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.

KHCO_3 activated carbon microsphere as excellent electrocatalyst for VO^(2+)/VO_2^+ redox couple for vanadium redox flow battery

In this paper,carbon microsphere prepared by hydrothermal treatment was activated by KHCO_3 at high temperature,and employed as the catalyst for VO^(2+)/VO_2^+redox reaction for vanadium redox flow battery(VRFB).Carbon microsphere can be etched by KHCO_3 due to the reaction between the pyrolysis products of KHCO_3 and carbon atoms.Moreover,KHCO_3 activation can bring many oxygen functional groups on carbon microsphere,further improving the wettability of catalyst and increasing the active sites.The electrocatalytic properties of carbon microsphere from hydrothermal treatment are improved by high temperature carbonization,and can further be enhanced by KHCO_3 activation.Among carbon microsphere samples,the VO^(2+)/VO_2^+redox reaction exhibits the highest electrochemical kinetics on KHCO_3 activated sample.The cell using KHCO_3 activated carbon microsphere as the positive catalyst demonstrates higher energy efficiency and larger discharge capacity,especially at high current density.The results reveal that KHCO_3 activated carbon microsphere is an efficient,low-cost carbon-based catalyst for VO^(2+)/VO_2^+redox reaction for VRFB system.

Progress on the electrode materials towards vanadium flow batteries (VFBs) with improved power density

The vanadium flow battery （VFB） has been considered as one of the most promising large-scale energy storage technologies in terms of its design flexibility, long cycle life, high efficiency and high safety. How- ever, the high cost prevents the VFB technology from broader market penetration. Improving the power density of the VFB is an effective solution to reduce its cost due to the reduced material consumption and stack size. Electrode, as one of the main components in the VFB, providing the reactions sites for redox couples, has an important effect on the voltage loss of the VFB associated with electrochemical polariza- tion, ohmic polarization and concentration polarization. Extensive research has been carried out on the electrode modification to reduce polarizations and hence improve the power density of the VFB. In this review, state-of-the-art of various modification methods on the VFB electrode materials is overviewed and summarized, and the future research directions helpful to reduce polarization loss are presented.

Stability of highly supersaturated vanadium electrolyte solution and characterization of precipitated phases for vanadium redox flow battery

The vanadium redox flow battery(VRFB)has been receiving great attention in recent years as one of the most viable energy storage technologies for large-scale applications.However,higher concentrations of vanadium species are required in the H_(2)O-H_(2)SO_(4) electrolyte in order to improve the VRFB energy density.This might lead to unwanted precipitation of vanadium compounds,whose nature has not been accurately characterized yet.For this purpose,this study reports the preparation ofⅤ^((Ⅱ)),ⅤV^((Ⅲ)),Ⅴ^((Ⅳ))andⅤ^((Ⅴ))supersaturated solutions in a 5 M H_(2)SO_(4)-H_(2)O electrolyte by an electrolytic method,from the only vanadium sulfate compound commercially available(VOSO_(4)).The precipitates obtained by ageing of the stirred solutions are representative of the solids that may form in a VRFB operated with such supersaturated solutions.The solid phases are identified using thermogravimetric analysis,X-ray diffraction and SEM.We report that dissolvedⅤ^((Ⅱ)),Ⅴ^((Ⅲ))andⅤ^((Ⅳ))species precipitate as crystals of VSO_(4),V_(2)(SO_(4))3 and VOSO_(4) hydrates and not in their anhydrous form;conversely V^((Ⅴ))precipitates as an amorphous V_(2) O_(5) oxide partially hydrated.The measured hydration degrees(respectively 1.5,9,3 and 0.26 mol of H_(2)O per mol of compound)might significantly affect the overall engineering of VRFB operating with high vanadium concentrations.

A phosphotungstic acid coupled silica-Nafion composite membrane with significantly enhanced ion selectivity for vanadium redox flow battery

An ultra-high ion-selective Nafion composite membrane modified by phosphotungstic acid(PWA)coupled silica for vanadium redox flow battery(VRB)was constructed and prepared through solution casting.The composite membrane exhibits excellent proton conductivity and vanadium ions blocking property by incorporating the nanohybrid composed of silica and PWA into the Nafion ionomer.Simple tuning for the filling amount of the nanohybrid endows the obtained membranes preeminent vanadium barrier property including a minimum vanadium permeability of 3.13×10-7cm2min-1and a maximum proton conductivity of 0.081 S cm-1at 25°C.These indicate an ion selectivity of 2.59×105S min cm-3,which is 6.8times higher than that of recast Nafion(0.33×105S min cm-3).As a result,the VRB with the composite membrane shows superior battery performance containing a lower self-discharge rate,higher capacity retention and more robust cyclic stability compared with recast Nafion over a range of current densities from 40 to 100 m A cm-2.

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.

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.

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 ℃.

Sucrose pyrolysis assembling carbon nanotubes on graphite felt using for vanadium redox flow battery positive electrode

In the present paper, multi-walled carbon nanotubes（MWCNTs） are successfully assembled on graphite felt（GF） using sucrose pyrolysis method for the first time. The in situ formed pyrolytic carbon is chosen as the binder because it is essentially carbon materials as well as CNTs and GF which has a natural tendency to achieve high bonding strength and low contact resistance. The MWCNTs/GF electrode is demonstrated to increase surface area, reduce polarization, lower charge transfer resistance and improve energy conversion efficiency comparing with GF. This excellent electrochemical performance is mainly ascribed to the high electro-catalytic activity of MWCNTs and increasing surface area.

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.

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.

Insights into the hydrogen evolution reaction in vanadium redox flow batteries:A synchrotron radiation based X-ray imaging study

The parasitic hydrogen evolution reaction(HER)in the negative half-cell of vanadium redox flow batteries(VRFBs)causes severe efficiency losses.Thus,a deeper understanding of this process and the accompanying bubble formation is crucial.This benchmarking study locally analyzes the bubble distribution in thick,porous electrodes for the first time using deep learning-based image segmentation of synchrotron X-ray micro-tomograms.Each large three-dimensional data set was processed precisely in less than one minute while minimizing human errors and pointing out areas of increased HER activity in VRFBs.The study systematically varies the electrode potential and material,concluding that more negative electrode potentials of-200 m V vs.reversible hydrogen electrode(RHE)and lower cause more substantial bubble formation,resulting in bubble fractions of around 15%–20%in carbon felt electrodes.Contrarily,the bubble fractions stay only around 2%in an electrode combining carbon felt and carbon paper.The detected areas with high HER activity,such as the border subregion with more than 30%bubble fraction in carbon felt electrodes,the cutting edges,and preferential spots in the electrode bulk,are potential-independent and suggest that larger electrodes with a higher bulk-to-border ratio might reduce HER-related performance losses.The described combination of electrochemical measurements,local X-ray microtomography,AI-based segmentation,and 3D morphometric analysis is a powerful and novel approach for local bubble analysis in three-dimensional porous electrodes,providing an essential toolkit for a broad community working on bubble-generating electrochemical systems.

P-doped electrode for vanadium flow battery with high-rate capability and all-climate adaptability

A phosphorous-doped graphite felt(PGF) is fabricated and examined as electrode for vanadium flow battery(VFB). P doping improves the electrolyte wettability of GF and induces more defect sites on its surface, resulting in significantly enhanced activity and reversibility towards VO2^+/VO2^+ and V^2+/V3^+couples. VFB with PGF electrode demonstrates outstanding performance such as high-rate capability under 50–400 mA cm^-2, wide-temperature tolerance at-20 °C–60 °C, and excellent durability over 1000 charge–discharge cycles. These merits enable PGF a promising electrode for the next-generation VFB,which can operate at high-power and all-climate conditions.

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).

SPES/PVDF Binary Membrane as an Alternative Proton Exchange Membrane in Vanadium Redox Flow Battery Application

SPES/PVDF blends were employed to prepare the ion exchange membranes for vanadium redox flow battery(VRB) application for the first time. The addition of the highly crystalline and hydrophobic PVDF effectively limited the swelling behavior of SPES. The vanadium ion permeability of SPES/PVDF membranes was one order of magnitude lower than that of Nafion 117 membrane and pristine SPES membrane. Single cells with SPES/PVDF composite membranes showed significantly lower capacity loss, higher coulombic efficiency and higher energy efficiency than that with Nafion117 and pristine SPES membranes. The blend membrane with 40 wt% of PVDF(denoted as S_(0.6) P_(0.4)) showed energy efficiency of 83.2% at 30 mA?cm^(-2), which was superior to that of the Nafion117 and SPES membranes. In the self-discharge test, S_(0.6) P_(0.4) membrane showed twice longer duration in open circuit decay than that with Nafion 117 membrane. With all the good properties and low cost, the SPES/PVDF membranes are expected to have excellent commercial prospects as ion exchange membranes for VRB system.

Reconstructing proton channels via Zr-MOFs realizes highly ion-selective and proton-conductive SPEEK-based hybrid membrane for vanadium flow battery

There is an urgent need to break through the trade-off between proton conductivity and ion selectivity of proton exchange membrane(PEM)in vanadium flow battery(VFB).Proton channels in PEM are the key to controlling the ion sieving and proton conductivity in VFB.Herein,two types of proton channels are reconstructed in the hybrid membrane via introducing modified Zr-MOFs(IM-UIO-66-AS)into SPEEK matrix.Internal proton channels in IM-UIO-66-AS and interfacial proton channels between grafted imidazole groups on Zr-MOFs and SPEEK greatly improve the conductivity of the IM-UIO-66-AS/SPEEK hybrid membrane.More importantly,both reconstructed proton channels block the vanadium-ion permeation to realize enhanced ion selectivity according to the size sieving and Donnan exclusion effects,respectively.Moreover,the hybrid membrane exhibits good mechanical property and dimensional stability.Benefiting from such rational design,a VFB loading with the optimized membrane exhibits enhanced voltage efficiency of 79.9%and outstanding energy efficiency of 79.6%at 200 m A cm^(-2),and keeps a notable cycle stability for 300 cycles in the long-term cycling test.Therefore,this study provides inspiration for preparing next-generation PEMs with high ion selectivity and proton conductivity for VFB application.

A review of electrolyte additives and impurities in vanadium redox flow batteries

As one of the most important components of the vanadium redox flow battery （VRFB）, the electrolyte can impose a significant impact on cell properties, performance and capital cost. In particular, the electrolyte composition will influence energy density, operating temperature range and the practical applications of the VRFB. Various approaches to increase the energy density and operating temperature range have been proposed. The presence of electrolyte impurities, or the addition of a small amount of other chemical species into the vanadium solution can alter the stability of the electrolyte and influence cell perfor- mance, operating temperature range, energy density, electrochemical kinetics and cost effectiveness. This review provides a detailed overview of research on electrolyte additives including stabilizing agents, im- mobilizing agents, kinetic enhancers, as well as electrolyte impurities and chemical reductants that can be used for different purposes in the VRFBs.

Modified carbon cloth as positive electrode with high electrochemical performance for vanadium redox flow batteries

Carbon cloth modified by hydrothermal treatment in ammonia water is developed as the positive electrode with high electrochemical performance for vanadium redox flow batteries. The SEM shows that the treatment has no obvious influence on the morphology of carbon cloth. XPS measurements indicate that the nitrogenous functional groups can be introduced on the surface of carbon cloth successfully. The electrochemical performance of V(IV)/V(V) redox couple on the prepared electrode is evaluated with cyclic voltammetry and linear sweep voltammetry measurements. The N-doped carbon cloth exhibits outstanding electrochemical activity and reversibility toward V(IV)/V(V) redox couple. The rate constant of V(IV)/V(V) redox reaction on carbon cloth can increase to 2.27 x 10(-4) cm/s from 1.47 x 10(-4) cm/s after nitrogen doping. The cell using N-doped carbon cloth as positive electrode has larger discharge capacity and higher energy efficiency compared with the cell using pristine carbon cloth. The average energy efficiency of the cell using N-doped carbon cloth for 50 cycles at 30 mA/cm(2) is 87.8%, 4.3% larger than that of the cell using pristine carbon cloth. It indicates that the N-doped carbon cloth has a promise application prospect in vanadium redox flow batteries. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Glucose-derived hydrothermal carbons as energy storage booster for vanadium redox flow batteries

Fabricating of high performance electrodes by a sustainable and cost effective method is essential to the development of vanadium redox flow batteries(VRFBs).In this work,an effective strategy is proposed to deposit carbon nanoparticles on graphite felts by hydrothermal carbonization method.This in-situ method minimizes the drop off and aggregation of carbon nanoparticles during electrochemical testing.Such integration of felts and hydrothermal carbons(HTC)produces a new electrode that combines the outstanding electrical conductivity of felts with the effective redox active sites provided by the HTC coating layer.The presence of the amorphous carbon layers on the felts is found to be able to promote the mass/charge transfer,and create oxygenated/nitrogenated active sites and hence enhances wettability.Consequently,the most optimized electrode based on a rational approach delivers an impressive electrochemical performance toward VRFBs in wide range of current densities from 200 to 500 mAcm^-2.The voltage efficiency(VE)of GFs-HTC is much higher than the VEs of the pristine GFs,especially at high current densities.It exhibits a 4.18 times increase in discharge capacity over the pristine graphite felt respectively,at a high current density of 400 mAcm^-2.The enhanced performance is attributed to the abundant active sites from amorphous hydrothermal carbon,which facilitates the fast electrochemical kinetics of vanadium redox reactions.This work evidences that the glucose-derived hydrothermal carbons as energy storage booster hold great promise in practical VRFBs application.

ZIF-derived holey electrode with enhanced mass transfer and N-rich catalytic sites for high-power and long-life vanadium flow batteries

Electrode materials with good redox kinetics,excellent mass transfer characteristics and ultra-high stability play a crucial role in reducing the life-cycle cost and prolonging the maintenance-free time of the vanadium flow batteries(VFB).Herein,a nitrogen-doped porous graphite felt electrode(N-PGF)is proposed by growing ZIF-67 nanoparticles on carbon fibers and then calcinating and acid etching.The multi-scale structure of“carbon fiber gap(electrolyte flow),micro/nano pore(active species diffusion)and Nitrogen active center(reaction site)”in N-PGF electrode effectively increases the catalytic sites and promotes mass transfer characteristics.Reasonable electrode design makes the battery show excellent rate performance and ultra-high cycling stability.The peak power density of the battery reaches 1006 mW cm^(-2).During 1000 cycles at 150 mA cm^(-2),the average discharge capacity and average discharge energy of N-PGF increase substantially by 11.6%and 23.4%compared with the benchmark thermal activated graphite felt,respectively.More excitingly,after ultra-long term(5000 cycles)operation at an ultra-high current density(300 mA cm^(-2)),N-PGF exhibits an unprecedented energy efficiency retention(99.79%)and electrochemical performance stability.