Swelling-Induced Quaternized Anthrone-Containing Poly(aryl ether ketone) Membranes with Low Area Resistance and High Ion Selectivity for Vanadium Flow Batteries

Zhang, Bengui; Fu, Yanshi; Liu, Qian; Li, Lü; Zhang, Xueting; Yang, Zhirong; Zhang, Enlei; Wang, Kangjun; Wang, Guosheng; Zhang, Zhigang; Zhang, Shouhai

doi:10.1021/acsami.2c14107

Cited by 8 publications

(9 citation statements)

References 61 publications

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“…The capacity retention of the C-PyPEKK-90 and Nafion212 membranes at 160 mA cm –2 is summarized in Figure b. The C-PyPEKK-90 membrane exhibited a high-capacity retention rate (75.54%), about 1.9 times better than that of the Nafion212 membrane (39.22%) due to the high ion selectivity of the C-PyPEKK-90 membrane resulting in low vanadium ion crossover …”

Section: Resultsmentioning

confidence: 99%

“…The C-PyPEKK-90 membrane exhibited a high-capacity retention rate (75.54%), about 1.9 times better than that of the Nafion212 membrane (39.22%) due to the high ion selectivity of the C-PyPEKK-90 membrane resulting in low vanadium ion crossover. 69 The in situ stability of C-PyPEKK and uncross-linked PyPEKK-90 membranes under strongly acidic and oxidative conditions was investigated. Uncross-linked PyPEKK-90 membranes and cross-linked C-PyPEKK membranes were immersed in 1.5 M VO 2 + in 3 M H 2 SO 4 for 9 months at room temperature.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Swelling-Induced Cross-Linked Pyridine-Containing Membranes with High Stability and Conductivity for Vanadium Redox Flow Batteries

Zhang

Yang

Liu

et al. 2023

ACS Sustainable Chem. Eng.

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Vanadium redox flow batteries (VRFB) have many advantages in overcoming the volatility of renewable energy. However, membranes, one of the key materials for VRFB, face crucial challenges, for example, membranes with high conductivity tend to exhibit high swelling, low selectivity, and poor mechanical stability. In this work, new cross-linked membranes (C-PyPEKK) were prepared by blending a novel chloromethylated adamantane-containing polymer (CAPEK) (with a bulky, rigid, twisted backbone) with a unique pyridine-containing polymer (PyPEKK). The synergistic effect of cross-linked structures and bulky, rigidly twisted adamantane-containing backbone gives the membrane excellent membrane swelling resistance and selectivity. C-PyPEKK membranes were selectively swelled and formed wide ion transport channels, enhancing conductivity. The resulting C-PyPEKK membranes exhibited low water uptake (<8.0%), a low swelling ratio (<13.0%) (the uncross-linked PyPEKK membrane showed a high swelling ratio of 28.6%), and high mechanical strength (about 60 MPa). The C-PyPEKK-130 membrane showed a superior conductivity of 52.83 mS cm −1 and outstanding energy efficiencies (EEs) (90.75% at 80 mA cm −2 ; 79.4% at 300 mA cm −2 ), which was superior to the Nafion212 membrane (EE = 81.87%, 80 mA cm −2 ; 75.48%, 300 mA cm −2 ). The C-PyPEKK membranes showed high cycling stability (3500 cycles) in VRFB. Moreover, the C-PyPEKK membranes were robust and showed good battery performance after being immersed in strongly acidic and oxidizing 1.5 M VO 2 + in 3 M H 2 SO 4 solutions for 9 months, showing excellent chemical stability. This work proposes a new preparation route for membranes with high conductivity, high stability, and excellent mechanical strength for potential VRFB applications from unique new membrane materials combined with cross-linked membrane structures and unique conduction enhancement strategies.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Swelling-Induced Cross-Linked Pyridine-Containing Membranes with High Stability and Conductivity for Vanadium Redox Flow Batteries

Zhang

Yang

Liu

et al. 2023

ACS Sustainable Chem. Eng.

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“…59 Zhang et al reported 85.0% EE at 200 mA cm −2 for a quaternized anthrone-containing poly(aryl ether ketone) membrane. 65 More recently, a functionalized carbon black-modified sulfonated polyether ether ketone membrane displayed 80.0% EE at 200 mA cm −2 . 67 An ion-selective membrane constructed by incorporating graphitic carbon nitride nanosheets into a nonionic host matrix achieved 85.0% EE at 200 mA cm −2 .…”

Section: Single-cell Vrfb Performancementioning

confidence: 99%

“…For example, a benzimidazole-functionalized adamantanecontaining poly(aryl ether ketone) membrane exhibited an EE of 80.0% at 200 mA cm −2 59. Zhang et al reported 85.0% EE at 200 mA cm −2 for a quaternized anthrone-containing poly(aryl ether ketone) membrane 65. More recently, a functionalized carbon black-modified sulfonated polyether ether ketone membrane displayed 80.0% EE at 200 mA cm −2 67.…”

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confidence: 99%

Robust Polyaniline-silica@polypropylene for High-Performance, High-Capacity Retention All-Vanadium Redox Flow Battery

P. S.,

Sreenath,

Ash

et al. 2024

ACS Appl. Energy Mater.

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The development of high-performance membranes to address the issue of vanadium ion crossover in vanadium redox flow batteries (VRFB) is a significant area of focus. Current commercial perfluorinated membranes suffer from economic impracticality, poor ion selectivity, and electrolyte leakage. In this report, we present a composite membrane called PANI-Si@PP, which exhibits exceptional selectivity for protons over vanadium ions due to Donnan exclusion by the positively charged polyaniline backbone and the presence of well-defined proton conductive channels. To begin, we successfully synthesized and characterized a composite of polyaniline and silica (PANI-Si). Subsequently, we coated a porous polypropylene (PP) film with the PANI-Si composite using the phase inversion technique followed by acid functionalization. We assessed the surface characteristics and extent of pore filling through microscopic analysis and water flux measurements. The resulting membrane displayed excellent electrochemical and physicochemical properties. In a single-cell commercial VRFB, the PANI-Si@PP membrane achieved a Coulombic efficiency and energy efficiency of approximately ∼99 and ∼70%, respectively, over 300 cycles at a current density of 200 mA cm −2 , while retaining a high capacity of ∼70%. Additionally, the membrane exhibited a peak power density of 322 mW cm −2 at a current density of 350 mA cm −2 . This work highlights that the synergy of effective material selection and proper fabrication techniques is a successful approach to develop cutting-edge separators for battery applications.

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“…As expected, the membrane shows an ultralow area resistance of 0.04 Ω cm 2 , much lower than those of previously reported nonperfluorinated membranes in VFBs (Figure c and Table S2). ,,,,− In addition, the free-standing sub-10 μm membrane surprisingly demonstrates very high mechanical performance with a high tensile strength of 45.5 MPa due to its cross-linked network, superior to the Nafion 115 membrane (21.7 MPa). The cross-linked structure can also efficiently inhibit the transference of vanadium ions, achieving a low vanadium permeability of 5.97 × 10 –6 cm 2 h –1 .…”

Section: Introductionmentioning

confidence: 99%

A sub-10 μm Ion Conducting Membrane with an Ultralow Area Resistance for a High-Power Density Vanadium Flow Battery

Shi

Lü

2023

ACS Appl. Energy Mater.

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With the outstanding features of high safety, high efficiency, and long lifespan, the vanadium flow battery (VFB) is well-suited for large-scale energy storage; however, it suffers from low power density. The high ion conductivity of membranes is very important to increase the performance of VFBs at high current densities and improve their power density. Here, we show a highly conductive free-standing sub-10 μm polybenzimidazole (PBI) membrane. The decrease in the membrane thickness contributes to shorter ion-transport pathways and lower resistance. The relatively loose cross-linked structure of the thin membrane provides sufficient free volume for ion transport. According to these results, the membrane exhibits an ultralow area resistance of 0.04 Ω cm2, much lower than that of commercial Nafion 115 membrane (0.20 Ω cm2), making the ion conductivity superior. Additionally, the sub-10 μm PBI membrane also shows a very high tensile strength of 45.5 MPa and high ion selectivity. The VFB assembled with a sub-10 μm PBI membrane delivers a high energy efficiency of approximately 80% at a high current density of 200 mA cm–2 and can run stably for more than 500 cycles without obvious performance decay. The increased performance of the VFB at a very high current density of 200 mA cm–2 contributes to its higher power density. Therefore, it is an available way to adopt free-standing sub-10 μm PBI membranes with high conductivity, selectivity, and mechanical stability to improve the power density of VFBs. Similarly, the application of it will also accelerate the practical application of VFB energy storage technology.

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Swelling-Induced Quaternized Anthrone-Containing Poly(aryl ether ketone) Membranes with Low Area Resistance and High Ion Selectivity for Vanadium Flow Batteries

Cited by 8 publications

References 61 publications

Swelling-Induced Cross-Linked Pyridine-Containing Membranes with High Stability and Conductivity for Vanadium Redox Flow Batteries

Swelling-Induced Cross-Linked Pyridine-Containing Membranes with High Stability and Conductivity for Vanadium Redox Flow Batteries

Robust Polyaniline-silica@polypropylene for High-Performance, High-Capacity Retention All-Vanadium Redox Flow Battery

A sub-10 μm Ion Conducting Membrane with an Ultralow Area Resistance for a High-Power Density Vanadium Flow Battery

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