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).

Highly efficient vanadium redox flow batteries enabled by a trilayer polybenzimidazole membrane assembly

A novel polybenzimidazole(PBI)-based trilayer membrane assembly is developed for application in vanadium redox flow battery(VRFB).The membrane comprises a 1μm thin cross-linked poly[2,2′-(p-oxydiphenylene)−5,5′-bibenzimidazole](OPBI)sandwiched between two 20μm thick porous OPBI membranes(p-OPBI)without further lamination steps.The trilayer membrane demonstrates exceptional properties,such as high conductivity and low area-specific resistance(ASR)of 51 mS cm^(−1) and 81mΩ cm^(2),respectively.Contact with vanadium electrolyte increases the ASR of trilayer membrane only to 158mΩ cm^(2),while that of Nafion is 193mΩ cm^(2).VO^(2+) permeability is 2.73×10^(-9) cm^(2) min^(−1),about 150 times lower than that of Nafion NR212.In addition,the membrane has high mechanical strength and high chemical stability against VO^(2+).In VRFB,the combination of low resistance and low vanadium permeability results in excellent performance,revealing high Coulombic efficiency(>99%),high energy efficiency(EE;90.8% at current density of 80mA cm^(−2)),and long-term durability.The EE is one of the best reported to date.

Review on current development of polybenzimidazole membrane for lithium battery

With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the key components of a lithium battery system,the separator plays a critical role as it directly influences the battery performance benchmark(cycling performance and safety).However,traditional polyolefin separators(polypropylene/polyethylene)are unable to meet the demands of highperformance and safer battery systems due to their poor electrolyte compatibility,thermal runaways,and ultimate growth of dendrites.In contrast,membranes fabricated using polybenzimidazole(PBI)exhibit excellent electrolyte wettability and outstanding thermal dimensional stability,thus holding great potential as separators for high-performance and high-safety batteries.In this paper,we present a comprehensive review of the general requirements for separators,synthesis technology for separators,and research trends focusing PBI membranes in lithium batteries to alleviate the current commercial challenges faced by conventional polyolefin separators.In addition,we discuss the future development direction for PBI battery separators by considering various factors such as production cost,ecological footprint,preparation technology,and battery component compatibility.By exploring these perspectives,we aim to promote the continued application and exploration of PBI-based materials to advance lithium battery technology.

Sulfonated polybenzimidazole/amine functionalized titanium dioxide(s PBI/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage

The novel sulfonated polybenzimidazole(sPBI)/amine functionalized titanium dioxide(AFT) composite membrane is devised and studied for its capability of the application of high temperature proton exchange membrane fuel cells(HT-PEMFCs),unlike the prior low temperature AFT endeavors.The high temperature compatibility was actualized because of the filling of free volumes in the rigid aromatic matrix of the composite with AFT nanoparticles which inhibited segmental motions of the chains and improved its thermal stability.Besides,amine functionalization of TiO2 enhanced their dispersion character in the sPBI matrix and shortened the interparticle separation gap which finally improved the proton transfer after establishing interconnected pathways and breeding more phosphoric acid(PA) doping.In addition,the appeared assembled clusters of AFT flourished a superior mechanical stability.Thus,the optimized sPBI/AFT(10 wt%) showed 65.3 MPa tensile strength;0.084 S·cm^-1 proton conductivity(at 160℃;in anhydrous conditions),28.6% water uptake and PA doping level of 23 mol per sPBI repeat unit.The maximum power density peak for sPBI/AFT-10 met the figure of0.42 W·cm^-2 at 160℃(in dry conditions) under atmospheric pressure with 1.5 and 2.5 stoichiometric flow rates of H2/air.These results affirmed the probable fitting of sPBI/AFT composite for HT-PEMFC applications.

Synthesis of a new aromatic diacid containing pyridine ring and related polybenzimidazole

A new aromatic diacid monomer containing pyridine unit,4-phenyl-2,6-bis[4-（4-carboxyphenoxy） phenyl]pyridine 3,was successfully synthesized in three steps,starting from 4-hydroxyacetophenone.The corresponding pyridine-containing polybenzimidazole was prepared via polycondensation of 3 with tetraaminodiphenyl ether（TADE） in poly（phosphoric acid）（PPA）.The resulting polybenzimidazole exhibits excellent solubility,good thermal stabilities and high thermal resistance.

Synthesis and Photophysical Properties of Dy^(3+) and Gd^(3+) Polymeric Complexes with Functionalized Polybenzimidazole Containing β-Diketone Side Group

The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.

Modified silicon carbide whisker reinforced polybenzimidazole used for high temperature proton exchange membrane

Polybenzimidazole containing ether bond（OPBI） was reinforced with silicon carbide whisker（m Si C） modified by 3-aminopropyltriethoxysilane（KH550）, and then doped with phosphoric acid（PA） to obtain OPBI/m Si C/PA membranes. These OPBI/m Si C/PA membranes have excellent mechanical strength and oxidative stability and can be used for high temperature proton exchange membrane（HT-PEM）. The tensile strength of OPBI/m Si C/PA membranes ranges from 27.3 to 36.8 MPa, and it increases at first and then decreases with the increase of m Si C content. The high m Si C content and PA doping level contribute to improving the proton conductivity of membranes. The proton conductivity of PBI/m Si C-10/PA membrane is 27.1 m S cm-1 at 170℃ without humidity, with an increase of 55.7% compared with that of OPBI/PA membrane. These excellent properties make OPBI/m Si C/PA membranes promising membrane materials for HT-PEM applications.

Gel-state polybenzimidazole proton exchange membranes with flexible alkyl sulfonic acid side chains for a wider operating temperature range(25–240 ℃)

High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sources, within the temperature range of 120–200 ℃. However, for practical automobile applications, it was crucial to broaden their low-temperature operating window and enable cold start-up capability. Herein, gel-state phosphoric acid(PA) doped sulfonated polybenzimidazole(PBI) proton exchange membranes(PEMs) were designed and synthesized via PPA sol-gel process and in-situ sultone ring-opening reactions with various proton transport pathways based on absorbed PA, flexible alkyl chain connected sulfonic acid groups and imidazole sites. The effects of flexible alkyl sulfonic acid side chain length and content on PA doping level, proton conductivity, and membrane stability under different temperature and relative humidity(RH) were thoroughly investigated. The prepared gel-state membranes contained a self-assembled lamellar and porous structure that facilitated the absorption of a large amount of PA with rapid proton transporting mechanisms. At room temperature, the optimized membrane exhibited a proton conductivity of 0.069 S cm^(-1), which was further increased to 0.162 and 0.358 S cm^(-1)at 80 and 200 ℃, respectively, without additional humidification. The most significant contribution of this work was demonstrating the feasibility of gel-state sulfonated PBI membranes in expanding HT-PEMFC application opportunities over a wider operating range of 25 to 240 ℃.

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.

POLYCAPROLACTAM MODIFIED BY POLYBENZIMIDAZOLE

Three polycaprolactam samples modified by 0.05—0.50% polybenzimidazole （PBI） by weight were prepared. Their structure and mechanical properties were characterized by means of FT-IR, SEM, DTA, density tensile, impact and viscoelastic method. PBI delayed the superimposed polymerization-crystallization process of the activated anionic polymerization of caprolactam. The monomer casting （MC） nylons modified by PBI had lower crystallinities, lower T;and more nearly perfect spherulites than MC nylon itself, and showed a typical toughening effect.

醚氧-烷基间隔三离子侧链型PBI碱性膜研究

基于侧链接枝改性合成了一系列具有醚氧-烷基-醚氧链段间隔分布的三阳离子侧链型聚苯并咪唑膜(oat-PBI-x)。侧链中两段柔性的含醚链段有助于亲水通道和氢键网络的形成,促进OH-快速传递,而己烷基间隔段可打破侧链全亲水属性,有效抑制膜过度溶胀。在IEC为1.40 mmol/g时膜的综合性能达到最佳。80℃时电导率为144.4 mS/cm,拉伸强度保持在21 MPa,在80℃、1 mol/L KOH溶液中浸泡900 h后电导率保留率为91.7%。将其应用于H_(2)/O_(2)燃料电池,可在1549 mA/cm^(2)的高电流密度下达到611 mW/cm^(2)的峰值功率密度。

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI)is a kind of proton transport membrane material,and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs).The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity.In this paper,3,3′-diaminobenzidine(DABz)and 4,4′-Dicarboxydiphenylether(DCDPE)were used as raw materials by solution condensation to prepare the PBI with ether bond groups.The chemical structure of PBI was determined by1H NMR and FT-IR,and the prepared PBI had good solubility which can be dissolved in a variety of solvents.The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF),N,N-dimethylacetamide(DMAc),dimethyl sulfoxide(DMSO),1-methyl-2-pyrrolidone(NMP),methane sulfonic acid(MSA).The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail.The results showed that the PBI membrane prepared by using MSA as solvent(the PBI+MSA membrane)exhibits high water uptake,acid doping level and low vanadium ion permeability.The VRFB assembled with the PBI+MSA membrane exhibited higher coulombic efficiency(CE)99.87%and voltage efficiency(VE)84.50%than that of the commercial Nafion115 membrane at100 m A·cm-2,and after 480 cycles,the EE value can still be maintained at 83.73%.The self-discharge time of a single battery was recorded to be as long as 1000 h.All experimental data indicated that MSA is the best solvent for casting PBI membrane.

Ionic potency regulation of coagulation bath induced by saline solution to control over the pore structure of PBI membrane for highperformance lithium metal batteries

In this study,we have explored the use of water as a non-solvent for tuning the microstructure of poly-benzimidazole(PBI)membranes,which are potential separators for lithium metal batteries(LMBs).The traditional method for membrane synthesis called nonsolvent-induced phase separation(NIPS),usually relies on hazardous and costly organic non-solvents.By dissolving sodium chloride(Nacl)in water,we could adjust the water ionic potency and the exchange speed of the non-solvent with the DMAC solution to change the micropore structure of the PBI membrane.With increasing Nacl concentration,the micro-pores in the PBI membrane transitioned from finger-like to sponge-like morphology.Compared to com-mercial separators like the Celgard separator,the PBI membrane with sponge-like micropores exhibited better regulation of lithium deposition and improved Li^(+) transportation capability due to its good wetta-bility with the electrolyte.Consequently,the PBI membrane-based Li/Li symmetric cell and Li/LiFePO_(4) full cell demonstrated superior performance compared to the Celgard-based ones.This research proposes an eco-friendly and scalable synthetic approach for fabricating commercial separators for LMBs,addressing the issue of lithium dendrite growth and improving overall battery safety and performance.

操作条件对PBI/H_3PO_4体系高温PEMFC的性能影响

全面研究了PBI/H3PO4体系高温质子交换膜燃料电池(PEMFC)的操作性能,研究了温度、压力、阴极气体成分(空气/氧气)对电池稳态操作性能的影响,同时,测试了电池的变压变温和变负载操作曲线,并且运用电化学交流阻抗谱的方法解释了操作条件对电池性能影响的原因,同时应用薄膜旋转圆盘电极技术初步研究了氧还原反应在两种不同的反应界面(Pt/C-PBI/H3PO4和Pt/C-Nafion/H2SO4)的差别。

磷酸流失对H_3PO_4/PBI高温PEMFC性能的影响

考察了H3PO4/PBI高温PEMFC单体电池间放时的磷酸流失及对电池性能的影响。用磷钼蓝法测定了电极排水中的磷酸流失量;运用交流阻抗技术测试了电池内阻的变化;用SEM-EDX测量了运行不同时间后MEA中磷酸的含量。在正常操作时,电极排水中都含有少量的磷酸,且阴极侧比阳极侧的流失量大;500 h磷酸的流失总量很小,约为H3PO4/PBI膜中吸附磷酸量的0.43%;单体电池500 h间歇运行过程中内阻的变化不明显;运行不同时间后,阴极催化层中的磷酸减少,而阳极催化层中的磷酸含量比阴极高,但H3PO4/PBI膜中的磷酸含量未明显减少。在电池中有液态水存在时,磷酸的流失严重,返水5 s的流失量约是正常操作时500 h两极流失总量的3倍。正常操作时,电池中没有液态水存在,磷酸流失对电池性能的影响很小;当电池中存在液态水时,磷酸的流失严重,导致电池的性能降低。

真空蒸发法制备PbI_2多晶薄膜研究

用真空蒸发法在玻璃衬底上制备了PbI2多晶薄膜,对样品的微结构、表面形貌、化学组分及电阻率进行了测试分析.结果表明,样品具有良好的多晶结构,并沿六角密堆积结构的c轴向高度择优取向.室温下样品暗电导率为3.09×10-11(Ω·cm)-1,电导激活能为0.78eV.

pBI121载体酶切位点添加及拟南芥Na^+/H^+逆向转运蛋白基因表达载体的构建

对pBI121载体GUS基因后的终止子序列(SacⅠ-EcoRⅠ)通过PCR扩增法进行了酶切位点的添加,即在SacⅠ后添加了XhoⅠ、在EcoRⅠ前添加了KpnⅠ。序列分析发现,两个酶切位点的添加是成功的,但扩增的终止子序列与原序列的同源性间有差异,即有4个碱基发生了变异,特别是第17个碱基位点出现了缺失。利用绿色荧光蛋白(GFP)对添加酶切位点载体进行了终止子活性的检测,结果发现,它与携带GFP的pBI121载体一样,GFP基因能正常表达,说明pBI121载体终止子序列酶切位点的添加是成功的。利用改造后的载体(pBI121-GZ)构建了CaMV35S启动子驱动AtNHX1基因的植物表达载体。

低温等离子体处理对PBI纤维性能的影响

探讨空气低温等离子体处理对PBI纤维性能的影响。测试了低温等离子体处理前后PBI纤维的断裂强度、表面摩擦因数、芯吸效应、接触角以及微观形态。试验表明:经过空气低温等离子体处理后PBI纤维的吸湿性得到进一步提高,强度和摩擦因数也适度增大,且在放电功率150W、放电气压20Pa和放电时间180s的条件下,纤维处理效果最好。认为:通过低温等离子体处理,PBI纤维在保证其吸湿性的基础上,可以提高其与其他材质复合黏结的牢度。

PBI/H_3PO_4体系高温PEMFC的性能预测

使用实际测量的PBI/H3PO4体系高温PEMFC,在不同温度、压力、阴极气体和负载下的稳态电位响应数据(500组)与该体系对温度变化、压力变化的动态电位响应数据(500组)作为训练数据,建立了基于BP神经网络和Matlab/Simulink的高温PEMFC稳定性能和动态性能的预测系统。利用神经网络模型模拟电池的稳态电位输出和单变量(温度或压力)动态电位响应。仿真结果表明:该模型能准确地模拟电池的稳态和动态行为,为PBI/H3PO4体系高温PEMFC的性能预测和控制提供了一条可行的途径。

酸化剂中H_2SO_4含量对PBI燃料电池性能的影响

目的探究高温酸化时在酸化剂中加入不同含量的H2SO4对PBI膜和高温燃料电池电极的影响.方法质子交换膜是高温质子交换膜(HT-PEM)燃料电池的核心部件,对燃料电池的性能起到主导作用.笔者制备了酸化剂中掺杂不同量H2SO4的PBI膜,测试了高温PBI燃料电池的I-V特性和交流阻抗特性,对比了PBI膜表面SEM照片的差异,分析了高温PBI膜掺杂硫酸的含量和电池温度对高温燃料电池性能的影响.结果研究发现:高温PEM燃料电池的PBI膜在高温酸化时及高温燃料电池运行时,H2SO4的强氧化性起主导作用,破坏了PBI膜的内部结构,阻碍了质子的传递,对PBI膜和燃料电池电极均有损伤.结论酸化剂中掺杂强电解质强氧化性的H2SO4不利于高温PBI膜燃料电池性能的提高,虽然常温下经H2SO4处理后的PBI膜的电导率能够显著提高,但高温运行的PBI膜燃料电池的性能有明显下降.H2SO4的加入对PBI膜的电导率没有明显的提升,反而对高温燃料电池的性能有所抑制.掺杂强电解质H2SO4对提升电池性能是不合适的.