WO2017190587A1 - 一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法 - Google Patents

一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法 Download PDF

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WO2017190587A1
WO2017190587A1 PCT/CN2017/080803 CN2017080803W WO2017190587A1 WO 2017190587 A1 WO2017190587 A1 WO 2017190587A1 CN 2017080803 W CN2017080803 W CN 2017080803W WO 2017190587 A1 WO2017190587 A1 WO 2017190587A1
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silicon
aluminum
diffusion welding
laser surface
lithium ion
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PCT/CN2017/080803
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French (fr)
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黄婷
孙丁月
肖荣诗
杨武雄
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北京工业大学
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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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the invention relates to the field of preparation of a negative electrode of a lithium ion battery, in particular to a method for preparing a silicon negative electrode of a lithium ion battery by composite diffusion welding and de-alloying using a laser surface remelting technique.
  • Lithium-ion batteries have been widely used in modern communications, portable electronic products, and hybrid vehicles due to their high specific energy, long life in charge and discharge, no pollution, and safety.
  • the lithium ion battery is mainly composed of four parts, a positive electrode, a negative electrode, a separator and an electrolyte.
  • the negative electrode is an important factor in determining the performance and price of a lithium ion battery.
  • the commercial anode material of lithium ion battery is mainly graphite carbon, the theoretical capacity is 372 mA ⁇ h/g, and the actual capacity is close to the theoretical value, which cannot meet the current demand.
  • the theoretical lithium storage capacity of silicon is 4200 mA ⁇ h/g, which is about ten times that of graphite.
  • the voltage platform is moderate, and it is expected to replace graphite as a new anode material for lithium ion batteries.
  • silicon materials prepared by template method (magnesium thermal reduction method, CVD method) and non-template method (chemical etching method, electrochemical etching method) are micro-nano powders, and it is necessary to add a conductive agent and a binder to the surface of the current collector. .
  • template method magnesium thermal reduction method, CVD method
  • non-template method chemical etching method, electrochemical etching method
  • the structure and function can be directly integrated, but the combination of them and the current collector is mechanically combined. After several cycles, the active material and the current collector fall off. Loss of electrical contact, so the cycle performance drops rapidly.
  • Cao Feifei et al. used magnetron sputtering to deposit silicon particles on the surface of copper. The current charge and discharge capacity was 1890m ⁇ Ah/g and 3800m ⁇ Ah/g at a current density of 300mA/g. (Cu-Si Nanocable Arrays as High-Rate Anode Materials for Lithium-Ion Batteries.. Feifei Cao et al. Adv. Mater. 2011, 23, 4415–4420) However, the silicon material prepared by the above method is still mechanically combined with the current collector. The damage of the electrode structure due to the volume change of silicon cannot be avoided.
  • the invention adopts a laser surface remelting composite diffusion welding and a de-alloying method, firstly preparing an aluminum-silicon precursor alloy coating on an aluminum alloy substrate by using a laser surface remelting technique, and then welding the precursor alloy with copper, and finally De-alloying, a silicon negative electrode metallurgically bonded to a copper current collector was prepared.
  • the present invention provides a method for preparing a silicon negative electrode of a lithium ion battery by composite diffusion welding and de-alloying using a laser surface remelting technique.
  • the invention adopts the following technical scheme: preparing a molten silicon layer of aluminum-silicon alloy by laser surface remelting technology, and separating the molten layer from the substrate to obtain an aluminum-silicon alloy precursor, and then using the diffusion welding to form the aluminum-silicon alloy precursor After welding with the current collector, the aluminum-silicon alloy precursor is subjected to chemical de-alloying treatment with an etchant to remove the elemental aluminum, and finally a silicon negative electrode combined with the current collector metallurgy is obtained.
  • the remelting material is an aluminum silicon alloy, and the chemical composition percentage thereof is: Al: 50-95%, Si: 5-50%.
  • the laser remelting treatment has a power density of 2 ⁇ 10 4 to 2.5 ⁇ 10 5 W/cm 2 and a scanning speed of 2 to 30 mm/s.
  • the current collector material is copper.
  • the diffusion welding temperature is 450 to 550 ° C
  • the pressure is 0.5 to 2 Mpa
  • the welding time is 0.5 to 1.5 hours.
  • the etchant used for chemical de-alloying is sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrofluoric acid.
  • the concentration of sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid for chemical alloying is 1 to 5 mol/L, and the etching time is 2 to 12 hours.
  • the active material silicon is too small, and when the silicon content is more than 50%, coarse primary silicon is formed, and the micro-nano silicon structure cannot be formed.
  • the invention adopts the method of laser surface remelting technology for compound diffusion welding and dealloying to prepare silicon negative electrode of lithium ion battery, and the advantages thereof are as follows:
  • the aluminum-silicon alloy precursor prepared by laser surface remelting technology has finer structure and obviously improves the uniformity of micro-nano silicon structure after chemical de-alloying.
  • the combination of silicon and copper current collector metallurgy can effectively prevent porous silicon from escaping from the current collector during charge and discharge, and can be directly used for the negative electrode of lithium ion battery.
  • Fig. 1 is a SEM image of a lower cross section of a silicon negative electrode of the present invention.
  • FIG. 2 is a SEM image of a high-power lower cross section of a silicon negative electrode of the present invention.
  • the laser remelting process was carried out on the IPG fiber laser YLS-6000 and its supporting KUKA robot.
  • the laser power was 4.5 kW
  • the scanning speed was 8 mm/s
  • the spot diameter was 5 mm.
  • the surface of the aluminum-silicon alloy was laser remelted.
  • protective gas argon
  • protective gas flow 18L / min.
  • the fused layer is then separated from the substrate to obtain an aluminum silicon alloy precursor.
  • the aluminum-silicon alloy precursor is closely adhered to the copper current collector, and the aluminum silicon cladding layer is closely adhered to the copper current collector, and heated in a vacuum atmosphere for 1 hour to raise the temperature from room temperature to 530 ° C. Applying a pressure of 0.5 KPa, the micro-plastic deformation of the joint interface is brought into close contact, and after 1 hour of heat preservation, the atoms mutually diffuse to form a strong metallurgical bond.
  • the sample obtained by diffusion welding was immersed in a 3 mol/L HCL solution for 2 hours, then washed 3 times with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours to dissolve the silicon surface. SiO 2 was washed several times with deionized water and absolute ethanol to obtain a silicon negative electrode, which was finally stored in alcohol for use.
  • Silicon anode performance index the first charge and discharge efficiency is 73.53%, the first charge and discharge capacity is 2500mA ⁇ h/g, 3400mA ⁇ h/g. The capacity after 500 cycles was 500 mA ⁇ h/g.
  • the laser remelting process was carried out on the IPG fiber laser YLS-6000 and its supporting KUKA robot.
  • the laser power was 5.5 kW
  • the scanning speed was 10 mm/s
  • the spot diameter was 5 mm.
  • the surface of the aluminum-silicon alloy was laser remelted.
  • protective gas argon
  • protective gas flow 18L / min.
  • the molten layer is then separated from the substrate to obtain an aluminum silicon alloy precursor.
  • the aluminum-silicon alloy precursor is closely adhered to the copper current collector, heated in a vacuum for 1 hour, and raised from room temperature to a temperature of 520 ° C, and a pressure of 0.5 KPa is applied thereto to make the joint interface micro-plastic deformation to achieve close contact. After 1 hour of heat retention, the atoms diffuse together to form a strong metallurgical bond.
  • the sample obtained after diffusion welding was immersed in a 3 mol/L HCL solution for 8 hours, then washed 3 times with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours, and the dissolved silicon surface may exist.
  • the SiO 2 was washed several times with deionized water and absolute ethanol to obtain a silicon negative electrode.
  • Silicon anode performance index The first charge and discharge capacity is 2400 mA ⁇ h/g, 3300 mA ⁇ h/g, the first charge and discharge cycle efficiency is 72.73%, and the capacity after 20 cycles is 460 mA ⁇ h/g.
  • the laser remelting process was carried out on the IPG fiber laser YLS-6000 and its supporting KUKA robot.
  • the surface of the aluminum-silicon alloy was laser remelted to obtain the aluminum-silicon alloy precursor.
  • the fused layer is then separated from the substrate to obtain an aluminum silicon alloy precursor.
  • the aluminum-silicon alloy precursor is closely adhered to the copper current collector, heated in a vacuum for 1 hour, and raised from room temperature to a temperature of 520 ° C, and a pressure of 0.5 KPa is applied thereto to make the joint interface micro-plastic deformation to achieve close contact. After 1 hour of heat retention, the atoms diffuse together to form a strong metallurgical bond.
  • the sample obtained by diffusion welding was immersed in a 3 mol/L HCL solution for 10 hours, the reaction was stopped, and then washed 3 times with deionized water, followed by stirring in a 2% by mass HF ethanol solution for 2 hours to dissolve the silicon surface.
  • the SiO 2 which may be present is washed several times with deionized water and absolute ethanol to obtain a silicon negative electrode.
  • Silicon anode performance index the first charge and discharge efficiency is 74.27%, the first charge and discharge capacity is 2540mA ⁇ h/g, 3420mA ⁇ h/g, and the capacity after 10 cycles is 750mA ⁇ h/g.
  • the laser remelting process was carried out on the IPG fiber laser YLS-6000 and its supporting KUKA robot.
  • the laser power was 5.5 kW
  • the scanning speed was 7 mm/s
  • the spot diameter was 5 mm.
  • the laser remelting treatment was performed on the surface of the aluminum-silicon alloy.
  • protective gas argon
  • protective gas flow 18L / min.
  • the molten layer is then separated from the substrate to obtain an aluminum silicon alloy precursor.
  • the aluminum-silicon alloy precursor is closely adhered to the copper current collector, heated in a vacuum for 1 hour, and raised from room temperature to a temperature of 550 ° C, and a pressure of 1 KPa is applied thereto to make the joint interface micro-plastic deformation reach close contact, and then After 1 hour of heat retention, the atoms diffuse together to form a strong metallurgical bond.
  • the sample obtained after the diffusion welding was immersed in a 3 mol/L HCL solution for 12 hours, then washed three times with deionized water, and then placed in a mass percentage of 2% HF ethanol solution for 2 hours, and the dissolved silicon surface may exist.
  • the SiO 2 was washed several times with deionized water and absolute ethanol to obtain a silicon negative electrode.
  • Silicon anode performance index The first charge and discharge capacity is 3900mA ⁇ h/g, 2800mA ⁇ h/g, the first charge and discharge cycle efficiency is 71.79%, and the capacity after 2000 cycles is 2000mA ⁇ h/g.
  • 1 and 2 are cross-sectional SEM images of a silicon negative electrode of Example 4 of the present invention.

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Abstract

一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，采用激光表面重熔技术制备铝硅合金前驱体，然后通过扩散焊将铝硅合金前驱体与集流体焊接在一起，最后采用腐蚀剂去掉前驱体中的元素铝，最终获得与集流体冶金结合的硅负极。该方法制备的硅材料和集流体冶金结合，可有效避免充放电过程中硅材料与集流体脱落，且操作简单，效率高。

Description

一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法 技术领域
本发明涉及锂离子电池负极的制备领域，具体地说，是一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法。
背景技术
锂离子电池由于比能量高、充放电寿命长、无污染和安全可靠等优点，已广泛应用于现代通讯、便携式电子产品以及混合动力汽车等领域。锂离子电池主要由四部分组成，正极，负极，隔膜和电解液。其中负极是决定锂离子电池性能以及价格的重要因素。目前商用的锂离子电池负极材料主要是石墨类碳，理论容量372mA·h/g，实际容量已接近理论值，不能满足目前需求。
而硅的理论储锂容量为4200mA·h/g，是石墨的十倍左右，电压平台适中，有望替代石墨成为锂离子电池的新型负极材料。目前采用模板法(镁热还原法﹑CVD法)和非模板法(化学腐蚀法﹑电化学腐蚀法)制备的硅材料为微纳米粉末，需要添加导电剂和粘结剂涂覆到集流体表面。但是硅在充放电过程中，发生300％的体积变化，对电极的结构造成巨大破坏，进而使硅材料与集流体脱落，失去电接触，使循环性能迅速衰减。
通过沉积溅射的方法在基体上直接溅射硅颗粒，可以直接实现结构与功能一体化制备，但是它们和集流体的结合方式都是机械结合，数次循环后，活性物质与集流体脱落，失去电接触，因此循环性能迅速下降。Cao Feifei等利用磁控溅射法在铜表面沉积硅颗粒，电流密度300mA/g条件下，首次充放电容量分别为1890m·Ah/g，3800m·Ah/g。(Cu-Si Nanocable Arrays as High-Rate Anode Materials for Lithium-Ion Batteries..Feifei Cao et al.Adv.Mater.2011,23,4415–4420)但是上述方法制备的硅材料与集流体仍然是机械结合，无法避免硅的体积变化对电极结构的破坏。
本发明采用激光表面重熔复合扩散焊和脱合金的方法，首先采用激光表面重熔技术在铝合金基底上制备铝硅前驱体合金涂层，然后将前驱体合金与铜焊接在一起，最后再去合金化，制备出了与铜集流体冶金结合的硅负极。
发明内容
为了解决以上问题，本发明提供了一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法。
1.本发明采用以下技术方案：采用激光表面重熔技术制备铝硅合金熔凝层，并将熔凝层从基体上分离，得到铝硅合金前驱体，然后采用扩散焊将铝硅合金前驱体与集流体焊接在一起，最后采用腐蚀剂对铝硅合金前驱体进行化学脱合金处理，去掉元素铝，最终获得与集流体冶金结合的硅负极。
2.进一步，采用激光表面重熔技术制备前驱体时，重熔材料为铝硅合金，其化学成份质量百分比为：Al：50～95％、Si：5～50％。
3.进一步，激光重熔处理功率密度为2×104～2.5×105W/cm2，扫描速度为2～30mm/s。
4.进一步，集流体材料为铜。
5.进一步，扩散焊温度450～550℃，压力0.5～2Mpa，焊接时间0.5～1.5小时。
6.进一步，化学脱合金所用腐蚀剂为氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、磷酸或氢氟酸。
7.进一步，化学脱合金用氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、氢氟酸的浓度为1～5mol/L，腐蚀时间为2～12小时。
硅含量小于5％时，活性物质硅太少，硅含量大于50％时，形成粗大的初晶硅，不能形成微纳米硅结构。
本发明采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其优点如下：
1)采用激光表面重熔技术制备的铝硅合金前驱体，组织更加细小，明显改善了化学脱合金后得微纳米硅结构的均匀性。
2)硅与铜集流体冶金结合，有效防止充放电过程中多孔硅脱离集流体，可直接用于锂离子电池负极。
附图说明
图1是本发明的硅负极低倍下截面SEM图。
图2是本发明的硅负极高倍下截面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，共提供两个实施例，但本发明不限于以下实施例。
实施例1
1.原料：
(1)铝硅块状合金，Al:Si＝95:5wt.％。
(2)腐蚀液：3mol/L的HCL溶液。
2.制备方法
一、铝硅合金前驱体的制备：
激光重熔工艺实验在IPG光纤激光器YLS-6000及其配套KUKA机械手上进行，激光以功率：4.5kW，扫描速度为：8mm/s，光斑直径：5mm，对铝硅合金表面进行激光重熔处理，其中保护气：氩气，保护气流量：18L/min。然后将熔凝层从基体上分离，得到铝硅合金前驱体。
二﹑扩散焊：
将铝硅合金前驱体与铜集流体紧密贴合，将铝硅熔覆层与铜集流体紧密贴合，置于真空气氛中加热1小时，使之从室温升至温度530℃，对其施加压力0.5KPa，使连接界面微观塑性变形达到紧密接触，再经保温1小时、原子相互扩散而形成牢固的冶金结合。
三﹑化学脱合金处理：
将扩散焊得到的样品浸入到3mol/L的HCL溶液中腐蚀2小时，然后经去离子水洗涤3次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解硅表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了硅负极，最后保存在酒精中备用。
硅负极性能指标：首次充放电效率为73.53％，首次充放电容量分别2500mA·h/g，3400mA·h/g。20次循环之后容量为500mA·h/g。
实施例2
1.原料：
(1)铝硅块体合金，Al:Si＝88:12wt.％。
(2)腐蚀液：3mol/L的HCL溶液。
2.制备方法
一﹑铝硅合金的制备：
激光重熔工艺实验在IPG光纤激光器YLS-6000及其配套KUKA机械手上进行，激光以功率：5.5kW，扫描速度为：10mm/s，光斑直径：5mm，对铝硅合金表面进行激光重熔处理，其中保护气：氩气，保护气流量：18L/min。然后将熔凝层与基体分离，得到铝硅合金前驱体。
二﹑扩散焊：
将铝硅合金前驱体与铜集流体紧密贴合，置于真空中加热1小时，使之从室温升至温度520℃，对其施加压力0.5KPa，使连接界面微观塑性变形达到紧密接触，再经保温1小时、原子相互扩散而形成牢固的冶金结合。
三﹑化学脱合金处理：
将扩散焊后得到的样品浸入到3mol/L的HCL溶液中腐蚀8小时，然后经去离子水洗涤3次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解硅表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了硅负极。
硅负极性能指标：首次充放电容量分别为2400mA·h/g，3300mA·h/g，首次充放电循环效率为72.73％，20次循环之后容量为460mA·h/g。
实施例3
1.原料：
(1)铝硅块体合金(-325目，99％)，Al:Si＝50:50wt.％。
(2)腐蚀液：3mol/L的HCL溶液。
2.制备方法
一﹑铝硅合金的制备：
激光重熔工艺实验在IPG光纤激光器YLS-6000及其配套KUKA机械手上进行，对铝硅合金表面进行激光重熔处理，得到铝硅合金前驱体。激光功率：5.5kW，扫描速度为：6mm/s，光斑直径：5mm，保护气：氩气，保护气流量：15L/min。然后将熔凝层从基体上分离，得到铝硅合金前驱体。
二﹑扩散焊过程：
将铝硅合金前驱体与铜集流体紧密贴合，置于真空中加热1小时，使之从室温升至温度520℃，对其施加压力0.5KPa，使连接界面微观塑性变形达到紧密接触，再经保温1小时、原子相互扩散而形成牢固的冶金结合。
三﹑化学脱合金处理：
将扩散焊得到的样品浸入到3mol/L的HCL溶液中腐蚀10小时，反应停止，然后经去离子水洗涤3次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解硅表面可能存在的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了硅负极。
硅负极性能指标：首次充放电效率为74.27％，首次充放电容量分别2540mA·h/g，3420mA·h/g，10次循环之后容量为750mA·h/g。
实施例4
1.原料：
(1)铝硅块体合金，Al:Si＝88:12wt.％。
(2)腐蚀液：3mol/L的HCL溶液。
2.制备方法
一﹑铝硅合金的制备：
激光重熔工艺实验在IPG光纤激光器YLS-6000及其配套KUKA机械手上进行，激光以功率：5.5kW，扫描速度为：7mm/s，光斑直径：5mm，对铝硅合金表面进行激光重熔处理，其中保护气：氩气，保护气流量：18L/min。然后将熔凝层与基体分离，得到铝硅合金前驱体。
二﹑扩散焊：
将铝硅合金前驱体与铜集流体紧密贴合，置于真空中加热1小时，使之从室温升至温度550℃，对其施加压力1KPa，使连接界面微观塑性变形达到紧密接触，再经保温1小时、原子相互扩散而形成牢固的冶金结合。
三﹑化学脱合金处理：
将扩散焊后得到的样品浸入到3mol/L的HCL溶液中腐蚀12小时，然后经去离子水洗涤3次，随后置于质量百分比为2％HF乙醇溶液中搅拌2小时，溶解硅表面可能存在 的SiO2，再用去离子水、无水乙醇分别多次洗涤，得到了硅负极。
硅负极性能指标：首次充放电容量分别为3900mA·h/g，2800mA·h/g，首次充放电循环效率为71.79％，10次循环之后容量为2000mA·h/g。
图1和图2是本发明的实施例4的硅负极的截面SEM图。

Claims (7)

  1. 一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：采用激光表面重熔技术制备铝硅合金熔凝层，并将熔凝层从基体上分离，得到铝硅合金前驱体，然后采用扩散焊将铝硅合金前驱体与集流体焊接在一起，最后采用腐蚀剂对铝硅合金前驱体进行化学脱合金处理，去掉元素铝，最终获得与集流体冶金结合的硅负极。
  2. 根据权利要求1所述的采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：采用激光表面重熔技术制备前驱体时，重熔材料为铝硅合金，其化学成份质量百分比为：Al：50～95％、Si：5～50％。
  3. 根据权利要求1所述的一种激光表面重熔复合脱合金复合制备锂离子电池硅负极的方法，其特征是：激光重熔处理功率密度为2×104～2.5×105W/cm2，扫描速度为2～30mm/s。
  4. 根据权利要求1所述的采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：集流体材料为铜。
  5. 根据权利要求1所述的采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：扩散焊温度450～550℃，压力0.5～2Mpa，焊接时间0.5～1.5小时。
  6. 根据权利要求1所述的采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：化学脱合金所用腐蚀剂为氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、磷酸或氢氟酸。
  7. 根据权利要求1所述的一种激光表面重熔复合扩散焊和脱合金制备锂离子电池硅负极的方法，其特征是：化学脱合金用氢氧化钠、氢氧化钾、盐酸、硫酸、硝酸、氢氟酸的浓度为1～5mol/L，腐蚀时间为2～12小时。
PCT/CN2017/080803 2016-05-02 2017-04-17 一种采用激光表面重熔技术复合扩散焊和脱合金制备锂离子电池硅负极的方法 WO2017190587A1 (zh)

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