Improved titanium-manganese flow battery with high capacity and high stability

Nan, Mingjun; Qiao, Lin; Liu, Yuqin; Zhang, Huamin; Ma, Xiangkun

doi:10.1016/j.jpowsour.2022.230995

Cited by 18 publications

(17 citation statements)

References 22 publications

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“…On the other hand, the Ti 4+ ions are mostly reduced to Ti 3+ in the anolyte with SOC of 80% by the charge process. Generally, the oxidation reactions are considered as follows [11–15,43] …”

Section: Resultsmentioning

confidence: 99%

“…Generally, the oxidation reactions are considered as follows. [11][12][13][14][15]43] Negative Electrode:…”

Section: Ti/mn L-edge Xas For the Catholyte And Anolyte Samplesmentioning

confidence: 99%

“…However, the material cost of vanadium is problematic to spread the V RFBs. On the other hand, Ti−Mn RFBs have been studied in order to further improve the energy density and reduce the material costs [11–15] . An important subject for the practical use of the Ti−Mn RFBs is to improve the stability of the catholyte.…”

Section: Introductionmentioning

confidence: 99%

“…An important subject for the practical use of the Ti−Mn RFBs is to improve the stability of the catholyte. When the state of charge (SOC) is high, precipitates are created in the catholyte, which decrease the energy density [11–15] . Thus, stabilization of the catholyte such as addition of some additives has been attempted.…”

Section: Introductionmentioning

confidence: 99%

“…In parallel, the chemical state and redox reaction of the electrolytes of Ti−Mn RFBs should be clarified by precise analyses, which lead to establishment of strategies to develop novel electrolytes with high stability. The catholyte/anolyte of Ti−Mn RFBs is generally made with aqueous solutions of MnSO 4 ⋅ n H 2 O, TiOSO 4 ⋅ n H 2 O, and H 2 SO 4 [11–15] . The formal valence of Ti and that of Mn in the initial state are thought to be Ti 4+ and Mn 2+ , respectively.…”

Section: Introductionmentioning

confidence: 99%

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Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Asakura

Hosono

Kitamura

et al. 2022

Chemistry An Asian Journal

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We performed X-ray absorption studies for the electrolytes of a TiÀ Mn redox flow battery (RFB) to understand the redox reaction of the Ti/Mn ions and formation of precipitates in charged catholyte, because suppression of the disproportionation reaction is a key to improve the cyclability of TiÀ Mn RFB and enhance the energy density. Hard X-ray absorption spectroscopy with a high transmittance and soft X-ray absorption spectroscopy to directly observe the 3d orbitals were complementarily employed. Moreover, the Ti/ Mn 3d electronic structure for each precipitate and solution in the charged catholyte was investigated by using scanning transmission X-ray microscopy: the valence of Mn in the precipitate is mostly attributed to 4 + , and the solution includes only Mn 2 + . This charge disproportionation reaction should occur after the Mn ions in the catholyte should be oxidized from Mn 2 + to Mn 3 + by charge.

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Section: Resultsmentioning

confidence: 99%

“…Generally, the oxidation reactions are considered as follows. [11][12][13][14][15]43] Negative Electrode:…”

Section: Ti/mn L-edge Xas For the Catholyte And Anolyte Samplesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Asakura

Hosono

Kitamura

et al. 2022

Chemistry An Asian Journal

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Lithium‐Free Redox Flow Batteries: Challenges and Future Prospective for Safe and Efficient Energy Storage

Kanti Hazra,

Kim,

Meskher

et al. 2024

Batteries & Supercaps

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Considering the costs, waste, and impact on the environment of current energy consumption, accurate, cost‐effective, and safely deployed energy storage systems are required. Lithium‐free redox flow batteries (RFBs) are a feasible solution. RFBs can store enormous amounts of energy effectively and are increasingly used for large‐scale applications. The use of RFBs has significantly enhanced the performance of energy storage systems and effectively reduced the costs and wastage of energy storage operations. Vanadium‐based RFBs are an emerging energy‐storage technology being explored for large‐scale deployment owing to their numerous benefits, including zero cross‐contamination, scalability, flexibility, extended life cycle, and nontoxic working state. This study describes the fundamental operating principles of redox flow battery‐based systems as well as the design considerations and constraints placed on each component. It discusses recent progress in the design and deployment of RFBs for energy‐related applications and the remaining obstacles and prospects. Finally, this study highlights the enormous potential of RFBs and suggests some solutions to scale up the use of RFBs in the near future.

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Boosting the Areal Capacity of Titanium‐Manganese Single Flow Battery by Fe²⁺/Fe³⁺ Redox Mediator

Nan

Liu

et al. 2022

Small Methods

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teries are also attempted. [5,6] However, the poor reversibility of the MnOOH/MnO 2 redox couple limits further development.Additionally, Mn 2+ /Mn 3+ redox coupled with high voltage and high activity was widely used in acid-aqueous manganesebased batteries. [7][8][9][10][11][12] However, the Mn 3+ ions spontaneously convert into Mn 2+ ions and uncontrolled MnO 2 particles (the disproportionation reaction of Mn 3+ ) in an aqueous electrolyte, which shortens the cycling life of the battery. Then, some strategies, for example, introducing inorganic additives (H 2 SO 4 , [7] VO 2+ , [8][9][10] TiO 2+[11,12] ) have been tried. The inorganic additives could alleviate the disproportionation reaction of Mn 3+ and increase the cycle performance of the battery to a certain extent. Unfortunately, the battery finally stops working due to the blockage of MnO 2 at high SOC. So, it is necessary to limit the SOC of the batteries simultaneously, which would lead to low electrolyte utilization and serious capacity loss. Compared with the single electron transfer reaction of MnOOH/MnO 2 or Mn 2+ /Mn 3+ mentioned above, the deposition-dissolution reaction of Mn 2+ /MnO 2 (s) with the two-electron transfer was applied successfully in the aqueous manganesebased battery. [13,14] The conversion of Mn 2+ directly to MnO 2 without Mn 3+ was achieved by the constant-voltage charging mode, [15] adding acetate-based additive, [16] or bromide-acetate coadditive. [17] However, the low voltage of the Mn 2+ /MnO 2 redox couple (+1.228 V vs SHE) limits the energy density of the battery.Given that, our group proposed an electrochemical-chemical coupling strategy, where Mn 2+ /Mn 3+ redox couple with the high voltage of 1.51 V (vs SHE) was used in the charging process and MnO 2 from the disproportionation reaction of Mn 3+ was converted into Mn 2+ in the discharging process. [18,19] Benefiting from the TiO 2+ additives, the particle size and crystal structure of MnO 2 from the disproportionation reaction were adjusted, and the polarization of the battery was also alleviated. Moreover, thanks to the specific battery structure of the titanium-manganese single flow battery (TMSFB) (Scheme 1), where the catholyte was sealed in the cathode without pump and lines, the risk of the particle blockage was avoided. [18] Therefore, both long life and high voltage of Mn 2+ /Mn 3+ were achieved in TMSFB for the electrolyte with 0.5 m MnSO 4 . However, the areal capacity of the TMSFB just reached 10 mAh cm −2 , [18] and then TMSFB faced capacity decay with unknown reasons for the higher concentration of MnSO 4 electrolyte. Aqueous manganese-based flow batteries (AMFBs) have attracted great attention due to the advantages of low cost and environmental friendliness. Extending the cycle life of AMFBs has long been a challenging theme. The titanium-manganese single-flow batteries (TMSFB) are promising due to their special structure and electrolyte composition. However, TMSFB with high areal capacity faces capacity decay for unknown reasons. In this work, the capaci...

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Improved titanium-manganese flow battery with high capacity and high stability

Cited by 18 publications

References 22 publications

Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Lithium‐Free Redox Flow Batteries: Challenges and Future Prospective for Safe and Efficient Energy Storage

Boosting the Areal Capacity of Titanium‐Manganese Single Flow Battery by Fe²⁺/Fe³⁺ Redox Mediator

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Improved titanium-manganese flow battery with high capacity and high stability

Cited by 18 publications

References 22 publications

Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Redox Reaction in Ti−Mn Redox Flow Battery Studied by X‐ray Absorption Spectroscopy

Lithium‐Free Redox Flow Batteries: Challenges and Future Prospective for Safe and Efficient Energy Storage

Boosting the Areal Capacity of Titanium‐Manganese Single Flow Battery by Fe2+/Fe3+ Redox Mediator

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Product

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Boosting the Areal Capacity of Titanium‐Manganese Single Flow Battery by Fe²⁺/Fe³⁺ Redox Mediator