Branched sulfonated polyimide/s-MWCNTs composite membranes for vanadium redox flow battery application

A novel sulfonated multi-wall carbon nanotubes (s-MWCNTs) filler is synthesized by ring-opening reaction. And then, a series of branched sulfonated polyimide (bSPI)/s-MWCNTs composite membranes are also prepared for application in vanadium redox flow batteries (VRFBs). The optimized bSPI/s-MWCNTs-2% composite membrane has lower vanadium ion permeability (2.01 × 10⁻⁷ cm² min⁻¹) and higher proton selectivity (1.06 × 10⁵ S min cm⁻³) compared to those of commercial Nafion 212 membrane. Moreover, the VRFB with bSPI/s-MWCNTs-2% composite membrane exhibits higher coulombic efficiencies (CEs: 96.0–98.2%) and energy efficiencies (EEs: 79.7–69.5%) than that with Nafion 212 membrane (CEs: 86.5–92.5% and EEs: 78.5–67.6%) at 80–160 mA cm⁻². The VRFB with bSPI/s-MWCNTs-2% composite membrane has stable battery performance over 400 cycles at 100 mA cm⁻², whose EE value is in the top level among previously reported SPI-based composite membranes. The results show that the bSPI/s-MWCNTs-2% composite membrane has a great prospect in VRFB application.     

Development of perfluorosulfonic acid polymer-based hybrid composite membrane with alkoxysilane functionalized polymer for vanadium redox flow battery

A new kind of alkoxy silane functionalized polymer (ASFP) is synthesized by selectively functionalized carboxyl groups as a novel inorganic precursor polymer to prepare organic-inorganic hybrid membrane for vanadium redox flow battery (VRFB) system. The novel hybrid membrane has been fabricated by interconnection between hydrophilic domains of Nafion and ASFP functional group. The effective concentration of ASFP for hybrid membrane is 25% (wt/wt). The proton conductivity and selectivity of the hybrid membrane are comparable with those of the Nafion212 membrane, which is mainly attributed by the presence of additional hydrophilic domains in the hybrid membrane. The proton conductivity and ion exchange capacity of the Nafion-ASFP (75:25) membrane is 0.061 S/cm and 0.68 meq/g, respectively. Remarkably, the Nafion-ASFP membrane shows a low vanadium permeability (1.259 × 10⁻⁷ cm²/min) and high selectivity, which is an excellent advantage. As a result, the hybrid membrane shows comparable efficiency performance with Nafion212 over 50 cycles. Notably, the VRFB unit cell with Nafion-ASFP membrane achieves higher coulombic efficiency than Nafion212. The hybrid membrane reveals a new route to develop an alternative fluorinated polymer membrane with numerous advantages especially cost-effectiveness, homogeneous dispersion of inorganic silica precursor materials in the hybrid membrane without deterioration of mechanical strength, and lower vanadium ion crossover for VRFB system.     

Proton exchange membranes containing densely alkyl sulfide sulfonated side chains for vanadium redox flow battery

Due to further increase the performance of aromatic sulfonated proton exchange membrane (PEM) and make it play a better role in vanadium redox flow battery (VRFB), a series of poly(aryl ether sulfone)s containing eight alkyl sulfide sulfonated side chains (8SPAES-xx) are designed and synthesized. Their molecular structure, phase morphology and some selective properties were investigated in detail, respectively. It is confirmed that 8SPAES-xx membranes have clear hydrophilic/hydrophobic phase separation morphology. These membranes with the ion exchange capacity values of 1.08–1.61 mmol/g exhibit excellent ionic conductivity as well as moderate water uptake and good dimensional stability, and their values are in the range of 25–96 mS/cm, 8–28% and 5–17% at 30 °C, respectively. Among them, the proton conductivity of 8SPAES-12 membrane is 82 mS/cm at 30 °C, which exceeds the ionic conductivity of Nafion 117 (79 mS/cm). The membrane also shows high ion selectivity and excellent battery performance. At current density of 60 mA/cm², the highest energy efficiency of VRFB with 8SPAES-12 membrane is 87.3%, which is higher than that of Nafion 117 (83.8%). Furthermore, the efficiency of VRFB with 8SPAES-12 membrane remains good cycle stability.     

A novel long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) membrane for vanadium redox flow battery

A novel long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (S-L-PPO) membrane was successfully prepared for VRFB applications. The long side chains were introduced onto the PPO backbones by a simple and controllable acylation with 4-fluorobenzoyl chloride and a subsequent condensation with sodium 4-hydroxybenzenesulfonate. The introduction of long side chains drives the formation of a good hydrophilic/hydrophobic micro-phase separation structure, which is evidenced by AFM. The S-L-PPO membrane with a degree of sulfonation (DS) of 51% showed an ultralow vanadium permeability (4.3 × 10^?9 cm² s^?1) and a decent proton conductivity (44 mS cm^?1). As a result, the energy efficiency of VRFB with S-L-PPO-51% membrane was up to 81.8% that was higher than that with Nafion 212 (78.0%) at a current density of 120 mA cm^?2. In addition, the self-discharge duration of the cell with S-L-PPO-51% membrane was 222 h that was nine times longer than that of Nafion 212 (23 h). All these indicate that the membrane prepared here is promising for the application in VRFB.     

Proton exchange membranes with ultra-low vanadium ions permeability improved by sulfated zirconia for all vanadium redox flow battery

Suppressing vanadium ions crossover is a top priority in the development of membranes for vanadium redox flow battery (VRFB). One method is to dope inorganic fillers into polymer matrix, which usually decreases membrane's ion conductivity. In this work, sulfated zirconia (SZrO₂) is synthesized as a novel additive doped in sulfated poly (ether sulfone) (SPES) to simultaneously enhance the proton conduction and inhibit vanadium migration of the membranes. Membrane characterizations including battery test are carried out to reveal the effects of SZrO₂ on the membrane performance. The SPES/SZrO₂ composite membranes show vanadium permeability one order of magnitude lower than that of Nafion 212 and enhanced proton conductivity, which lead to superior cell performance. The columbic efficiency and energy efficiency of the VRFB reach 98.89% and 86.78%, respectively, at 100 mA cm⁻². Cycling test is carried out to evaluate the chemical and electrochemical stability of the membrane. Energy efficiency above 86% is maintained after70 charge-discharge cycles at 100 mA cm⁻².     

Orientated graphene oxide/Nafion ultra-thin layer coated composite membranes for vanadium redox flow battery

Graphene oxide (GO)/Nafion composite membranes, with orientated GO nanosheets in parallel to the surface of the ultra-thin coating layer (400–440 nm), are prepared by spin coating method and evidenced by electron microscopy analysis. Orientation of GO maximizes the vanadium ions barrier effect of GO. The GO/Nafion membrane (M-2) achieves lower vanadium ion permeability (8.2 × 10^?8 cm² min^?1, only 2.64% of the pristine Nafion membrane), and higher coulombic efficiency and energy efficiency (92.9–98.8% and 81.5–88.4%, respectively) comparing with the pristine Nafion membrane (73.3–90.5% and 68.9–79.1%, respectively) at current densities of 20–100 mA cm^?2. With the design of orientated GO nanosheets and ultra-thin GO/Nafion coating layer, good balance between vanadium crossover suppression and protons conduction retention is achieved. M-2 exhibits excellent battery performances over 200 charge-discharge cycles. The capacity decay rate is about 0.23% per cycle, much lower than those assembled with Nafion 212 (0.40% per cycle) and the recast Nafion membrane (0.44% per cycle). Spin coating with water suspensor leads to uniform dispersion of GO and good binding between GO/Nafion coating layer and substrate Nafion membrane. Therefore, the composite membrane could be reinforced by GO and keep integration even with 200 cycles operation.     

Highly stable graphene oxide composite proton exchange membrane for electro-chemical energy application

Proton exchange membrane is a basic element for any redox flow battery. Nafion is the only commercial available proton exchange membrane used in different electro-chemical energy systems. High cost restrict it's used for energy generation devices. In present work, we synthesised styrene divinylbenzene based composite proton exchange membranes (PEMs) with varying sulfonated graphene oxide (sGO) content for redox flow battery (RFB). Synthesized copolymer PEMs were analyzed in terms of their chemical structure with the help of FT-IR spectroscopy to confirm desired functional groups at appropriate position. Electrochemical characterization was performed in terms proton-exchange capacity, protonic conductivity and water uptake. Membrane shows adequate proton exchange capacity with good proton conductivity. Vanadium ion permeability was also tested for the prepared membrane to assess capability for vanadium redox flow battery (VRFB) in contrast with commercially available Nafion 117 PEM. Higher VO⁺² ion cross-over resistance was found for CEM-4 with 7.17 × 10⁻⁷ cm² min⁻¹ permeability, which is about half of the CEM-1. Further CEM-4 was also evaluated for charging-discharging phenomenon for single cell VRFB. The values of columbic, voltage and energy efficiency for VRFB confirms prepared membrane as a good candidate for redox flow battery. Composite PEM also shows better mechanical and thermal stability. Results indicates that synthesized composite membrane can be used in vanadium redox flow battery.     

Nafion/polyvinylidene fluoride blend membranes with improved ion selectivity for vanadium redox flow battery application

Nafion/PVDF blends are 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 confines the swelling behavior of Nafion. In VRB single cell test, the Nafion/PVDF binary membranes exhibit higher columbic efficiency than recast Nafion at various current densities. The blend membrane with 20 wt% of PVDF (N_0.8P_0.2) shows energy efficiency of 85% at 80 mA cm⁻², which is superior to that of recast Nafion. N_0.8P_0.2 membrane also possesses twice longer duration in OCV decay test and much lower permeation of VO²⁺ compared with recast Nafion. These results indicate that the addition of PVDF is a simple and efficient way to improve the ion selectivity of Nafion, and the polymer blends with optimized mass fraction of PVDF show good potential for VRB application.     

Nafion/organically modified silicate hybrids membrane for vanadium redox flow battery

In our previous work, Nafion/SiO₂ hybrid membrane was prepared via in situ sol–gel method and used for the vanadium redox flow battery (VRB) system. The VRB with modified Nafion membrane has shown great advantages over that of the VRB with Nafion membrane. In this work, a novel Nafion/organically modified silicate (ORMOSIL) hybrids membrane was prepared via in situ sol–gel reactions for mixtures of tetraethoxysilane (TEOS) and diethoxydimethylsilane (DEDMS). The primary properties of Nafion/ORMOSIL hybrids membrane were measured and compared with Nafion and Nafion/SiO₂ hybrid membrane. The permeability of vanadium ions through the Nafion/ORMOSIL hybrids membrane was measured using an UV–vis spectrophotometer. The results indicate that the hybrids membrane has a dramatic reduction in crossover of vanadium ions compared with Nafion membrane. Fourier transform infrared spectra (FT-IR) analysis of the hybrids membrane reveals that the ORMOSIL phase is well formed within hybrids membrane. Cell tests identify that the VRB with Nafion/ORMOSIL hybrids membrane presents a higher coulombic efficiency (CE) and energy efficiency (EE) compared with that of the VRB with Nafion and Nafion/SiO₂ hybrid membrane. The highest EE of the VRB with Nafion/ORMOSIL hybrids membrane is 87.4% at 20 mA cm⁻², while the EE of VRB with Nafion and the EE of VRB with Nafion/SiO₂ hybrid membrane are only 73.8% and 79.9% at the same current density. The CE and EE of VRB with Nafion/ORMOSIL hybrids membrane is nearly no decay after cycling more than 100 times (60 mA cm⁻²), which proves the Nafion/ORMOSIL hybrids membrane possesses high chemical stability during long charge–discharge process under strong acid solutions. The self-discharge rate of the VRB with Nafion/ORMOSIL hybrids membrane is the slowest among the VRB with Nafion, Nafion/SiO₂ and Nafion/ORMOSIL membrane, which further proves the excellent vanadium ions blocking characteristic of the prepared hybrids membrane.     

PVDF proton conductive membranes for vanadium redox flow batteries

全钒液流电池(VRFB)是一种大规模蓄电储能设备,在可再生能源利用和节能技术领域将发挥重要作用,该过程所需的质子传导膜要具备优良的导电性,阻钒性,稳定性以及合理的成本.该研究突破以往离子交换膜的概念限制,提出利用纳米尺度孔径膜材料的"筛分"效应,满足全钒液流电池对隔膜综合性能的需求.首次提出分子间亲水/疏水相互作用诱导高分子溶液相分离的成膜原理,通过在疏水性高分子溶液中引入亲水性单体聚合形成的低聚物方式,调控铸膜液中分子间相互作用和相分离过程动力学,制备纳米尺度的高稳定性多孔膜.在大量科学研究工作基础上,完成工业规模的制膜工艺放大和批量化生产,所制聚偏氟乙烯(PVDF)质子传导膜面积为800 mm×900 mm,厚度在60~150 μm之间可调,电导率达到3×10^-2 S/cm.利用自制膜装配成8 kW的电堆,其能量效率达到72%,基本满足全钒液流电池产业化发展需求.     

Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test.     

Role of UV irradiated Nafion in power enhancement of hydrogen fuel cells

The influence of optimum UV ray exposure of pristine Nafion polymer membranes on the improvement of proton conductivity and hydrogen fuel cell performance has been examined. Nafion membranes with thickness 183  μm (117), 90  μm (1035), 50  μm (212) and 25  μm (211) were irradiated with ultraviolet rays with doses in the range 0–250 mJ cm^?2 and their proton conductivities have been measured with standard method. The Nafion membranes have also been studied by measuring their water uptake, swelling-ratios and porosity using standard procedures. Hydrogen fuel cells with dual serpentine microchannels with active area 1.9 x 1.6 cm^-2 were assembled with anode gas diffusion layer, Nafion membrane, cathode gas diffusion layer and other components. An external humidifier was used to humidify hydrogen for the fuel cell. The experimental Results have shown an increase in the value of Nafion proton conductivity with an optimum UV irradiation which depends on the thickness of Nafion membrane: the optimum doses for peak proton conductivity were 196mJ/cm^?2 for Nafion 117, 190mJ/cm^?2for Nafion 1035, 180mJ/cm^?2 for Nafion 212 and 160mJ/cm^?2 for Nafion 211. This enhancement of proton conductivity is because of the optimal photo-crosslinking of –SO₃H groups in Nafion. This causes optimum pore-size in Nafion thereby facilitating increased proton-hopping between –SO₃H sites in Nafion. Hydrogen fuel cells were developed with pristine as well as with optimal UV irradiated Nafion with thicknesses of 90 and 50  μm. The polarization plots obtained for these devices showed an increase in power densities approximately by a factor of 1.8–2.0 for devices with optimally UV irradiated Nafion. These results indicate that optimal UV irradiation of Nafion is an excellent technique for enhancing power output of hydrogen fuel cells.     

Novel branched sulfonated poly(ether ether ketone)s membranes for direct methanol fuel cells

In this article, novel branched sulfonated poly(ether ether ketone)s (Br-SPEEK) containing various amounts of 1,3,5-tris(4-fluorobenzoyl)benzene as the branching agent have been successfully prepared. Compared with the traditional linear polymer membranes, the membranes prepared by Br-SPEEK showed improved mechanical strength, excellent dimensional stability and superior oxidative stability with similar proton conductivity. Notably, the Br-SPEEK-10 membrane began to break after 267 min in Fenton's reagent at 80 °C, which was 4 times longer than that of the L-SPEEK. Although the proton conductivity decreased with the addition of the branching agent, satisfying methanol permeability value was observed (down to 6.3 × 10⁻⁷ cm² s⁻¹), which was much lower than Nafion 117 (15.5 × 10⁻⁷ cm² s⁻¹). All the results indicated that the novel branched sulfonated poly(ether ether ketone)s membrane was potential candidate as proton conductive membranes for application in fuel cells.     

Robust proton exchange membrane for vanadium redox flow batteries reinforced by silica-encapsulated nanocellulose

High ion selectivity and mechanical strength are critical properties for proton exchange membranes in vanadium redox flow batteries. In this work, a novel sulfonated poly(ether sulfone) hybrid membrane reinforced by core-shell structured nanocellulose (CNC-SPES) is prepared to obtain a robust and high-performance proton exchange membrane for vanadium redox flow batteries. Membrane morphology, proton conductivity, vanadium permeability and tensile strength are investigated. Single cell tests at a range of 40–140 mA cm⁻² are carried out. The performance of the sulfonated poly(ether sulfone) membrane reinforced by pristine nanocellulose (NC-SPES) and Nafion® 212 membranes are also studied for comparison. The results show that, with the incorporation of silica-encapsulated nanocellulose, the membrane exhibits outstanding mechanical strength of 54.5 MPa and high energy efficiency above 82% at 100 mA cm⁻², which is stable during 200 charge-discharge cycles.     

Highly branched poly(arylene ether)/surface functionalized fullerene‐based composite membrane electrolyte for DMFC applications

Sulfonated branched polymer membranes have been gaining immense attention as the separator in energy‐related applications especially in fuel cells and flow batteries. Utilization of this branched polymer membranes in direct methanol fuel cell (DMFC) is limited because of large free volume and high methanol permeation. In the present work, sulfonated fullerene is used to improve the methanol barrier property of the highly branched sulfonated poly(ether ether ketone sulfone)s membrane without sacrificing its high proton conductivity. The existence of sulfonated fullerene with larger size and the usage of small quantity in the branched polymer matrix effectively prevent the methanol transportation channel across the membrane. The composite membrane with an optimized loading of sulfonated fullerene displays the highest proton conductivity of 0.332 S cm^?1 at 80°C. Radical scavenging property of the fullerene improves the oxidative stability of the composite membrane. Composite membrane exhibits the peak power density of 74.38 mW cm^?2 at 60°C, which is 30% larger than the commercial Nafion 212 membrane (51.78 mW cm^?2) at the same condition. From these results, it clearly depicts that sulfonated fullerene‐incorporated branched polymer electrolyte membrane emerges as a promising candidate for DMFC applications.     

Fatigue crack propagation behavior of fuel cell membranes after chemical degradation

The durability of fuel cells is significantly impaired by chemical and mechanical degradations of perfluorosulfonic-acid membranes. However, how the mechanical degradation, especially the fatigue crack propagation behavior, is impacted by chemical degradation is not clear. In this paper, the fatigue crack propagation behavior of Nafion 212 and Nafion XL composite membranes after chemical degradation are investigated. The fluoride release rates of Nafion 212 and Nafion XL membrane are 0.335 and 0.095 μmol cm⁻² h⁻¹, respectively. Likewise, the fatigue crack propagation rate of Nafion 212 membrane is also larger, which is attributed to two fatigue crack propagation mechanisms induced by chemical degradation, including bubble collapsing and pore interconnecting. By contrast, the fatigue crack propagation mechanism of Nafion XL membrane is not significantly changed where chemical degradation only accelerates crack growth in exterior surface layers. These findings provide new insights into the failure mechanisms under combined chemical and mechanical degradations.     

Investigations on transfer of water and vanadium ions across Nafion membrane in an operating vanadium redox flow battery

Diffusion coefficients of the vanadium ions across Nafion 115 (Dupont) in a vanadium redox flow battery (VRFB) are measured and found to be in the order of V²⁺ > VO²⁺ > VO₂⁺ > V³⁺. It is found that both in self-discharge process and charge-discharge cycles, the concentration difference of vanadium ions between the positive electrolyte (+ve) and negative electrolyte (−ve) is the main reason causing the transfer of vanadium ions across the membrane. In self-discharge process, the transfer of water includes the transfer of vanadium ions with the bound water and the corresponding transfer of protons with the dragged water to balance the charges, and the transfer of water driven by osmosis. In this case, about 75% of the net transfer of water is caused by osmosis. In charge-discharge cycles, except those as mentioned in the case of self-discharge, the transfer of protons with the dragged water across the membrane during the electrode reaction for the formation of internal electric circuit plays the key role in the water transfer. But in the long-term cycles of charge-discharge, the net transfer of water towards +ve is caused by the transfer of vanadium ions with the bound water and the transfer of water driven by osmosis.     

Amphoteric ion exchange membrane synthesized by direct polymerization for vanadium redox flow battery application

Novel sulfonated poly (fluorenyl ether ketone) with pendant quaternary ammonium groups (SPFEKA) was successfully synthesized by one-pot copolymerization of bis(4-fluoro-3-sulfophenyl)sulfone disodium salt, 4,4′-difluorobenzophenone, bisphenol fluorene and 2,2′-dimethylaminemethylene-9,9′-bis(4-hydroxyphenyl) fluorene (DABPF). The chemical structures were confirmed by FT-IR, and ¹H NMR. The thermal properties were fully investigated by TGA. The synthesized copolymers SPFEKAs are soluble in aprotic solvents, and can be cast into membranes on a glass plate from their N,N′-dimethylacetamide (DMAc) solution. A new kind of amphoteric ion exchange membrane (AIEM) was obtained by immersed SPFEKA into 1 M sulfuric acid. The proton conductivities of these membranes are comparable to the most reported sulfonated polymers under the same conditions. The permeability of vanadium ions in vanadium redox flow battery (VRB) was effectively suppressed by introducing quaternary ammonium groups for Donnan exclusion effect. AIEM-20% possess a only 4.4% vanadium ion permeability of Nafion 115. Cell performance tests showed that the VRB assembled with AIEM-20% shows the highest coulombic efficiency (CE) at the current density of 50 mA/cm², because of its lowest VO²⁺ permeability. In conclusion, these ionomers could be promising candidates for ion-exchange membranes for VRB applications.     

Nafion/SiO2 hybrid membrane for vanadium redox flow battery

Sol–gel derived Nafion/SiO₂ hybrid membrane is prepared and employed as the separator for vanadium redox flow battery (VRB) to evaluate the vanadium ions permeability and cell performance. Nafion/SiO₂ hybrid membrane shows nearly the same ion exchange capacity (IEC) and proton conductivity as pristine Nafion 117 membrane. ICP-AES analysis reveals that Nafion/SiO₂ hybrid membrane exhibits dramatically lower vanadium ions permeability compared with Nafion membrane. The VRB with Nafion/SiO₂ hybrid membrane presents a higher coulombic and energy efficiencies over the entire range of current densities (10–80 mA cm⁻²), especially at relative lower current densities (<30 mA cm⁻²), and a lower self-discharge rate compared with the Nafion system. The performance of VRB with Nafion/SiO₂ hybrid membrane can be maintained after more than 100 cycles at a charge–discharge current density of 60 mA cm⁻². The experimental results suggest that the Nafion/SiO₂ hybrid membrane approach is a promising strategy to overcome the vanadium ions crossover in VRB.     

Bioinspired layered proton-exchange membranes with high strength and proton conductivity

High-performance proton exchange membranes (PEMs) are crucial to the overall performance of PEM fuel cells. However, there always exists a conflict between the high ion conductivity and mechanical properties of traditional PEMs. Herein, we have demonstrated a simple bioinspired strategy for fabricating nacre-inspired layered membrane (GPS-X) based on GO sheets by crosslinking two kinds of long-chain polymers (PDA and SPVA) via vacuum filtration. Strikingly, the resulting GPS-50 membrane is endowed with high tensile strength (216.5 MPa) and high proton conductivity (0.303 S cm^?1 at 80 °C) due to the combination of strong interfacial interactions and well-developed 2D channels, which surpasses Nafion and many other reported GO-based PEMs. Furthermore, the membrane exhibits higher output-power but lower weight than Nafion 212. Considering the achieved excellent properties induced by the independently adjustable 2D channels and mechanical properties, the bioinspired strategy offers guidance for constructing advanced membrane materials with potential applications in fuel cells.