Capacitive deionisation (CDI) electrodes with identical composition were prepared using three deposition methods: (1) slurry infiltration by calendering (SIC), (2) ink infiltration dropwise (IID), and (3) ink deposition by spray coating (IDSC). The SIC method clearly showed favourable establishment of an electrode with superior desalination capacity. Desalination results showed that electrodes produced from slurries mixed longer than 30 min displayed a significant reduction in the maximum salt adsorption capacity, due to the agglomeration of carbon black. The electrodes were then thermally treated at 130, 250, and 350 °C. Polyvinylidene difluoride (PVDF) decomposition was observed when the electrodes were treated at temperatures higher than 180 °C. The electrodes treated at 350 °C showed contact angles of θ = 0°. The optimised electrodes showed a salt adsorption capacity value of 24.8 mg/g (130 °C). All CDI electrodes were analysed using specific surface area by N2 adsorption, contact angle measurements, conductivity by the four-point probe method and salt adsorption/desorption experiments. Selected reagents and CDI electrodes were characterised using thermogravimetric analysis coupled with mass spectrometry (TGA-MS) and differential scanning calorimetry (DSC), as well as scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS). Electrode structure and the development of the critical balance between ion- and electron- conductive pathways were found to be a function of the electrode slurry mixing procedure, slurry deposition technique and thermal treatment of the electrodes.