In situ infrared nanospectroscopy of the local processes at the Li/polymer electrolyte interface.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
17 Mar 2022
17 Mar 2022
Historique:
received:
16
11
2021
accepted:
23
02
2022
entrez:
18
3
2022
pubmed:
19
3
2022
medline:
19
3
2022
Statut:
epublish
Résumé
Solid-state batteries possess the potential to significantly impact energy storage industries by enabling diverse benefits, such as increased safety and energy density. However, challenges persist with physicochemical properties and processes at electrode/electrolyte interfaces. Thus, there is great need to characterize such interfaces in situ, and unveil scientific understanding that catalyzes engineering solutions. To address this, we conduct multiscale in situ microscopies (optical, atomic force, and infrared near-field) and Fourier transform infrared spectroscopies (near-field nanospectroscopy and attenuated total reflection) of intact and electrochemically operational graphene/solid polymer electrolyte interfaces. We find nanoscale structural and chemical heterogeneities intrinsic to the solid polymer electrolyte initiate a cascade of additional interfacial nanoscale heterogeneities during Li plating and stripping; including Li-ion conductivity, electrolyte decomposition, and interphase formation. Moreover, our methodology to nondestructively characterize buried interfaces and interphases in their native environment with nanoscale resolution is readily adaptable to a number of other electrochemical systems and battery chemistries.
Identifiants
pubmed: 35301308
doi: 10.1038/s41467-022-29103-z
pii: 10.1038/s41467-022-29103-z
pmc: PMC8931078
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
1398Informations de copyright
© 2022. The Author(s).
Références
Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291 (2019).
pubmed: 31427742
doi: 10.1038/s41563-019-0431-3
Xiao, Y. et al. Understanding interface stability in solid-state batteries. Nat. Rev. Mater. 5, 105–126 (2020).
doi: 10.1038/s41578-019-0157-5
Manthiram, A., Yu, X. W. & Wang, S. F. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017).
doi: 10.1038/natrevmats.2016.103
Agrawal, R. C. & Pandey, G. P. Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview. J. Phys. D: Appl. Phys. 41, 223001 (2008).
doi: 10.1088/0022-3727/41/22/223001
Xue, Z. G., He, D. & Xie, X. L. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J. Mater. Chem. A 3, 19218–19253 (2015).
doi: 10.1039/C5TA03471J
Nair, J. R., Imholt, L., Brunklaus, G. & Winter, M. Lithium metal polymer electrolyte batteries: opportunities and challenges. Electrochem. Soc. Interface 28, 55–61 (2019).
doi: 10.1149/2.F05192if
Sheng, O. et al. In situ construction of a LiF-enriched interface for stable all-solid-state batteries and its origin revealed by cryo-TEM. Adv. Mater. 32, 2000223 (2020).
doi: 10.1002/adma.202000223
Narayan, S. & Anand, L. On modeling the detrimental effects of inhomogeneous plating-and-stripping at a lithium-metal/solid-electrolyte interface in a solid-state-battery. J. Electrochem. Soc. 167, 040525 (2020).
doi: 10.1149/1945-7111/ab75c1
Yu, X. W. & Manthiram, A. Electrode-electrolyte interfaces in lithium-based batteries. Energy Environ. Sci. 11, 527–543 (2018).
doi: 10.1039/C7EE02555F
Li, Y. et al. Advanced characterization techniques for interface in all‐solid‐state batteries. Small Methods 4, 2000111 (2020).
doi: 10.1002/smtd.202000111
He, X. et al. The passivity of lithium electrodes in liquid electrolytes for secondary batteries. Nat. Rev. Mater. https://doi.org/10.1038/s41578-021-00345-5 (2021).
Ma, C. et al. Interfacial stability of Li metal-solid electrolyte elucidated via in situ electron microscopy. Nano Lett. 16, 7030–7036 (2016).
pubmed: 27709954
doi: 10.1021/acs.nanolett.6b03223
Cheng, D. Y. et al. Unveiling the stable nature of the solid electrolyte interphase between lithium metal and LiPON via cryogenic electron microscopy. Joule 4, 2484–2500 (2020).
doi: 10.1016/j.joule.2020.08.013
Sang, L. Z., Haasch, R. T., Gewirth, A. A. & Nuzzo, R. G. Evolution at the solid electrolyte/gold electrode interface during lithium deposition and stripping. Chem. Mater. 29, 3029–3037 (2017).
doi: 10.1021/acs.chemmater.7b00034
Dietrich, C. et al. Spectroscopic characterization of lithium thiophosphates by XPS and XAS - a model to help monitor interfacial reactions in all-solid-state batteries. Phys. Chem. Chem. Phys. 20, 20088–20095 (2018).
pubmed: 30024004
doi: 10.1039/C8CP01968A
Simon, F. J., Hanauer, M., Richter, F. H. & Janek, J. Interphase formation of PEO20:LiTFSI-Li6PS5Cl composite electrolytes with lithium metal. ACS Appl. Mater. Interfaces 12, 11713–11723 (2020).
pubmed: 32052956
doi: 10.1021/acsami.9b22968
Wang, C. et al. In situ neutron depth profiling of lithium metal-garnet interfaces for solid state batteries. J. Am. Chem. Soc. 139, 14257–14264 (2017).
pubmed: 28918627
doi: 10.1021/jacs.7b07904
Seitzman, N. et al. Toward all-solid-state lithium batteries: three-dimensional visualization of lithium migration in β-Li3PS4 ceramic electrolyte. J. Electrochem. Soc. 165, A3732–A3737 (2018).
doi: 10.1149/2.0301816jes
Wang, M. J., Carmona, E., Gupta, A., Albertus, P. & Sakamoto, J. Enabling “lithium-free” manufacturing of pure lithium metal solid-state batteries through in situ plating. Nat. Commun. 11, 5201 (2020).
pubmed: 33060571
pmcid: 7567811
doi: 10.1038/s41467-020-19004-4
Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).
doi: 10.1038/s41560-019-0428-9
O’Callahan, B. T. et al. In Liquid infrared scattering scanning near-field optical microscopy for chemical and biological nanoimaging. Nano Lett. 20, 4497–4504 (2020).
pubmed: 32356991
doi: 10.1021/acs.nanolett.0c01291
Wu, C. Y. et al. High-spatial-resolution mapping of catalytic reactions on single particles. Nature 541, 511–515 (2017).
pubmed: 28068671
doi: 10.1038/nature20795
Ni, G. X. et al. Fundamental limits to graphene plasmonics. Nature 557, 530–533 (2018).
pubmed: 29795255
doi: 10.1038/s41586-018-0136-9
Lee, W. et al. A rewritable optical storage medium of silk proteins using near-field nano-optics. Nat. Nanotechnol. 15, 941–947 (2020).
pubmed: 32778805
doi: 10.1038/s41565-020-0755-9
McLeod, A. S. et al. Nanotextured phase coexistence in the correlated insulator V2O3. Nat. Phys. 13, 80–86 (2016).
doi: 10.1038/nphys3882
Lucas, I. T. et al. IR near-field spectroscopy and imaging of single Li(x)FePO4 microcrystals. Nano Lett. 15, 1–7 (2015).
pubmed: 25375874
doi: 10.1021/nl5010898
Ayache, M., Lux, S. F. & Kostecki, R. IR near-field study of the solid electrolyte interphase on a tin electrode. J. Phys. Chem. Lett. 6, 1126–1129 (2015).
pubmed: 26262960
doi: 10.1021/acs.jpclett.5b00263
Ayache, M., Jong, D., Syzdek, J. & Kostecki, R. Near-field IR nanoscale imaging of the solid electrolyte interphase on a HOPG electrode. J. Electrochem. Soc. 162, A7078–A7082 (2015).
doi: 10.1149/2.0101513jes
Lu, Y. H. et al. Infrared nanospectroscopy at the graphene-electrolyte interface. Nano Lett. 19, 5388–5393 (2019).
pubmed: 31306028
doi: 10.1021/acs.nanolett.9b01897
Mester, L., Govyadinov, A. A., Chen, S., Goikoetxea, M. & Hillenbrand, R. Subsurface chemical nanoidentification by nano-FTIR spectroscopy. Nat. Commun. 11, 3359 (2020).
pubmed: 32620874
pmcid: 7335173
doi: 10.1038/s41467-020-17034-6
Zaera, F. Probing liquid/solid interfaces at the molecular level. Chem. Rev. 112, 2920–2986 (2012).
pubmed: 22277079
doi: 10.1021/cr2002068
Yoshihara, T., Tadokoro, H. & Murahashi, S. Normal vibrations of the polymer molecules of helical conformation. IV. polyethylene oxide and polyethylene‐d4Oxide. J. Chem. Phys. 41, 2902–2911 (1964).
doi: 10.1063/1.1726373
Rey, I. et al. Spectroscopic and theoretical study of (CF3SO2)2N- (TFSI-) and (CF3SO2)2NH (HTFSI). J. Phys. Chem. A 102, 3249–3258 (1998).
doi: 10.1021/jp980375v
Muller, E. A., Pollard, B., Bechtel, H. A., van Blerkom, P. & Raschke, M. B. Infrared vibrational nanocrystallography and nanoimaging. Sci. Adv. 2, e1601006 (2016).
pubmed: 27730212
pmcid: 5055384
doi: 10.1126/sciadv.1601006
Rey, I., Lassegues, J. C., Grondin, J. & Servant, L. Infrared and raman study of the PEO-LiTFSI polymer electrolyte. Electrochim. Acta 43, 1505–1510 (1998).
doi: 10.1016/S0013-4686(97)10092-5
Lascaud, S. et al. Phase diagrams and conductivity behavior of poly(ethylene oxide)-molten salt rubbery electrolytes. Macromolecules 27, 7469–7477 (1994).
doi: 10.1021/ma00103a034
Mirsakiyeva, A. et al. Initial steps in PEO decomposition on a Li metal electrode. J. Phys. Chem. C. 123, 22851–22857 (2019).
doi: 10.1021/acs.jpcc.9b07712
Li, X. & Hsu, S. L. An analysis of the crystallization behavior of poly(ethylene oxide) poly(methyl methacrylate) blends by spectroscopic and calorimetric techniques. J. Polym. Sci. Polym. Phys. Ed. 22, 1331–1342 (1984).
doi: 10.1002/pol.1984.180220715
Schultz, B. J., Dennis, R. V., Lee, V. & Banerjee, S. An electronic structure perspective of graphene interfaces. Nanoscale 6, 3444–3466 (2014).
pubmed: 24562654
doi: 10.1039/c3nr06923k
Unge, M., Gudla, H., Zhang, C. & Brandell, D. Electronic conductivity of polymer electrolytes: electronic charge transport properties of LiTFSI-doped PEO. Phys. Chem. Chem. Phys. 22, 7680–7684 (2020).
pubmed: 32242576
doi: 10.1039/D0CP01130D
Parimalam, B. S. & Lucht, B. L. Reduction reactions of electrolyte salts for lithium ion batteries: LiPF6, LiBF4, LiDFOB, LiBOB, and LiTFSI. J. Electrochem. Soc. 165, A251–A255 (2018).
doi: 10.1149/2.0901802jes
Wang, X. & Andrews, L. Infrared spectra and theoretical calculations of lithium hydride clusters in solid hydrogen, neon, and argon. J. Phys. Chem. A 111, 6008–6019 (2007).
pubmed: 17547379
doi: 10.1021/jp071251y
Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid-liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).
pubmed: 30111789
doi: 10.1038/s41586-018-0397-3
Shadike, Z. et al. Identification of LiH and nanocrystalline LiF in the solid-electrolyte interphase of lithium metal anodes. Nat. Nanotechnol. 16, 549–554 (2021).
pubmed: 33510453
doi: 10.1038/s41565-020-00845-5
Rikka, V. R. et al. In situ/ex situ investigations on the formation of the mosaic solid electrolyte interface layer on graphite anode for lithium-ion batteries. J. Phys. Chem. C. 122, 28717–28726 (2018).
doi: 10.1021/acs.jpcc.8b09210
Abramowitz, S., Acquista, N. & Levin, I. W. Infrared matrix spectra of lithium fluoride. J. Res. Natl Bur. Stand. A Phys. Chem. 72A, 487–493 (1968).
pubmed: 31824111
pmcid: 6696582
doi: 10.6028/jres.072A.041
Tian, N., Hua, C. X., Wang, Z. X. & Chen, L. Q. Reversible reduction of Li2CO3. J. Mater. Chem. A 3, 14173–14177 (2015).
doi: 10.1039/C5TA02499D
Vivek, J. P., Berry, N. G., Zou, J. L., Nichols, R. J. & Hardwick, L. J. In situ surface-enhanced infrared spectroscopy to identify oxygen reduction products in nonaqueous metal-oxygen batteries. J. Phys. Chem. C. 121, 19657–19667 (2017).
doi: 10.1021/acs.jpcc.7b06391
Yu, T. et al. Understanding the role of lithium sulfide clusters in lithium-sulfur batteries. J. Mater. Chem. A 5, 9293–9298 (2017).
doi: 10.1039/C7TA01006K
Bechtel, H. A., Johnson, S. C., Khatib, O., Muller, E. A. & Raschke, M. B. Synchrotron infrared nano-spectroscopy and -imaging. Surf. Sci. Rep. 75, 100493 (2020).