Abstract
The phase composition, electrotransport properties, and spectral characteristics of the (1 − x)CsH2PO4–xButvar system (х = 0–0.2 wt%) were investigated in details. Butvar was proved to be a chemically suitable matrix for CsH2PO4 with a good adhesion to acid salt permitting the formation of flexible membrane. The chemical interaction of organic matrix with acid salt was not observed. A new method of “polymer-CsH2PO4” composites preparation through alcohol solutions of initial components was proposed. The flexible and thin (~ 200 μm) proton membranes with uniform salt distribution were obtained. Composite polymer electrolytes are characterized by high proton conductivity values (~ 5 × 10−3 S/cm) at 240 °C and are stable under conditions of high humidity (PH2O ~ 0.3 atm.).
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References
Baranov AI, Khiznichenko VP, Sandler VA, Shuvalov LA (1988) Frequency dielectric dispersion in the ferroelectric and superionic phases of CsH2PO4. Ferroelectrics 81:1147–1150
Baranov AI, Shuvalov LA, Schagina NM (1982) Superion conductivity and phase transitions in CsHSO4 and CsHSeO4 crystals. JETP Lett 36:459–462
Baranov AI (2003) Crystals with disordered hydrogen-bond networks and superprotonic conductivity. Review, Cryst. Rep. 48(6):1012–1037
Taninouchi Y, Uda T, Awakura Y, Ikeda A, Haile SM (2007) Dehydration behavior of the superprotonic conductor CsH2PO4 at moderate temperatures: 230 to 260°C. J Mater Chem 17:3182–3189
Otomo J, Minagawa N, Wen CJ, Eguchi K, Takahashi H (2003) Protonic conduction of CsH2PO4 and its composite with silica in dry and humid atmospheres. Solid State Ionics 156:357–369
Boysen DA, Uda T, Chisholm CRI, Haile SM (2004) High-performance solid acid fuel cells through humidity stabilization. Science 303:68–70
Nikiforov AV, Berg RW, Bjerrum NJ (2018) Vapor pressure and specific electrical conductivity in the solid and molten H2O-CsH2PO4-CsPO3 system—a novel electrolyte for water electrolysis at ~ 225–400°C. Ionics 24:2761–2782
Botez CE, Martinez I, Price A, Martinez H, Leal JH (2019) Superprotonic CsH2PO4 in dry air. J Phys Chem Solids 129:324–328
Martsinkevich VV, Ponomareva VG (2012) Double salts Cs1-xMxH2PO4 (M=Na, K, Rb) as proton conductors. Solid State Ionics 225:236–240
Anfimova T, Jensen AH, Christensen E, Jensen JO, Bjerrum NJ, Li Q (2015) CsH2PO4/NdPO4 composites as proton conducting electrolytes for intermediate temperature fuel cells. JElectrochem Soc 162(4):F436–F441
Matsui T, Kukino T, Kikuchi R, Eguchi K (2006) Intermediate-temperature fuel cell employing CsH2PO4/SiP2O7-based composite electrolytes. J Electrochem Soc 153(2):A339–A342
Mohammad N, Mohamad AB, Kadhum AAH, Loh KS (2017) Effect of silica on the thermal behavior and ionic conductivity of mixed salt solid acid composites. J Alloys Compd 690:896–902
Haile SM, Chisholm CRI, Sasaki K, Boysen DA, Uda T (2007) Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes. Faraday Discuss 134:17–39
Boysen DA, Chisholm CRI, Haile SM, Narayanan SR (2000) Polymer solid acid composite membranes for fuel-cell applications. J Electrochem Soc 147:3610–3613
Uda T, Haile SM (2005) Thin-membrane solid-acid fuel cell. Electrochem Solid-State Lett 8(5):A245–A246
Aili D, Gao Y, Han J, Li Q (2017) Acid-base chemistry and proton conductivity of CsHSO4, CsH2PO4 and their mixtures with N-heterocycles. Solid State Ionics 306:13–19
Oh S-Y, Kawamura G, Muto H, Matsuda A (2012) Mechanochemical synthesis of proton conductive composites derived from cesium dihydrogen phosphate and guanine. Solid State Ionics 225:223–227
Jensen H (2014) Preparation and characterization of components for intermediate temperature fuel cells and electrolyzers, PhD Thesis, Denmark
Qing G, Kikuchi R, Takagaki A, Sugawara T, Oyama ST (2015) CsH2PO4/epoxy composite electrolytes for intermediate temperature fuel cells. Electrochim Acta 169:219–226
Qing G, Kikuchi R, Takagaki A, Sugawara T, Oyama ST (2014) CsH2PO4/polyvinylidene flouride composite electrolytes for intermediate temperature fuel cells. J Electrochem Soc 161:F451–F457
Xie Q, Li Y, Hu J, Chen X, Li H (2015) A CsH2PO4-based composite electrolyte membrane for intermediate temperature fuel cells. J of Membrane Science 489:98–105
Bagryantseva IN, Ponomareva VG, Lazareva NP (2019) Proton-conductive membranes based on CsH2PO4 and ultra-dispersed polytetrafluoroethylene. Solid State Ionics 329:61–66
Ahn YS, Mangani IR, Park CW, Kim J (2006) Study on the morphology of CsH2PO4 using the mixture of methanol and polyols. J Power Sources 163:107–112
Lohmann-Richters FP, Odenwald C, Kickelbick G, Abel B, Varga Á (2018) Facile and scalable synthesis of sub-micrometer electrolyte particles for solid acid fuel cells. RSC Adv 8:21806–21815
Hosseini S, Daud WRW, Badiei M, Kadhum AAH, Mohammad AB (2011) Effect of surfactants in synthesis of CsH2PO4 as protonic conductive membrane. Bull Mater Sci 34:759–765
Varga A, Brunelli NA, Louie MW, Giapis KP, Haile SM (2010) Composite nanostructured solid-acid fuel-cell electrodes via electrospray deposition. J Mater Chem 20:6309–6315
Suryaprakash RC, Lohmann FP, Wagner M, Abel B, Varga A (2014) Spray drying as a novel and scalable fabrication method for nanostructured CsH2PO4. Pt-thin-film composite electrodes for solid acid fuel cells RSC Adv 4:60429–60436
Hallensleben ML, Fuss R, Mummy F (2000) Polyvinyl compounds, others. Ullmann’s Encyclopedia of Industrial Chemistry, Wiley Online Library
Chaudhry AU, Mittal V, Mishra B (2015) Inhibition and promotion of electrochemical reactions by graphene in organic coatings. RSC Adv 5:80365–80368
Dang D, Zhao B, Chen D, Yoo S, Lai SY, Doyle B, Dai S, Chen Y, Qu C, Zhang L, Liao S, Liu M (2017) A durable polyvinyl butyral-CsH2PO4 composite electrolyte for solid acid fuel cells. J. Power Sources 359:1–6
Matsunaga H, Itoh K, Nakamura E (1980) X-ray structural study of CDP at room temperature. Journal of Physical Society of Japan 48(6):2011–2014
Otomo J, Minagawa N, Wen C, Eguchi K, Takahashi H (2003) Protonic conduction of CsH2PO4 and its composite with silica in dry and humid atmospheres. Solid State Ionics 156:357–369
Marchon B, Novak A (1983) Vibrational study of CsH2PO4 and CsD2PO4 single crystals. J Chem Phys 78:2105–2120
Howie FMP (2014) Materials used for conserving fossil specimens since 1930: a review, stud. Conserv. 29(1):92–97
Acknowledgements
This work was supported by Russian Foundation for Basic Research (RFBR) grant no. 18-08-01279 and the state assignment to ISSCM SB RAS(project no. АААА-А17-117030310281-3).
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Bagryantseva, I.N., Gaydamaka, A.A. & Ponomareva, V.G. Intermediate temperature proton electrolytes based on cesium dihydrogen phosphate and Butvar polymer. Ionics 26, 1813–1818 (2020). https://doi.org/10.1007/s11581-020-03505-9
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DOI: https://doi.org/10.1007/s11581-020-03505-9