复合铜集流体制造工艺及其支撑层改性方案综述

A Review of the Manufacturing Process of Composite Copper Current Collectors and the Modification Schemes of Their Support Layers

  • 摘要: 复合铜集流体通过“铜膜-高分子支撑层-铜膜”三层结构设计,以轻量化(铜用量减少50%以上)显著提升锂离子电池能量密度,以纵向断裂与横向绝缘特性可阻断热失控蔓延,同步解决能量密度与安全性间的矛盾,在新能源市场领域具有重要应用价值。其制造工艺分为三类路径:一步法(全干法,以磁控溅射设备升级为迭代方向,设备投资大)、二步法(磁控溅射-电化学镀,当前产业化主流)、三步法(磁控溅射-真空蒸镀-电化学镀,蒸镀提高铜层完整性,但高温易损伤基膜)。核心制造工艺为磁控溅射镀膜,通常采用卷对卷镀膜方式。复合铜集流体支撑层研究聚焦PP基膜(成本低、耐电解液腐蚀、断裂伸长率高),但其非极性表面导致PP/Cu界面结合力不足。改性方案分两类:表面原位改性(等离子体刻蚀和化学刻蚀,通过增加粗糙度和引入极性官能团强化机械互锁,但存在时效性衰退和基膜损伤风险);涂层功能修饰(如TA-APTES纳米球和PDA涂层,通过C=O和N-H与铜配位实现化学键合,更具潜力)。复合铜集流体产业化需解决界面强化和工艺效率问题,未来研究应整合材料创新(如功能涂层)与设备升级,推动其规模化应用。

     

    Abstract: The composite copper current collector, designed with a three-layer structure of "metal-polymer support layer-metal", significantly enhances the energy density of lithium-ion batteries by reducing copper usage by more than 50% and achieving lightweighting. Its longitudinal fracture and lateral insulation properties can prevent the spread of thermal runaway, simultaneously addressing the industry's contradiction between energy density and safety, and exhibits significant application potential in the new energy market. Its manufacturing process is divided into three categories: one-step method (all dry process, with the upgrade of magnetron sputtering equipment as the iterative direction, but with high equipment investment), two-step method (magnetron sputtering-electrochemical plating, the current mainstream of industrialization), and three-step method (magnetron sputtering-vacuum evaporation-electrochemical plating, where evaporation improves the integrity of the copper layer but is prone to damage the base film at high temperatures). Among these, the core of the manufacturing process is magnetron sputtering, which typically uses a roll-to-roll coating method. Research on the support layer of the composite copper current collector focuses on PP base films (low cost, resistant to electrolyte corrosion, and high elongation at break), but the non-polar surface of PP leads to insufficient interfacial bonding strength between PP and Cu. The modification schemes are divided into two types: in-situ surface modification (plasma etching and chemical etching, which enhance mechanical interlocking by increasing roughness and introducing polar functional groups, but have risks of time-dependent degradation and base film damage); and coating functional modification (such as TA-APTES nanospheres and PDA coatings, which achieve chemical bonding through C=O and N-H coordination with copper, and are more promising). The industrialization of composite copper current collectors needs to solve the problems of interface strengthening and process efficiency. Future research should integrate material innovation (such as functional coatings) and equipment upgrades to promote its large-scale application.

     

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