PREPARATION AND CHARACTERIZATION OF TETRA-IMIDAZOLIUM HYDROXIDES POLYPHENYLENE MEMBRANES VIA NICKEL CATALYZED C-C COUPLING POLYMERIZATION

Sabuj Chandra Sutradhar,Jae Seong Ha,Jae Seung Pyo,Kun Young Choi,Chae Kyun Lee,Whan Gi KIM 한국신재생에너지학회 2015 AFORE Vol.2015 No.11

Thermally and chemically stable poly(phenylenebenzophenone) membranes for proton exchange membrane fuel cells by Ni (0) catalyst

Sabuj Chandra Sutradhar,Md Mahabubur Rahman,Faiz Ahmed,류태욱,윤수진,이승찬,김재웅,이용훈,Yongcheng Jin,김환기 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.76 No.-

Thermally and chemically stable sulfonated poly(phenylenebenzophenone)s (SPPBP) membranes havebeen synthesized from 1,4-dichloro-2,5-diphenylene methoxy benzophenone (PMBP) and 1,4-dichloro-2,5-dibenzoyl benzene (PBP) monomers by using Ni (0) catalyst for proton exchange membrane fuel cells(PEMFC). The synthesized SPPBP membranes exhibited ion exchange capacity from 1.18 to 2.30 meq/g.,water uptake from 34.2 to 78.3% and proton conductivity from 36.94 to 92.90 mS/cm. Additionally, the C–C coupling polymerization improved the thermal and chemical stability of the SPPBP membranes. Furthermore, the pendent benzophenone acid moiety provided the well hydrophilic/hydrophobic phaseseparation morphology with increased conductivity. Therefore, the SPPBP membranes can be a potentialcandidate for proton exchange membrane fuel cell (PEMFC).

Synthesis and characterization of sulfonated mutiphenyl conjugated polyimide for PEMFC

류태욱,Sabuj Chandra Sutradhar,Faiz Ahmed,최건영,양한모,윤수진,이성권,김환기 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.49 No.-

A new monomer, di-sulfuricacid-1,1-bis(4-aminophenyl)-2,2-diphenylethylene (SBAPDPE), was synthesizedby direct sulfonation of the parent diamine, 1,1-bis(4-aminophenyl)-2,2-diphenylethylene(BAPDPE) using concentrated sulfuric acid. A series of the side-chain-type sulfonated conjugatedtetraphenylethylene polyimides (SCTPPIs) with different degrees of sulfonation were prepared fromdianhydrides with SBAPDPE and non-sulfonated diamine. The SCTPPIs generally showed good solubilityin m-cresol and DMSO. The membranes were studied by FT-IR, 1H NMR spectroscopy, and TGA. Sorptionexperiments were conducted to observe the interaction of sulfonated polymers with water. The ionexchange capacity (IEC) and proton conductivity were evaluated with increase of degree of sulfonation

Synthesis and characterization of fluorosulfonyl imide isatin biphenylene block copolymer for PEMFC

Ryu, Taewook,Chandra, Sabuj Sutradhar,Ahmed, Faiz,Lopa, Nasrin Siraj,Yoon, Soojin,Yang, Hanmo,Lee, Seungchan,Choi, Inhwan,Kim, Whangi Elsevier 2018 International journal of hydrogen energy Vol.43 No.26

<P><B>Abstract</B></P> <P>In this study, A fluorosulfonyl imide-containing precursor derived from fluorosulfonyl isocyanate was synthesized and grafted on poly (isatin-biphenylene) random and block copolymers. The carbon-carbon structured poly (isatin biphenylene)s were prepared by super acid catalyzed polyhydroxyalkylation reaction with istain, 2,2′-biphenyl, 2,2′-dihydroxybiphenyl. A fluorosulfonyl imide-containing precursor was prepared from chlorosulfuric acid and fluorosulfonylisocyanate. Fluorosulfonyl imide group have higher acidity than sulfonic acid group, therefore the membranes containing fluorosulfonyl imide groups instead of sulfonic acid groups were studied. These membranes showed slightly higher performance of proton conductivity, low water uptake, and good dimensional stability. The structure of the synthesized polymer was investigated by <SUP>1</SUP>H NMR spectroscopy. Surface morphologies will also be assessed by atomic force microscope (AFM). Microphase-separated block copolymers are preferred over random copolymers.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Block and random copolymers were synthesized from biphenyl, 2,2′-biphenol and isatin via super acid catalyzed. </LI> <LI> Fluorosulfonyl imide super strong acid was grafted on copolymers instead of sulfonic acid. </LI> <LI> Block copolymer showed better proton conductivity, physical, and chemical stability than random copolymer. </LI> <LI> Block copolymer showed the IEC and water uptake value 1.45 meq./g and 19.14% respectively. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Random and block copolymers successfully synthesized from isatin, biphenyl and 2.2′-biphenol with super acid catalyst. Block copolymer membranes show higher proton conductivity than random copolymers. The block copolymer showed the IEC value 1.45 meq./g, water uptake 19.14% and the proton conductivity 78.89 mS/cm at 80 °C under 90% RH. Block copolymer membrane showed a greater dependence of proton conductivity on the relative humidity, and had higher conductivity and cell performance than that of random copolymer with similar IEC value. These results showed that the morphology of polymer matrix greatly affected the cell performance and membrane with well-separated hydrophilic/hydrophobic phase is very important in the fuel cell application. This research demonstrated the possibility of promising BPIIB membranes for excellent proton conductivity and cell performance.</P> <P>[DISPLAY OMISSION]</P>

Preparation and Characterization of Anti-Scratch Polycarbonate Containing Acrylate Group

Jang, Hohyoun,Sutradhar, Sabuj Chandra,Ryu, Taewook,Choi, Kunyoung,Yoon, Sujin,Lee, Sungkwun,Kim, Whangi American Scientific Publishers 2017 Journal of Nanoscience and Nanotechnology Vol.17 No.10

<P>Polycarbonate copolymers containing valeric ester were synthesized from bisphenol A and valeric acid as the comonomer by the interfacial polymerization. The oligomer was synthesized from an aqueous bisphenol A and valeric acid in sodium hydroxide solution with solution of tetra butyl ammonium chloride (TBAC) in water (85%) as the phase transfer catalyst (PTC) and triphosgene in methylene chloride, followed by further reaction with triethylamine (TEA) to increase the molecular weight. The valeric acid groups were converted into the acrylate form by substitution reaction with iodomethane. The chemical structure and thermal properties of copolycarbonates were measured by H-1-NMR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Moreover, the surface morphologies were assessed by atomic force microscopy (AFM), and the contact angle measurement of a sessile water drop onto the polymer firms was also performed. The hardness increased from 6B for linear polycarbonate to 45B grades of the copolymer films (100 mu m).</P>

Comparative study of sulfonated branched and linear poly(phenylene)s polymer electrolyte membranes for fuel cells

Ahmed, Faiz,Sutradhar, Sabuj Chandra,Ryu, Taewook,Jang, Hohyoun,Choi, Kunyoung,Yang, Hanmo,Yoon, Sujin,Rahman, Md. Mahbubur,Kim, Whangi Pergamon Press 2018 International journal of hydrogen energy Vol.43 No.10

<P><B>Abstract</B></P> <P>Branched and linear sulfonated poly(phenylene)s (BSPs and LSPs, respectively) polymer electrolyte membranes (PEMs) containing benzophenone moiety were successfully synthesized and the performance of the LSPs and BSPs were compared in conjunction with Nafion 211<SUP>®</SUP>. The LSPs and BSPs were synthesized by the CC coupling polymerization reaction between 1,4-dichloro-2,5-dibenzoylbenzene (PBP) and 1,4-dichloro-2-benzoylbenzene, and from PBP, 1,4-dichloro-2-benzoylbenzene, and 1,3,5-trichlorobenzene (branching agent), respectively. The degree of sulfonation in both LSPs and BSPs were controlled by varying the concentrations of chlorosulfonic acid and the structures of the resultant PEMs were confirmed by <SUP>1</SUP>H-NMR spectroscopy. The optimal LSP (LSP-2) and BSP (BSP-2) PEMs showed excellent chemical stability due to the absence of ether linkages in the polymer backbone, while the BSP-2 exhibited better proton conductivity (94.6 mS/cm under 90% relative humidity at 80 °C), water resistivity, and lower dimensional changes compared to the LSP-2, which is comparable to Nafion 211<SUP>®</SUP>. The maximum power density for BSP-2 and LSP-2 were 0.60 and 0.49 W/cm<SUP>2</SUP>, respectively, while it was 0.62 W/cm<SUP>2</SUP> for Nafion 211<SUP>®</SUP>. Membrane properties were studied with regard to ion exchange capacity, dimensional stability, proton conductivity, thermogravimetric analysis, and water uptake. The surface morphology of membranes was also analyzed by atomic force microscope.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Branched and linear sulfonated (BSP and LSP, respectively) polymer electrolyte membranes (PEMs) were synthesized. </LI> <LI> The properties and the performance of the synthesized PEMs were compared in conjunction with Nafion 211<SUP>®</SUP>. </LI> <LI> The optimal BSP showed better proton conductivity, physical, and chemical stability than LSPs. </LI> <LI> The power density in fuel cells based on optimized BSP, LSP, and Nafion 211<SUP>®</SUP> were 0.60, 0.49 and 0.62 W/cm<SUP>2</SUP>, respectively. </LI> </UL> </P>

Synthesis and characterization of block copolymer and comparative study with random copolymer via superacid–catalyzed reaction

Ryu, Taewook,Ahmed, Faiz,Sutradhar, Sabuj Chandra,Lopa, Nasrin Siraj,Yang, Hanmo,Yoon, Soojin,Lee, Seungchan,Choi, Inhwan,Kim, Whangi Elsevier 2018 International journal of hydrogen energy Vol.43 No.26

<P><B>Abstract</B></P> <P>The grafted block copolymer based polymer electrolyte membrane (PEM) was successfully synthesized by the superacid-catalyzed polyhydroxyalkylation reaction from biphenyl, 2,2′-biphenol and isatin and the performance of the block copolymer were compared in conjunction with the random copolymer. These polymers have all carbon-carbon structure on polymer backbone without ether linkage. The bromoalkylsulfone potassium salt was prepared from 1,3-propane sultone and potassium bromide. Particularly, the attached alkyl sulfone groups were afforded better stability due to less reactivity towards nucleophilic substitution reaction. Moreover, the block copolymer exhibited better proton conductivity (76.84 mS/cm under 90% relative humidity at 80 <SUP>°</SUP>C), water resistivity, chemical, and thermal stability compared to the random copolymer, because block copolymer membranes showed good hydrophilic/hydrophobic phase separation and wide ionic channels. The structures of the resultant PEMs were confirmed by <SUP>1</SUP>H NMR spectroscopy and thermogravimetric analysis (TGA). These membranes were studied by proton conductivity, water uptake (WU), and ion exchange capacity (IEC). Fenton test was attended by Fenton's reagent (4 ppm Fe<SUP>2+</SUP>, 3% H<SUB>2</SUB>O<SUB>2</SUB>) for confirmation of the polymer degradation and the surface morphology of membranes was also analyzed by atomic force microscope.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The grafted block copolymer was synthesized via super acid catalyzed reaction. </LI> <LI> The properties of the block copolymer were compared in conjunction with random copolymer. </LI> <LI> Block copolymer exhibited better cell performance compared to random copolymer. </LI> <LI> Grafted block copolymer showed 18.75% water uptake. </LI> </UL> </P>

Novel divalent organo-lithium salts with high electrochemical and thermal stability for aqueous rechargeable Li-Ion batteries

Ahmed, Faiz,Rahman, Md Mahbubur,Chandra Sutradhar, Sabuj,Lopa, Nasrin Siraj,Ryu, Taewook,Yoon, Soojin,Choi, Inhwan,Lee, Seungchan,Kim, Whangi Elsevier 2019 ELECTROCHIMICA ACTA Vol.298 No.-

<P><B>Abstract</B></P> <P>Novel electrolytes with wide electrochemical potential window and high thermal stability have great potential for aqueous rechargeable lithium-ion batteries (ARLBs). Herein, we report the synthesis of two ionic salts of lithium sulfonylbis(fluorosulfonyl)imide (LiSFSI) and lithium carbonylbis(fluorosulfonyl)imide (LiCFSI) with divalent Li<SUP>+</SUP> for ARLBs. These ionic compounds are the derivatives of monovalent lithium bis(fluorosulfonyl)imide (LiFSI). The LiSFSI and LiCFSI exhibit the kinetic electrochemical stability window of ca. 3.78 and 3.52 V, respectively, which can be further expanded due to the formation of a stable solid electrolyte interface (SEI) layer. While LiFSI exhibits the kinetic electrochemical stability window of ca. 2.22 V without the formation of an SEI layer. Full ARLBs based on LiSFSI and LiCFSI electrolytes with a LiCoO<SUB>2</SUB> cathode and graphite anode can deliver the specific discharge capacity of ca. 113.50 and 95.0 mAh/g, respectively, at 0.1C rate. Whereas, it is ca. 52.53 mAh/g for LiFSI at 0.1C rate. The capacity retention for LiSFSI, LiCFSI, and LiFSI based ARLBs are ca. 97.3, 89.6, and 67.8%, respectively, after 500 cycles. Furthermore, both LiSFSI and LiCFSI reveal much higher thermal stability compared to LiFSI. Thus, the derivatization of conventional ionic compounds is an effective strategy to enhance the battery performance and its lifetime.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Novel divalent organo-lithium electrolytes (LiSFSI and LiCFSI) were prepared and characterized. </LI> <LI> The electrolytes exhibited enhanced thermal and electrochemical stability. </LI> <LI> Both LiSFSI and LiCFSI have formed a stable and dense SEI layer. </LI> <LI> A maximum specific discharge capacity of 113.50 mAh/g was attained with LiSFSI in ARLBs. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Synthesis of an imidazolium functionalized imide based electrolyte salt and its electrochemical performance enhancement with additives in li-ion batteries

Faiz Ahmed,Mohammad Mahbubur Rahman,Sabuj Chandra Sutradhar,Nasrin Siraj Lopa,류태욱,윤수진,최인환,김재웅,Yongcheng Jin,김환기 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.78 No.-

This research demonstrates the synthesis of an imidazolium functionalized imide based electrolyte salt,lithium (fluorosulfonyl)((3-(1-methyl-1H-imidazol-3-ium-3-yl)propyl)sulfonyl)imide) bis(trifluorosulfonyl)imide (LiFSMIPTFSI) for the development of lithium-ion battery (LIB). The LiFSMIPTFSI electrolytewith a mix-solvent of ethylene carbonate (EC) and dimethyl sulfoxide (DMSO) (75:25 v/v) shows highelectrochemical oxidative stability (up to 5.3 V vs. Li/Li+), good Li+ conductivity (ca. 6.10 mS/cm at 30 C)and transference number (ca. 0.55), and low viscosity, which concurrently provide a specific capacity ofca. 141 mAhg 1 at 0.1 C with a full LIB structure of LiFePO4/LiFSMIPTFSI/graphite. The electrochemicalperformance of this electrolyte is enhancing additionally by adding conventional imide salts (lithium bis(fluoro-sulfonyl)imide (LiFSI) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)) (20% each) asadditives with the specific capacity of ca. 160 and 150 mAhg 1, respectively, at 0.1 C. This is mainly due tothe additional enhancement of Li+ conductivity and transference number of the LiFSMIPTFSI electrolyteinduce by the additives. The LiFSMIPTFSI electrolyte with LiFSI additive based LIB shows the maximumcapacity retention of ca. 95.50% among the electrolytes after 500 charge-discharge cycles, along with highcoulombic efficiency (98.50%).

Synthesis of Fluorosulfonylimide Acid Poly(isatin-biphenylene) for Fuel Cell Electrolyte

Hohyoun Jang,Taewook Ryu,Jiho Yoo,Sabuj Chandra Sutradhar,Hanmo Yang,Whangi Kim 한국고분자학회 2016 한국고분자학회 학술대회 연구논문 초록집 Vol.41 No.2