Structural analyses have been performed for sulfuric acid (H2SO4) aqueous solutions containing Ti and/or Mn. These solutions are used as the positive electrolyte in the Ti–Mn redox flow (RF) battery, in which it had been found that adding Ti4+ in the positive electrolyte is very effective to reduce the MnO2 precipitation at a high state of charge. X-ray diffraction and x-ray absorption fine structure (XAFS) measurements were employed in order to obtain total correlation functions, T(r)’s, and coordination numbers around Mn and Ti in the solutions, respectively. The T(r)’s showed some peculiar peaks that were assigned to correspond to S—O, O—O, Mn—O, and Ti—O pairs in the solutions. The XAFS analysis demonstrated that both Mn and Ti have 6-coordinating oxygen atoms in the solutions. The classical molecular dynamics simulation was also carried out to obtain structural models of the solutions. By tuning the Born-Mayer type potential parameters, the T(r)’s calculated from the models showed good agreement with the experimental ones. Regarding the coordination number, the 6-coordinated Mn—O was reproduced successfully, while we need further investigation to find parameters that can reproduce the 6-coordinated Ti—O in the solutions. The simulation results also indicated the existence of Ti—SO4 bonds, which should promote the H+ dissociation from HSO4− and increase the H+ concentration in the solutions. This may be effective to suppress the MnO2 precipitation at a high state of charge in the RF battery.
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7 July 2018
Research Article|
July 05 2018
Structural analysis of sulfuric acid solutions containing Ti and Mn using x-ray diffraction, x-ray absorption fine structure, and molecular dynamics simulation
Kazuya Tokuda;
Kazuya Tokuda
1
Analysis Technology Research Center, Sumitomo Electric Industries, Ltd.
, 1-1-1, Koyakita, Itami, Hyogo 664-0016, Japan
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Junji Iihara;
Junji Iihara
1
Analysis Technology Research Center, Sumitomo Electric Industries, Ltd.
, 1-1-1, Koyakita, Itami, Hyogo 664-0016, Japan
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Yoshihiro Saito;
Yoshihiro Saito
1
Analysis Technology Research Center, Sumitomo Electric Industries, Ltd.
, 1-1-1, Koyakita, Itami, Hyogo 664-0016, Japan
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Atsunobu Masuno
;
Atsunobu Masuno
2
Institute of Industrial Science, The University of Tokyo
, 4-6-1 Komaba, Meguro-Ku, Tokyo 153-8505, Japan
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Hiroyuki Inoue
Hiroyuki Inoue
2
Institute of Industrial Science, The University of Tokyo
, 4-6-1 Komaba, Meguro-Ku, Tokyo 153-8505, Japan
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J. Chem. Phys. 149, 014503 (2018)
Article history
Received:
February 05 2018
Accepted:
June 15 2018
Citation
Kazuya Tokuda, Junji Iihara, Yoshihiro Saito, Atsunobu Masuno, Hiroyuki Inoue; Structural analysis of sulfuric acid solutions containing Ti and Mn using x-ray diffraction, x-ray absorption fine structure, and molecular dynamics simulation. J. Chem. Phys. 7 July 2018; 149 (1): 014503. https://doi.org/10.1063/1.5024950
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