Multiple-dimensioned defect engineering for graphite felt electrode of vanadium redox flow battery

The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.

Unraveling the coordination behavior and transformation mechanism of Cr^(3+) in Fe–Cr redox flow battery electrolytes

Currently,the iron chromium redox flow battery(ICRFB)has become a research hotspot in the energy storage field owing to its low cost and easily-scaled-up.However,the activity of electrolyte is still ambiguous due to its complicated solution environment.Herein,we performed a pioneering investigation on the coordination behavior and transformation mechanism of Cr^(3+)in electrolyte and prediction of impurity ions impact through quantum chemistry computations.Based on the structure and symmetry of electrostatic potential distribution,the activity of different Cr^(3+)complex ions is confirmed as[Cr(H2O)5Cl]^(2+)>[Cr(H2O)4Cl2]+>[Cr(H2O)6]^(3+).The transformation mechanism between[Cr(H2O)6]^(3+)and[Cr(H2O)5Cl]^(2+)is revealed.We find the metal impurity ions(especially Mg^(2+))can exacerbate the electrolyte deactivation by reducing the transformation energy barrier from[Cr(H2O)5Cl]^(2+)(24.38 kcal mol^(−1))to[Cr(H2O)6]^(3+)(16.23 kcal mol^(−1)).The solvent radial distribution and mean square displacement in different solvent environments are discussed and we conclude that the coordination configuration limits the diffusivity of Cr^(3+).This work provides new insights into the activity of electrolyte,laying a fundamental sense for the electrolyte in ICRFB.

Tetrathiafulvalene esters with high redox potentials and improved solubilities for non-aqueous redox flow battery applications

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.

A Hydrogen Iron Flow Battery with High Current Density and Long Cyclability Enabled Through Circular Water Management

The hydrogen-iron(HyFe)flow cell has great potential for long-duration energy storage by capitalizing on the advantages of both electrolyzers and flow batteries.However,its operation at high current density(high power)and over continuous cycling testing has yet to be demonstrated.In this paper,we discuss our design and demonstration of a water management strategy that supports high current and long cycling performance of a HyFe flow cell.Water molecules associated with the movement of protons from the iron electrode to the hydrogen electrode are sufficient to hydrate the membrane and electrode at a low current density of 100 mA cm^(-2)during the charge process.At higher charge current density,more aggressive measures must be taken to counter back-diffusion driven by the acid concentration gradient between the iron and hydrogen electrodes.Our water management approach is based on water vapor feeding in the hydrogen electrode,and water evaporation in the iron electrode,thus enabling the high current density operation of 300 mA cm^(-2).

A Hydrogen Iron Flow Battery with High Current Density and Long Cyclability Enabled Through Circular Water Management

The hydrogen-iron(HyFe)flow cell has great potential for long-duration energy storage by capitalizing on the advantages of both electrolyzers and flow batteries.However,its operation at high current density(high power)and over continuous cycling testing has yet to be demonstrated.In this article,we discuss our design and demonstration of a water-management strategy that supports high current and long-cycling performance of a HyFe flow cell.Water molecules associated with the movement of protons from the iron electrode to the hydrogen electrode are sufficient to hydrate the membrane and electrode at a low current density of 100 mA cm^(-2)during the charge process.At higher charge current density,more aggressive measures must be taken to counter back-diffusion driven by the acid concentration gradient between the iron and hydrogen electrodes.Our water-management approach is based on water vapor feeding in the hydrogen electrode and water evaporation in the iron electrode,thus enabling high current density operation of 300 mA cm^(-2).

Enlarging Zn deposition space via regulating Sn-induced effective interface for high areal capacity zinc-based flow battery

Zinc-based flow batteries(ZFBs)have aroused great favor in large-scale energy storage due to the high security and low cost.However,the low areal capacity arising from the limited space for Zn plating hinders the further development.Herein,a novel carbon felt-Sn-carbon felt sandwich host(CSCH)is designed and constructed.Benefiting from the strong chemical absorption and the dehydration effect on Zn(H_(2)O)_(6)^(2+),the Sn activation layer in the CSCH demonstrates the lowest comprehensive resistance for Zn deposition.Thus,Zn is induced to nucleate preferentially on the Sn activation layer,and grows towards the membrane,regulating the spatial distribution of Zn electrochemical deposits,which remarkably improves the areal capacity and cyclic stability of Zn anode.Consequently,the zinc-bromine flow batteries equipped with CSCH electrodes can achieve the ultra-high areal capacity of 120 mA h cm^(-2)at 80 mA cm^(-2),and run stably for 140 h with average energy efficiency of 80.3%in the extreme condition(80 mA cm^(-2),80 mA h cm^(-2)).This innovative work will inspire future advanced designs for high areal capacity electrodes in ZFBs.

From aqueous Zn-ion battery to Zn-MnO_(2) flow battery:A brief story

Aqueous Zn-ion battery(AZIB)has become an attractive technology because of its unique features of low cost,high safety and the eco-friendliness.MnO_(2) is the model cathode material for AZIB since the first report on reversible Zn-MnO_(2) battery,but recent studies have unveiled different charge storage mechanisms.Due to revamping of the electrochemistry and redesigning of the electrolyte and interface,there is tremendous performance enhancement in AZIB.This mini Review will first give a brief introduction of ZIB,including fundamentals of materials and components,and the progress in recent years.Then,a general classification of working mechanisms related to MnO_(2) in neutral and mildly acidic electrolyte is elaborated.Our focus is put on the recent blossoming Zn-MnO_(2) electrolytic mechanism,which has given birth to the Zn-MnO_(2) redox flow batteries that are highly promising for large-scale static energy storage.

A highly concentrated vanadium protic ionic liquid electrolyte for the vanadium redox flow battery

A protic ionic liquid is designed and implemented for the first time as a solvent for a high energy density vanadium redox flow battery.Despite being less conductive than standa rd aqueous electrolytes,it is thermally stable on a 100 ℃ temperature window,chemically stable for at least 60 days,equally viscous and dense with typical aqueous solvents and most importantly able to solubilize to 6 mol L^(-1) vanadium sulfate,thus increasing the VRFB energy density by a factor of 2.5.Electrochemical measurements revealed quasi-reversible redox transitions for both catholyte and anolyte at 25 ℃ while a proof-of-concept redox flow cell with the proposed electrolyte was tested for a total of 150 cycles at 25 ℃,showing an open circuit potential of 1.39 V and energy and coulombic efficiencies of 65% and 93%,respectively.What’s more,the battery can be equally cycled at 45℃ showing good thermal stability.This study underlines a new route to improve the energy-to-volume ratio of energy storage system.

Nanostructured N-doped carbon materials derived from expandable biomass with superior electrocatalytic performance towards V^(2+)/V^(3+) redox reaction for vanadium redox flow battery

Vanadium redox flow battery(VRFB)is one of the most promising large-scale energy storage systems,which ranges from kilowatt to megawatt.Nevertheless,poor electrochemical activity of electrode for two redox couples still restricts the extensive applications of VRFB.Compared with V^(2+)/V^(3+)redox reaction,V^(2+)/V^(3+)reaction plays a more significant role in voltage loss of VRFB owing to slow heterogeneous electron transfer rate.Herein,N-doped carbon materials derived from scaphium scaphigerum have been developed as negative electrocatalyst by hydrothermal carbonization and high-temperature nitridation treatments.The undoped carbon material hardly has electrocatalytic ability for V^(2+)/V^(3+)reaction.Based on this,N-doped carbon materials with urea as nitrogen source exhibit excellent electrocatalytic properties.And the material nitrided at 850°C(SSC/N-850)exhibits the best performance among those from700 to 1000℃.SSC/N-850 can accelerate the electrode process including V^(2+)/V^(3+)reaction and mass transfer of active ions due to the large reaction place,more active sites,and good hydrophilicity.The effect of catalyst on comprehensive performance of cell was evaluated.SSC/N-850 can improve the charge-discharge performance greatly.Utilization of SSC/N-850 can lessen the electrochemical polarization of cell,further resulting in increased discharge capacity and energy efficiency.Discharge capacity and energy efficiency increase by 81.5%and 9.8%by using SSC/N-850 as negative catalyst at 150 m A cm^(-2),respectively.Our study reveals that the developed biomass-derived carbon materials are the low-cost and efficient negative electrocatalyst for VRFB system.

A new long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide)(PPO)/polybenzimidazole(PBI)amphoteric membrane for vanadium redox flow battery

A new amphoteric membrane was prepared by blending long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide)(S-L-PPO)and polybenzimidazole(PBI)for vanadium redox flow battery(VRFB)application.An acid-base pair structure formed between the imidazole of PBI and sulfonic acid of S-L-PPO resulted in lowered swelling ratio.It favors to reduce the vanadium permeation.While,the increased sulfonic acid concentration ensured that proton conductivity was still at a high level.As a result,a better balance between the vanadium ion permeation(6.1×10^-9 cm^2·s^-1)and proton conductivity(50.8 m S·cm^-1)in the S-L-PPO/PBI-10%membrane was achieved.The VRFB performance with S-L-PPO/PBI-10%membrane exhibited an EE of 82.7%,which was higher than those of pristine S-L-PPO(81.8%)and Nafion 212(78.0%)at 120 m A·cm^-2.In addition,the S-LPPO/PBI-10%membrane had a much longer self-discharge duration time(142 h)than that of Nafion 212(23 h).

Towards an all-vanadium redox flow battery with higher theoretical volumetric capacities by utilizing the VO^2＋/V^3＋ couple

An all-vanadium redox flow battery with V（IV） as the sole parent active species is developed by accessing the VO2＋/V3＋ redox couple. These batteries, referred to as V4RBs, possess a higher theoretical volumetric capacity than traditional VRBs. Copper ions were identified as an effective additive to boost the battery performance.

Low-cost all-iron flow battery with high performance towards long-duration energy storage

Long duration energy storage(LDES)technologies are vital for wide utilization of renewable energy sources and increasing the penetration of these technologies within energy infrastructures.Herein,we propose a low-cost alkaline all-iron flow battery by coupling ferri/ferro-cyanide redox couple with ferric/ferrous-gluconate complexes redox couple.The designed all-iron flow battery demonstrates a coulombic efficiency of above 99%and an energy efficiency of~83%at a current density of80 m A cm^(-2),which can continuously run for more than 950 cycles.Most importantly,the battery demonstrates a coulombic efficiency of more than 99.0%and an energy efficiency of~83%for a long duration(~12,16 and 20 h per cycle)charge/discharge process.Benefiting from the low cost of iron electrolytes,the overall cost of the all-iron flow battery system can be reached as low as$76.11 per k Wh based on a10 h system with a power of 9.9 k W.This work provides a new option for next-generation cost-effective flow batteries for long duration large scale energy storage.

Broad temperature adaptability of vanadium redox flow battery-part4:Unraveling wide temperature promotion mechanism of bismuth for V^(2+)/V^(3+) couple

Vanadium flow battery （VFB） is a fast going and promising system for large-scale stationary energy stor- age. However, drawbacks such as low power density and narrow temperature window caused by poor catalytic activity of graphite felt （GF） electrodes limit its worldwide application. In this paper, bismuth, as a low-cost, no-toxic and high-activity electrocatalyst, is used to modify the thermal activated GF （TGF） via a facile hydrothermal method. Bismuth can effectively inhibit the side reaction of hydrogen evolution in wide temperature range, while promoting the V2＋/V3＋ redox reaction. As a result, the VFB assembled with Bi/TGF as negative electrode demonstrates outstanding rate performance under the current density up to 400 mAcm-2, as well as a long-term stability over 600 charging/discharging cycles at a high cur- rent density of 150mA cm-2. Moreover, it also shows excellent temperature adaptability from -10 ℃ to 50 ℃ and high durability for life test at the temperature of 50 ℃.

Opportunities and challenges of organic flow battery for electrochemical energy storage technology

For flow batteries(FBs), the current technologies are still expensive and have relatively low energy density, which limits their large-scale applications. Organic FBs(OFBs) which employ organic molecules as redox-active materials have been considered as one of the promising technologies for achieving lowcost and high-performance. Herein, we present a critical overview of the progress on the OFBs, including the design principles of key components(redox-active molecules, membranes, and electrodes) and the latest achievement in both aqueous and nonaqueous systems. Finally, future directions in explorations of the high-performance OFB for electrochemical energy storage are also highlighted.

The effect of phosphate additive on the positive electrolyte stability of vanadium redox flow battery

The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trolyte is limited by the low stability of VO2＋ at a higher temperature. Phosphate is proved to be a very effective additive to improve the stability of VO2＋. Even though, the stabilizing mechanism is still not clear, which hinders the further development of VRFBs. In this paper, to clarify the effect of phosphate additive on the positive electrolyte stability, the hydration structures of VO2＋ cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4 solutions were investigated in detail based on calculations of electronic structure. The stable configurations of com- plexes were optimized at the B3LYP/6-311 ＋ G（d,p） level of theory. The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory. It shows that a structure of [VO_2（H_2O）_2]＋ surrounded by water molecules in H2S04 solution can be formed at the room temperature. With the temperature rises, [VO_2（H_2O）_2]＋ will lose a proton and form the interme- diate of VO（OH）_3, and the further dehydration among VO（OH）_3 molecules will create the precipitate of V_2O_5. When H_3PO_4 was added into electrolytes, the V-O-P bond-containing neutral compound could be formed through interaction between VO（OH）_3 and H_3PO_4, and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal tool-1 lower than that of the VO（OH）_3 dehydration, which could avoid the precipitation of V_2O_5 and improve the electrolyte stability.

Facile fabrication of amphoteric semi-interpenetrating network membranes for vanadium flow battery applications

For improvement of vanadium redox flow battery （VRB） performance, novel amphoteric semi- interpenetrating membranes （ASIPN） were prepared using poly（ether ether ketone） （PEEK） and polysul- fone （PSf）, the former bearing sulfonic groups and the latter imidazolium. These two groups form ionic crosslinks between PEEK and PSf; meanwhile, covalent cross links were built between PSf chains with ad- dition of N-（3-aminopropyl）-imidazole. The amphoteric nature of the membrane allows facile proton and anion transport; the IPN structure and the presence of imidazolium cation effectively suppress vanadium ion crossover through the membrane. Therefore, the ASIPN based VRBs show higher Coulombic efficiency and energy efficiency than that assembled with pristine SPEEK and Nation 212 membranes. Our work demonstrates that the ASIPN membranes are promising for VRB applications.

Porous polybenzimidazole membranes with positive charges enable an excellent anti-fouling ability for vanadium-methylene blue flow battery

A cost-effective, high-performance and highly stable membrane has always been in intensively needed in aqueous organic-based flow batteries. Here we present a porous polybenzimidazole(PBI) membrane with positive charges that endow the membrane with a high rejection and an excellent anti-fouling ability for target organic molecule and asymmetric structure that affords a high conductivity for vanadiummethylene blue flow battery(V-MB FB). The morphologies and thickness of separating layer in particular of the porous PBI can be well adjusted by simply altering the polymer concentration in the cast solution and further afford the membrane with a controllable property in terms of both ion selectivity and ion conductivity. As a result, a V-MB FB assembled with a porous PBI membrane delivers a coulombic efficiency(CE) of 99.45% and an energy efficiency(EE) of 86.10% at a current density of 40 mA cm^(-2), which is 12% higher than that afforded by a Nafion 212 membrane. Most importantly, the V-MB FB demonstrates a methylene blue(MB) utilization of 97.55% at a theoretical capacity of 32.16 Ah L^(-1)(based on the concentration of MB in the electrolyte) because of the high ion conductivity of the membrane, which favors reducing the cost of a battery. The results suggest that the designed porous PBI membranes exhibit a very promising prospect for methylene blue-vanadium flow battery.

High performance of zinc-ferrum redox flow battery with Ac^-/HAc buffer solution

A green low-cost redox flow battery using Zn/Znredox couple in HAc/NaAc medium and Fe/Feredox couple in HSOmedium was first proposed and investigated for potential stationary energy storage applications. The presence of HAc/NaAc in the negative electrolyte can keep the pH between 2.0 and 6.0even when a large amount of Hions move into negative electrolyte from positive electrolyte through ion exchange membrane. In the pH range of 2.0–6.0, the chemical reaction of Zn species with Hspecies is very insignificant; furthermore, the electroreduction of Hion on the negative electrode is significantly suppressed at this pH range. The zinc-ferrum redox flow battery（Zn/Fe RFB） operated within a voltage window of 0.5–2.0 V with a nearly 90% utilization ratio, and its energy efficiency is around 71.1% at room temperature. These results show that Zn/Fe RFB is a promising option as a stationary energy storage equipment.

In situ compression and X-ray computed tomography of flow battery electrodes

Redox flow batteries offer a potential solution to an increase in renewable energy generation on the grid by offering long-term, large-scale storage and regulation of power. However, they are currently un- derutilised due to cost and performance issues, many of which are linked to the microstructure of the porous carbon electrodes used. Here, for the first time, we offer a detailed study of the in situ effects of compression on a commercially available carbon felt electrode. Visualisation of electrode structure us- ing X-ray computed tomography shows the non-linear way that these materials compress and various metrics are used to elucidate the changes in porosity, pore size distribution and tortuosity factor under compressions from 0%-90%.

Bromine-Graphite Intercalation Enabled Two-Electron Transfer for a Bromine-Based Flow Battery

Br_(2)/Br^(−)is a promising redox couple in fl ow batteries because of its high potential,solubility,and low cost.However,the reaction between Br^(−)and Br_(2)only involves a single-electron transfer process,which limits its energy density.Herein,a novel two-electron transfer reaction based on Br^(−)/Br^(+) was studied and realized through Br^(+) intercalation into graphite to form a bromine-graphite intercalation compound(Br-GIC).Compared with the pristine Br^(−)/Br_(2)redox pair,the redox potential of Br intercalation/deintercalation in graphite is 0.5 V higher,which has the potential to substantially increase the energy density.Diff erent from Br_(2)/Br^(−)in the electrolyte,the diff usion rate of Br intercalation in graphite decreases with increasing charge state because of the decreasing intercalation sites in graphite,and the integrity of the graphite structure is important for the intercalation reaction.As a result,the battery can continuously run for more than 300 cycles with a Coulombic effi-ciency exceeding 97%and an energy effi ciency of approximately 80%at 30 mA/cm^(2),and the energy density increases by 65%compared with Br^(−)/Br_(2).Combined with double-electron transfer and a highly reversible electrochemical process,the Br intercalation redox couple demonstrates very promising prospects for stationary energy storage.