WO2017190588A1 - 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法 - Google Patents

一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法 Download PDF

Info

Publication number
WO2017190588A1
WO2017190588A1 PCT/CN2017/080804 CN2017080804W WO2017190588A1 WO 2017190588 A1 WO2017190588 A1 WO 2017190588A1 CN 2017080804 W CN2017080804 W CN 2017080804W WO 2017190588 A1 WO2017190588 A1 WO 2017190588A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
aluminum
diffusion welding
ion battery
lithium ion
Prior art date
Application number
PCT/CN2017/080804
Other languages
English (en)
French (fr)
Inventor
黄婷
孙丁月
肖荣诗
杨武雄
Original Assignee
北京工业大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京工业大学 filed Critical 北京工业大学
Publication of WO2017190588A1 publication Critical patent/WO2017190588A1/zh

Links

Images

Classifications

    • 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
    • H01M4/13—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

Definitions

  • 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 laser cladding composite diffusion welding and dealloying.
  • the commercial lithium-ion battery anode is mainly graphite carbon material, which has the advantages of good cycle stability and long life, but the capacity is close to the theoretical value of 372 mAh/g, which cannot meet the wide demand of large-capacity and high-power chemical power sources.
  • the micro-nano silicon powder is mainly prepared by magnesium thermal reduction method, electrochemical corrosion method, chemical etching method and de-alloying method, and the silicon negative electrode is structured by mixing silicon powder with binder and conductive agent on the surface of the current collector.
  • silicon undergoes a 300% volume change during lithiation, and the large stress generated by volume expansion causes damage to the structure of the electrode, causing electrode cracking and silicon powder to fall off from the current collector, reducing the cycle stability of the silicon negative electrode.
  • the addition of the binder and the conductive agent reduces the quality of the silicon, thereby reducing the battery capacity.
  • the micro-nano silicon structure is directly prepared on the surface of the current collector by deposition method, magnetron sputtering, etc., and the structure of the silicon negative electrode is realized without adding a binder and a conductive agent.
  • Huabin Yang et al. used a DC magnetron sputtering method to sputter a 2 ⁇ m thick micro-nano silicon film on a copper foil, which exhibited good electrochemical performance when used as a negative electrode of a lithium ion battery. (Alumina-Coated Patterned Amorphous Silicon as the Anode for a Lithium-Ion Battery with High Coulombic Efficiency. Yu He et al. Adv. Mater. 2011, 23, 4938 - 4941).
  • the micro-nano-silicon structure prepared by the above method is still mechanically combined with the current collector, and the damage of the electrode structure due to the volume change of silicon cannot be avoided.
  • the invention adopts the method of laser cladding composite diffusion welding and dealloying, firstly adopts laser cladding technology to prepare an aluminum silicon precursor alloy coating on an aluminum or aluminum alloy substrate, and then diffusion-weld the precursor alloy with the copper current collector. Finally, alloying is performed to prepare a silicon negative electrode metallurgically combined with a copper current collector.
  • the present invention provides a method for preparing a silicon negative electrode of a lithium ion battery by laser cladding composite diffusion welding and dealloying.
  • the invention adopts the following technical scheme: preparing a cladding layer of an aluminum-silicon alloy by laser cladding technology, separating the cladding layer from the substrate to obtain an aluminum-silicon alloy precursor, and then using the diffusion welding to the aluminum-silicon alloy precursor and current collector After welding together, 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. under:
  • the cladding material is an aluminum silicon alloy
  • the base material is aluminum or aluminum alloy.
  • the cladding material is powder material, wire material or powder core wire, and the total chemical composition percentage is: Al: 50-95%, Si: 5-50%.
  • the silicon content is less than 5%, a silicon skeleton cannot be formed, and when the silicon content is more than 50%, coarse primary silicon is formed.
  • the laser cladding has a laser power density of 1.5 ⁇ 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 h.
  • the corrosive agent used in the 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 invention adopts the method of laser cladding composite diffusion welding and de-alloying to prepare a silicon negative electrode of a lithium ion battery, and the advantages thereof are as follows:
  • the active material silicon and copper current collector metallurgical combination can be directly used in the negative electrode structure of lithium ion battery.
  • the aluminum-silicon alloy precursor prepared by laser cladding technology has fine structure and uniform composition, which obviously improves the uniformity of silicon structure after chemical de-alloying.
  • 1 is a cross-sectional SEM image of the aluminum silicon precursor alloy of the present invention after diffusion welding with a copper current collector.
  • FIG. 2 is a surface SEM image of a silicon negative electrode of the present invention.
  • the aluminum silicon powder was placed on a base material aluminum plate (100 mm ⁇ 50 mm ⁇ 5 mm) with a preset thickness of about 1.5 mm, and was coated with an IPG fiber laser.
  • the laser power was 4.5 kW, the spot diameter was 5 mm, and the scanning speed was 2 mm. / s, shielding gas: argon gas, shielding gas flow rate: 15 L / min, and then using a wire cutting to separate the cladding layer from the substrate to obtain a precursor alloy material.
  • 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 then the atoms are mutually diffused for 45 minutes 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.
  • the first charge and discharge efficiency of the silicon negative electrode was 62.5%, the first charge and discharge capacity was 800 mAh/g, 500 mAh/g, and the capacity was 180 mAh/g after 20 cycles.
  • the aluminum silicon powder was placed on a base material aluminum plate (100 mm ⁇ 50 mm ⁇ 5 mm) with a preset thickness of about 2 mm, and cladding was performed using an IPG fiber laser YLS-6000.
  • the laser power was 5 kW
  • the spot diameter was 5 mm
  • the scanning speed was: 4mm/s
  • shielding gas argon gas
  • shielding gas flow rate 15L/min
  • the cladding layer is separated from the substrate by wire cutting to obtain a precursor alloy material.
  • 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 heat retention for 45 minutes, 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 8 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.
  • the first charge and discharge cycle efficiency was 86.66%
  • the first charge and discharge capacity was 600 mA.h/g, 520 mAh/g
  • the capacity was 150 mAh/g after 20 cycles.
  • the aluminum silicon powder was placed on a base material aluminum plate (100 mm ⁇ 50 mm ⁇ 5 mm), the preset thickness was about 1.5 mm, and laser cladding was performed using an IPG fiber laser YLS-6000.
  • the laser power was 5.5 kW, the spot diameter was 5 mm, and scanning was performed.
  • the speed is: 6 mm/s, shielding gas: argon gas, shielding gas flow rate: 15 L/min, and then the cladding layer is separated from the substrate by wire cutting to obtain a precursor alloy material.
  • 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 heat retention for 45 minutes, 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 12 hours, then washed three 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.
  • the first charge and discharge efficiency was 57.18%, the first charge and discharge capacity was 700 mAh/g, 400 mAh/g, and the capacity was 200 mAh/g after 20 cycles.
  • Example 1 is a cross-sectional SEM image of the aluminum silicon precursor alloy of Example 2 of the present invention after diffusion welding of a copper current collector.
  • Fig. 2 is a surface SEM image of a silicon negative electrode of Example 2 of the present invention.

Abstract

一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法，采用激光熔覆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。所述方法制备的硅负极可有效避免充放电过程中硅材料与集流体的脱落，且操作简单，效率高。

Description

一种采用激光熔覆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，是一种采用激光熔覆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
在便携式电子产品、电动汽车、无线通讯和可再生能源的储存与应用等领域，发展具有比能量高、循环寿命长的高性能锂离子电池迫在眉睫，其性能主要取决于电池负极材料。目前商品化的锂离子电池负极主要为石墨碳材料，具有循环稳定性好、寿命长的优点，但容量已接近理论值372mAh/g，不能满足大容量、高功率化学电源的广泛需求。
硅嵌锂能力很强，理论储锂容量高，为4200mAh/g，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。目前主要采用镁热还原法﹑电化学腐蚀法﹑化学腐蚀法﹑脱合金法制备微纳米硅粉末，通过将硅粉末和粘结剂、导电剂混合涂覆在集流体表面实现硅负极的结构化。但是，硅在锂化过程中会发生300％的体积变化，体积膨胀产生的较大应力对电极的结构造成破坏，导致电极开裂以及硅粉末从集流体上脱落，降低了硅负极的循环稳定性。此外，粘结剂、导电剂的加入减小了硅的质量，从而降低电池容量。
采用沉积法﹑磁控溅射等方法在集流体表面直接制备微纳米硅结构，在不添加粘结剂和导电剂的同时实现硅负极的结构化。Huabin Yang等利用直流磁控溅射法在铜箔上溅射2μm厚的微纳米硅薄膜，作为锂离子电池负极使用时，表现出良好的电化学性能。(Alumina-Coated Patterned Amorphous Silicon as the Anode for a Lithium-Ion Battery with High Coulombic Efficiency.Yu He et al.Adv.Mater.2011,23,4938–4941)。但是上述方法制备的微纳米硅结构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。
本发明采用激光熔覆复合扩散焊和脱合金的方法，首先采用激光熔覆技术在铝或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集流体扩散焊接在一起，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熔覆复合扩散焊和脱合金的方法制备锂离子电池硅负极的方法。
本发明采用以下技术方案：采用激光熔覆技术制备铝硅合金熔覆层，并将熔覆层从基体上分离，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。下：
采用激光熔覆技术制备前驱体时，熔覆材料为铝硅合金，基体材料为铝或铝合金。
采用激光熔覆技术制备前驱体时，熔覆材料是粉末材料、丝材或粉芯丝材，其总化学成份质量百分比为：Al：50～95％、Si：5～50％。硅含量小于5％时，不能形成硅骨架，硅含量大于50％时，形成粗大的初晶硅。
进一步，激光熔覆采用的激光功率密度为1.5×104～2.5×105W/cm2，扫描速度为2～30mm/s。
进一步，集流体材料为铜。
进一步，扩散焊温度450～550℃，压力0.5～2Mpa，焊接时间0.5～1.5h。
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。
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。
本发明采用激光熔覆复合扩散焊和脱合金的方法制备锂离子电池硅负极的方法，其优点如下：
1)活性物质硅和铜集流体冶金结合，可直接用于锂离子电池负极结构。
2)采用激光熔覆技术制备的铝硅合金前驱体，组织细小﹑成分均匀，明显改善了化学脱合金后硅结构的均匀性。
附图说明
图1是本发明的铝硅前驱体合金与铜集流体扩散焊之后截面SEM图。
图2是本发明的硅负极的表面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，但本不限于以下实施例。
实施例1
1.原料：
(1)铝硅粉末(-325目，99％)，Al:Si＝95:5wt.％。
(2)铝板，纯度：99.0％，尺寸：100mm×50mm×5mm。
(3)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：
将铝硅粉末置于基体材料铝板(100mm×50mm×5mm)上，预置厚度约为1.5mm，采用IPG光纤激光器进行熔覆，激光功率：4.5kW，光斑直径：5mm，扫描速度为：2mm/s，保护气：氩气，保护气流量：15L/min，然后采用线切割将熔覆层从基体上分离，得到前驱体合金材料。
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45分钟、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。硅负极首次充放电效率为62.5％，首次充放电容量分别为800mAh/g，500mAh/g，20次循环之后容量为180mAh/g。
实施例2
1.原料：
(1)铝硅粉末(-325目，99％)，Al:Si＝88:12wt.％。
(2)铝板，纯度：99.0％，尺寸：100mm×50mm×5mm。
(3)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：
将铝硅粉末置于基体材料铝板(100mm×50mm×5mm)上，预置厚度约为2mm，采用IPG光纤激光器YLS-6000进行熔覆，激光功率：5kW，光斑直径：5mm，扫描速度为：4mm/s，保护气：氩气，保护气流量：15L/min，然后采用线切割将熔覆层从基体上分离，得到前驱体合金材料。
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45分钟、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。首次充放电循环效率为86.66％，首次充放电容量分别为600mA.h/g，520mAh/g，20次循环之后容量为150mAh/g。
实施例3
1.原料：
(1)铝硅合金粉末(-325目，99％)，Al:Si＝50:50wt.％。
(2)铝板，纯度：99.0％，尺寸：100mm×50mm×5mm。
(3)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：
将铝硅粉末置于基体材料铝板上(100mm×50mm×5mm)，预置厚度约为1.5mm，采用IPG光纤激光器YLS-6000进行激光熔覆，激光功率：5.5kW，光斑直径：5mm，扫描速度为：6mm/s，保护气：氩气，保护气流量：15L/min，然后采用线切割将熔覆层从基体上分离，得到前驱体合金材料。
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45分钟、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。首次充放电效率为57.18％，首次充放电容量分别为700mAh/g，400mAh/g，20次循环之后容量为200mAh/g。
图1是本发明的实施例2的铝硅前驱体合金与铜集流体扩散焊之后截面SEM图。
图2是本发明的实施例2的硅负极的表面SEM图。

Claims (8)

  1. 一种采用激光熔覆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：采用激光熔覆技术制备铝硅合金熔覆层，并将熔覆层从基体上分离，得到铝硅合金前驱体，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所述的采用激光熔覆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：采用激光熔覆技术制备前驱体时，熔覆材料为铝硅合金，基体材料为铝或铝合金。
  3. 根据权利要求1所述的采用激光熔覆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：采用激光熔覆技术制备前驱体时，熔覆材料是粉末材料、丝材或粉芯丝材，其总化学成份质量百分比为：Al：50～95％、Si：5～50％。
  4. 根据权利要求1所述的采用激光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：激光熔覆采用的激光功率密度为1.5×104～2.5×105W/cm2，扫描速度为2～30mm/s。
  5. 根据权利要求1所述的采用激光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。
  6. 根据权利要求1所述的采用激光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0.5～1.5h。
  7. 根据权利要求1所述的采用激光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。
  8. 根据权利要求1所述的一种激光熔覆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/CN2017/080804 2016-05-02 2017-04-17 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法 WO2017190588A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610282672.5A CN105789560B (zh) 2016-05-02 2016-05-02 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法
CN201610282672.5 2016-05-02

Publications (1)

Publication Number Publication Date
WO2017190588A1 true WO2017190588A1 (zh) 2017-11-09

Family

ID=56400363

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/080804 WO2017190588A1 (zh) 2016-05-02 2017-04-17 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法

Country Status (2)

Country Link
CN (1) CN105789560B (zh)
WO (1) WO2017190588A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113865966A (zh) * 2021-08-19 2021-12-31 唐山钢铁集团有限责任公司 一种用于显示铝硅层富铝相枝晶的腐蚀液及枝晶测量方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105870405B (zh) * 2016-05-02 2018-02-09 北京工业大学 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
CN105789560B (zh) * 2016-05-02 2018-02-09 北京工业大学 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法
CN106848182B (zh) * 2017-01-12 2023-01-10 保力新(内蒙古)电池有限公司 一种锂离子电池负极极片的制作方法
CN108023065B (zh) * 2017-12-01 2020-06-19 北京工业大学 基于选区熔化技术的锂离子电池硅电极制造方法
CN108705076B (zh) * 2018-05-21 2019-12-03 江苏大学 稀土增强的激光增材制造用FeMnSi微纳粉芯丝材及其制备方法
CN108746581B (zh) * 2018-05-21 2019-12-03 江苏大学 稀土增强的激光增材制造用CuZnAl微纳粉芯丝材及其制备方法
CN108746586B (zh) * 2018-05-21 2019-12-03 江苏大学 激光增材制造用功能低损型形状记忆合金微纳粉芯丝材
CN108746584B (zh) * 2018-05-21 2019-11-29 江苏大学 硼化硅增强的激光增材制造用FeMnSi微纳粉芯丝材及其制备方法
CN108746582B (zh) * 2018-05-21 2019-12-03 江苏大学 稀土增强的激光增材制造用NiTi微纳粉芯丝材及其制备方法
CN108746583B (zh) * 2018-05-21 2019-12-03 江苏大学 激光增材制造用功能低损型CuZnAl微纳粉芯丝材及其制备方法
CN108746585B (zh) * 2018-05-21 2019-12-03 江苏大学 激光增材制造用功能低损型FeMnSi微纳粉芯丝材及其制备方法
CN114959683B (zh) * 2022-05-18 2024-03-26 江苏科技大学 一种锆合金表面激光熔覆方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1442916A (zh) * 2003-03-28 2003-09-17 中国科学院上海微系统与信息技术研究所 锂离子电池负极用硅铝合金/碳复合材料及其制备方法
JP2011006724A (ja) * 2009-06-24 2011-01-13 Sumitomo Light Metal Ind Ltd レーザ溶接性に優れた電池ケース蓋用アルミニウム合金板
CN102414333A (zh) * 2009-05-07 2012-04-11 奈克松有限公司 形成用于可再充电电池元的硅阳极材料的方法
CN103474632A (zh) * 2012-06-07 2013-12-25 中国科学院物理研究所 一种用于锂电池的负极材料及其制备方法和应用
CN104617276A (zh) * 2015-02-10 2015-05-13 南开大学 锂离子二次电池多孔硅/碳复合负极材料及其制备方法
CN105789560A (zh) * 2016-05-02 2016-07-20 北京工业大学 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1483212A (zh) * 2000-11-09 2004-03-17 FOC�����ϱ���ʯ�Ͳ�ҵ��˾ 超级电容器及其制造方法
CN100491593C (zh) * 2007-02-01 2009-05-27 天津工业大学 一种激光熔覆铝合金表面强化方法
KR101702987B1 (ko) * 2009-11-04 2017-02-23 삼성에스디아이 주식회사 리튬 이차 전지용 음극 및 이를 포함하는 리튬 이차 전지
CN102534467A (zh) * 2012-02-22 2012-07-04 浙江理工大学 一种铝合金表面制备高硅涂层的方法
CN105070894B (zh) * 2015-07-31 2018-02-23 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用多孔硅基复合负极材料、制备方法及用途

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1442916A (zh) * 2003-03-28 2003-09-17 中国科学院上海微系统与信息技术研究所 锂离子电池负极用硅铝合金/碳复合材料及其制备方法
CN102414333A (zh) * 2009-05-07 2012-04-11 奈克松有限公司 形成用于可再充电电池元的硅阳极材料的方法
JP2011006724A (ja) * 2009-06-24 2011-01-13 Sumitomo Light Metal Ind Ltd レーザ溶接性に優れた電池ケース蓋用アルミニウム合金板
CN103474632A (zh) * 2012-06-07 2013-12-25 中国科学院物理研究所 一种用于锂电池的负极材料及其制备方法和应用
CN104617276A (zh) * 2015-02-10 2015-05-13 南开大学 锂离子二次电池多孔硅/碳复合负极材料及其制备方法
CN105789560A (zh) * 2016-05-02 2016-07-20 北京工业大学 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113865966A (zh) * 2021-08-19 2021-12-31 唐山钢铁集团有限责任公司 一种用于显示铝硅层富铝相枝晶的腐蚀液及枝晶测量方法

Also Published As

Publication number Publication date
CN105789560A (zh) 2016-07-20
CN105789560B (zh) 2018-02-09

Similar Documents

Publication Publication Date Title
WO2017190588A1 (zh) 一种采用激光熔覆复合扩散焊和脱合金制备锂离子电池硅负极的方法
JP5951014B2 (ja) 高性能リチウムイオン電池における多孔質フィルムシリコン負極材料及びその製造方法
WO2017190587A1 (zh) 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
KR101621133B1 (ko) 리튬이온전지 3d다공성 실리카계 복합 음극재료 및 그 제조방법
JP5684207B2 (ja) シリコン又はシリコンベースの材料で構成される構造化粒子の製造方法及びリチウム蓄電池におけるそれらの使用
WO2018170976A1 (zh) 锂离子电池多孔结构Si/Cu复合电极及其制造方法
WO2018161742A1 (zh) 一种纳米多孔铜锌铝形状记忆合金及其制备方法与应用
JP4245270B2 (ja) 二次電池用電極の製造方法
CN108923037B (zh) 一种富硅SiOx-C材料及其制备方法和应用
CN110767891B (zh) 一种多孔球形硅基复合负极材料的制备方法
CN108963203A (zh) 一种碳包覆的多孔硅复合材料的制备方法
CN104810505A (zh) 一种锂离子电池负极片及其二次电池
CN109326798B (zh) 一种用于金属锂负极保护层的制备方法及应用
CN112768697A (zh) 一种复合锂金属负极集流体及其制备方法和应用
JP2021530835A (ja) 負極材料、およびその調製方法と用途
CN112820847A (zh) 硅基负极材料及其制备方法、锂离子电池以及电器
CN109524622A (zh) 基于铜锡合金的三维氧化亚铜-纳米多孔铜锂离子电池负极的一步制备法
WO2018113267A1 (zh) 锂离子电池负极材料及其制备方法
CN110534710A (zh) 硅/碳复合材料及其制备方法和应用
CN108023065B (zh) 基于选区熔化技术的锂离子电池硅电极制造方法
CN111082035B (zh) 片状-石墨烯@硅@无定型碳-三明治结构复合材料的制备方法及其产品和应用
CN106602001B (zh) 一种锂离子电池用多孔负极材料的制备方法及应用
CN112670490A (zh) 掺杂钛和/或锆的硅基负极材料及制备方法、锂离子电池
CN114695866A (zh) 一种锂离子电池双过渡金属氧化物负极材料的制备方法
CN109950521B (zh) 激光超非稳态扩散制备锂离子电池锡-石墨复合电极的方法

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17792414

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 17792414

Country of ref document: EP

Kind code of ref document: A1