Energy storage technologies based on solid-liquid redox-targeting reactions: materials, devices, and kinetics

doi:10.11949/0438-1157.20231268

Abstract

Abstract:

With the advancement of the carbon neutrality and the rapid development of renewable energy, energy storage technology has become a crucial pillar for addressing energy transition and sustainable development. Redox flow battery (RFB) is an electrochemical device used for large-scale energy storage. It has the characteristics of flexible design, large storage capacity, long cycle life, and high safety. However, limited by the solubility of redox mediator molecules, its energy density is relatively low, and there are few practical systems. To meet this challenge, energy storage technologies based on solid-liquid redox-targeting reactions, i.e. redox-targeting flow batteries (RTFBs) have emerged to enhance energy density, maintain excellent flowability and elevate the constraint of traditional RFBs. This review provides a comprehensive perspective of recent research progress in materials, devices, and kinetics related to RTFBs including characteristics of various materials, the design and performance of devices, as well as the characterization and modeling of kinetic processes. The bottleneck of current research is summarized and the insights into future development trends are also provided.

Key words: electrochemistry, redox-targeting reactions, redox-targeting flow batteries, electrolyte, flow batteries, chemical reactors

摘要：

随着双碳政策的推进和可再生能源的快速发展，能源存储技术成为解决能源转型和可持续发展的关键支撑。氧化还原液流电池（RFB）是一种用于大规模储能的电化学器件，具有设计灵活、存储容量大、循环寿命长、安全性高等特点。然而受氧化还原介质分子溶解度的限制，其能量密度相对较低，同时可实用化的体系较少。为解决这一问题，基于固液氧化还原靶向反应的能量存储技术应运而生。氧化还原靶向液流电池（RTFB）在提高能量密度的同时保持良好流动性，克服了传统RFB的限制。综述了近年来该技术在材料、器件及动力学方面的研究进展，包括各种材料的特点、器件的设计及性能以及动力学过程的表征与建模。最后总结当前研究的不足之处并展望未来发展趋势。

关键词: 电化学, 氧化还原靶向反应, 氧化还原靶向液流电池, 电解液, 液流电池, 化学反应器

CLC Number:

TQ 152

Yunxuan LI, Xinyue LIU, Xi CHEN, Wen LIU, Mingyue ZHOU, Xingying LAN. Energy storage technologies based on solid-liquid redox-targeting reactions: materials, devices, and kinetics[J]. CIESC Journal, 2024, 75(4): 1222-1240.

李云璇, 刘新悦, 陈熙, 刘文, 周明月, 蓝兴英. 基于固液氧化还原靶向反应的能量存储技术：材料、器件及动力学[J]. 化工学报, 2024, 75(4): 1222-1240.

Figures/Tables 9

Fig.1 (a) Schematic diagram of RFB[7];(b) Schematic diagram of RTFB; (c) The redox-targeting reaction principle of freely diffusing shuttle molecules S and insulating electrode materials such as LiFePO4[8]; (d) Energy diagram and charge transfer of SMRT reaction between RM+ and LiFePO4[9]

Table 1 Characteristics of redox pairs in conventional RFB and RTFB

场景	电对的作用	电对的溶解度要求	电对与电池性能关联
常规RFB	储能介质	大于1 mol/L	决定能量密度、功率性能
氧化还原靶向RFB	传递能量+储能	大于0.05 mol/L	决定功率性能

Fig.2 (a) Redox potential of metal ions[16]; (b) Comparison of redox potential and equivalent electron concentration of organic small molecules[33]; (c) Redox potential of intercalation materials

Table 2 Electrochemical performance of traditional flow batteries

指标

全钒

电池^[54]

铁铬

电池^[55]

锌铁

电池^[56]

锌溴

电池^[57]

Fig.3 (a) Schematic diagram of a redox flow sodium-ion battery based on redox-targeting reaction[45]; (b) Schematic diagram of redox-targeting vanadium flow battery (RT-VRB)[58]; (c) Schematic diagram of the structure and operation of a redox mediated zinc air fuel cell (RM-ZAFC)[69]; (d) Schematic diagram of solar rechargeable batteries based on redox-targeting reaction[70]

Fig.4 (a) An electrochemical approach based on a double-layer electrode to determine the reaction kinetics[82]; (b) FTIR spectra of standard PB and BG, Br2-oxidized PB, and Br--reduced BG[66]; (c) Fe 2p XPS spectra of PB and Br2-oxidized PB[66]; (d) XRD patterns of NVP collected from the catholyte tank before and after charging[45]; (e) ND patterns of pristine and partially reduced PB by [Fe(CN)6]4-[66]; (f) The most probable structures of pristine (bottom) and reduced PB (or PW, top) unit cells obtained from the refinement of ND patterns[66]

Fig.5 (a) Interfacial charge-transfer kinetics of redox-targeting reactions measured by SECM[83]; (b) In situ UV-Vis spectra of DHPS electrolyte before and after addition of excess zinc[84]; (c) Operando ATR-FTIR spectra of DHPS electrolyte recorded during resting, after adding excess zinc and during discharge process[84]; (d) Fluorescence microscopic images of a planar quartz reactor filled with 20 mmol/L fully reduced FL upon reacting with a compact NVP granule assembly[45]

Fig.6 (a) Utilization of LiFePO4 as a function of power in an SMRT system and correlation of power and energy at different utilizations of solid material[9]; (b) lgieffn- η relationship (including polarization curve)[84]; (c) Kinetic data of SMRT reaction in NVP/MPTZ system[45];(d) Oxidation kinetics of LFP30 oxidized by [Fe(CN)6]3- [85]

Fig.7 (a) An energy-storage tank filled with active materials[10]; (b) Photograph of a bottle filled with LiFePO4 processed into granules[9]; (c) Adsorption column to remove a substance[88]; (d) The utility model relates to a sewage treatment device[89]; (e) Outlook for future study of redox-targeting flow battery energy storage technology

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