：3mol/L的HCl溶液。
制备过程：
步骤一、压制成型
采用上海新诺SYP-30T型压片机，将混合后的Si/Cu/Al粉末压制成型，压力：0.4MPa，时间：5min，得到直径为8mm，厚度约为200μm的压制成型的Si/Cu/Al材料。该材料的前驱体合金截面SEM图及EDS元素分布如图2所示。
步骤二、烧结和扩散焊接
采用北京航天金翔设备有限公司的真空扩散焊接炉HT-QA-25，将压制成型的Si/Cu/Al材料与Cu集流体紧密贴合，置于真空炉中加热至470℃，并施加压力0.4MPa，保温保压45min，原子相互扩散而形成牢固的冶金结合。烧结和扩散焊接后的前驱体合金XRD图如图3所示。
步骤三、化学脱合金处理
将烧结和扩散焊得到的样品浸入到3mol/L的HCl溶液中腐蚀4-10h，然后经去离子水洗涤2次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解Si表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了多孔结构Si/Cu复合电极,截面SEM图如图4所示。
实施例2
原料：Si、Cu、Al粉末，重量百分比为Si:Cu:Al＝14:72:14，Si粉末目数为-325目，Cu粉末目数为-300目，铝粉末目数为-325目。
腐蚀液：3mol/L的HCl溶液。
制备过程：
步骤一、压制成型
采用上海新诺SYP-30T型压片机，将混合后的Si/Cu/Al粉末压制成型，压力：0.4MPa，时间：5min，得到直径为8mm，厚度约为200μm的压制成型的Si/Cu/Al材料。
步骤二、烧结和扩散焊接
采用北京航天金翔设备有限公司的真空扩散焊接炉HT-QA-25，将压制成型的Si/Cu/Al材料与Cu集流体紧密贴合，置于真空炉中加热至470℃，并施加压力0.4MPa，保温保压45min，原子相互扩散而形成牢固的冶金结合。
步骤三、化学脱合金处理
将烧结和扩散焊得到的样品浸入到3mol/L的HCl溶液中腐蚀4-10h，然后经去离子水洗涤2次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解Si表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了多孔结构Si/Cu复合电极。
实施例3
原料：Si、Cu、Al粉末，重量百分比为Si:Cu:Al＝25:50:25，Si粉末目数为-325目，Cu粉末目数为-300目，铝粉末目数为-325目。
腐蚀液：3mol/L的HCl溶液。
制备过程：
步骤一、压制成型
采用上海新诺SYP-30T型压片机，将混合后的Si/Cu/Al粉末压制成型，压力：0.4MPa，时间：5min，得到直径为8mm，厚度约为200μm的压制成型的Si/Cu/Al材料。
步骤二、烧结和扩散焊接
采用北京航天金翔设备有限公司的真空扩散焊接炉HT-QA-25，将压制成型的Si/Cu/Al材料与Cu集流体紧密贴合，置于真空炉中加热至470℃，并施加压力0.4MPa，保温保压45min，原子相互扩散而形成牢固的冶金结合。
步骤三、化学脱合金处理
将烧结和扩散焊得到的样品浸入到3mol/L的HCl溶液中腐蚀4-10h，然后经去离子水洗涤2次，随后置于质量百分比为2％HF乙醇溶液中搅拌2 小时，溶解Si表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了多孔结构Si/Cu复合电极。
电化学性能测试
对实施例1所制备的多孔结构Si/Cu复合电极进行性能测试，测试过程中采用武汉蓝电CT2001D测试系统，电流密度取100mA/g，测试结果的面积比容量达9.6mAh/cm2，首次放电库伦效率为76％，从第二次充放电开始，库伦效率维持在93％以上。可见，本发明的复合电极具有良好的综合性能。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (10)

  1. 一种锂离子电池的多孔电极，包括：
    块体多孔金属，其具有连续的多孔结构；
    活性物质，其嵌入到所述块体多孔金属的多孔结构之中；
    集流体，其与所述块体多孔金属冶金结合。
  2. 根据权利要求1所述的锂离子电池的多孔电极，其特征在于，所述块体多孔金属的材料为Cu。
  3. 根据权利要求1所述的锂离子电池的多孔电极，其特征在于，所述集流体的材料为Cu。
  4. 根据权利要求1所述的锂离子电池的多孔电极，其特征在于，所述活性物质为Si颗粒。
  5. 一种锂离子电池，包括根据权利要求1-4中任一项所述的多孔电极。
  6. 一种制备多孔电极的方法，其包括：
    将Si、Cu、Al三种粉末充分混合后压制成型；
    将压制成型的Si/Cu/Al材料与Cu集流体压合在一起放入真空炉中进行烧结和扩散焊接，形成Si-Cu-Al前驱体合金，并实现前驱体合金与集流体的冶金结合；
    采用化学腐蚀法脱去Si-Cu-Al前驱体合金中的Al元素，最终得到与集流体冶金结合的多孔Si/Cu复合电极。
  7. 根据权利要求6所述的方法，其特征在于，所述Si、Cu、Al三种粉末的重量百分比为8～25％Si、50～72％Cu、其余为Al。
  8. 根据权利要求6所述的方法，其特征在于，所述真空烧结和扩散焊接温度为450-550℃，压力为0.2-1.0MPa，时间为0.5-1.5h。
  9. 根据权利要求6所述的方法，其特征在于，所述化学腐蚀法所用的腐蚀剂选自氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、磷酸、氢氟酸。
  10. 根据权利要求9所述的方法，其特征在于，所述化学腐蚀法所用的腐蚀剂的浓度为1-5mol/L，腐蚀时间为4-10h。
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CN109817883B (zh) * 2019-01-21 2021-04-23 珠海冠宇电池股份有限公司 一种锂电池极片及其制备方法及锂电池
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CN116130589A (zh) * 2022-11-25 2023-05-16 贵州贵航新能源科技有限公司 一种锂电池涂布方法及其装置

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