Lithium-ion batteries (Li-IBs) are the go-to option for energy storage in electric vehicles (EVs) due to their high energy density and power. The lack of competition in this space means that Li-IBs will continue to dominate EV applications into the future. Na-metal batteries (Na-MBs) may be an upcoming competitor to Li-IBs with similarly high energy density and power however fabrication challenges are a major barrier to metal battery commercialisation. Again, there is an alternative – the sodium anode-free battery (Na-AFB). The Na-AFB operates as a metal battery but is constructed without an alkali metal anode. Instead, a bare anodic current collector (CC) acts as a plating surface for alkali metal deposition during battery charging. The AFB has lower manufacturing and material costs and increased energy density. However, it is still not commercially viable due to inadequate cycle lifespan from lost active material. Active material losses are reduced when the alkali metal plates evenly and remains well adhered to the CC, but this can only occur if deposition on the CC is favourable. Additionally, the solid electrolyte interphase (SEI) that forms between the electrodes and electrolyte must adequately protect the electrodes during cycling. The aim of this project is to improve metal plating in Na-AFBs and to enhance our understanding of heterogenous plating in electrochemical systems. Chapter 1 introduces the project background and outlines the research scope and objectives. This is followed by Chapter 2 which reviews the published literature relating to: (1) The commercial prospects of Na-AFBs, (2) the metal plating process, and (3) current research concerning CC design, natural SEI, artificial SEI, and characterisation techniques.In the first experimental chapter (Chapter 3), Zn, Cu, and α-brass CCs were predicted to have high metallic lattice compatibility with Na. This compatibility was hypothesised to benefit Na plating and improve cell lifespan by decreasing the deposition energy barrier. The results show Zn was the best performing CC, inducing a small nucleation overpotential of -16.5 mV and increasing cycling stability to over 200 cycles with an average Coulombic efficiency of 98.9%. It is proposed that this high performance was due not only to the high lattice compatibility between Na and Zn, but also the formation of a favourable ZnF2-rich SEI.The objective in Chapter 4 was to confirm epitaxial Na metal plating on Zn CCs via the predicted low-misfit plane pairings. Such interactions involving alkali metals had not previously been observed. Here, a new transmission electron microscopy (TEM) preparation procedure was developed where small amounts of Na were electroplated onto a thinned Zn substrate in such a way that epitaxial planes between the Na and Zn could be identified. This procedure led to the first non-cryogenic, atom-resolution TEM images of Na metal nuclei and identified epitaxial growth of Na (002) planes on (01-11) Zn planes. The Zn CCs improved cycling life, however full cell lifespan was still insufficient. In Chapter 5, Na3V2(PO4)3 AFB full cell lifespan was improved by optimising initial cycling parameters to improve SEI formation. First, key parameters were screened including capacity, cutoff voltage, cycling current, and final deposition current. The statistically significant capacity and final current parameters were then optimised in a second stage. Subsequent full cells had improved lifespans of 137 cycles. The impact of capacity and final current on the composition of the SEI was analysed using X-ray photoelectron spectroscopy, which showed that the optimal conditions produced a thin and conductive SEI. Analysing the SEI also suggested a more complicated structure than that typically reported in published literature which may inspire future works.