Abstract: Capacitive deionization has been considered an emerging desalination technique in recent years, especially for its economic and energy-saving characteristics for brackish water. However, there are currently few studies on chloride ion removal electrodes, and the slow desalination kinetics limits their development. Ar-NiCoAl-layered double hydroxide (LDHs)@ACC materials with an increased interlayer spacing were prepared by the in-situ growth of NiCoAl-LDHs nanosheet arrays on acid-treated carbon cloth (ACC) and subsequent argon plasma treatment. The carbon cloth suppresses the agglomeration of the NiCoAl-LDHs nanosheets and improves the electrical conductivity, while the plasma treatment increases the interlayer spacing of NiCoAl-LDHs and improves its hydrophilicity. This provides rapid diffusion channels and more interlayer active sites for chloride ions, achieving high desalination kinetics. A hybrid capacitive deionization (HCDI) cell was assembled using Ar-NiCoAl-LDHs@ACC as the chloride ion removal electrode and activated carbon as the sodium ion removal electrode. This HCDI cell achieved a high desalination capacity of 93.26 mg g⁻¹ at 1.2 V in a 1 000 mg L⁻¹ NaCl solution, a remarkable desalination rate of 0.27 mg g⁻¹ s⁻¹, and a good charge efficiency of 0.97. The capacity retention remained above 85% after 100 cycles in a 300 mg L⁻¹ NaCl solution at 0.8 V. The work provides new ideas for the controlled preparation of two-dimensional metal hydroxide materials with a large interlayer spacing and the design of high-performance electrochemical chlorine ion removal electrodes.