Chlorine gas and sodium chlorate are two base chemicals produced through electrolysis of sodium chloride brine which find uses in many areas of industrial chemistry. Although the industrial production of these chemicals started over 100 years ago, there are still factors that limit the energy efficiencies of the processes. This review focuses on the unwanted production of oxygen gas, which decreases the charge yield by up to 5%. Understanding the factors that control the rate of oxygen production requires understanding of both chemical reactions occurring in the electrolyte, as well as surface reactions occurring on the anodes. The dominant anode material used in chlorate and chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high, the fundamental reasons for this high selectivity are just now becoming elucidated. This review summarizes the research, since the early 1900s until today, concerning the selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions, electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.
Recently, a need for mechanically flexible and strong batteries has arisen to power technical solutions such as active RFID tags and bendable reading devices. In this work, a method for making flexible and strong battery cells, integrated into a single flexible paper structure, is presented. Nano-fibrillated cellulose (NFC) is used both as electrode binder material and as separator material. The battery papers are made through a paper-making type process by sequential filtration of water dispersions containing the battery components. The resulting paper structure is thin, 250 mm, and strong with a strength at break of up to 5.6 MPa when soaked in battery electrolyte. The cycling performances are good with reversible capacities of 146 mA h g À1 LiFePO 4 at C/10 and 101 mA h g À1 LiFePO 4 at 1 C. This corresponds to an energy density of 188 mW h g À1 of full paper battery at C/10.
Hypochlorite decomposition has been investigated by the combined measurement of aqueous concentrations of total hypochlorite, chlorate, and chloride, as well as that of evolved oxygen. In all experiments, the initial concentrations of NaOCl and NaCl were 80 mM, and the temperature was 80 °C. The pH was kept constant in the range 5−10.5. The uncatalyzed decomposition of hypochlorite and the formation of chlorate and oxygen were all found to be third order of the form r i = k i [HOCl] 2 [OCl − ], and k O 2 was determined to be 0.046 M −2 s −1 . A reaction mechanism in which oxygen and chlorate formation share an intermediate is proposed. Several compounds were tested for catalytic effects. The addition of chloride salts of cobalt and iridium showed catalytic effects on oxygen formation. The addition of iridium chloride also catalyzed the formation of chlorate with increasing selectivity for chlorate with increasing pH.
Ruthenium dioxide as electrocatalyst on an activated cathode for chlorate production was investigated with respect to its activity towards hydrogen evolution, hypochlorite reduction, and chlorate reduction, respectively. Investigations were made in the presence, as well as in the absence, of a chromium hydroxide film in 1M
normalNaOH
and in typical chlorate electrolyte. Low overvoltages for hydrogen evolution were found and, at technical current densities, an effect of catalyst coating thickness. Commercial DSA® electrodes with
RuO2
as the active compound were tested as cathodes and were less active but more stable than the coatings produced by us. Hypochlorite and chlorate were reduced in the absence of chromate, chlorate reduction being fast on ruthenium dioxide compared to the other electrode materials and by far the dominating cathodic reaction in chlorate electrolyte without chromate and hypochlorite at 70°C, 3 kA/m2.
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