新能源产业的快速发展对锂电池储能提出更高要求，锂电池负极材料在电池工作中起着能量的储存与释放的作用，因此负极材料的研发成为提高电池能量密度的关键。平面铜箔作为传统的锂电池负极材料，在充放电过程中难以缓解金属锂的体积膨胀和抑制锂枝晶的生长，已经无法满足高功率负极材料的要求。新一代负极材料中具备极高比表面积的多孔铜箔不仅可以为金属锂提供更多容纳空间，缓解锂枝晶的生长，还可以承载更多的活性物质，增大电池容量。因此，设计具有三维空间结构的多孔铜箔成为一种提升锂电池性能的有效策略。

本课题采用“低铜高酸”的基础电解液探究稳定、高效的电沉积工艺参数，明确三种添加剂及其对应的复合添加剂在多孔铜箔电沉积过程中的浓度配比及作用机制，以期优化制备工艺，提升多孔铜箔品质。本课题主要研究内容及结论如下：

(1) 研究了铜离子浓度、电沉积时间以及电流密度对多孔铜箔微观组织以及电学性能的影响。研究表明：选用稳定的基础电解液25 g/L Cu²⁺、110 g/L H₂SO₄，合适的工艺参数电沉积时间25 s、电流密度3 A/cm²，制备的多孔铜箔表面孔径分布均匀且孔壁间结合力强。此时，沉积层平均孔径约68.15 μm，孔面积占比达41.43%，表面粗糙度Sa和Sz分别达29.08 μm和238 μm，表明所制备的多孔铜箔具有较高的比表面积。此外，多孔铜箔较低的电阻(11.98 mΩ)使其具有良好的导电性。Li/Cu半电池测试结果显示多孔铜箔性能明显优于商用平面铜箔。电化学阻抗谱表明多孔铜集流体具备更低的电荷转移阻抗。

(2) 研究了Cl^-(浓HCl)、羟乙基纤维素(HEC)和聚乙二醇(PEG)三种单一添加剂对多孔铜箔微观组织以及电学性能的影响，进一步研究其对多孔铜箔电沉积作用机制。结果表明：Cl^-、HEC和PEG的加入均会起到细化晶粒的作用。Cl^-可以促进铜沉积量，而HEC和PEG则抑制铜沉积量。当Cl^-浓度为20 mg/L时，沉积层孔径尺寸较大，孔壁间致密性高，铜箔厚度增加；当HEC浓度为9 mg/L时，沉积层表面晶粒细小，微孔数量多且分布均匀，铜箔光亮度明显增加；当PEG浓度为15 mg/L时，沉积层枝晶状特征减弱，铜晶粒以颗粒状平整的堆叠生长。此外，当Cl^-浓度为20 mg/L时，所制备的多孔铜集流体表现出良好的循环性能和电导率。

(3) 研究了Cl^-、HEC和PEG组成的双组份和三组份复合添加剂体系对多孔铜箔微观组织及电学性能的影响，进一步研究了三组份添加剂体系对多孔铜箔电沉积作用机制。结果表明：在一定浓度内的Cl^-和HEC复合添加剂体系制备的多孔铜箔孔壁间致密性明显提升；Cl^-和PEG复合添加剂体系制备的多孔铜箔表面微孔数量明显增多，孔径尺寸明显减小；三组份复合添加剂体系制备的多孔铜箔沉积层孔径尺寸进一步减小，三维多孔结构特征显著。当三组份添加剂体系浓度为Cl^-浓度20 mg/L，HEC浓度6 mg/L，PEG浓度7 mg/L时，多孔铜箔表面微孔数量多且分布均匀，同时，该浓度下的多孔铜箔具备较低的电阻值(8.21 mΩ)，并且其装配的半电池具备优异的循环性能和导电性能。

The rapid development of the new energy industry has put forward higher requirements for lithium battery energy storage. Lithium battery anode material plays the role of energy storage and release in the working of the battery, so the development of anode material becomes the key to improve the energy density of the battery. Planar copper foil as a traditional lithium battery anode material, it is difficult to alleviate the volume expansion of lithium metal and inhibit the growth of lithium dendrites during the charging and discharging process, which has failed to meet the requirements of high-power anode materials. Among the new generation of anode materials, porous copper foil with a high specific surface area can not only provide more space for lithium metal and alleviate the growth of lithium dendrites, but also carry more active material and increase the battery capacity. Therefore, the design of porous copper foils with a three-dimensional (3D) space structure has become an effective strategy to improve the performance of lithium batteries.

In this study, the basic electrolyte 'low copper and high acid' is used to explore stable and efficient electrodeposition process parameters. The concentration ratios and mechanisms of the three additives and their corresponding composite additives in the electrodeposition process of porous copper foil are clarified, aiming to optimize the preparation process and improve the quality of porous copper foil. The main research and conclusions of this paper are as follows:

(1) The effects of copper ion concentration, electrodeposition time and current density on the microstructure and electrical properties of the porous copper foil were investigated. The results show that the porous copper foil prepared with the stable basic electrolyte 25 g/L Cu²⁺ and 110 g/L H₂SO₄，and the appropriate process parameters of 25 s electrodeposition time and current density of 3 A/cm² has a uniform pore size distribution and a strong adhesion between the pore walls. Simultaneously, the average pore size of the deposited layer is about 68.15 μm, with a pore area ratio of 41.43% and the surface roughness Sa and Sz reach 29.08 and 238 μm, respectively, indicating that the prepared porous copper foil possesses a high specific surface area. In addition, the low resistance of the porous copper foil (11.98 mΩ) gives it good electrical conductivity. The test results of Li/Cu half-cells show that the porous copper foil performance is significantly better than that of commercial planar copper foils. Electrochemical impedance spectra indicate that the porous copper collector has a lower charge transfer impedance.

(2) The effects of three single additives such as Cl^- (HCl), hydroxyethyl cellulose (HEC) and polyethylene glycol (PEG), on the microstructure and electrical properties of porous copper foils were studied, and the mechanism of electrodeposition on porous copper foil was further explored. The results show that the addition of Cl^-, HEC and PEG play a role in refining the grain size. The Cl^- can promote the copper deposition, while the HEC and PEG inhibited the copper deposition. When the concentration of Cl^- is 20 mg/L, the pore size of the deposited layer is larger, the denseness between the pore walls is higher, and the thickness of the copper foil increases. when the concentration of HEC is 9 mg/L, the surface grains of the deposited layer are fine, the number of micro-pores is large and uniformly distributed, and the brightness of the copper foil increases significantly. when the concentration of PEG is 15 mg/L, the dendritic characteristics of the deposited layer are weakened, and the copper grains grow in flat stacks of granular shape. In addition, the porous copper collectors prepared at a Cl^- concentration of 20 mg/L presented good circulation performance and electrical conductivity.

(3) The effects of the two-component and three-component composite additive systems consisting of Cl^-, HEC and PEG on the microstructure and electrical properties of porous copper foils were studied, and the mechanism of the effect of the three-component additive systems on the electrodeposition of porous copper foils was further explored. The results demonstrate that the density between the pore walls of the porous copper foil prepared by the Cl^- and HEC additive system at a certain concentration is significantly improved. the number of micropores on the surface of the porous copper foil prepared by the Cl^- and PEG additive system is significantly increased, and the pore size is significantly reduced. the pore size of the deposited layer of the porous copper foil prepared by the three-component additive system is further reduced and the 3D porous structure characteristics are significant. When the concentration of the three-component additive system is Cl^- 20 mg/L, HEC 6 mg/L and PEG 7 mg/L, the porous copper foil exhibits a high number of micropores with a uniform distribution. Meanwhile, the porous copper foil has a lower resistance value (8.21 mΩ) and the assembled half-cell has excellent cycling performance and electrical conductivity.

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