Pushing the limit of layered transition metal oxides with heterolattice oxygen-mediated redox for capacitive deionization

利用异质晶格氧介导氧化还原反应,突破层状过渡金属氧化物在电容去离子领域的极限

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Abstract

The use of transition metal oxides to achieve capacitive deionization (CDI) via salt adsorption is based mainly on cation electrochemistry. Activating anionic (oxygen) redox chemistry can enable additional salt adsorption on transition metal oxides, but most conventional lattice oxygen‒metal configurations require high voltages (>4 V) for activation and are prone to lattice oxygen loss. Here, we propose a heterolattice oxygen-mediated redox mechanism to activate oxygen (O(2p)) redox at <2 V by constructing a V(2)O(5)/V(2)CO(2p) heterostructure. Unlike the synthetic strategy based on excess Li/Na, we develop a barrier strategy based on an oxidative nucleophilic reaction using V(2)CF(x) as a precursor to induce the formation of heterolattice oxygen in V(2)O(5)/V(2)CO(2p) heterostructures. Consequently, ultrahigh CDI performance is achieved, including a salt adsorption capacity of 185.8 mg g(-1) at 1.4 V and a salt adsorption rate of 12.1 mg g(-1) min(-1), which exceed those of reported other faradaic materials. Further mechanistic studies reveal that the induced O(2p) electrons that dominate the Fermi level provide an additional pathway for electron movement, activating additional oxygen redox processes and forming a sodium-rich vanadate (Na(4)V(2)O(7))/V(2)CO(2p) heterostructure. This strategy provides insights into the development of high-performance CDI materials with oxygen redox based on lattice oxygen‒metal configurations.

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