Abstract
Electrochemical cells based on alkali metal (Li, Na) anodes have attracted significant recent attention because of their promise for producing large increases in gravimetric energy density for energy storage in batteries. To facilitate stable, long-term operation of such cells, a variety of structured electrolytes have been designed in different physical forms, ranging from soft polymer gels to hard ceramics, including porous ceramics that host a liquid or molten polymer in their pores. In almost every case, the electrolytes are reported to be substantially more effective than anticipated by early theories in improving uniformity of deposition and lifetime of the metal anode. These observations have been speculated to reflect the effect of electrolyte structure in regulating ion transport to the metal-electrolyte interface, thereby stabilizing metal electrodeposition processes at the anode. Here, we create and study model structured electrolytes composed of covalently linked polymer-grafted nanoparticles that host a liquid electrolyte in the pores. The electrolytes exist as freestanding membranes with effective pore size that can be systematically manipulated through straightforward control of the volume fraction of the nanoparticles. By means of physical analysis and direct visualization experiments, we report that at current densities approaching the diffusion limit, there is a clear transition from unstable to stable electrodeposition at Li metal electrodes in membranes with average pore sizes below 500 nm. We show that this transition is consistent with expectations from a recent theoretical analysis that takes into account local coupling between stress and ion transport at metal-electrolyte interfaces.
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References
Lin, D., Liu, Y., Cui, Y.: Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017)
Cheng, X., et al.: A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3, 1–20 (2016)
Cheng, X.-B., Zhang, R., Zhao, C.-Z., Zhang, Q.: Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017)
Ma, L., Hendrickson, K.E., Wei, S., Archer, L.A.: Nanomaterials: science and applications in the lithium–sulfur battery. Nano Today. 10, 315–338 (2015)
Zhang, W., et al.: Design principles of functional polymer separators for high-energy, metal-based batteries. Small. 1703001–n/a. https://doi.org/10.1002/smll.201703001
Wei, S., Choudhury, S., Tu, Z., Zhang, K., Archer, L.A.: Electrochemical interphases for high-energy storage using reactive metal anodes. Acc. Chem. Res. (2017). https://doi.org/10.1021/acs.accounts.7b00484
Tikekar, M.D., Archer, L.A., Koch, D.L.: Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions. Sci. Adv. 2, e1600320 (2016)
Chazalviel, J.-N.: Electrochemical aspects of the generation of rampified metallic electrodeposits. Phys. Rev. A. 42, 7355–7367 (1990)
Bai, P., Li, J., Brushett, F.R., Bazant, M.Z.: Transition of lithium growth mechanisms in liquid electrolytes. Energy Environ. Sci. 9, 3221–3229 (2016)
Choudhury, S., et al.: Electroless formation of hybrid lithium anodes for fast interfacial ion transport. Angew. Chem. Int. Ed. 56, 13070–13077 (2017)
Choudhury, S., Wei, S., Ozhabes, Y., Gunceler, D., Nath, P.: Designing solid-liquid interphases for sodium batteries. Nat. Commun. 8, 898 (2017)
Wood, K.N., et al.: Dendrites and pits: untangling the complex behavior of lithium metal anodes through operando video microscopy. ACS Cent. Sci. 2, 790–801 (2016)
Zheng, G., et al.: Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 9, 618–623 (2014)
Monroe, C., Newman, J.: The effect of interfacial deformation on electrodeposition kinetics. J. Electrochem. Soc. 151, A880 (2004)
Monroe, C., Newman, J.: The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 152, A396 (2005)
Stone, G.M., et al.: Resolution of the modulus versus adhesion dilemma in solid polymer electrolytes for rechargeable lithium metal batteries. J. Electrochem. Soc. 159, A222–A227 (2012)
Agrawal, A., Choudhury, S., Archer, L.A.: A highly conductive, non-flammable polymer–nanoparticle hybrid electrolyte. RSC Adv. 5, 20800–20809 (2015)
Choudhury, S., Mangal, R., Agrawal, A., Archer, L.A.: A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 6, 10101 (2015)
Lu, Y., Korf, K., Kambe, Y., Tu, Z., Archer, L.A.: Ionic-liquid-nanoparticle hybrid electrolytes: applications in lithium metal batteries. Angew. Chem. 126, 498–502 (2014)
Zhang, J., Sun, B., Huang, X., Chen, S., Wang, G.: Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety. Sci. Rep. 4, 6007 (2014)
Stephan, A.M.: Review on gel polymer electrolytes for lithium batteries. Eur. Polym. J. 42, 21–42 (2006)
Wu, H., et al.: Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles. Nat. Commun. 4, 1943 (2013)
Khurana, R., Schaefer, J.L., Archer, L.A., Coates, G.W.: Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 136, 7395–7402 (2014)
Porcarelli, L., Gerbaldi, C., Bella, F., Nair, J.R.: Super soft all-ethylene oxide polymer electrolyte for safe all-solid lithium batteries. Sci. Rep. 6, 19892 (2016)
Long, L., Wang, S., Xiao, M., Meng, Y.: Polymer electrolytes for lithium polymer batteries. J. Mater. Chem. A. 4, 10038–10069 (2016)
Gurevitch, I., et al.: Nanocomposites of titanium dioxide and polystyrene-poly(ethylene oxide) block copolymer as solid-state electrolytes for lithium metal batteries. J. Electrochem. Soc. 160, A1611–A1617 (2013)
Zhao, C.-Z., et al.: An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes. Proc. Natl. Acad. Sci. 114, 11069 LP-11074 (2017)
Tu, Z., et al.: Designing artificial solid-electrolyte interphases for single-ion and high-efficiency transport in batteries. Joule. (2017). https://doi.org/10.1016/j.joule.2017.06.002
Choudhury, S., et al.: Designer interphases for the lithium-oxygen electrochemical cell. Sci. Adv. 3, e1602809 (2017)
Ma, L., Nath, P., Tu, Z., Tikekar, M., Archer, L.A.: Highly conductive, sulfonated, UV-cross-linked separators for Li–S batteries. Chem. Mater. 28, 5147–5154 (2016)
Lu, Y., et al.: Stable cycling of lithium metal batteries using high transference number electrolytes. Adv. Energy Mater. 5, 1402073 (2015)
Oh, H., et al.: Poly(arylene ether)-based single-ion conductors for lithium-ion batteries. Chem. Mater. 28, 188–196 (2016)
Bouchet, R., et al.: Single-ion BAB triblock copolymers as efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013)
Choudhury, S., Archer, L.A.: Lithium fluoride additives for stable cycling of lithium batteries at high current densities. Adv. Electron. Mater. 1–6 (2015). https://doi.org/10.1002/aelm.201500246
Lu, Y., Tu, Z., Archer, L.A.: Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014)
Seh, Z.W., Sun, J., Sun, Y., Cui, Y.: A highly reversible room-temperature sodium metal anode. ACS Cent. Sci. 1, 449–455 (2015)
Zhang, X., Cheng, X., Chen, X., Yan, C., Zhang, Q.: Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries. Adv. Funct. Mater. 27, 1605989 (2017)
Tikekar, M.D., Archer, L.A., Koch, D.L.: Stability analysis of electrodeposition across a structured electrolyte with immobilized anions. J. Electrochem. Soc. 161, A847–A855 (2014)
Choudhury, S., Agrawal, A., Kim, S.A., Archer, L.A.: Self-suspended suspensions of covalently grafted hairy nanoparticles. Langmuir. 31, 3222–3231 (2015)
Choudhury, S., Agrawal, A., Wei, S., Jeng, E., Archer, L.A.: Hybrid hairy nanoparticle electrolytes stabilizing lithium metal batteries. Chem. Mater. 28, 2147–2157 (2016)
Wei, S., et al.: Highly stable sodium batteries enabled by functional ionic polymer membranes. Adv. Mater. 29, 1605512 (2017)
Stalin, S., Choudhury, S., Zhang, K., Archer, L.A.: Multifunctional cross-linked polymeric membranes for safe, high-performance lithium batteries. Chem. Mater. 30, 2058–2066 (2018)
Agarwal, P., Kim, S.A., Archer, L.A.: Crowded, confined, and frustrated: dynamics of molecules tethered to nanoparticles. Phys. Rev. Lett. 109, 258301 (2012)
Ding, Y., et al.: Dielectric spectroscopy investigation of relaxation in C 60 - polyisoprene nanocomposites. 3201–3206 (2009). https://doi.org/10.1021/ma8024333
Adachi, K., Kotaka, T.: Dielectric normal mode relaxation. Prog. Polym. Sci. 18, 585–622 (1993)
Nyman, A., Behm, M., Lindbergh, G.: Electrochemical characterisation and modelling of the mass transport phenomena in LiPF6-EC-EMC electrolyte. Electrochim. Acta. 53, 6356–6365 (2008)
Valoen, L.O., Reimers, J.N.: Transport properties of LiPF6-based Li-ion battery electrolytes. J. Electrochem. Soc. 152, A882 (2005)
Tu, Z., Nath, P., Lu, Y., Tikekar, M.D., Archer, L.A.: Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries. Acc. Chem. Res. 48, 2947–2956 (2015)
Tu, Z., et al.: Nanoporous hybrid electrolytes for high-energy batteries based on reactive metal anodes. Adv. Energy Mater. 7, 1602367 (2017)
Acknowledgments
This work was supported by the National Science Foundation, Division of Materials Research, through Award No. DMR–1609125.
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Choudhury, S. (2019). Confining Electrodeposition of Metals in Structured Electrolytes. In: Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-28943-0_4
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DOI: https://doi.org/10.1007/978-3-030-28943-0_4
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