폴리에테르설폰-폴리페닐렌설파이드설폰 블렌딩 고분자를 이용한 음이온교환막의 제조

이경한,한주영,유철휘,황갑진 한국막학회 2019 멤브레인 Vol.29 No.3

The anion exchange membrane using the blending polymer of poly(ether sulfone) and poly(phenylene sulfide sulfone) was prepared. It was confirmed by EDXS and FT-IR analysis that the prepared anion exchange membrane had the -N- as an anion exchange group. The ionic conductivity in 1 mol/L H2SO4 aqueous solution was measured. The ionic conductivity of the prepared anion exchange membrane was 0.015~0.083 S/cm, and had a high value compared with AFN and APS as a commercial anion exchange membrane. Permeabilities of the vanadium ions through the prepared anion exchange membrane were tested to evaluate the possibility as a separator in vanadium redox flow battery. Vanadium ion permeation rate in the prepared anion exchange membrane had a low value compared with Nafion 117 as a commercial cation exchange and AFN as a commercial anion exchange membrane. 폴리에테르설폰(PES)과 폴리페닐렌설파이드설폰(PPSS)을 블렌딩한 고분자를 이용하여 음이온교환막을 제작하였다. EDXS와 FT-IR 분석으로부터 제작한 음이온교환막이 음이온교환기인 -N-을 갖는다는 것을 확인하였다. 1 mol/L의 황산용액에서 이온전도도를 측정하였다. 제작한 음이온교환막은 0.015~0.083 S/cm의 이온전도도를 가졌으며, 시판의 음이온교환막인 AFN과 APS의 값과 비교하여 동등 이상의 값을 가졌다. 제작한 음이온교환막의 바나듐 레독스 흐름 전지용 격막으로사용한지를 평가하기 위해 각 바나듐 이온의 투과를 측정하였다. 제작한 음이온교환막의 각 바나듐 이온의 투과도는 시판의양이온교환막인 Nafion 117과 시판의 음이온교환막인 AFN과 비교하여 낮은 값을 가졌다.

알칼리 수전해용 격막으로서 폴리염화비닐(polyvinyl chloride) 음이온교환막의 제조에 관한 연구

박종호,봉수연,유철휘,황갑진 한국막학회 2013 멤브레인 Vol.23 No.6

알칼리 수전해용 격막으로 사용하기 위해 음이온교환막을 제작하였다. 음이온교환막은 PVC (polyvinyl chloride)를 출발물질로 하여 클로로메틸화 및 아민화에 의해 제작하였다. 제작한 막은 막 특성(막 저항, 이온교환용량)을 평가하였다.제작한 음이온교환막의 1M NaOH수용액에서의 최저 막 저항은 2.9 Ω·cm2를 나타냈다. 이 막은 2.17 meq./g-dry-membrane의 이온교환용량과 43.4%의 함수율을 보였다. 제작한 음이온교환막의 막 특성을 시판의 막 특성과 비교 평가하였다. 1M NaOH수용액에서의 막 저항은 AHT>IOMAC>Homemade membrane>AHA>APS=AFN의 순으로 저항 값이 높았다. 이온교환용량은 Homemade membrane>AFN>APS>AHT>AHA>IOMAC의 순으로 높은 값을 가졌다. An anion exchange membrane was prepared for a separator in the alkaline water electrolysis. An anion ex-change membrane was prepared by the chloromethylation and amination of polyvinyl chloride (PVC) used as a base polymer. The membrane properties of the prepared anion exchange membrane such as the membrane resistance and ion ex-change capacity were measured. The minimum membrane resistance of the prepared anion exchange membrane was 2.9 Ω·cm2in 1M NaOH aq. solution. This membrane had 2.17 meq./g-dry-membrane and 43.4% for the ion exchange capacity and wa-ter content, respectively. The membrane properties of the prepared anion exchange membrane was compared with that of the commercial anion exchange membrane. The membrane resistance decreased in the order; AHT>IOMAC> Homemade mem-brane>AHA>APS=AFN. The ion exchange capacity decreased in the order; Homemade membrane>AFN>APS>AHT> AHA>IOMAC.

Durability enhancement of anion exchange membranes for water electrolysis: an updated review

마하무다아크테르,박종혁,김범석,이민영,정다혜,신지윤,박진수 한국표면공학회 2022 한국표면공학회지 Vol.55 No.6

Ion exchange membranes have been developed from laboratory tools to industrial products with significant technical and trade impacts in the last 70 years. Today, ion exchange membranes are successfully applied for water and energy for different electro-membrane processes. Hydrogen could be produced by electrochemical water splitting using renewable energy, for example, solar, biomass, geothermal and wind energy. This review briefly summarizes the recent studies reporting the state-of-the-art anion-exchange membrane water electrolysis, especially focusing on the enhancement of the durability of anion-exchange membranes. Anion-exchange membrane water electrolysis could be used as inexpensive non-noble metal electrocatalysts that are capable of producing low cost of hydrogen. However, the main challenge of anion-exchange membrane water electrolysis is to increase the performance and durability. In this mini review, the limiting factors of the durability and the technology enhancing the durability will be discussed for anion exchange membrane water electrolysis.

화학적 가교를 이용한 Poly(2,6-dimethyl-1,4-phenylene oxde)계 음이온 교환막의 제조 및 알칼리 연료전지용 특성평가

성승화,이보련,최욱,김태현 한국막학회 2019 멤브레인 Vol.29 No.3

화석연료 사용이 증가하면서 온실가스 및 대기오염가스 등의 환경오염 문제가 심각해졌다. 이를 해결하기 위한신재생에너지, 친환경적인 대체에너지원을 찾기 위한 많은 연구가 이뤄지고 있다. 연료전지는 전기에너지를 발생하며 부산물로 물만이 생성되는 친환경 에너지 발생장치다. 특히, 전해질로 음이온 교환막을 사용하는 음이온 교환막 연료전지(Anion Exchange Membrane Fuel Cell)는 높은 촉매의 활성으로 양이온 교환막 연료전지(Proton Exchange Membrane Fuel cell)와다르게 저가의 금속 촉매를 사용할 수 있는 장점 때문에 관심이 높아지고 있다. 음이온 교환막으로써 요구되는 주요 특성은높은 이온(OH- ) 전도도 및 높은 pH의 구동조건에서의 안정성이다. 본 연구에서는 PPO계 고분자의 화학적 가교 반응을 이용해 얻어진 가교형 고분자 막의 낮은 기계적인 특성과 치수 안정성을 높이기 위해 보다 높은 분자량을 갖는 고분자 사용과 함께 가교율 증대를 통해 보다 높은 이온 전도도와 기계적인 성질, 높은 화학적인 안정성뿐만 아니라 실제 연료전지 구동조건에서 높은 셀 성능을 갖는 AEMFC용 고분자 전해질 막을 개발했다. Much research has been made for finding new and eco-friendly alternative sources of energy to solve the problems related with the pollution caused by emissions of greenhouse gases such as carbon dioxide as the use of fossil fuels increases worldwide. Among them, fuel cells draws particular interests as an eco-friendly energy generator because only water is obtained as a by-product. Anion exchange membrane-based alkaline fuel cell (AEMFC) that uses anion exchange membrane as an electrolyte is of increased interest recently because of its advantages in using low-cost metal catalyst unlike the PEMFC (potton exchange membrane fuel cell) due to the high-catalyst activity in alkaline conditions. The main properties required as an anion exchange membrane are high hydroxide conductivity and chemical stability at high pH. Recently we reported a chemically crosslinked poly(2-dimethyl-1,4-phenylene oxide) (PPO) by reacting PPO with N,N,N’,N’- tetramethyl-1,6-hexanediamine as novel anion exchange membranes. In the current work, we further developed the same crosslinked polymer but having enhanced physicochemical properties, including higher conductivity, increased mechanical and dimensional stabilities by using the PPO with a higher molecular weight and also by increasing the crosslinking density. The obtained polymer membrane also showed a good cell performance.

음이온교환막 적용을 위한 이온교환입자의 합성 및 특성평가

남상용,이동준,임광섭,류가연 한국막학회 2023 멤브레인 Vol.33 No.3

In this study, Br-PPO was developed by applying additive organic particles through a suspension polymerization synthesis method. The anion exchange membrane fuel cell system performance was evaluated using it to an anion exchange membrane. To improve the performance, organic ion exchange particles were prepared and added to the anion exchange membrane. Chemical structure analysis and synthesis were determined through FT-IR and NMR, and tensile strength and thermal stability were measured through TGA and UTM to determine whether it could be driven. Before the anion exchange membrane fuel cell test, the performance was evaluated by measuring the ion conductivity and ion exchange capacity. Finally, the Br-PPO-TMA-SDV (0.7%) anion exchange membrane with excellent ion conductivity and ion exchange capacity was introduced into the fuel cell system. Its performance was compared with FAA-3-50, a commercial membrane, to determine whether it could be introduced into a fuel cell system. 본 연구에서는 현탁중합을 통해 이온교환입자를 합성하였다. 또한 음이온 교환막을 제조하기 위해 brominated poly(phenylene oxide) (Br-PPO)로 교환막 합성을 진행하였으며, 합성한 이온교환입자를 Br-PPO에 첨가하여 음이온 교환막에 성능을 향상시키고자 하였고, 이를 적용하여 음이온 교환막 연료전지 시스템의 성능 평가를 진행했다. 이온교환입자는FT-IR, TGA 및 UTM을 통해 구조 분석, 열적 기계적 특성을 평가하였다. Br-PPO는 NMR을 통해 화학적 구조 분석 및 합성여부를 확인하였고, 음이온 교환막 연료 전지 셀 테스트를 진행하기 전 이온전도도와 이온교환용량, 팽윤도 및 수분함수율을측정해 연구되고 있는 다른 음이온 교환막들과 비교를 통해 성능을 평가했다. 최종적으로 가장 성능이 우수했던 이온교환입자를 0.7 wt%를 첨가한 Br-PPO-TMA- SDV 음이온 교환막을 연료전지 시스템에 도입하여 상용 막인 FAA-3-50과 성능을 비교했다.

Vinyl Benzyl Chloride로 제조된 음이온 교환막의 구조적 고찰 및 전기화학적 특성

송지혜,서봉국,최용진 한국막학회 2015 멤브레인 Vol.25 No.4

음이온 교환막의 치환체 특성을 파악하기 위하여 탄화수소의 분자구조가 다른 세 종류의 음이온 교환기를 vinyl benzyl chloride (VBC) base 막에 도입하였다. 지방족계로 trimethylamine (TMA), 고리형계로 N-methylpiperidine (MP), 방향족계로 pyridine (Py)은 아민화 반응을 통하여 도입되었다. 각각의 반응속도는 막저항(MER)과 이온교환능력(IEC) 변화의 관측으로부터 Py < MP < TMA의 순서로 반응하고 있음을 보여주었다. 한편 SEM image에서는 Py 치환체 막이 가장 균일하고 치밀한 구조를 보여주었으며, 전기화학적 특성에서도 Py이 상용막(AMX)과 비슷한 막저항(5.0 Ω·cm2 >, in 0.5 mol/L NaCl)을 나타내었다. 이 모든 결과로부터 치환체의 공명구조는 균질한 이온교환막의 제조에 기여하고 있음을 알 수 있었다. Three kinds of anion-exchangeable functional groups with different hydrocarbon molecular structures were introduced to vinyl benzyl chloride-based membrane to understand the effect of attached function in anion-exchange membrane. Trimethylamine (TMA) as an aliphatic fuction, N-methylpiperidine (MP) as an alicyclic fuction and pyridine (Py) as an aromatic function were introduced by amination. The respective reactivity was observed by the trace of membrane resistance(MER)/ion exchange capacity (IEC) and the increasing order of reactivity was Py < MP < TMA. Meanwhile, SEM photograph showed the attached Py ion-exchange membrane was the most homogenous and compact structure in the study. In electrochemical properties, the attached Py ion-exchange membrane showed the MER (5.0 Ω·cm2 >, in 0.5 mol/L NaCl), comparable to those of commercial membrane (AMX). All results showed that the resonance structure of attached functional group might contribute to the preparation of homogenous anion-exchange membrane.

Poly(ethylene glycol)methyl Ether Methacrylate를 이용한 세공충전 폴리스티렌계 음이온 교환막의 제조 및 전기화학적 특성

문혜진,최재학,홍영택,장봉준 한국막학회 2015 멤브레인 Vol.25 No.6

While commercial polystyrene-based ion exchange membranes have simple manufacturing processes, they also possess poor durability due to their brittleness. Poly(ethylene glycol)methyl ether methacrylate with hydrophilic side chains of poly(ethylene glycol) was used as a co-monomer to make the membranes have improved flexibility. Hydrophilicity/hydrophobicity of the anion exchange membranes were able to be adjusted by varying the chain lengths of the poly(ethylene glycol). For the preparation of the anion exchange membranes, a porous PE substrate was immersed into monomer solutions and thermally polymerized. The prepared membranes were subsequently reacted with trimethylamine to produce anion exchange functional groups, Quaternary ammonium salts. The prepared pore-filled anion exchange membranes were evaluated in terms of ion exchange capacity, electric resistance, elongation at break and water uptake. 상업적으로 이용되는 폴리스티렌계 이온교환막은 제조 공정이 쉽고 간단하지만 막이 가지는 취성 때문에 내구성이약하다는 단점을 가지고 있다. 이를 보완하기 위하여 친수성 그룹인 poly(ethylene glycol)을 곁사슬로 가지고 있는 poly(ethylene glycol)methyl ether methacrylate를 공중합시켜 음이온 교환막을 합성하였다. 지지체로는 내화학성 및 기계적 강도가 우수한 다공성 PE 지지체를 사용하였고, 여기에 다양한 조성의 vinylbenzyl chloride, styrene, poly(ethylene glycol)methyl ether methacrylate, divinylbenzene, benzoyl peroxide를 녹인 단량체 용액을 지지체 기공에 채운 뒤 열중합 가교시켜 trimethylamine을 이용하여 음이온 교환기를 도입해 세공충전 음이온 교환막을 합성하였다. 또한 poly(ethylene glycol)methyl ether methacrylate의곁사슬 길이와 각 단량체가 차지하는 비율의 변화가 음이온 교환막의 전기화학적 특성에 미치는 영향을 알아보았다.

Quaternized chitosan-based anion exchange membrane for alkaline direct methanol fuel cells

류정관,서정용,최빛나,김우재,정찬화 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.73 No.-

We synthesized a novel quaternized anion exchange membrane (AEM) that exhibits high ionicconductivity and structural stability, even under high pH conditions, by copolymerizing a chitosan-basedmembrane with vinylimidazole derivatives. During the process, a quaternized poly[O-(2-imidazoly-ethylene)-N-picolylchitosan (QPIENPC) was synthesized by modifying chitosan with a 4-pyridinecar-boxaldehyde derivative and then copolymerizing the modified chitosan with 1-vinylimidzaole. Theresults revealed that the degree of quaternization is correlated with ionic exchange capacity, waterabsorption ability, linear expansion ratio, and hydroxide conductivity of the resulting membrane. TheQPIENPC membrane was characterized by a high ionic conductivity of 10.15 mS cm 1, 14 times greaterthat of the unfunctionalized chitosan membrane, as well as by low water absorption ability (36.17%) andlinear expansion ratio (20.49%) at 80 C. An alkaline direct methanol fuel cell (ADMFC) was fabricatedusing the prepared QPIENPC membrane as an anion exchange electrolyte membrane, with PtRu/C and Pt/C as the anode and cathode, respectively. The performance of this ADMFC is promising even under highpH conditions, with the peak power density of 10.42 mW cm 2 and corresponding current density of28.76 mA cm 2. Moreover, the thermochemical and mechanical strengths of the QPIENPC membranewere higher than those of the chitosan membrane.

Vinyl Benzyl Chloride로 제조된 음이온 교환막의 구조적 고찰 및 전기화학적 특성

송지혜,서봉국,최용진 한국막학회 2015 멤브레인 Vol.25 No.4

Three kinds of anion-exchangeable functional groups with different hydrocarbon molecular structures were introduced to vinyl benzyl chloride-based membrane to understand the effect of attached function in anion-exchange membrane. Trimethylamine (TMA) as an aliphatic fuction, N-methylpiperidine (MP) as an alicyclic fuction and pyridine (Py) as an aromatic function were introduced by amination. The respective reactivity was observed by the trace of membrane resistance( MER)/ion exchange capacity (IEC) and the increasing order of reactivity was Py < MP < TMA. Meanwhile, SEM photograph showed the attached Py ion-exchange membrane was the most homogenous and compact structure in the study. In electrochemical properties, the attached Py ion-exchange membrane showed the MER (5.0 Ω⋅cm2 >, in 0.5 mol/L NaCl), comparable to those of commercial membrane (AMX). All results showed that the resonance structure of attached functional group might contribute to the preparation of homogenous anion-exchange membrane. 음이온 교환막의 치환체 특성을 파악하기 위하여 탄화수소의 분자구조가 다른 세 종류의 음이온 교환기를 vinyl benzyl chloride (VBC) base 막에 도입하였다. 지방족계로 trimethylamine (TMA), 고리형계로 N-methylpiperidine (MP), 방향족계로 pyridine (Py)은 아민화 반응을 통하여 도입되었다. 각각의 반응속도는 막저항(MER)과 이온교환능력(IEC) 변화의 관측으로부터 Py < MP < TMA의 순서로 반응하고 있음을 보여주었다. 한편 SEM image에서는 Py 치환체 막이 가장 균일하고치밀한 구조를 보여주었으며, 전기화학적 특성에서도 Py이 상용막(AMX)과 비슷한 막저항(5.0 Ω⋅cm2 >, in 0.5 mol/L NaCl)을 나타내었다. 이 모든 결과로부터 치환체의 공명구조는 균질한 이온교환막의 제조에 기여하고 있음을 알 수 있었다.

Fabrication of photocured anion-exchange membranes using water-soluble siloxane resins as cross-linking agents and their application in reverse electrodialysis

Yang, SeungCheol,Kim, Won-Sik,Choi, Jiyeon,Choi, Young-Woo,Jeong, Namjo,Kim, Hanki,Nam, Joo-Youn,Jeong, Haejun,Kim, Yong Ho Elsevier 2019 Journal of membrane science Vol.573 No.-

<P><B>Abstract</B></P> <P>The utilization of large amounts of volatile organic solvents and the complicated process required for industrial manufacturing of ion-exchange membranes necessitate the development of simple, rapid, and environmentally friendly fabrication methods such as those based on photopolymerization. We employed hydrolytic sol–gel reactions between ammonium- and acrylamide-functionalized silane coupling agents to synthesize water-soluble siloxane resins that exhibit high condensation levels (>80%) and comprise oligomers with molecular weights below 2000 Da. These resins were then mixed with a hydrophilic monomer bearing ammonium and acrylamide groups, and porous polyethylene substrates were impregnated with the resulting mixtures and then irradiated with ultraviolet light. The hydrophilicity, mechanical strength, and other properties of the resulting membranes depended on the resin composition, indicating that the substrate pores were efficiently filled with the prepared resins and further suggesting that the membrane performance could be effectively altered by varying the resin composition. Moreover, the obtained membranes exhibited chemical stability in the pH range between 0 and 11 and in hot water at 60 °C. The reverse electrodialysis stack consisting of these membranes showed higher power density than a stack of commercial membranes. Therefore, it can be concluded that without employing volatile organic solvents for reverse electrodialysis, the developed technique is well-suited for the fabrication of ion-exchange membranes.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Photocured anion-exchange membranes were fabricated using water-soluble siloxane resins. </LI> <LI> All resins had a high condensation degree, containing oligomers with <I>M</I> <SUB>w</SUB> < 2000 Da. </LI> <LI> These resins acted as cross-linkers and helped to avoid the use of organic solvents. </LI> <LI> The properties of the prepared anion-exchange membranes depended on resin composition. </LI> <LI> Reverse electrodialysis using the prepared membrane shows higher power density than that of the commercial membrane. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>