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A Review of Inorganic Aqueous Flow Battery

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

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1402 -1413.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1402-1413 DOI: 10.7536/PC210727
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A Review of Inorganic Aqueous Flow Battery
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Abstract

Flow battery (FB), an important technology for large-scale energy storage, has the advantages of high safety, long cycle life, environmental friendliness, and so on. FBs can stabilize the fluctuation of renewable energy output, help to promote the large-scale application of renewable energy, and further achieve the goal of peak carbon dioxide emissions and carbon neutrality. Inorganic aqueous flow batteries with high energy efficiency and stable cycle performance are attracting increasing attention. This paper introduces the technology status and application demonstration of the commercial inorganic aqueous flow battery. Then, the principle, current state, and technology challenges of new-type inorganic aqueous flow batteries are summarized. Finally, this paper points out the goals of inorganic aqueous flow batteries for the next 15 years, pointing out the development direction of inorganic aqueous flow batteries.

Contents

1 Introduction

2 liquid-liquid aqueous flow battery

2.1 Fe-Cr flow battery

2.2 Vanadium flow battery

2.3 Other types of liquid-liquid aqueous flow battery

3 Liquid-deposition aqueous flow battery

3.1 Zn-Br flow battery

3.2 Other types of liquid-deposition aqueous flow battery

4 Conclusion and outlook

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Keywords

flow battery / inorganic aqueous flow battery / liquid-liquid aqueous flow battery / liquid-deposition aqueous flow battery

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Mingjun Nan, Lin Qiao, Yuqin Liu, Huamin Zhang, Xiangkun Ma. A Review of Inorganic Aqueous Flow Battery. Progress in Chemistry, 2022, 34(6): 1402-1413 DOI:10.7536/PC210727

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1 Introduction

With the rapid development of society and economy, human demand for energy is increasing. At present, coal, oil, natural gas and other traditional fossil energy are still the main energy consumed by human beings, but the extensive use of fossil energy will bring serious environmental problems and the greenhouse effect of the earth. Looking forward to the future, in addition to the rational development and clean utilization of fossil energy and the development of hydropower resources, it is necessary to further develop renewable energy, including nuclear energy, solar energy, biomass energy, hydrogen energy, geothermal energy, tidal energy and wind energy[1]. China has made it clear that China's carbon dioxide emissions will peak by 2030 and achieve carbon neutrality by 2060. By 2030, the proportion of non-fossil energy in primary energy consumption will reach 25%, and the installed capacity of wind and solar power will reach more than 1.2 billion kilowatts. China's renewable energy industry has ushered in unprecedented opportunities for development[2].
Renewable energy generation such as solar energy, wind energy and tidal energy has unsteady characteristics such as volatility and randomness, and the direct integration of the generated power into the grid will have a negative impact on the operation of the grid. Energy storage technology is the key technology to ensure the efficient and stable operation of smart grid and realize the large-scale application of renewable energy. At present, the research and development of power energy storage technologies include pumped storage, compressed air energy storage, flywheel energy storage, superconducting magnetic energy storage and electrochemical energy storage[3][4][5][6][7⇓⇓⇓~11]. Electrochemical energy storage technologies include supercapacitor energy storage, lead-acid battery (lead-acid battery, lead-carbon battery) energy storage, lithium-ion battery energy storage and flow battery energy storage[6][8,9][10,11]. Flow battery plays an important role in the field of large-scale energy storage because of its high safety performance, strong stability and good cycle performance. At the same time, it also has high application value as a backup power supply for power grid.
The flow battery realizes the storage and conversion between chemical energy and electrical energy by the active material gaining and losing electrons on the electrode surface. The most significant feature of the flow battery is that the active material is stored in the electrolyte, so its output power and capacity are independent of each other, and the system design is flexible[12,13]. Flow batteries can be divided into aqueous flow batteries and organic flow batteries according to the classification of solvents. In the organic flow battery, the poor conductivity of the solvent leads to the large polarization of the battery, which leads to the low working current density of the battery[14]. At the same time, organic solvents have the risk of combustion and explosion, so it is difficult to be commercialized. Aqueous flow battery has the most commercial application prospect because of its good conductivity and high safety.
Aqueous flow batteries can be divided into organic aqueous flow batteries and inorganic aqueous flow batteries according to the type of active material. There are many kinds of active materials for organic aqueous flow batteries, and they have the advantages of controllable physical and chemical properties, so they have good application prospects, but the cycle stability and the synthesis process of active materials need to be further improved[15,16]. Inorganic aqueous flow batteries, especially all-vanadium flow batteries, have the advantages of high conductivity, excellent cycle performance and high solubility, and are the most widely used flow batteries in engineering.
The common redox couples of inorganic aqueous flow batteries are shown in Figure 1. Up to now, many combinations of ionic couples have been studied in the development of flow batteries, and the energy density is the primary factor to be considered when selecting metal or non-metal couples.The energy density is determined by the solubility and the standard potential of the battery, so,The most studied pairs are Zn0/2+, V2+/V3+, Sn0/2+,I3-/I- 、Fe2+/Fe3+ 、VO2+/ VO 2 + 、Br2/Br- and Mn2+/Mn3+.
Inorganic aqueous flow batteries can be divided into liquid-liquid flow batteries and liquid-deposition flow batteries according to the form of active couple. In this paper, the inorganic aqueous flow batteries that have been used in engineering and demonstration applications are described.Such as all vanadium flow battery, iron-chromium flow battery and zinc-bromine flow battery, etc. The research progress, engineering application, existing problems and development trend of these flow batteries were summarized. On this basis, the new inorganic aqueous flow battery was introduced, and the future development of inorganic aqueous flow battery was prospected.

2 Liquid-liquid flow battery

The structure of the traditional (liquid-liquid type) flow battery system is shown in Figure 2. The positive and negative electrolytes enter the positive and negative inlets of the stack through the circulating pump from the positive and negative electrolyte storage tanks respectively, flow through the stack electrodes, flow out from the positive, negative outlets of the stack, and then return to the positive, negative electrolyte storage tanks respectively through the electrolyte pipeline. The electric stack is assembled by a double-side end plate, a double-side collector plate, a plurality of single cells (bipolar plate, electrode frame, electrode, membrane, electrode, electrode frame, bipolar plate) and the like in sequence. The characteristic of liquid-liquid flow battery is that both the positive and negative active materials undergo electrochemical reaction on the electrode, and only the valence state changes without phase transformation during the reaction process. At present, the liquid-liquid flow batteries with engineering applications and demonstration applications mainly include all-vanadium flow batteries, iron-chromium flow batteries, etc.

2.1 Fe-Cr flow battery

In 1974, the National Aeronautics and Space Administration (NASA) proposed the concept of flow battery and developed the iron-chromium flow battery (ICFB)[17]. ICFB uses chromium and iron chlorides dissolved in hydrochloric acid as redox active substances. The battery reaction principle of ICFB is shown in formulas (1) ~ (3):
正极: Fe2+-e-→Fe3+ E0= +0.77 V (vs. SHE)
负极: Cr3++e-→Cr2+ E0= - 0.41 V (vs. SHE)
电池反应: Fe2++Cr3+→Cr2++Fe3+ ΔE= +1.18 V
Compared with other chemical energy storage batteries, ICFB has the advantages of high safety performance, strong temperature adaptability, environmental friendliness and low electrolyte cost, so researchers have made a scale-up demonstration of ICFB energy storage technology.
In the late 1970s, NASA's Lewis Research Center developed a 1 kW ICFB energy storage system[18]. In cooperation with NASA, Japan New Energy Industry Corporation carried out further research on ICFB energy storage technology and introduced an improved 1 kW ICFB system in 1983. By improving the electrode material and increasing the specific surface area of the electrode, the energy efficiency of the stack was increased to 82.9% at an average current density of 24.4 mA·cm-2[19]. Subsequently, the battery manufacturing process was transferred to Mitsui Shipyard for scale-up, and a 10 kW ICFB system was introduced in the late 1980s[20]. From 1985 to 1990, Sumitomo Electric Co., Ltd. also developed a 10 kW stack module and completed the integration and amplification of the system, but the development work was terminated because the inherent problems of the ICFB system were not solved[21]. In the next 20 years, ICFB technology has not been greatly developed at the battery system level because of the bottleneck of ICFB technology.
In recent years, with the development of renewable energy, the demand for energy storage technology has become more and more urgent. EnerVault Company of the United States has scaled up the ICFB and built the world's first 250 kW/1000 kW · H ICFB energy storage power station in 2014[22]. In December 2020, the "250 kW/1.5 MW · H ICFB Energy Storage Demonstration Project" jointly developed and constructed by the Central Research Institute of State Power Investment Corporation and Dongfang Energy (Hebei Company) in Zhangjiakou, Hebei Province, passed the project acceptance smoothly, marking that the first self-developed ICFB energy storage technology in China has formally entered the commissioning stage[23].
Although ICFB has some demonstration projects, there are still some technical problems that limit its large-scale commercial application. One is the poor electrochemical activity of the Cr3+/Cr2+ in the negative electrode of the battery: researchers have improved the electrochemical activity of the Cr3+/Cr2+ by depositing Au and Pb, solid bismuth hydride and SiO 2 on the surface of the electrode[24][25][26]; The second is the problem of hydrogen evolution on the anode: researchers inhibit hydrogen evolution by modifying Pb catalyst and Bi catalyst on the electrode surface[27][28]. Although the above methods can improve the performance of the battery, the process is complex, the stability of the modified material is poor, and it is difficult to solve the two problems of inhibiting the hydrogen evolution reaction (HER) and improving the electrochemical activity of Cr ions in the negative electrode at the same time. Zhang et al. Found that polyacrylonitrile graphite felt as ICFB electrode not only increased the electrochemical activity of Cr3+/Cr2+ but also maintained the capacity of ICFB, and the energy efficiency was 84.99% at 60 mA·cm-2 current density;Yan et al. Added In3+ to the electrolyte, which not only effectively inhibited HER, but also increased the electrochemical activity of Cr3+/Cr2+ and Fe3+/Fe2+ to some extent, showing an energy efficiency of 77.0% at a current density of 200 mA·cm-2[29][30]. Although researchers have done a lot of work to improve the performance of ICFB, the battery performance still needs to be further improved.

2.2 Vanadium redox flow battery

Since 1984, the research team of Skyllas-Kazacos at the University of New South Wales (UNSW) in Australia has conducted systematic research on VFB technology, mainly including research on key battery materials such as membranes and electrodes, research on electrolyte components and additives, research on stack structure simulation and design, and research on battery system operation characteristics[31][32~33][34⇓~36][37⇓⇓~40][41,42][43⇓~45].
VFB uses four kinds of vanadium ions with different valence States as the active material of the electrolyte, and sulfuric acid as the supporting electrolyte of the electrolyte and also as a reactant to participate in the electrochemical reaction of the battery cathode[46,47]. The specific reaction principle is shown in formulas (4) to (6):
正极: VO2+ - e-+H2O→ VO 2 ++2H+E0=+1.0 V (vs. SHE)
负极: V3++e-→V2+E0= -0.25 V (vs. SHE)
电池反应:VO2++V3++H2O→ VO 2 ++V2++2H+ΔE= +1.25 V
The two redox couples of vanadium have good kinetic activity, and VFB can also achieve good performance without the help of other catalysts. The active substances of the positive and negative electrolytes are vanadium ions. In the long-term operation process, the long-term accumulation of trace side reactions makes the capacity of the battery decline, and the capacity of the battery can be restored by a simple treatment method[48]. Based on this, researchers have done a lot of work to further improve the performance of VFB.
In the research of VFB key materials, the first is the development of electrolyte. The researchers found that the electrolyte configuration suitable for VFB stable operation under the condition of sulfuric acid aqueous solution is :3~4 mol·L-1 sulfuric acid to dissolve 1.5~1.7 mol·L-1 vanadium ions, which is relatively stable. Due to the limited solubility of vanadium ions in four valence States, the energy density is low (about 25 Wh·L-1)[49]. In order to obtain an electrolyte with high vanadium ion concentration, Wang et al. Of the Western Pacific National Laboratory in the United States developed a mixed acid electrolyte system of hydrochloric acid and sulfuric acid, which can dissolve vanadium in 2.5 mol·L-1, and obtained the maximum energy density (40 Wh·L-1) reported by the current VFB electrolyte.However, due to the use of high concentration of hydrochloric acid aqueous solution, side reactions such as chlorine evolution are prone to occur during the charging and discharging process of the battery, so it is necessary to further develop electrolytes with high stability, high energy density and wide temperature window[50]. The second is the research and development of ionic membrane. At present, most of the membrane materials used in the demonstration of VFB stack are perfluorosulfonic acid membrane, such as Nafion membrane. However, the poor selectivity of Nafion membrane to vanadium ions leads to the mutual crossing of vanadium ions in the positive and negative electrolytes, which reduces the coulombic efficiency of the stack, thus affecting the charge-discharge energy efficiency of the stack. Therefore, the researchers modified the perfluorosulfonic acid membrane to reduce the interaction of vanadium ions[51,52]. At the same time, because of the high price of Nafion membrane, researchers have also developed new membrane materials to replace Nafion membrane, including non-fluorinated materials and partially fluorinated materials, but because of the poor stability of these ion exchange membranes.Therefore, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, has done a lot of research on the regulation of ion exchange groups in non-fluorine ion exchange membranes and the oxidative degradation mechanism of non-fluorine ion exchange membranes in VFB to improve the stability of ion exchange groups[53,54][55][56,57]. At the same time, the non-fluorine porous ion conduction membrane for the vanadium redox flow battery is proposed for the first time, the internal morphology of the non-fluorine porous ion conduction membrane is regulated and controlled, the ion selectivity and ion conductivity are improved, the battery performance is improved, and the cost is greatly reduced compared with the perfluorosulfonic acid membrane[58,59][60,61]. The Dalian Institute of Chemical Physics of the Chinese Academy of Sciences has also carried out engineering scale-up of non-fluoride ion conducting membranes, which have been successfully applied to 200 kW/300 kW · H and 125 kW/500 kW · H container systems to promote the industrialization of flow batteries in China. Although researchers have done a lot of work on the development of VFB membrane materials, further research is needed to obtain VFB membrane materials with high stability, high selectivity and low cost. The third is the development of electrode materials. In order to develop electrode materials with higher performance, researchers have improved the activity of electrodes through electrode modification, development of new electrode materials, catalyst deposition and other methods.However, due to the high material cost and poor stability of the above methods, their commercial application is difficult, so it is necessary to develop low-cost, high-activity and high-stability electrode materials to improve the performance of VFB batteries[62⇓~64][65][66].
In terms of VFB stack development, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian Rongke Energy Storage Technology Development Co., Ltd. and Sumitomo Electric Co., Ltd. have developed 35 kW and 42 kW high-performance stacks respectively.By optimizing the flow field structure of the stack and selecting high-performance electrodes, the average current density of the stack can reach more than 280 mA·cm-2 under the condition of constant power charge and discharge and keeping the energy efficiency of charge and discharge of the stack greater than 80%, which greatly reduces the cost of the stack. However, in terms of single cell, Jiang et al. Achieved the optimal performance of VFB single cell by modifying the electrode, screening the membrane and optimizing the flow field structure of the cell, that is, the energy efficiency of the cell was 91.98%, 86.45% and 80.83%, and the electrolyte utilization was 87.97%, 85.21% and 76.98% at the current density of 200, 400 and 600 mA·cm-2, respectively[67]. The battery can run continuously for more than 20,000 cycles. It can be seen that the performance of VFB stack still has a lot of room for improvement, and researchers can take this as a goal to further improve the performance of the stack and reduce the cost of VFB.
Due to the advantages of VFB and a lot of work done by researchers in the early stage, VFB is the flow battery technology with the largest number of engineering application projects and the widest scale at present. Thai Gypsum Company in Thailand uses 5 kW/12 kW · H VFB in solar demonstration houses to store the electricity generated by solar photovoltaic cells during the day for use at night. This project is the earliest application demonstration project of VFB[68]. Mitsubishi Chemical Corporation of Japan has built a 200 kW/800 kW · H VFB peak shaving demonstration system, which is the first medium-sized field test of VFB[69]. Sumitomo Electric Co., Ltd. has been in the forefront of the world in the field of VFB energy storage, and has demonstrated a number of VFB energy storage projects in Japan's domestic power station peak shaving, wind storage and grid connection, which are used for peak shaving and valley leveling, so as to improve the grid's acceptance of wind power and photovoltaic power generation. Including the 4 MW/6 MW · H project of Sebaru Wind Farm in Hokkaido and the 15 MW/60 MW · H project of Minamisara Substation of Hokkaido Power Grid Co., Ltd. completed in 2015, which laid the foundation for the development of VFB energy storage. With the state's emphasis on the field of renewable energy, domestic research institutions and enterprises, such as Dalian Institute of Chemical Physics of the Chinese Academy of Sciences, Institute of Metal Research of the Chinese Academy of Sciences, Tsinghua University, Central South University, Dalian Rongke Energy Storage, Beijing General Energy, Shanghai Electric and other units, have conducted a lot of research on VFB and established kW ~ MW application demonstration projects. Table 1 shows the typical VFB demonstration projects implemented in China from 2010 to 2021. Among them, the 200 MW/800 MW · H energy storage project undertaken by Dalian Rongke Energy Storage is the first 100-megawatt project approved by the National Energy Administration and the largest electrochemical energy storage demonstration project in the world. After the project is completed and put into operation, it will further establish China's leading position in the field of large-scale energy storage of all-vanadium redox flow batteries[70].
Although VFB is the most widely used flow battery for demonstration at present, VFB still faces some problems, such as: the price of vanadium is unstable, which leads to the price fluctuation of VFB electrolyte[71]; The strong oxidation of the cathode leads to higher requirements for the oxidation resistance of battery materials, thus increasing the cost of the VFB stack[72,73]. Therefore, it is very important to develop VFB key materials with high performance and low cost, optimize the stack structure design to improve the power density of the stack, and develop the comprehensive utilization of vanadium-titanium magnetite and stone coal to reduce the cost of electrolyte, so as to promote the popularization and application of VFB and ultimately achieve the goal of carbon neutralization and carbon peak.

2.3 Other liquid-liquid flow batteries

2.3.1 V-Mn flow battery

In order to find a flow battery with low cost and high energy density, researchers have also explored many new flow battery systems. Mn is abundant in the earth's crust, relatively low in price, and the electrode potential of Mn2+/Mn3+ is relatively high, so researchers have done more research on manganese-based flow batteries.
In order to study the performance of the Mn2+/Mn3+ couple on different electrodes, Wang et al. Used the V3+/V2+ couple as the negative electrode of the battery to form a V-Mn flow battery, which was the first time to study the flow battery. The results showed that the coulombic efficiency, voltage efficiency and energy efficiency of the battery were 69.4%, 90.4% and 62.7% respectively at 20 mA·cm-2 current density, and the average voltage was 1.66 V[74]. Because the electrolyte is not a mixed electrolyte, the active ions of the positive and negative electrolytes cross each other seriously, and the Mn3+ is very easy to disproportionate under acidic conditions, which leads to the low coulombic efficiency of the battery. Park et al. Used V-Mn/V-Mn mixed system to study the effect of VO 2 + of VO2+/ on the disproportionation of Mn3+, and the specific battery reaction mechanism is shown in Figure 3.Results Under the condition of 50 mA·cm-2 current density, the energy efficiency of the cell reached 80%, and the presence of VO2+/ VO 2 + inhibited the dismutation of Mn3+[75].

2.3.2 Fe-Mn flow battery

Although the V-Mn flow battery with mixed electrolyte inhibited the disproportionation of Mn3+ and the crossing of positive and negative ions, it did not fundamentally solve the problem of electrolyte cost.
Kaliyaraj et al. Studied the flow battery with Mn3+/Mn2+ and Fe3+/Fe2+ as the positive and negative electrode pairs, respectively, namely Fe-Mn flow battery[77]. Exhibited a Coulombic efficiency of about 96% at a current density of 7 mA·cm-2, an energy efficiency of 70% with good capacity retention over 100 charge-discharge cycles. In addition, high concentrations of positive and negative electrolytes are used to increase the actual energy density of the system to more than 40 Wh L-1.

2.3.3 Ti-Mn flow battery

Using Fe3+/Fe2+ instead of V3+/V2+ can reduce the cost of electrolyte, but there is a problem of disproportionation of Mn3+. Meanwhile, the vs. SHE electrode was not suitable as a negative electrode pair due to its high potential (+ 0.77 vs. SHE). As a negative electrode, V vs. SHE has a low electrode potential (+ 0.1 V vs. SHE), and it is easy to form coordination with SO 4 2 -, so that HSO 4 - can release more H+, so it has a good inhibitory effect on the disproportionation of Mn3+[78]. Kaku et al. Studied the battery performance of Ti-Mn flow battery under different membranes, and the results showed that the energy efficiency of single cell using thin electrode (NR-211 membrane) under 200 mA·cm-2 conditions can reach 84.3%, which is also the highest battery performance of Ti-Mn flow battery reported at present, but the problems of poor cycle performance and low energy density of the battery need to be solved[79].

2.3.4 V-Fe flow battery

Vanadium is widely used in the field of flow batteries because of its multiple valence States under acidic conditions. For example, Wang et al. Proposed a V-Fe flow battery using Fe2+/Fe3+ and V2+/V3+ couples in chloride electrolyte, and the specific reaction principle is shown in Fig. 4. The V-Fe flow battery with mixed electrolyte works in the voltage window of 0.5 – 1.35 V, the utilization rate is close to 100%, and it can stably operate for more than 50 cycles at a current density of 50 mA·cm-2, with an energy efficiency of 80%[80]. Without catalyst and external thermal management, the electrolyte with high stability and high electrochemical activity can be obtained in the temperature range of 0-50 deg C, and the stable battery performance can be obtained in the temperature range.

2.3.5 Polysulfide-halogen flow battery

Halogen salts have attracted much attention due to their high solubility and suitable electrode potential. Sulfur is abundant in the earth, and polysulfides have high solubility and reaction reversibility in aqueous media. At present, great progress has been made in the research of polysulfide-bromine flow battery. Regenesys, a British company, built the world's first sodium polysulfide-bromine energy storage system (15 MW/120 MW · H) in 2000, and built a 12 MW/120 MW · H sodium polysulfide/bromine flow battery energy storage system for Colombia Air Force Base in 2001 to supply power to the base in extraordinary times[81⇓~83][84]. After that, the two systems were shut down, indicating that the technology is still immature, such as serious cross-talk between positive and negative electrodes, large side reactions of batteries and large pollution of Br2[85,86]. Compared with Br2, I2 are more suitable for polysulfides to form flow batteries because of their low toxicity, high solubility and good electrochemical activity. Based on this, Lu et al. Proposed a sodium polysulfide-iodine flow battery (PSIB) with a theoretical cell voltage of 1.05 V[87]. The final energy density of PSIB with polysulfide as negative active material and iodine as positive active material reached 43.1 Wh·L-1, but the coulombic efficiency of the cell was only 93.08% and 85.86% at 37 and 25 mA·cm-2 current densities. The cycle life is short due to the very low coulombic efficiency. This may be due to the oxidation of I- and the instability of I 3 -. Meanwhile, the S2- of the negative electrode can be over-oxidized to insoluble S 4 2 -, S 6 2 -, or S 8 2 -. Therefore, further work should involve improving the stability of polysulfides and triiodides.

2.3.6 Liquid-liquid type all-iron flow battery

As a transition metal element, iron has abundant valence States (Fe0, Fe2+, Fe3+). Fe2+ can be selected as the active material of the positive and negative electrolyte in the flow battery to form a traditional all-iron flow battery (OIFB). The battery has no cross contamination, wide sources of active materials and low cost, but the OIFB has the limitation that the negative electrode is prone to hydrogen evolution reaction, which seriously affects the performance of the battery. Therefore, Gong et al. Used the complex [Fe(TEOA)OH]- formed by triethanolamine and iron ions under alkaline conditions to replace the negative electrode pair (Fe2+/0) of OIFB to solve the problem of hydrogen evolution, and combined with the Fe(CN) 6 3 -/ Fe(CN) 6 4 - pair to form a liquid-liquid all-iron flow battery (SIFB)[88]. The energy efficiency of the cell is always above 70% at 40 mA·cm-1 current density, but the coulombic efficiency is only 85%, mainly due to the serious electrolyte crosstalk. In order to solve this problem, Sreenath et al. Prepared a polyethylene/polystyrene copolymer cation exchange membrane. Compared with Nafion 212 membrane, the coulombic efficiency of SIFB was improved to 98% at 15 mA·cm-1 current density, which largely solved the problem of ion crossing. However, the working current density of SIFB still needs to be improved[89]. Shin et al. Utilized the complex Fe (DIPSO) formed by the new organic ligand 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) and iron ions as the negative active material, and Fe(CN) 6 3 -/ Fe(CN) 6 4 - as the positive active couple to form a novel SIFB[90]. The cell can stably operate for 100 cycles at a working current density of 80 mA·cm-2, and the coulombic efficiency is more than 99%, and the energy efficiency is maintained at about 70%.

3 Liquid-deposited flow battery

The difference between liquid-deposition flow battery and liquid-liquid flow battery is that the metal material with high capacity and low potential is used as the energy storage medium of the negative electrode instead of the electrolyte with low concentration. Or a metal oxide material with high capacity and high potential is used as a positive electrode energy storage medium instead of a positive electrode electrolyte with low concentration, so that the energy density of the flow battery can be greatly improved. The active substance on one side of the system is not completely dissolved in the electrolyte, and there is a deposition-dissolution phase transformation reaction in the reaction process. At present, the practical application of liquid-deposition flow battery is zinc-bromine flow battery.

3.1 Zinc-bromine liquid-deposition type flow battery

Zinc-bromine flow battery (ZBFB) is a liquid-deposition flow battery, and the reaction principle is shown in equations (7) ~ (9). There is a deposition-dissolution reaction in the charge-discharge process of the negative electrode pair, that is, the charge product is insoluble in the electrolyte and deposits on the electrode (Formula 8). The positive and negative half cells are separated by a separator, and the electrolyte on both sides is ZnBr2 solution[91]. In addition, the Zn0/2+ couple has good electrochemical activity, high hydrogen evolution overpotential, not easy to occur side reactions, and has a high specific capacity (5.85 Ah·cm-3), while the high solubility of Zn ions can obtain high energy density, compared with VFB, the cost of Zn is low, so it has been concerned by people[92][93].
正极:2Br--2e-→Br2 E0=1.087 V (vs. SHE)
负极:Zn2++2e-→Zn E0=0.763 V (vs. SHE)
电池反应:ZnBr2→Zn2++Br2 ΔE=1.85 V
ZBFB began to attract the attention of researchers in the 1970s. First, Exxon Mobil optimized the electrolyte ratio of the battery to solve the problem of zinc dendrite, which alleviated the self-discharge problem and zinc deposition problem of the first generation of ZBFB, and laid the foundation for the demonstration application of ZBFB[94]. Subsequently, ZBB Energy Company of the United States and RedFlow Company of Australia conducted a lot of research on ZBFB and established a 100-kW demonstration project. The foreign development process of ZBFB is shown in Figure 5.
With the state's emphasis on the energy storage industry, some domestic research institutions, enterprises and universities have carried out the development of ZBFB, such as Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Anhui Meineng Energy Storage Co., Ltd., Beijing Baineng Huitong Technology Co., Ltd. Today, the localization of ZBFB key materials has been realized. In 2012, Beijing Baineng Huitong Technology Co., Ltd. developed the first ZBFB energy storage system in China[95]. In 2014, the ZBFB energy storage system developed by Anhui Meineng Energy Storage Co., Ltd. passed the State Grid test and was qualified to be connected to the grid[96]. In 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences designed the first 5 kW/5 kW · H zinc-bromine single flow battery (ZBSFB) energy storage demonstration system in China to solve the problem of bromine corrosion on pipeline system in ZBFB, which was put into operation in the plant area of Huayin Science and Technology Co., Ltd. in Ankang City, Shaanxi Province.
Although ZBFB has some demonstration projects, there are still some problems to be solved for commercial application.For example, the accumulation of zinc on the zinc electrode causes the irreversible decay of energy storage capacity, the formation of zinc dendrite causes the short circuit of positive and negative electrodes, the energy density of battery system is low due to the limited amount of zinc deposition on the electrode, the power density of the stack is low due to the low rated current density of the stack, and the environmental pollution caused by the leakage of Br2[96⇓~98].

3.2 Other liquid-deposition type flow battery

3.2.1 Zn-I flow battery

In 2015, Pacific Northwest National Laboratory (PNNL) reported a high energy density zinc-iodine flow battery (ZIFB)[99]. This type of flow battery utilizes I 3 - /I- and Zn0/2+ couples, and the voltage of the cell is 1.22 V. Since the number of electrons transferred by its electrode reaction is 2 and the concentration of iodide ions can reach 5~7 mol L-1, the capacity of the electrolyte reaches 167 Wh·L-1. Compared with the strong corrosivity of Br2 in ZBFB, the corrosivity of I 3 - in ZIFB is weaker, which greatly reduces the requirements for stack materials, and at the same time, there is no environmental problem caused by the volatilization of active substances. However, the above ZIFB system still faces many problems, such as low working current density, poor cycle stability of the battery (about 50 cycles), and high price of iodine. To solve the above problems, Xie et al. Employed ZIFB with KI and ZnBr2 as electrolytes combined with low-cost polyolefin porous membranes[100]. The oxide filled in the pores of the porous membrane can react with the zinc dendrite, and the battery can achieve self-recovery from the micro-short circuit after overcharge to ensure high cycle stability. Meanwhile, the introduction of Br- can form a complex with I2 to inhibit the deposition of I2. In addition, the replacement of ZnI2 by KI can effectively prevent the precipitation of zinc hydroxide and oxide in the anolyte during circulation. The results show that the ZIFB has an energy efficiency of 82% at a current density of 80 mA·cm-2, an energy density of 80 Wh·L-1, and a cycle life of more than 1000 cycles. More importantly, the stack with 700 W power output can operate continuously for 300 cycles, which further confirms the reliability and applicability of the new generation ZIFB. However, due to the low solubility of I2, in order to prevent the clogging of pumps and pipelines, the positive I- can only be controlled to charge to I 3 -, resulting in relatively low electrolyte utilization, which limits the theoretical advantage of high energy density of ZIFB.
Xie et al. Proposed a zinc-iodine single flow battery (ZISFB) based on the ZIFB battery[101]. The specific principle is shown in Figure 6. The pump and pipeline of the anode are removed, and the anode electrolyte is fixed in the anode chamber, so that the I- in the anode electrolyte can be charged to solid I2, which not only solves the problem of pipeline and pump blockage, but also makes the utilization rate of the electrolyte close to 100%.At the current density of 40 mA·cm-2, the coulombic efficiency reaches 97% and the energy conversion efficiency reaches 81%, and the cell can continuously operate for more than 500 cycles, greatly improving the energy density (205 Wh·L-1) of the electrolyte, which is the highest value reported in ZIFB at present.

3.2.2 Zn-V flow battery

Ulaganathan et al. First proposed the zinc-vanadium flow battery (ZVFB) system (Figure 7A)[102]. The open-circuit voltage of the ZVFB is 1.85 V (Fig. 7 B), which is very close to that of the ZBFB, and the voltage efficiency, coulombic efficiency, and energy efficiency are 88%, 82%, and 72% at a current density of 20 mA·cm-2. The ZVFB cell can stably operate for 50 charge-discharge cycles by using the microporous membrane instead of the Nafion membrane, which reduces the cost a lot compared with the ZBFB.

3.2.3 Zn-Ce flow battery

In order to seek higher battery performance, researchers have carried out research on Ce4+/Ce3+ pairs. The V vs. NHE couple has a high electrode potential (1.72 V vs. NHE), which is suitable as a positive electrode couple, and the matching with zinc can achieve good results. Zinc-cerium flow battery (ZCFB) was proposed by Clarke in 2003, and the open circuit voltage can reach 2.5 V[103]. However, there are still some problems, such as the low solubility of cerium and the low energy density of the electrolyte[104]; The high voltage of ZCFB and the side reaction of hydrogen and oxygen evolution at the positive and negative electrodes during charging seriously affect the energy efficiency and operation safety of the battery[105].

3.2.4 Zn-Mn flow battery

In the Zn-based flow battery mentioned above, although better battery performance has been achieved, it is very important to select a more economical positive electrode pair. Xie et al. Developed a Zn-Mn flow battery under neutral conditions. In order to avoid the disproportionation reaction of the Mn3+ generated by the Mn2+→Mn3+, the additive acetic acid (HAc) was added to inhibit the generation of the Mn3+, thereby fully utilizing the Mn2+/MnO2 couple, thus greatly improving the cycle stability of the battery. The open-circuit voltage of the Zn-Mn flow battery formed with the Zn0/2+ couple was 1.58 V[106]. The results show that the battery can operate stably at a current density of 40 mA·cm-2 for more than 400 charge-discharge cycles, and the energy efficiency can reach 78%.

3.2.5 Sn-based liquid-deposition type flow battery

Tin as the anode of flow battery has a solid-liquid conversion mechanism similar to that of zinc, but compared with Zn-based, the standard electrode potential of V vs. SHE is more moderate (-0. 14 V vs. SHE), so it has better stability. And that Sn0/2+ has less side effect on electricity. Chen et al. Studied the charge-discharge performance of Sn-V flow battery with VO2+/ VO 2 + as the positive electrode and Sn0/2+ as the negative electrode, and the results showed that the deposition of tin was almost completely dissolved during discharge[107]. The Sn-V flow battery exhibited a Coulombic efficiency of 96% and an energy efficiency of 70% at an operating current density of 180 mA·cm-2. However, the cost of vanadium raw materials limits the application of Sn-V batteries.
Zhou et al. Proposed a tin-iron flow battery, which uses Fe3+/Fe2+ as the positive active couple and Sn0/2+ as the negative active couple (Figure 8 a)[108]. The energy efficiency can reach 78.5% at a current density of 200 mA·cm-2. The hydrogen evolution overvoltage of metal tin is high, which can largely avoid the hydrogen evolution reaction of the negative electrode, so that the battery can run stably for 700 times (Fig. 8B) without significant efficiency degradation. However, Sn-based flow battery is easily affected by the interaction of positive and negative active materials, which leads to capacity fading during operation. The tin-bromine flow battery proposed by Zeng et al. Can solve the cross-connection problem and has lower cost, but the voltage of a single cell is lower and the energy density is lower[109].

3.2.6 Conventional all iron flow battery

Using iron complexes instead of Fe2+/0 can solve the problem of hydrogen evolution in traditional OIFB anode, but the addition of organic ligands will inhibit the electrochemical activity of the original metal ions, thereby affecting the performance of the battery. At present, the main problem of OIFB is the mismatch of positive and negative optimal pH, that is, the Fe3+ generated on the positive side during charge is very easy to form Fe(OH)3 precipitation when pH > 3. However, the Fe produced on the negative side is extremely unstable under acidic conditions, resulting in the attenuation of battery capacity. Therefore, McGrath et al. Used anion exchange membranes in OIFB to maintain a certain pH gradient of the positive and negative electrolytes, so that the positive and negative electrolytes can reach their respective optimal pH[110]. However, the traditional all-iron flow battery uses FeCl2 as the initial electrolyte solute, when the battery is charged, the Fe3+ generated by the positive electrode will produce strong oxidizing FeCl 4 - in the Cl- environment, which will make the anion exchange membrane oxidized and ineffective, affecting the cycle performance of the battery[110]. Hawthorne et al. Proposed to use FeSO4 instead of FeCl2, which can reduce the oxidizability of the positive electrolyte, but the solubility of FeSO4 is low (<1.4 mol L-1,FeCl2 solubility >3 mol L-1), which affects the theoretical capacity of the all-iron flow battery[111][112]. In order to improve the solubility of FeSO4, Yu et al. Introduced 1-hexadecyl-3-methylimidazolium chloride (EMIC) into FeSO4 solution to enhance the binding strength between sulfate and water molecules.Thus, the solubility of FeSO4 was improved (2 mol L-1), and the energy density of the cell was increased to 32 Wh L-1, which was stably operated for 800 cycles at a current density of 20 mA·cm-2[113].

3.2.7 Ti-Mn flow battery

As mentioned in Section 2.3.3, liquid-liquid Ti-Mn flow battery has been studied by researchers, but the life of flow battery will be affected by the deposits (MnO2) produced by the disproportionation reaction of Mn3+, so researchers have done a lot of work to limit the disproportionation of Mn3+, but this will greatly limit the energy storage capacity of the battery. Based on this, our team proposed a stable titanium-manganese single flow battery (TMSFB), and the specific reaction principle is shown in Fig. 9 a. In the design, a positive electrode without storage tank, tube and circulating pump is used to realize the double electron transfer reaction of Mn2+/MnO2 (Fig. 9 B)[114]. The results show that the utilization of TMSFB reaches 180% of the single-electron reaction, which improves the electrolyte utilization of titanium-manganese flow battery. At a current density of 40 mA·cm-2, the TMSFB has a Coulombic efficiency of 99%, an energy efficiency of 85%, and can operate stably for more than 1000 cycles (Figure 9 C) without significant degradation of the energy storage capacity.

4 Conclusion and prospect

In order to achieve the goal of "carbon peak and carbon neutralization" and alleviate the increasingly serious energy and environmental problems, large-scale utilization of renewable energy such as wind and solar energy has become an inevitable trend.Large-scale energy storage technology is the key technology to solve the intermittence of large-scale renewable energy generation, so as one of the preferred technologies for large-scale energy storage, flow battery technology, especially all-vanadium flow battery technology, has ushered in an opportunity for rapid development. The important indicators of large-scale energy storage technology application include high safety, good life cycle economy and low life cycle environmental load, which are the advantages of inorganic aqueous flow batteries, especially all-vanadium flow batteries.The initial investment cost is the main bottleneck affecting its popularization and application at present. In the future, the cost of flow batteries will be reduced mainly from the following aspects.
(1) Reduce the cost of key materials such as electrolyte, membrane, electrode and bipolar plate of flow battery. Taking the all-vanadium redox flow battery as an example, the vanadium electrolyte has the highest cost, and increasing the concentration and stabilization temperature window of the vanadium electrolyte, reducing the impurity requirements of the vanadium electrolyte, and thus reducing the cost of raw materials are effective means to reduce its cost. At the same time, a new type of inorganic aqueous flow battery system is developed to reduce the cost of electrolyte, but the new type of inorganic aqueous flow battery generally has the problems of low rated working current density, low energy density and poor cycle stability.Therefore, the corresponding electrolyte additives, the modification of supporting electrolyte and the modification of electrode materials are carried out to improve the cycle stability and energy density. The second is to reduce the cost of ion exchange membrane. At present, the commonly used Nafion membrane is expensive, so the development of low-cost non-fluoride ion conductive membrane materials will effectively reduce the cost of the membrane. At present, the carbon felt weaving process for the electrode of the flow battery has not been completely localized, and the cost of the electrode can be further reduced by realizing the complete localization of the carbon felt production process for the electrode.
(2) To further increase the power density of the stack, that is, to increase the rated working current density of the stack. Similar to proton exchange membrane fuel cell, the internal polarization of aqueous flow cell stack mainly includes activation polarization, ohmic polarization and concentration polarization. The activation polarization can be reduced by increasing the reactivity of the electrode material. The ohmic polarization of the stack can be effectively reduced by developing ion exchange (conducting) membranes with high selectivity and high conductivity, optimizing the stack structure, and reducing the interfacial contact resistance among the membrane, electrode, and bipolar plate. At that same time, the concentration polarization of the stack can be effectively reduce through the structural design innovation of the stack, including a short flow field structure, an annular flow field structure, an electrode flow channel structure, a bipolar plate flow channel structure and a guide groove structure,The power density of the stack, namely the rated working current density, is improved, so that the use amount of the stack material can be reduced, and the manufacturing cost of the stack can be greatly reduced.
To sum up, inorganic water flow battery is the most promising energy storage technology for commercial application. However, due to the high initial cost, large-scale popularization and application are affected. The solution is to reduce the initial investment cost of inorganic water flow battery. As shown in Fig. 10, through the improvement of membrane and electrode materials and the optimization of stack structure, the current density and energy density are improved. With the gradual reduction of the cost of inorganic aqueous flow batteries, inorganic aqueous flow batteries will surely usher in the development stage of large-scale popularization and application.

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Funding

Fundamental Research Funds for the Central Universities(3132021179)

Strategic Priority Research Program of Chinese Academy of Sciences(XDA21070100)

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