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these electrochemical couples in neutral and alkaline electrolyte. Note that an alkaline Zn-ClO2 battery can have 2.15V equilibrium cell voltage, which ranks amongst the highest of aqueous battery systems. Li et al. [8] introduced the chemical cost of storage energy ($/kWh), defined as the cost of starting electrode materials and electrolyte divided by stored energy, as a metric that represents the floor on cost of any battery system. The ClO2/ClO2- based battery chemistries mentioned above, assuming the use of NaClO2 as a starting material, have chemical costs of $3-$10/kWh. This chemical cost range compares favorably to Li-ion chemistries at $20-30/kWh, vanadium redox flow batteries at ~$100/kWh, and iron-air batteries at $1.3/kWh.[4,5] Rechargeable Zn-ClO2 cells are demonstrated in this work as an example. Table 1. Equilibrium cell voltages for aqueous battery systems using Cl(III)/Cl(IV) couple as the positive electrode. Positive electrode ClO2 / ClO2- ClO2 / ClO2- ClO2 / ClO2- ClO2 / ClO2- ClO2 / ClO2- Negative electrode Zn / Zn(OH)42- Zn / Zn2+ Fe / Fe(OH)2 Fe / Fe2+ S22-/S42- Electrolyte Alkaline Neutral Alkaline Neutral Alkaline Equilibrium cell voltage 2.15V 1.72V 1.85V 1.40V 1.38V While the electrochemical oxidation of chlorite to chlorine dioxide is well-known and is the basis for significant commercial production of ClO2, an industrial chemical most widely used for disinfection,[9] the reverse reaction, electrochemical reduction to ClO2-, appears little-studied. We reasoned that this reaction, ClO2- ↔ ClO2 + e-, might be highly reversible since only electron transfer, rather than atomic bond breaking or formation (e.g., as in chlorine oxidation 2Cl- ↔ Cl2 + 2e-), is required. Simple electron transfer is advantageously used for several transition metal cations used as redox-active battery electrodes in aqueous solution (e.g., Fe(II)/Fe(III), V(II)/V(III), V(IV)/V(V), Cr(II)/Cr(III), Ce(III)/Ce(IV), etc.), particularly in flow batteries.[10] However, to our knowledge anion analogs have not previously been identified for use as battery electrodes. 2PDF Image | Reversible Chlorite Chlorine Dioxide Anion Redox Storage
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