Abstract
Many modern energy storage technologies operate via the nominally reversible shuttling of alkali ions between an anode and a cathode capable of hosting them. The degradation process that occurs with normal usage is not yet fully understood, but emerging progress in analytical tools may help address this knowledge gap. By interrogating ionic fluxes over electrified surfaces, scanning probe methods may identify features that impact the local cyclability of a material and subsequently help inform rational electrode design for future generations of batteries. Methods developed for identifying ion fluxes for batteries show great promise for broader applications, including biological interfaces, corrosion, and catalysis.
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Scott ER, White HS, Phipps JB. Iontophoretic transport through porous membranes using scanning electrochemical microscopy: application to in vitro studies of ion fluxes through skin. Anal Chem. 1993;65(11):1537–45.
Novak P, Li C, Shevchuk AI, Stepanyan R, Caldwell M, Hughes S, et al. Nanoscale live-cell imaging using hopping probe ion conductance microscopy. Nat Methods. 2009;6(4):279–81.
Shen M, Ishimatsu R, Kim J, Amemiya S. Quantitative imaging of ion transport through single nanopores by high-resolution scanning electrochemical microscopy. J Am Chem Soc. 2012;134(24):9856–9.
Chen C-C, Zhou Y, Morris CA, Hou J, Baker LA. Scanning ion conductance microscopy measurement of paracellular channel conductance in tight junctions. Anal Chem. 2013;85(7):3621–8.
Yamada H, Haraguchi D, Yasunaga K. Fabrication and characterization of a K+-selective nanoelectrode and simultaneous imaging of topography and local K+ flux using scanning electrochemical microscopy. Anal Chem. 2014;86(17):8547–52.
Dauphin-Ducharme P, Asmussen RM, Shoesmith DW, Mauzeroll J. In-situ Mg2+ release monitored during magnesium alloy corrosion. J Electroanal Chem. 2015;736(C):61–8.
Kang B, Ceder G. Battery materials for ultrafast charging and discharging. Nature. 2009;458(7235):190–3.
Goodenough JB, Kim Y. Challenges for rechargeable Li batteries. Chem Mater. 2010;22(3):587–603.
Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci. 2011;4(9):3243–62.
Goodenough JB, Park K-S. The Li-ion rechargeable battery: a perspective. J Am Chem Soc. 2013;135(4):1167–76.
Tavassol H, Chan MKY, Catarello MG, Greeley JP, Cahill DG, Gewirth AA. Surface coverage and SEI induced electrochemical surface stress changes during Li deposition in a model system for Li-ion battery anodes. J Electrochem Soc. 2013;160(6):A888–96.
Aurbach D, Daroux ML, Faguy PW, Yeager E. Identification of surface films formed on lithium in propylene carbonate solutions. J Electrochem Soc. 1987;134(7):1611–20.
Verma P, Maire P, Novák P. A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochim Acta. 2010;55(22):6332–41.
Norberg NS, Lux SF, Kostecki R. Interfacial side-reactions at a LiNi0.5Mn1.5O4 electrode in organic carbonate-based electrolytes. Electrochem Commun. 2013;34(C):29–32.
Smith AJ, Burns JC, Zhao X, Xiong D, Dahn JR. A high precision coulometry study of the SEI growth in Li/graphite cells. J Electrochem Soc. 2011;158(5):A447–52.
Aurbach D. Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. J Power Sources. 2000;89(2):206–18.
Petibon R, Sinha NN, Burns JC, Aiken CP, Ye H, VanElzen CM, et al. Comparative study of electrolyte additives using electrochemical impedance spectroscopy on symmetric cells. J Power Sources. 2014;251:187–94.
Wang DY, Sinha NN, Burns JC, Petibon R, Dahn JR. A high precision study of the electrolyte additives vinylene carbonate, vinyl ethylene carbonate and lithium bis(oxalate)borate in LiCoO2/graphite pouch cells. J Power Sources. 2014;270:68–78.
Persson K, Sethuraman VA, Hardwick LJ, Hinuma Y, Meng YS, van der Ven A, et al. Lithium diffusion in graphitic carbon. J Phys Chem Lett. 2010;1(8):1176–80.
Zheng J, Gu M, Xiao J, Zuo P, Wang C, Zhang J-G. Corrosion/fragmentation of layered composite cathode and related capacity/voltage fading during cycling process. Nano Lett. 2013;13(8):3824–30.
Darling RM, Gallagher KG, Kowalski JA, Ha S, Brushett FR. Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries. Energy Environ Sci. 2014;7:3459–77.
Jaber-Ansari L, Puntambekar KP, Tavassol H, Yildirim H, Kinaci A, Kumar R, et al. Defect evolution in graphene upon electrochemical lithiation. ACS Appl Mater Interfaces. 2014;6(20):17626–36.
Inaba M, Yoshida H, Ogumi Z, Abe T, Mizutani Y, Asano M. In Situ Raman study on electrochemical Li intercalation into graphite. J Electrochem Soc. 1995;142(1):20–6.
Sole C, Drewett NE, Hardwick LJ. In situ Raman study of lithium-ion intercalation into microcrystalline graphite. Faraday Discuss. 2014;172:223–37.
Dahn JR. Phase diagram of LixC6. Phys Rev B. 1991;44(17):9170–7.
Hatchard TD, Dahn JR. In situ XRD and electrochemical study of the reaction of lithium with amorphous silicon. J Electrochem Soc. 2004;151(6):A838–42.
Chen Z, Dahn JR. Methods to obtain excellent capacity retention in LiCoO2 cycled to 4.5 V. Electrochim Acta. 2004;49(7):1079–90.
Lipson AL, Hersam MC. Conductive scanning probe characterization and nanopatterning of electronic and energy materials. J Phys Chem C. 2013;117(16):7953–63.
Balke N, Jesse S, Kim Y, Adamczyk L, Tselev A, Ivanov IN, et al. Real space mapping of Li-ion transport in amorphous Si anodes with nanometer resolution. Nano Lett. 2010;10(9):3420–5.
Harris SJ, Lu P. Effects of inhomogeneities—nanoscale to mesoscale—on the durability of Li-ion batteries. J Phys Chem C. 2013;117(13):6481–92.
Bard AJ, Fan F-R, Kwak J, Lev O. Scanning electrochemical microscopy. Introduction and principles. Anal Chem. 1989;61(2):132–8.
Bard AJ, Denuault G, Lee C, Mandler D, Wipf DO. Scanning electrochemical microscopy—a new technique for the characterization and modification of surfaces. Acc Chem Res. 1990;23(11):357–63.
Bard AJ, Fan F-R, Pierce DT, Unwin PR, Wipf DO, Zhou F. Chemical imaging of surfaces with the scanning electrochemical microscope. Science. 1991;254:68–74.
Sun P, Laforge FO, Mirkin MV. Scanning electrochemical microscopy in the 21st century. Phys Chem Chem Phys. 2007;9(7):802–23.
Bertoncello P. Advances on scanning electrochemical microscopy (SECM) for energy. Energy Environ Sci. 2010;3(11):1620–33.
Mirkin MV, Nogala W, Velmurugan J, Wang Y. Scanning electrochemical microscopy in the 21st century. Update 1: 5 years after. Phys Chem Chem Phys. 2011;13(48):21196–212.
Kranz C. Recent advancements in nanoelectrodes and nanopipettes used in combined scanning electrochemical microscopy techniques. Analyst. 2014;139(2):336–52.
Bülter H, Peters F, Schwenzel J, Wittstock G. Spatiotemporal changes of the solid electrolyte interphase in lithium-ion batteries detected by scanning electrochemical microscopy. Angew Chem Int Ed. 2014;53(39):10531–5.
Ventosa E, Schuhmann W. Scanning electrochemical microscopy of Li-ion batteries. Phys Chem Chem Phys. 2015;17:28441–50.
Chen C-C, Zhou Y, Baker LA. Scanning ion conductance microscopy. Annu Rev Anal Chem. 2012;5(1):207–28.
Lipson AL, Ginder RS, Hersam MC. Nanoscale in situ characterization of Li-ion battery electrochemistry via scanning ion conductance microscopy. Adv Mater. 2011;23(47):5613–7.
Ebejer N, Güell AG, Lai SCS, McKelvey K, Snowden ME, Unwin PR. Scanning electrochemical cell microscopy: a versatile technique for nanoscale electrochemistry and functional imaging. Annu Rev Anal Chem. 2013;6(1):329–51.
Takahashi Y, Kumatani A, Munakata H, Inomata H, Ito K, Ino K, et al. Nanoscale visualization of redox activity at lithium-ion battery cathodes. Nat Commun. 2014;5:1–7.
Momotenko D, Byers JC, McKelvey K, Kang M, Unwin PR. High-speed electrochemical imaging. ACS Nano. 2015;9(9):8942–52.
Alpuche-Aviles M, Baur JE, Wipf DO. Imaging of metal ion dissolution and electrodeposition by anodic stripping voltammetry-scanning electrochemical microscopy. Anal Chem. 2008;80(10):3612–21.
Souto RM, González-García Y, Battistel D, Daniele S. In situ scanning electrochemical microscopy (SECM) detection of metal dissolution during zinc corrosion by means of mercury sphere-cap microelectrode tips. Chem Eur J. 2011;18(1):230–6.
Barton ZJ, Rodríguez-López J. Lithium ion quantification using mercury amalgams as in situ electrochemical probes in nonaqueous media. Anal Chem. 2014;86(21):10660–7.
Hansma P, Drake B, Marti O, Gould S, Prater C. The scanning ion-conductance microscope. Science. 1989;243(4891):641–3.
Lipson AL, Puntambekar K, Comstock DJ, Meng X, Geier ML, Elam JW, et al. Nanoscale investigation of solid electrolyte interphase inhibition on Li-ion battery MnO electrodes via atomic layer deposition of Al2O3. Chem Mater. 2014;26(2):935–40.
Rheinlaender J, Schäffer TE. Lateral resolution and image formation in scanning ion conductance microscopy. Anal Chem. 2015;87(14):7117–24.
Sa N, Lan W-J, Shi W, Baker LA. Rectification of Ion current in nanopipettes by external substrates. ACS Nano. 2013;7(12):11272–82.
Takahashi Y, Shevchuk AI, Novak P, Zhang Y, Ebejer N, Macpherson JV, et al. Multifunctional nanoprobes for nanoscale chemical imaging and localized chemical delivery at surfaces and interfaces. Angew Chem Int Ed. 2011;50(41):9638–42.
O’Connell MA, Wain AJ. Mapping electroactivity at individual catalytic nanostructures using high-resolution scanning electrochemical-scanning ion conductance microcopy. Anal Chem. 2014;86(24):12100–7.
Ebejer N, Schnippering M, Colburn AW, Edwards MA, Unwin PR. Localized high resolution electrochemistry and multifunctional imaging: scanning electrochemical cell microscopy. Anal Chem. 2010;82(22):9141–5.
Paulose Nadappuram B, McKelvey K, Byers JC, Güell AG, Colburn AW, Lazenby RA, et al. Quad-barrel multifunctional electrochemical and ion conductance probe for voltammetric analysis and imaging. Anal Chem. 2015;87(7):3566–73.
Wehmeyer KR, Wightman RM. Cyclic voltammetry and anodic stripping voltammetry with mercury ultramicroelectrodes. Anal Chem. 1985;57(9):1989–93.
Selzer Y, Mandler D. Scanning electrochemical microscopy. Theory of the feedback mode for hemispherical ultramicroelectrodes: steady-state and transient behavior. Anal Chem. 2000;2(11):2383–90.
Mauzeroll J, Hueske EA, Bard AJ. Scanning electrochemical microscopy. 48. Hg/Pt hemispherical ultramicroelectrodes: fabrication and characterization. Anal Chem. 2003;75(15):3880–9.
Aaronson BDB, Byers JC, Colburn AW, McKelvey K, Unwin PR. Scanning electrochemical cell microscopy platform for ultrasensitive photoelectrochemical imaging. Anal Chem. 2015;87(8):4129–33.
Danis L, Gateman SM, Snowden ME, Halalay IC, Howe JY, Mauzeroll J. Anodic stripping voltammetry at nanoelectrodes: trapping of Mn2+ by crown ethers. Electrochim Acta. 2015;162:169–75.
Singhal R, Bhattacharyya S, Orynbayeva Z, Vitol E, Friedman G, Gogotsi Y. Small diameter carbon nanopipettes. Nanotechnology. 2009;21(1):015304.
Actis P, Tokar S, Clausmeyer J, Babakinejad B, Mikhaleva S, Cornut R, et al. Electrochemical nanoprobes for single-cell analysis. ACS Nano. 2014;8(1):875–84.
Danis L, Snowden ME, Tefashe UM, Heinemann CN, Mauzeroll J. Development of nano-disc electrodes for application as shear force sensitive electrochemical probes. Electrochim Acta. 2014;136:121–9.
Alpuche-Aviles M, Wipf DO. Impedance feedback control for scanning electrochemical microscopy. Anal Chem. 2001;73(20):4873–81.
Lazenby RA, McKelvey K, Unwin PR. Hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM): visualizing interfacial reactions and fluxes from surfaces to bulk solution. Anal Chem. 2013;85(5):2937–44.
Luo W, Wan J, Ozdemir B, Bao W, Chen Y, Dai J, et al. Potassium ion batteries with graphitic materials. Nano Lett. 2015;15(11):7671–7.
Gu M, Kushima A, Shao Y, Zhang J-G, Liu J, Browning ND, et al. Probing the failure mechanism of SnO2 nanowires for sodium-ion batteries. Nano Lett. 2013;13(11):5203–11.
Islam MS, Fisher CAJ. Lithium and sodium battery cathode materials: computational insights into voltage, diffusion, and nanostructural properties. Chem Soc Rev. 2013;43(1):185–204.
Acknowledgements
Z.J.B. acknowledges the support of the National Science Foundation Graduate Research Fellowship Program (DGE-1144245). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. J. R.-L. acknowledges support from the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences. The authors also thank UIUC for generous start-up funds.
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Published in the topical collection featuring Young Investigators in Analytical and Bioanalytical Science with guest editors S. Daunert, A. Baeumner, S. Deo, J. Ruiz Encinar, and L. Zhang.
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Barton, Z.J., Rodríguez-López, J. Emerging scanning probe approaches to the measurement of ionic reactivity at energy storage materials. Anal Bioanal Chem 408, 2707–2715 (2016). https://doi.org/10.1007/s00216-016-9373-7
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DOI: https://doi.org/10.1007/s00216-016-9373-7