静电纺丝制备质子交换膜燃料电池催化剂层综述
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摘要
质子交换膜燃料电池催化剂层在成本、耐久性以及性能上的局限是制约燃料电池汽车商业化的瓶颈.已有文献证明静电纺丝技术制备的纳米纤维催化剂层能提高催化剂利用率、增加三相界面和三相通道以及提高耐久性.作者结合所在课题组的工作综述了静电纺丝技术制备质子交换膜燃料电池催化剂层的研究进展.首先,介绍了质子交换膜燃料电池催化剂层的发展历程,并从制备方式和结构两个方面对其进行分类和总结;接下来,从静电纺丝纳米纤维催化剂层的制备、物理特性表征、电化学性能分析及耐久性表征等方面进行了总结;最后,从三相界面、三相通道以及量产适用性的视点比较了三种结构的催化剂层,介绍了质子交换膜燃料电池催化剂层的发展趋势,并梳理了静电纺丝法制备质子交换膜燃料电池催化剂层领域待研的问题.
The limitation of catalyst layer for proton exchange membrane fuel cell(PEMFC) in cost,durability and performance constitutes the bottleneck for the commercialization of fuel cell vehicles.Electrospun catalyst layer,with high catalyst utilization,increased triple phase boundary(TPB) and triple phase channel(TPC),has been developed by many researchers.This paper reviews the research progress in the electrospun catalyst layer for PEMFC,combined with the author's work.Firstly,the development progress of catalyst layer is summarized,and the catalyst layer is classified and analyzed based on its fabrication method and structure character.Next,the fabrication process,physical property characterization,electrochemical performance analysis and durability characterization of the electrospun nanofiber catalyst layer are described.Finally,further develoment tendency in catalyst layer for PEMFC is viewed by comparion of three kinds of catalyst layers from the viewpoints of TPB,TPC and mass production.Future research topics are discussed.
The limitation of catalyst layer for proton exchange membrane fuel cell(PEMFC) in cost,durability and performance constitutes the bottleneck for the commercialization of fuel cell vehicles.Electrospun catalyst layer,with high catalyst utilization,increased triple phase boundary(TPB) and triple phase channel(TPC),has been developed by many researchers.This paper reviews the research progress in the electrospun catalyst layer for PEMFC,combined with the author's work.Firstly,the development progress of catalyst layer is summarized,and the catalyst layer is classified and analyzed based on its fabrication method and structure character.Next,the fabrication process,physical property characterization,electrochemical performance analysis and durability characterization of the electrospun nanofiber catalyst layer are described.Finally,further develoment tendency in catalyst layer for PEMFC is viewed by comparion of three kinds of catalyst layers from the viewpoints of TPB,TPC and mass production.Future research topics are discussed.
引文
[1]Ouyang M G(欧阳明高).Technology strategy and R&Dprogress of automotive new energy and powertrain[J]Transactions of CSICE(内燃机学报),2008(s1):107-114.
[2]Wang C(王诚),Zhao B(赵波),Zhang J B(张剑波).Progress of membrane electrode assembly technology for proton exchange membrane fuel cell[J].Science&Technology Review(科技导报),2016,34(6):62-68.
[3]Ohma A,Mashio T,Sato K,et al.Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan[J].Electrochimica Acta,2011,56(28):10832-10841.
[4]Huang J,Li Z,Zhang J B.Review of characterization and modeling of polymer electrolyte fuel cell catalyst layer:The blessing and curse of ionomer[J].Frontiers in Energy,2017,11(3):334-364.
[5]Jiang S F(蒋尚峰),Yi B L(衣宝廉).Progress of orderstructured membrane electrode assembly[J].Journal of electrochemistry(电化学),2016,22(3):213-218.
[6]Cho Y H,Park H S,Cho Y H,et al.Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell[J].Journal of Power Sources,2007,172(1):89-93.
[7]Litster S,Mclean G.PEM fuel cell electrodes[J].Journal of Power Sources,2004,130(1):61-76.
[8]Ticianelli E A.Methods to advance technology of proton-exchange membrane fuel-cells[J].Journal of The Electrochemical Society,1988,135(9):2209-2214.
[9]Paganin V A,Ticianelli E A,Gonzalez E R.Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells[J].Journal of Applied Electrochemistry,1996,26(3):297-304.
[10]O’Hayre R,Lee S J,Cha S W,et al.A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading[J].Journal of Power Sources,2002,109(2):483-493.
[11]Fofana D,Hamelin J,Bénard P.Modelling and experimental validation of high performance low platinum multilayer cathode for polymer electrolyte membrane fuel cells(PEMFCs)[J].International Journal of Hydrogen Energy,2013,38(24):10050-10062.
[12]Debe M K,Schmoeckel A,Hendricks S,et al.Durability aspects of nanostructured thin film catalysts for PEM fuel cells[J].ECS Transactions,2006,1(8):51-66.
[13]Tian Z Q,Lim S H,Poh C K,et al.A highly order-structured membrane electrode assembly with vertically aligned carbon nanotubes for ultra-low Pt loading PEMfuel cells[J].Advanced Energy Materials,2011,1(6):1205-1214.
[14]Park J H,Ju Y W,Park S H,et al.Effects of electrospun polyacrylonitrile-based carbon nanofibers as catalyst support in PEMFC[J].Journal of Applied Electrochemistry2009,39(8):1229-1236.
[15]Zhang W,Brodt M W,Pintauro P N.Nanofiber cathodes for low and high humidity hydrogen fuel cell operation[J].ECS Transactions,2011,41(1):891-899.
[16]Si D,Zhang S,Huang J,et al.Electrochemical characterization of pre-conditioning process of electrospun nanofiber electrodes in polymer electrolyte fuel cells[J]Fuel Cells,2018,18(5):576-585.
[17]Lu Y X,Du S F,Steinberger-Wilckens R.One dimensional nanostructured electrocatalyst for polymer electrolyte membrane fuel cell-A review[J].Applied Catalysis B:Environmental,2016,199:292-314.
[18]van der Vliet D F,Wang C,Tripkovic D,et al.Mesostructured thin films as electrocatalysts with tunable composition and surface morphology[J].Nature Materials,201211(12):1051-1058.
[19]Zhang S S,Yuan X Z,Hin J N C,et al.A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells[J].Journal of Power Sources,2009194(2):588-600.
[20]Brodt M,Wycisk R,Pintauro P N.Nanofiber electrodes with low platinum loading for high power hydrogen/air PEM fuel cells[J].Journal of The Electrochemical Society2013,160(8):F744-F749.
[21]Park Y C,Tokiwa H,Kakinuma K,et al.Effects of carbon supports on Pt distribution,ionomer coverage and cathode performance for polymer electrolyte fuel cells[J].Journa of Power Sources,2016,315:179-191.
[22]Debe M K.Nanostructured thin film electrocatalysts for PEM fuel cells-A tutorial on the fundamental characteristics and practical properties of NSTF catalysts[M]//Editors.Zawodzinski T,Mukerjee S,Strasser P.Tutorials on Electrocatalysis in Low Temperature Fuel Cells,ECSTransactions,2012,45(2):47-68.
[23]Zeng Y,Shao Z,Zhang H,et al.Nanostructured ultrathin catalyst layer based on open-walled Pt Co bimetallic nanotube arrays for proton exchange membrane fuel cells[J]Nano Energy,2017,34:344-355.
[24]Pintauro P N.Electrospun nanofiber cathode for hydrogen/air fuel cells[C]//ECS 220th ECS Meeting,Boston October 9-14,2011.
[25]Brodt M,Han T,Dale N,et al.Fabrication,in-situ performance,and durability of nanofiber fuel cell electrodes[J].Journal of The Electrochemical Society,2015,162(1):F84-F91.
[26]Zhang W,Pintauro P N.High-performance nanofiber fuel cell electrodes[J].Chemsuschem,2011,4(12):1753-1757.
[27]Slack J J,Wycisk R,Dale N,et al.Electrospun nanofiber fuel cell MEA cathodes with Pt Co/C catalyst[J].ECS Transactions,2017,80(8):829-837.
[28]Brodt M,Wycisk R,Dale N,et al.Power output and durability of electrospun fuel cell fiber cathodes with PVDFand Nafion/PVDF binders[J].Journal of The Electrochemical Society,2016,163(5):F401-F410.
[29]Brodt M,Wycisk R,Pintauro P N,et al.Nanofiber fuel cell electrodes I.Fabrication and performance with commercial Pt/C catalysts[C]//ECS 220th ECS Meeting,San Francisco,California,October 27-November 1,2013.
[30]Han T,Dale N,Adjemian K,et al.Nanofiber fuel cell electrodes II.In-situ performance and durability studies[C]//ECS 220th ECS Meeting,San Francisco,California,October 27-November 1,2013:F84-F91.
[31]Hong S J,Hou M,Xiao Y,et al.Investigation of high-performance nanofiber cathode with ultralow platinum for PEM fuel cells[J].Energy Technology,2017,5(8):1457-1463.
[32]Hong S J,Hou M,Zeng Y C,et al.High-performance lowplatinum electrode for proton exchange membrane fuel cells:Pulse electrodeposition of Pt on Pd/C nanofiber mat[J].ChemElectroChem,2017,4(5):1007-1010.
[33]Hong S J,Hou M,Zhang H J,et al.A high-performance PEM fuel cell with ultralow platinum electrode via electrospinning and underpotential deposition[J].Electrochimica Acta,2017,245:395-401.
[34]Cavaliere S,Subianto S,Savych I,et al.Dopant-driven nanostructured loose-tube SnO2architectures:Alternative electrocatalyst supports for proton exchange membrane fuel cells[J].Journal of Physical Chemistry C,2013,117(36):18298-18307.
[35]Savych I,Subianto S,Nabil Y,et al.Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode[J].Physical Chemistry Chemical Physics,2015,17(26):16970-16976.
[36]Cavaliere S,Jiménez-Morales I,Ercolano G,et al.Highly stable PEMFC electrodes based on electrospun antimonydoped SnO2[J].ChemElectroChem,2016,2(12):1966-1973.
[37]Nabil Y,Cavaliere S,Harkness I A,et al.Novel niobium carbide/carbon porous nanotube electrocatalyst supports for proton exchange membrane fuel cell cathodes[J].Journal of Power Sources,2017,363:20-26.
[38]Lee J,Yoo J M,Ye Y,et al.Development of highly stable and mass transfer-enhanced cathode catalysts:Support-free electro spun intermetallic FePt nanotubes for polymer electrolyte membrane fuel cells[J].Advanced Energy Materials,2015,5(11):1402093.
[39]Wang X H,Richey F W,Wujcik K H,et al.Ultra-low platinum loadings in polymer electrolyte membrane fue cell electrodes fabricated via,simultaneous electrospinning/electrospraying method[J].Journal of Power Sources2014,264:42-48.
[40]Wang X H,Richey F W,Wujcik K H,et al.Effect of polytetrafluoroethylene on ultra-low platinum loaded electrospun/electrosprayed electrodes in proton exchange membrane fuel cells[J].Electrochimica Acta,2014,139(26):217-224.
[41]Reneker D H,Yarin A L,Hao F,et al.Bending instability of electrically charged liquid jets of polymer,solutions in electrospinning[J].Journal of Applied Physics,2000,87(9):4531-4547.
[42]Levitt A S,Vallett R,Dion G,et al.Effect of electrospinning processing variables on polyacrylonitrile nanoyarns[J].Journal of Applied Polymer Science,2018,135(25)46404.
[43]Ding B(丁彬),Yu J Y(俞建勇).Electrospinning and nanofibers[M].China Textile Publishing House(中国纺织出版社),2011:26-59.
[44]Sener A G,Altay A S,Altay F.Effect of voltage on morphology of electrospun nanofibers[C]//International conference on electrical and electronics engineering,December 1-4,2011,Bursa,Turkey.IEEE,2011:I-324-I-328.
[45]Zargham S,Bazgir S,Tavakoli A,et al.The effect of flow rate on morphology and deposition area of electrospun nylon 6 nanofiber[J].Journal of Engineered Fabrics&Fibers,2013,7(4):42-49.
[46]Hekmati A H,Rashidi A,Ghazisaeidi R,et al.Effect of needle length,electrospinning distance,and solution concentration on morphological properties of polyamide-6electrospun nanowebs[J].Textile Research Journal,2013,83(14):1452-1466.
[47]Chan S,Jankovic J,Susac D,et al.Electrospun carbon nanofiber catalyst layers for polymer electrolyte membrane fuel cells:Structure and performance[J].Journal of Power Sources,2018,392(16):239-250.
[48]Chan S,Jankovic J,Susac D,et al.Electrospun carbon nanofiber catalyst layersfor polymer electrolyte membrane fuel cells:fabrication and optimization[J].Journal of Materials Science,53(16):11633-11647.
[49]Ohma A,Shinohara K,Iiyama A,et al.Membrane and catalyst performance targets for automotive fuel cells by FCCJ Membrane,Catalyst,MEA WG[C]//ECS 220th ECSmeeting,Boston,October 9-14,2011:775-784.
[50]Zhang G,Shao Z G,Lu W,et al.Core-shell Pt modified Pd/C as an active and durable electrocatalyst for the oxygen reduction reaction in PEMFCs[J].Applied Catalysis BEnvironmental,2013,132(12):183-194.
[51]Huang J,Zhang J B.Theory of impedance response of porous electrodes:simplifications,inhomogeneities,non-stationarities and applications[J].Journal of The Electrochemical Society,2016,163(9):A1983-A2000.
[2]Wang C(王诚),Zhao B(赵波),Zhang J B(张剑波).Progress of membrane electrode assembly technology for proton exchange membrane fuel cell[J].Science&Technology Review(科技导报),2016,34(6):62-68.
[3]Ohma A,Mashio T,Sato K,et al.Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan[J].Electrochimica Acta,2011,56(28):10832-10841.
[4]Huang J,Li Z,Zhang J B.Review of characterization and modeling of polymer electrolyte fuel cell catalyst layer:The blessing and curse of ionomer[J].Frontiers in Energy,2017,11(3):334-364.
[5]Jiang S F(蒋尚峰),Yi B L(衣宝廉).Progress of orderstructured membrane electrode assembly[J].Journal of electrochemistry(电化学),2016,22(3):213-218.
[6]Cho Y H,Park H S,Cho Y H,et al.Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell[J].Journal of Power Sources,2007,172(1):89-93.
[7]Litster S,Mclean G.PEM fuel cell electrodes[J].Journal of Power Sources,2004,130(1):61-76.
[8]Ticianelli E A.Methods to advance technology of proton-exchange membrane fuel-cells[J].Journal of The Electrochemical Society,1988,135(9):2209-2214.
[9]Paganin V A,Ticianelli E A,Gonzalez E R.Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells[J].Journal of Applied Electrochemistry,1996,26(3):297-304.
[10]O’Hayre R,Lee S J,Cha S W,et al.A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading[J].Journal of Power Sources,2002,109(2):483-493.
[11]Fofana D,Hamelin J,Bénard P.Modelling and experimental validation of high performance low platinum multilayer cathode for polymer electrolyte membrane fuel cells(PEMFCs)[J].International Journal of Hydrogen Energy,2013,38(24):10050-10062.
[12]Debe M K,Schmoeckel A,Hendricks S,et al.Durability aspects of nanostructured thin film catalysts for PEM fuel cells[J].ECS Transactions,2006,1(8):51-66.
[13]Tian Z Q,Lim S H,Poh C K,et al.A highly order-structured membrane electrode assembly with vertically aligned carbon nanotubes for ultra-low Pt loading PEMfuel cells[J].Advanced Energy Materials,2011,1(6):1205-1214.
[14]Park J H,Ju Y W,Park S H,et al.Effects of electrospun polyacrylonitrile-based carbon nanofibers as catalyst support in PEMFC[J].Journal of Applied Electrochemistry2009,39(8):1229-1236.
[15]Zhang W,Brodt M W,Pintauro P N.Nanofiber cathodes for low and high humidity hydrogen fuel cell operation[J].ECS Transactions,2011,41(1):891-899.
[16]Si D,Zhang S,Huang J,et al.Electrochemical characterization of pre-conditioning process of electrospun nanofiber electrodes in polymer electrolyte fuel cells[J]Fuel Cells,2018,18(5):576-585.
[17]Lu Y X,Du S F,Steinberger-Wilckens R.One dimensional nanostructured electrocatalyst for polymer electrolyte membrane fuel cell-A review[J].Applied Catalysis B:Environmental,2016,199:292-314.
[18]van der Vliet D F,Wang C,Tripkovic D,et al.Mesostructured thin films as electrocatalysts with tunable composition and surface morphology[J].Nature Materials,201211(12):1051-1058.
[19]Zhang S S,Yuan X Z,Hin J N C,et al.A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells[J].Journal of Power Sources,2009194(2):588-600.
[20]Brodt M,Wycisk R,Pintauro P N.Nanofiber electrodes with low platinum loading for high power hydrogen/air PEM fuel cells[J].Journal of The Electrochemical Society2013,160(8):F744-F749.
[21]Park Y C,Tokiwa H,Kakinuma K,et al.Effects of carbon supports on Pt distribution,ionomer coverage and cathode performance for polymer electrolyte fuel cells[J].Journa of Power Sources,2016,315:179-191.
[22]Debe M K.Nanostructured thin film electrocatalysts for PEM fuel cells-A tutorial on the fundamental characteristics and practical properties of NSTF catalysts[M]//Editors.Zawodzinski T,Mukerjee S,Strasser P.Tutorials on Electrocatalysis in Low Temperature Fuel Cells,ECSTransactions,2012,45(2):47-68.
[23]Zeng Y,Shao Z,Zhang H,et al.Nanostructured ultrathin catalyst layer based on open-walled Pt Co bimetallic nanotube arrays for proton exchange membrane fuel cells[J]Nano Energy,2017,34:344-355.
[24]Pintauro P N.Electrospun nanofiber cathode for hydrogen/air fuel cells[C]//ECS 220th ECS Meeting,Boston October 9-14,2011.
[25]Brodt M,Han T,Dale N,et al.Fabrication,in-situ performance,and durability of nanofiber fuel cell electrodes[J].Journal of The Electrochemical Society,2015,162(1):F84-F91.
[26]Zhang W,Pintauro P N.High-performance nanofiber fuel cell electrodes[J].Chemsuschem,2011,4(12):1753-1757.
[27]Slack J J,Wycisk R,Dale N,et al.Electrospun nanofiber fuel cell MEA cathodes with Pt Co/C catalyst[J].ECS Transactions,2017,80(8):829-837.
[28]Brodt M,Wycisk R,Dale N,et al.Power output and durability of electrospun fuel cell fiber cathodes with PVDFand Nafion/PVDF binders[J].Journal of The Electrochemical Society,2016,163(5):F401-F410.
[29]Brodt M,Wycisk R,Pintauro P N,et al.Nanofiber fuel cell electrodes I.Fabrication and performance with commercial Pt/C catalysts[C]//ECS 220th ECS Meeting,San Francisco,California,October 27-November 1,2013.
[30]Han T,Dale N,Adjemian K,et al.Nanofiber fuel cell electrodes II.In-situ performance and durability studies[C]//ECS 220th ECS Meeting,San Francisco,California,October 27-November 1,2013:F84-F91.
[31]Hong S J,Hou M,Xiao Y,et al.Investigation of high-performance nanofiber cathode with ultralow platinum for PEM fuel cells[J].Energy Technology,2017,5(8):1457-1463.
[32]Hong S J,Hou M,Zeng Y C,et al.High-performance lowplatinum electrode for proton exchange membrane fuel cells:Pulse electrodeposition of Pt on Pd/C nanofiber mat[J].ChemElectroChem,2017,4(5):1007-1010.
[33]Hong S J,Hou M,Zhang H J,et al.A high-performance PEM fuel cell with ultralow platinum electrode via electrospinning and underpotential deposition[J].Electrochimica Acta,2017,245:395-401.
[34]Cavaliere S,Subianto S,Savych I,et al.Dopant-driven nanostructured loose-tube SnO2architectures:Alternative electrocatalyst supports for proton exchange membrane fuel cells[J].Journal of Physical Chemistry C,2013,117(36):18298-18307.
[35]Savych I,Subianto S,Nabil Y,et al.Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode[J].Physical Chemistry Chemical Physics,2015,17(26):16970-16976.
[36]Cavaliere S,Jiménez-Morales I,Ercolano G,et al.Highly stable PEMFC electrodes based on electrospun antimonydoped SnO2[J].ChemElectroChem,2016,2(12):1966-1973.
[37]Nabil Y,Cavaliere S,Harkness I A,et al.Novel niobium carbide/carbon porous nanotube electrocatalyst supports for proton exchange membrane fuel cell cathodes[J].Journal of Power Sources,2017,363:20-26.
[38]Lee J,Yoo J M,Ye Y,et al.Development of highly stable and mass transfer-enhanced cathode catalysts:Support-free electro spun intermetallic FePt nanotubes for polymer electrolyte membrane fuel cells[J].Advanced Energy Materials,2015,5(11):1402093.
[39]Wang X H,Richey F W,Wujcik K H,et al.Ultra-low platinum loadings in polymer electrolyte membrane fue cell electrodes fabricated via,simultaneous electrospinning/electrospraying method[J].Journal of Power Sources2014,264:42-48.
[40]Wang X H,Richey F W,Wujcik K H,et al.Effect of polytetrafluoroethylene on ultra-low platinum loaded electrospun/electrosprayed electrodes in proton exchange membrane fuel cells[J].Electrochimica Acta,2014,139(26):217-224.
[41]Reneker D H,Yarin A L,Hao F,et al.Bending instability of electrically charged liquid jets of polymer,solutions in electrospinning[J].Journal of Applied Physics,2000,87(9):4531-4547.
[42]Levitt A S,Vallett R,Dion G,et al.Effect of electrospinning processing variables on polyacrylonitrile nanoyarns[J].Journal of Applied Polymer Science,2018,135(25)46404.
[43]Ding B(丁彬),Yu J Y(俞建勇).Electrospinning and nanofibers[M].China Textile Publishing House(中国纺织出版社),2011:26-59.
[44]Sener A G,Altay A S,Altay F.Effect of voltage on morphology of electrospun nanofibers[C]//International conference on electrical and electronics engineering,December 1-4,2011,Bursa,Turkey.IEEE,2011:I-324-I-328.
[45]Zargham S,Bazgir S,Tavakoli A,et al.The effect of flow rate on morphology and deposition area of electrospun nylon 6 nanofiber[J].Journal of Engineered Fabrics&Fibers,2013,7(4):42-49.
[46]Hekmati A H,Rashidi A,Ghazisaeidi R,et al.Effect of needle length,electrospinning distance,and solution concentration on morphological properties of polyamide-6electrospun nanowebs[J].Textile Research Journal,2013,83(14):1452-1466.
[47]Chan S,Jankovic J,Susac D,et al.Electrospun carbon nanofiber catalyst layers for polymer electrolyte membrane fuel cells:Structure and performance[J].Journal of Power Sources,2018,392(16):239-250.
[48]Chan S,Jankovic J,Susac D,et al.Electrospun carbon nanofiber catalyst layersfor polymer electrolyte membrane fuel cells:fabrication and optimization[J].Journal of Materials Science,53(16):11633-11647.
[49]Ohma A,Shinohara K,Iiyama A,et al.Membrane and catalyst performance targets for automotive fuel cells by FCCJ Membrane,Catalyst,MEA WG[C]//ECS 220th ECSmeeting,Boston,October 9-14,2011:775-784.
[50]Zhang G,Shao Z G,Lu W,et al.Core-shell Pt modified Pd/C as an active and durable electrocatalyst for the oxygen reduction reaction in PEMFCs[J].Applied Catalysis BEnvironmental,2013,132(12):183-194.
[51]Huang J,Zhang J B.Theory of impedance response of porous electrodes:simplifications,inhomogeneities,non-stationarities and applications[J].Journal of The Electrochemical Society,2016,163(9):A1983-A2000.