Journal of Materials Chemistry A
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2024
·Vol. 12
·期 26
·15914-15921
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IF 10.7
Bo Pang,Wanting Chen,Weiming Yu,Yujie Guo,Xuemei Wu,Xiaoming Yan,Fujun Cui,Shouhai Zhang,Gaohong He
The design of ion conductive functional side chains is critical to tune the selectivity of protons to vanadium ions in ion conductive membranes for vanadium redox flow batteries (VRFBs); however, it is far from satisfactory. Herein, the concept of a quinone convertible sulfated ion conductive side chain is proposed with tunable Donnan effect and strong proton conducting ability. The electrically neutral phenol group in the side chain will be chemically converted to quinone of lower electronegativity in situ in the highly acidic VRFB operating environment, which leads to about a 5 fold increase in zeta potential to repel vanadium ions. Meanwhile the sulfate ester cationic exchange group in the side chain dominates the well-formed ion clusters (7.85 nm) and hydrogen bonding for fast proton conduction. With a quinone group capacity (IECQ) of 2.43 mmol g−1 in the polybenzimidazole (PBIPhOSO3-q-2.43), the low area resistance (0.23 Ω cm2) and vanadium permeability (3.2 × 10−9 s cm−2) contribute to about a 16.5 fold increase in H+/Vn+ selectivity as compared with the Nafion 212 membrane. The corresponding VRFB shows a low discharge capacity decay rate (0.31% per cycle) and high energy efficiency (87.7%) at 100 mA cm−2 and remains stable during the 500 cycle test. The performance is superior to that of the most recently reported amphiprotic ion conductive membranes.
研究领域:
能源材料科学
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电化学工程
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高影响因子
JOURNAL OF POWER SOURCES
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2024
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IF 8.1
Xiaoyu Meng,Qiwang Peng,Luman Peng,Yuanyuan Wang,Xiaocan Zhang,Tianyu Wu,Chuanbo Cong,Haimu Ye,Qiong Zhou
Perfluorosulfonic acid (PFSA) is the most widely used membrane material for all-vanadium redox flow batteries (VRFB). However, severe vanadium ion permeation of PFSA membranes remains to be solved. In this work, a series of PFSA-based composite membranes are prepared by introducing two-dimensional continuous covalent organic framework (COF) to achieve enhanced performance. Two dimensional continuous Schiff base network-type COFs (GO/SNW) are synthesized by using the two-dimensional multi-functionalized surface of graphene oxide (GO) as a reaction site. Compared to the original form of agglomerated particles, two-dimensional continuous structure obtained a larger vanadium resistance area. Comparing to conventional PFSA membranes, the special pores of COF have a size sieving mechanism for selectively proton transfer, leading to simultaneously enhancement of proton conductivity and vanadium barrier property. VRFB assembled with PFSA-GO/SNW-7 showed high Coulombic efficiency (CE: 97.47%–98.18 % VS PFSA: 80.73%–91.92 %) and energy efficiency (EE: 93.04%–85.71 % VS PFSA: 77.53%–81.78 %) at 40–120 mA cm −2 . In addition, there is no significant decrease in the efficiency of battery assembled with PFSA-GO/SNW-7 after 800 cycle (than 650 h) tests. This work provides a new direction in the design of fillers for mixed matrix membranes.
研究领域:
材料科学
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电化学工程
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Yongzheng Jia,Yu Qing,Baoyan Feng,Yiwei Zhong,Lei Dai,Mingyong Wang
Green separation and efficient extraction of vanadium and chromium from vanadium-chromium leaching solution are serious challenges for the utilization of chrome-vanadium slag. A green sucrose reduction-H 2 O 2 selective oxidation route is proposed for deep separation of vanadium and chromium from vanadium-chromium leaching solution based on different redox properties. Eh-pH diagram of V-Cr-H 2 O system and existence forms of vanadium and chromium ions are calculated. Obvious difference of redox properties between V(V) and Cr(VI) exists in acidic environment. The dependences of selective separation on pH for reduction, temperature, m (sucrose) /m (Cr(VI)) and n (H2O2) /n (V(V)) are studied. The concentration ratio of vanadium to chromium in solution after selective separation of chromium decreases from 1.6 to 0.06. The extraction ratios of Cr 2 O 3 and V 2 O 5 are 96.3% and 93.8%, respectively. The redox behavior of V(V) and Cr(VI) is revealed. Cr(VI) and V(V) are reduced to Cr(Ⅲ) and V(IV) by 5-hydroxymethylfurfural, a hydrolysate of sucrose, and then V(IV) is selectively oxidized to V(V) by H 2 O 2 . Cr 2 O 3 ·n(H 2 O) and ammonium polyvanadate obtained by hydrolysis and ammonium precipitation are calcined to Cr 2 O 3 and V 2 O 5 , respectively. Cr 2 O 3 with the purity of 99.4% can be used as high-quality pigment. The purity of V 2 O 5 meets the requirements of YB/T 5304–2011 for 98 V 2 O 5 .
研究领域:
冶金工程
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环境科学
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高影响因子
ACS Applied Materials & Interfaces
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2018
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IF 8.097
Xiaoming Yan,Caimian Zhang,Ziwei Dong,Bowen Jiang,Yan Dai,Xuemei Wu,Gaohong He
A novel amphiprotic side-chain-functionalized membrane was for the first time designed for vanadium redox flow battery (VFB). Different from frequently used blending amphiprotic membranes, the one proposed here is allowed to possess high anion-exchange capacity (IECa) without sacrificing the cation-exchange capacity (IECc) because both IECa and IECc increased with the grafting degree of side chains. Having a high IECa, the membrane prepared here exhibits an ultralow vanadium permeability (<10–8 cm2 s–1), which leads to very high Coulombic efficiencies (97–98% at 40–200 mA cm–2) of VFB and good cell self-discharge durability. Moreover, the high IECc contributes to a decent ionic conductivity (area resistance: 0.5 Ω cm–2), which ensures a high-voltage efficiency of the cell. On the basis of these good properties, the VFB single cell with this membrane achieves a high energy efficiency (e.g., 77.4% at 200 mA cm–2) that is higher than those of Nafion 212 and other reported amphiprotic membranes. These results indicate that the approach proposed here is an ideal option to prepare amphiprotic membranes for VFBs with high efficiency and good durability.
研究领域:
材料科学
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电化学能源
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Jiaye Ye,Shuhui Yu,Chunhua Zheng,Tianfu Sun,Jie Liu,Huiyun Li
As a key component of vanadium redox flow battery (VRFB), ion exchange membrane determines the performance of VRFB, wherein commercial membrane (such as Nafion) exacerbate problems including high permeability of vanadium ions and poor cyclic stability. In this study, a low vanadium ion permeation hybrid membrane is developed by dispersing functionalized silicon carbide nanowires in perfluorinated sulfonic acid (PFSA) matrix and sandwiching an ultrathin porous polytetrafluoroethylene (PTFE) layer. This hybrid membrane greatly improves the performance of VRFB cell exhibiting good Coulombic efficiency (up to 96.2%) and high energy efficiency (up to 87.1%) at 120 mA cm −2 , contrasted with the Nafion 212 membrane (91.3% and 79.8%). Furthermore, a single cell with the hybrid membrane possesses ultra-stable cyclicity (1000 cycles, over 233.4 h). This can be assigned to the unique structure of the membrane in which the functionalized nanowires are uniformly dispersed in PFSA matrix to sandwich an ultra-thin PTFE layer to block or lengthen the diffusion paths of vanadium ions, while the functionalized groups on the surface of the rigid nanowires facilitate protons transportation. This strategy of reshaping membrane may serve in relative fields including proton exchange membrane fuel cells and water treatment.
研究领域:
材料科学
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能源技术
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DOI
高影响因子
HYDROMETALLURGY
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2022
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IF 4.217
Rongrong Chen,Chunlv Feng,Jun Tan,Cheng Zhang,Shenghua Yuan,Mei Liu,Huiping Hu,Qinxiang Li,Jiugang Hu
Recovering metal values in hazardous spent hydrogenation catalysts is of vital economic and environmental importance. Herein, the selective recovery of valuable molybdenum (Mo), vanadium (V), and nickel (Ni) from spent hydroprocessing catalysts are achieved by using a sulfuric acid leaching-stepwise extraction process. After roasting in the air at 400 °C, the valuable metals are effectively leached within 20 min by 1 mol/L sulfuric acid at 75 °C. The leaching efficiency of Al, Ni, Mo, and V is 22.16%, 99.44%, 98.59%, and 100%, respectively. Based on the species analysis of the leachate, a stepwise extraction separation route was established for selective recovery of Mo, Ni, and V from the acidic leachate. Mo and V are preferentially co-extracted by the mixed TOA/Cyanex272 with a molar ratio of 7:3, which exhibits an excellent extraction selectivity over Ni and Al. Increasing the concentration of Cyanex272 in the mixed system can effectively improve the selective stripping of vanadium but slightly inhibit its extraction. Residual Ni in the raffinate can be selectively separated by 50%( V / V ) commercial HBL110 with an extraction efficiency of 98.5%. Especially, the reductive sodium sulfite can greatly enhance the selective stripping of vanadium from the loaded organic phase. Residual Mo in the organic phase can be well stripped with an alkaline solution. The selective stripping mechanism of vanadium is revealed by the FT-IR and Raman spectra . This work proposes a sustainable stepwise separation route for recovering valuable metals in the spent hydroprocessing catalyst.
研究领域:
化学工程
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环境科学
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2015
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IF 5.056
Jinchao Li,Yaping Zhang,Shuai Zhang,Xiaodong Huang
We report the fabrication and properties of high performance and inexpensive composite membranes of sulfonated polyimide (SPI) and sulfonated molybdenum disulfide (s-MoS 2 ) for the vanadium redox flow battery (VRFB) application. Scanning electron microscopy (SEM) images reveal the uniformity of SPI/s-MoS 2 membrane. Both EDS and XRD results verify the existence of s-MoS 2 in SPI/s-MoS 2 membrane and show the interaction between SPI and s-MoS 2 . The physico-chemical properties of as-prepared SPI/s-MoS 2 membrane, including water uptake and ion exchange capacity, etc. are evaluated and compared to those of SPI, SPI/MoS 2 and Nafion 117 membranes, respectively. The SPI/s-MoS 2 membrane possesses increased proton conductivity and reduced vanadium ion permeability than pure SPI membrane, and it has the highest proton selectivity (2.24×10 5 S min cm −3 ) among all membranes. The VRFB with SPI/s-MoS 2 membrane presents a higher coulombic efficiency ( CE ) and energy efficiency ( EE ) compared with Nafion 117 at the current density ranging from 20 to 80 mA cm −2 . The SPI/s-MoS 2 membrane shows a longer discharge time (193 h above 0.8 V) than Nafion 117 (72 h). Moreover, the SPI/s-MoS 2 membrane exhibits stable operation performance up to 500 cycles with no significant decline in CE and EE . All experimental results confirm that the SPI/s-MoS 2 membrane is suitable for use in VRFB.
研究领域:
材料科学
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电化学
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2023
·
IF 9.5
Bo Pang,Xuemei Wu,Yusong guo,Min Yang,Ruohan Du,Wanting Chen,Xiaoming Yan,Fujun Cui,Gaohong He
Anionic conductive group repels vanadium ions but is difficult to be incorporated into the selectively ionic conductive channels of the amphoteric ion conductive membrane with tunable ratio. Herein, the novel hydroxyl bromopropane anionic precursor side chain is proposed, in which the hydrophilic hydroxyl groups aggregate into ionic clusters with the sulfate ester cationic conductive side chains of polybenzimidazole via hydrogen bond during membrane casting. The subsequent conversion of the bromopropane precursor to quaternary ammonium can easily tune the anionic exchange capacity and integrate cations into the hydroxyl involved ionic conductive channels for selectively repelling vanadium ions. Compared with Nafion 212 membrane, the obtained amphoteric membrane exhibits much lower vanadium ion permeability (1.9 × 10 −9 cm 2 s −1 ) and slightly lower area resistance (0.25 Ω cm 2 ). Excellent performance of vanadium redox flow battery (coulombic efficiency, 99.2%, energy efficiency, 85.9% at 100 mA cm −2 and 0.31% discharge decay rate) is achieved, and efficiencies keep stable during the 500 cycles test. The performance of VRFB is surpass than that of most reported amphoteric ion conductive and Nafion 212 membranes.
研究领域:
材料科学
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电化学
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2022
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IF 10.53
Jun Liu,Jun Long,Wenheng Huang,Wenjie Xu,Xiujuan Qi,Jinchao Li,Yaping Zhang
Vanadium redox flow battery (VFB) is promising for use as an energy storage/conversion device, however membrane imposes a limitation in enhancing the performance of VFB. Herein, a novel diamine monomer bis(2-trifluoromethyl-4-aminobenzene) amine containing imino groups is synthesized by nucleophilic substitution and reduction reactions. Then, we develop four branched sulfonated polyimide (I-bSPI) membranes with 40%–70% theoretical sulfonation degrees for application in VFB. The trade-off between proton conduction and vanadium ion blocking of I-bSPI membrane is broken, and the stability of I-bSPI membrane is also effectively enhanced owing to hydrogen bonds network and Donnan repulsion effect. Surprisingly, the proton selectivity of I-bSPI-50 membrane is 4.6 times that of commercial Nafion 212 membrane. In addition, I-bSPI-50 membrane exhibits superior coulomb and energy efficiencies to Nafion 212 membrane at 100–300 mA cm −2 . And I-bSPI-50 membrane has steady efficiencies and high capacity holding abilities during 600-time cycles. This work illustrates a promising pathway to obtain cost-effective membrane by hydrogen bonds construction strategy for VFB application.
研究领域:
材料科学
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电化学
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DOI
高影响因子
Materials Science and Engineering B-Advanced Functional Solid-State Materials
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2023
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IF 3.6
Kezhong Wu,Feifei Nie,Xi Qi,Yingshan Wu,Hui Zhao,Mingxing Wu
Vanadium-based nitrides have been applied as Pt-free counter electrodes (CEs) electro-catalysts for dye-sensitized solar cells (DSSCs) due to inexpensive cost and easy doping and modification. Herein, polyoxovanadate (NH 4 ) 2 V 6 O 16 assisted by melamine to prepare VN@C composites by five different synthesis routes, including solvothermal, sol–gel, hydrothermal, ball milling, and chemical mixing method. And then, five VN@C composites were assembled as CEs in the encapsulated DSSCs, and yielded power conversion efficiencies of 4.47, 5.04, 5.35, 5.49 and 6.11% for regenerate traditional I 3 − /I − shuttles by the photocurrent-photovoltage ( J - V ) test, respectively. The catalytic performances of VN@C composites CEs were assessed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Tafel polarization experiments, and the significant effects of different synthetic routes were confirmed. The results revealed that VN@C composite CEs prepared by chemical mixing method had higher catalytic performance in DSSCs, which is due to the improvement of conductivity and the high concentration of active sites.
研究领域:
材料科学
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能源科学
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DOI
高影响因子
METALLURGICAL AND MATERIALS TRANSACTIONS B-PROCESS METALLURGY AND MATERIALS PROCESSING SCIENCE
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2025
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IF 3.1
Zhang Ningyu,Zhang Yang,Xiang Junyi,Xue Yuxiao,Yu Wenhao,Lv Xuewei
The conventional vanadium extraction and dephosphorization processes in the converter are carried out separately, which results in high energy consumption and operational complexity. Calcium ferrates possess the dual function of oxidizing agents and alkaline sources, which provides a novel approach for integrating vanadium extraction and dephosphorization processes. Accordingly, the simultaneous extraction of vanadium and dephosphorization from V-bearing hot metal by the addition of calcium ferrates was proposed in this study for the first time. The experiments were conducted in a low-frequency induction furnace at 1523 K to 1673 K in an inert atmosphere. Thermodynamic calculations and experimental studies demonstrate the potential of calcium ferrates to facilitate vanadium extraction and dephosphorization simultaneously. Especially CaFe 4 O 7 and CaFe 2 O 4 , due to their low melting point and high Oxidizing ability, can reduce the vanadium and phosphorus contents in hot metal to below 0.024 and 0.010 wt pct at 1623 K for 6 minutes of reaction. Correspondingly, the lg L V are 2.42 and 2.37, whereas the lg L P are 2.13 and 2.14, respectively. In the slag, vanadium is oxidized from V 3+ to V 5+ by Fe 2 O 3 with the CaO content increases. A shift from spinel to calcium vanadium silicate is observed. Phosphorus is always present in calcium silicate. The simultaneous vanadium extraction and dephosphorization are achieved only by adding calcium ferrate, effectively recovering vanadium resources and improving semi-steel purity.
研究领域:
冶金学
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材料科学
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化学工程
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提取冶金
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高影响因子
JOURNAL OF POWER SOURCES
·
2019
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IF 7.467
Pan Yang,Jun Long,Sensen Xuan,Yanlin Wang,Yaping Zhang,Jinchao Li,Hongping Zhang
The trade-off between high proton conductivity and low vanadium ion permeability needs to be overcome urgently for membrane in vanadium redox flow battery (VRFB). A series of fluorine-containing branched sulfonated polyimide membranes with ionic cross-linking (c-FbSPI) and different degrees of sulfonation (40–70%) are prepared through polycondensation by introducing –CF 3 group, branched structure and ionic cross-linking. The c-FbSPI membranes have much lower vanadium ion permeabilities (0.36–3.87 ✕ 10 −7 cm 2 min −1 ) and higher proton selectivities (0.89–4.20 ✕ 10 5 S min cm −3 ) comparing with Nafion 115 membrane, respectively. Besides, c-FbSPI membranes have outstanding chemical stabilities when immersing in strong acidic and oxidizing solution for 38 days. The VRFB with selected c-FbSPI-60 membrane shows lower self-discharge speed and higher charge-discharge capacity and energy comparing to those with Nafion 115 membrane. During 300-time cyclical charge-discharge measurement, the VRFB assembled with c-FbSPI-60 membrane shows higher coulombic efficiency (97–99.5%), energy efficiency (68.2–75.1%) and capacity retention (50.5–55.1%) compared with the VRFB using Nafion 115 membrane at 80–60 mA cm −2 . This work provides a new approach for preparing high cost-performance aromatic polymer membrane, which is significant for accelerating the industrialization process of VRFB.
研究领域:
材料科学
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电化学工程
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DOI
高影响因子
危险品化学品经营许可证（带存储）