Electrochemical metal 3D printing
Creators: name: Chen, Xiaolong
Publisher: name: Imperial College London
Year: 2021

description: Additive manufacturing (AM) is the process of creating 3D objects from digital models through the layer-by-layer deposition of materials. Electrochemical additive manufacturing (ECAM) is a relatively new technique which can create metallic components-based on depositing layers of metal onto the surface of the conductive substrate through the reduction of metal ions. It is advantageous compared to other metal AM processes due to the absence of high temperature processes enabling a lower-cost and safer fabrication process, however, to date, all of the presented ECAM methods (Localized Electrochemical Deposition (LED) and Meniscus Confined Electrochemical Deposition (MCED) have been designed to achieve micro or nanoscale structures with limited deposition rates, and only focused on single material fabrication. Furthermore, all the printed structures are limited in the complexity of geometries, with the majority being wire-based architectures of porous and rough morphologies, with limited characterisation of the properties of the printed structures. Additionally, there is no available system able to create temperature-reactive multi-metallic functional 4D structures and no research has been presented on the potential application of ECAM in the field of electrochemical energy storage devices. To bridge the gaps, this thesis investigates the development of a low-cost ECAM system capable of producing single and multi-metal structures by using multi-meniscus confined extrusion heads with volumetric deposition rates 3 times higher than what has previously been reported (~ 2×104 μm3.s-1), enabling large-scale fabrication of complex structures in multiple metallic materials. Scanning electron microscopy, X-ray computed tomography and energy dispersive X-ray spectroscopy measurements confirm that multi-metallic structures can be successfully created, with a tightly bound interface. Analysis of the thermo-mechanical properties of the printed strips shows that mechanical deformations can be generated in Cu-Ni strips at temperatures up to 300 °C, which is due to the thermal expansion coefficient mismatch generating internal stresses in the printed structures. Electrical conductivity measurements show that the bimetallic structures have a conductivity between those of nanocrystalline copper and nickel. Vicker’s hardness tests, show that there is a clear correlation between the applied potential and the hardness of the printed product, with higher potentials resulting in a harder deposition. This increased hardness was found to be due to the smaller grain sizes produced during higher potential deposition which restricted dislocation movement through the material. Finally, this thesis presents the first reported combination of electrochemical 3D printing and electrospinning for building a high mass loading and high performance copper-fibre based supercapacitor which enables the potential to create more integrated electrodes and eventually to enhance the performance of supercapacitors. The results highlight the influence of the substrate conditioning and the resulting effects on the wetting characteristics of the meniscus and the subsequent distribution of the deposition which impacts the electronic conductivity of the overall electrode. In this the fibre-based supercapacitor was constructed, the carbon was doped with manganese oxides to enhance the capacitance through introducing pseudo-capacitance at the cost of electronic conductivity. With the printing of current collectors, a highly bound electrode-current collector interface was formed, reducing the interfacial resistance and enhancing the accessible capacitance at high scan rates. In summary, this thesis presents work towards creating lower cost metal additive manufacturing through the development of an electrochemical metal 3D printer. A meniscus confined approach was taken to localise the deposition, with subsequent microstructural, mechanical and spectroscopic analysis of the printed product. Novel contributions to the field were further presented through developing understanding around multi-metal ECAM, with investigations around their coupled thermo-mechanical properties. Finally, the applicability of this approach was investigated in the field of electrochemical devices, where the influence of a porous substrate was investigated, whereby tightly bound and highly conductive current collectors were printed onto fibre based supercapacitors, enhancing their accessible capacitance. This work, therefore, demonstrates the potential for the ECAM approach in a diversity of applications.