과불소화된 아크릴레이트 가교제로 제조된 직접 가교형 겔 고분자 전해질의 전기화학적 특성

오시진,심효진,김동욱,이명훈,이창진,강영구,Oh, Si-Jin,Shim, Hyo-Jin,Kim, Dong-Wook,Lee, Myong-Hoon,Lee, Chang-Jin,Kang, Yong-Ku 한국전기화학회 2010 한국전기화학회지 Vol.13 No.2

본 연구에서는 organophosphate를 기반으로 한 과불소화된 아크릴레이트 가교제를 사용하여 제조한겔 고분자 전해질의 이온 전도도 및 전기화학적 특성을 평가하였다. 과불소화된 아크릴레이트 가교제를 사용하여 만든 겔 고분자 전해질은 액체전해질의 함량이 최대 97 wt%까지 안정한 겔 상태를 유지하였다. 본 연구에서 제조한 겔 고분자 전해질의 이온전도도는 $30^{\circ}C$에서 $1.0\;{\times}\;10^{-2}\;S/cm$의 값을 가졌다. 또한 전기화학적 안정성 테스트에서도 약 4.5V로 이상까지 산화에 의한 열화가 없이 안정하였다. 합성된 겔고분자 전해질을 리튬이온 고분자 전지에 적용하여 그 활용성을 평가하였다. 양극으로는 $LiCoO_2$를 사용하였으며 음극으로는 카본을 사용하였다. 이렇게 만든 리튬이온 고분자 전지는 0.1C에서 136.11 mAh/g의 용량으로 이론용량과 거의 비슷한 값을 나타내었으며, 2C 방전에서도 초기 용량의 91%를 유지하였다. 또한 500번의 충방전 후에도 초기 용량의 70%정도의 용량을 유지하였다. The gel polymer electrolyte(GPE) were prepared by in-situ thermal cross-linking reaction of homogeneous precursor solution of perfluorinated phosphate-based cross-linker and liquid electrolyte. Ionic conductivities and electrochemical properties of the prepared gel polymer electrolyte with the various contents of liquid electrolytes and perfluorinated organophosphate-based cross-linker were examined. The stable gel polymer electrolyte was obtained up to 97 wt% of the liquid electrolyte. Ionic conductivity and electrochemical properties of the gel polymer electrolytes with the various chain length of perfluorinated ethylene oxide and different content of liquid electrolytes were examined. The maximum ionic conductivity of liquid electrolyte was measured to be $1.02\;{\times}\;10^{-2}\;S/cm$ at $30^{\circ}C$ using the cross-linker($PFT_nGA$). The electrochemical stability of the gel polymer electrolyte was extended to 4.5 V. The electrochemical performances of test cells composed of the resulting gel polymer electrolyte were also studied to evaluate the applicability on the lithium polymer batteries. The test cell carried a discharge capacity of 136.11mAh/g at 0.1C. The discharge capacity was measured to be 91% at 2C rate. The discharge capacity decreased with increase of discharge rate which was due to the polarization. After 500th charge/discharge cycles, the capacity of battery decreased to be 70% of the initial capacity.

Star-Shaped Block Copolymers: Effective Polymer Gelators of High-Performance Gel Electrolytes for Electrochemical Devices

Hwang, Heedong,Park, So Yeong,Kim, Jin Kon,Kim, Yong Min,Moon, Hong Chul American Chemical Society 2019 ACS APPLIED MATERIALS & INTERFACES Vol.11 No.4

<P>Ion gels composed of copolymers and ionic liquids (ILs) have attracted great interest as polymer gel electrolytes for various electrochemical applications. Here, we present highly robust ion gels based on a six-arm star-shaped block copolymer of (poly(methyl methacrylate)-<I>b</I>-polystyrene)<SUB>6</SUB> ((MS)<SUB>6</SUB>) and an ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([EMI][TFSI]). Compared to typical ion gels based on linear polystyrene-<I>b</I>-poly(methyl methacrylate)-<I>b</I>-polystyrene (SMS), the (MS)<SUB>6</SUB>-based gels show mechanical moduli of more than twice under various strains (e.g., stretching, compression, and shear). In addition, the outstanding mechanical property is maintained even up to 180 °C without a gel-sol transition. To demonstrate that (MS)<SUB>6</SUB>-based ion gels can serve as effective gel electrolytes for electrochemical applications, tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)<SUB>3</SUB><SUP>2+</SUP>), a representative electrochemiluminescent (ECL) luminophore, is incorporated into the gels. In particular, flexible ECL devices based on (MS)<SUB>6</SUB> gels exhibit high durability against bending deformation compared to devices with gels based on linear SMS having a similar molecular weight and a composition. This result implies that star-shaped block copolymers are effective gelators for achieving flexible/wearable electrochemical electronics.</P> [FIG OMISSION]</BR>

Improvement in Long-Term Stability and Photovoltaic Performance of UV Cured Resin Polymer Gel Electrolyte for Dye-Sensitized Solar Cell

Geun Woo Park,Chul Gyun Hwang,Jae Won Jung,정영미 대한화학회 2012 Bulletin of the Korean Chemical Society Vol.33 No.12

We introduced a new UV-cured resin polymer gel as an electrolyte for dye-sensitized solar cells (DSSCs) that is cured with UV irradiation to form a thin film of UV-cured resin polymer gel in the cells. The gel film was characterized and its potential for use as an electrolyte in DSSCs was investigated. This new UV-cured resin polymer gel was successfully applied as a gel polymer electrolyte in DSSCs overcoming the problems associated with the liquid electrolytes in typical DSSCs. The effect of γ-butylrolactone (GBL) on the long-term stability and photovoltaic performance in DSSCs using this UV-cured resin polymer gel electrolyte was also investigated. The results of the energy conversion efficiency, ionic conductivity and Raman spectra of the UVcured resin polymer gel electrolyte with the addition of 6 wt % GBL to the UV-cured resin polymer electrolyte showed good long-term stability and photovoltaic performance for the DSSCs with the UV-cured polymer gel electrolyte.

Poly[(ethylene glycol) diacrylate]-Poly(vinylidene fluoride) 전해질을 이용한 전기 이중층 캐패시터의 전기화학적 특성

양천모 ( Chun Mo Yang ),이중기 ( Joong Kee Lee ),조원일 ( Won Il Cho ),조병원 ( Byung Won Cho ),주재백 ( Jeh Beck Ju ),유관표 ( Kwan Pyo Yoo ),임병오 ( Byung O Rim ) 한국공업화학회 2002 공업화학 Vol.13 No.8

자외선 경화법으로 제조한 PEGDA-PVdF 젤상 고분자 전해질을 전기이중층캐패시터에 적용하였고, 액상 유기 전해질을 이용한 전기이중층캐패시터와 전기화학적 특성을 비교 조사하였다. 자외선 경화법으로 제조된 젤상 고분자 전해질[GPE:poly[(ethylene glycol) diacrylate]-poly(vinylidene fluoride) blend]을 이용한 전기이중층캐패시터의 경우, 비축전용량이 120 F/g으로 액상 유기 전해질 [LOE:1 M LiPF_6/EC:DMC:EMC (1:1:1 volume ratio)]을 이용한 전기이중층캐패시터의 비축전용량인 110 F/g보다 우수하였고, 100회 충방전 후에도 초기 비축전용량대비 92% 이상 유지하는 우수한 싸이클 특성을 나타내었으며 3.7 Ω의 낮은 ESR(equivalent series resistance)을 보여주었다. Cyclic voltammetry 분석 결과에서 보면 액상 유기 전해질과 젤상 고분자 전해질을 이용한 모든 전기이중층캐패시터에서 2.5 V까지 전해질의 분해 없이 전기화학적으로 안정하였고, 산화와 환원과 관련된 전류값 또한 관찰되지 않았다. 젤상 고분자 전해질을 이용한 전기이중층캐패시터의 경우에서 직사각형 모양의 이상적인 전기이중층캐패시터의 특성과 49 ㎂의 낮은 누설 전류값을 나타내었다. 자가방전 특성 결과, 젤상 고분자 전해질을 이용한 전기이중층캐패시터의 경우 2.5 V의 정전압 충전 시 OCV(open circuit voltage) 상태에서 100 h 경과 후 1.76 V의 전압을 유지하고 있어 0.25 V의 액상 유기 전해질을 이용한 전기이중층캐패시터보다 매우 우수함을 확인하였다. Poly[(ethylene glycol) diacrylate] (PEGDA)-poly(vinylidene fluoride) (PVdF) gel polymer was employed as an electrolyte for electric double layer capacitor (EDLC) and compared its electrochemical characteristics with that of liquid organic electrolyte. The used organic electrolyte was 1 mole of lithium hexafluorophosphate (LiPF_6) salt containing in the solvent mixture of ethylene carbonate(EC):dimethyl carbonate(DMC):ethylmethyl carbonate(EMC)(1:1:1 volume ratio). The specific capacitance of EDLC with gel polymer electrolyte showed 120 F/g, which was superior to that of 110 F/g with liquid organic electrolyte. Good cyclability was observed for gel polymer electrolyte of EDLC. The 92% of initial specific capacitance was retained after 100 cycles of charge-discharge runs. Equivalent series resistance of 3.7 Ω of the EDLC with gel polymer electrolyte was lower than that of EDLC with liquid organic electrolyte. The EDLC with gel polymer electrolyte exhibited rectangular cyclic voltammogram of ideal EDLC in operating voltage range of 0∼2.5 V and low leakage current of 49 ㎂. Voltage drop from self-discharge was low for gel polymer electrolyte. The 29.6% of initial voltage decreased for gel polymer electrolyte, but significantly decreased to 99% for liquid organic electrolyte. The good retentivity with gel polymer electrolyte possible comes from the difference in viscosity compared with that of liquid organic electrolyte.

Improvement in Long-Term Stability and Photovoltaic Performance of UV Cured Resin Polymer Gel Electrolyte for Dye-Sensitized Solar Cell

Park, Geun Woo,Hwang, Chul Gyun,Jung, Jae Won,Jung, Young Mee Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.12

We introduced a new UV-cured resin polymer gel as an electrolyte for dye-sensitized solar cells (DSSCs) that is cured with UV irradiation to form a thin film of UV-cured resin polymer gel in the cells. The gel film was characterized and its potential for use as an electrolyte in DSSCs was investigated. This new UV-cured resin polymer gel was successfully applied as a gel polymer electrolyte in DSSCs overcoming the problems associated with the liquid electrolytes in typical DSSCs. The effect of ${\gamma}$-butylrolactone (GBL) on the long-term stability and photovoltaic performance in DSSCs using this UV-cured resin polymer gel electrolyte was also investigated. The results of the energy conversion efficiency, ionic conductivity and Raman spectra of the UV-cured resin polymer gel electrolyte with the addition of 6 wt % GBL to the UV-cured resin polymer electrolyte showed good long-term stability and photovoltaic performance for the DSSCs with the UV-cured polymer gel electrolyte.

젤형 염료 태양전지의 광전변환 특성에 관한 연구

박병욱(Byung-Wook Park),곽동주(Dong-Joo Kwak),성열문(Youl-Moon Sung) 한국조명·전기설비학회 2009 조명·전기설비학회논문지 Vol.23 No.2

본 연구에서는 Poly(VdF-HFP)를 사용한 Gel Polymer 전해질을 제작하여 기존의 액상전해질과 비교하였다. 제작된 젤 고분자 전해질의 성분은 FTIR 분석을 사용하여 화학적 구조를 고찰한 후, 성분조사를 통해 Gel Polymer 전해질임을 확인 하였으며, SEM 관측을 통해 Polymer 상태의 Gel 전해질의 구조를 확인하였다. 본 실험에서 제작된 젤 고분자 전해질을 구성하는 DEC와 PC의 최적의 성분비는 5 : 5임을 확인할 수 있었다. 최적조건의 젤 고분자 전해질을 이용하여 제작된 염료 태양전지(DSCs)의 효율은 3~4[%]정도의 측정값을 얻었으며, 이상의 결과로부터 기존의 액상 전해질을 대체할 수 있는 준 고체형 염료태양전지의 제작이 가능함이 확인되었다. In this paper Gel polyrrer electrolyte using Poly(Vdf-HFP) was fabricated and compared with liquid type electrolyte. The chemical structure and ingredients of fabricated gel electrolyte was investigated and identified to gel polymer electrolyte by FTIR, gel electrolyte was verified to polymer state by SEM From the experiment result, the better component ratio of Propylene carbonate and Diethyl carbonate for gel type electrolyte was 5 : 5. The conversion efficiency of fabricated DSCs using gel electrolyte was 3~4[%], expected to alternate with liquid type electrolyte.

Lithium metal polymer cells assembled with gel polymer electrolytes containing ionic liquid

Yun, Y.S.,Song, S.W.,Lee, S.Y.,Kim, S.H.,Kim, D.W. Elsevier 2010 CURRENT APPLIED PHYSICS Vol.10 No.4

Gel polymer electrolytes containing a mixture of organic solvent and ionic liquid were prepared and their electrochemical properties were investigated. The gel polymer electrolytes exhibited good electrochemical stability and stable interfacial properties toward lithium metal. Using these gel polymer electrolytes, lithium metal polymer cells composed of a lithium anode and a LiFePO<SUB>4</SUB> cathode were assembled, and their cycling performances were evaluated. The cells showed good cycling performance comparable to that of a cell assembled with gel polymer electrolyte containing only organic liquid electrolyte. The Li/LiFePO<SUB>4</SUB> cells assembled with a gel polymer electrolyte containing ionic liquid are expected to be one of the promising candidates for high energy density lithium batteries with improved safety.

나노복합 고분자 겔 전해질: 합성 및 유변학적 특성

장동욱 ( Dong Wook Chang ) 대구가톨릭대학교 자연과학연구소 2013 자연과학연구논문집 Vol.11 No.1

The development of a simple preparation method for high-performance polymer gel electrolyte is an important issue for many energy-related applications such as batteries, fuel cells and solar cells. Herein, we report a versatile method to produce polymer gel electrolytes via simple thermal polymerization of vinyl monomers using radical initiator. In addition, multi walled carbon nanotubes (MWNTs) have been incorporated into 3-dimensional networks of polymer gel electrolyte as fillers. Poly (ethylene glycol dimethacrylate) based nanocomposite polymer gel electrolyte has been successfully obtained with enhanced stability and superior mechanical property. Therefore, this newly developed nanocomposite polymer gel electrolytes can be considered as good candidates for the next generation of energy related devices.

Effect of Li_1.3Al_0.3Ti_1.7(PO₄)₃ in Polymer Gel Electrolytes Consisting of PVdF-HFP and Hydroxypropylcellulose

김주미,오지민,신동옥,김주영,이명주,이영기,김광만 한국공업화학회 2018 한국공업화학회 연구논문 초록집 Vol.2018 No.0

The composite polymer gel electrolytes(CPGE) for lithium-ion batteries are prepared by combining the binary polymer components of hydroxypropylcellulose (HPC), poly vinylidenefluoride-co-hexafluoropropylene (PVdF-HFP), the inorganic filler of Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) and the electrolyte solution of 1 M LiPF₆/EC:PC:EMC. Three main solid components play their own roles in the composite electrolytes. The synergy among each component is expected to lead highly ionic conductive electrolytes with excellent mechanical strength. In this study, the effect of LATP content on the physical and electrochemical properties of the CPGE is particularly investigated. The LATP is used as powder obtained after the calcination at 900℃ and before pressing the hydrothermally synthesized product. In the presentation, how each component and its content contribute to the electrochemical performance of the cell will also be discussed in detail.

Quasi-Solid-State Polymer Electrolytes Based on a Polymeric Ionic Liquid with High Ionic Conductivity and Enhanced Stability

Jeon, Nawon,Jo, Sung-Geun,Kim, Sang-Hyung,Park, Myung-Soo,Kim, Dong-Won The Korean Electrochemical Society 2017 Journal of electrochemical science and technology Vol.8 No.3

A polymeric ionic liquid, poly(1-methyl 3-(2-acryloyloxypropyl) imidazolium iodide) (PMAPII), was synthesized as a single-iodide-ion-conducting polymer and employed in a gel polymer electrolyte. Gel polymer electrolytes prepared from iodine, 4-tert-butylpyridine, ${\gamma}$-butyrolactone, and PMAPII were applied in quasi-solid-state dye-sensitized solar cells (DSSCs). The addition of 16 wt.% PMAPII provided the most favorable environment, striking a compromise between the iodide ion concentration and the ionic mobility, which resulted in the highest conversion efficiency of the resulting DSSCs. The quasi-solid-state DSSC assembled with the optimized gel polymer electrolyte exhibited a relatively high conversion efficiency of 7.67% under AM 1.5 illumination at $100mA\;cm^{-2}$ and better stability than that of the DSSC with a liquid electrolyte.