TY - JOUR
T1 - A Surface Modification Strategy Towards Reversible Na-ion Intercalation on Graphitic Carbon Using Fluorinated Few-Layer Graphene
AU - Sarbapalli, Dipobrato
AU - Lin, Yu Hsiu
AU - Stafford, Sean
AU - Son, Jangyup
AU - Mishra, Abhiroop
AU - Hui, Jingshu
AU - Nijamudheen, A.
AU - Romo, Adolfo I.B.
AU - Gossage, Zachary T.
AU - van der Zande, Arend M.
AU - Mendoza-Cortes, Jose L.
AU - Rodriguez Lopez, Joaquin
N1 - Funding Information:
The research reported here was funded by NSF DMR Award 1905803. J.S. and A.M.v.d.Z were supported by the National Science Foundation through the University of Illinois Urbana-Champaign Materials Research Science and Engineering Center DMR-1720633. The authors acknowledge the use of facilities and instrumentation supported by NSF through the University of Illinois Materials Research Science and Engineering Center DMR-1720633. CVD synthesis, SEM, XPS, and Raman measurements were carried out in the Materials Research Laboratory Central Research Facilities, University of Illinois. We acknowledge central facilities at the Holonyak Micro & Nanotechnology Laboratory, and the Beckman Institute, University of Illinois, for graphene fluorination, sputter coating, and optical transmittance and in situ Raman measurements. We also acknowledge David Williams and the School of Chemical Sciences Machine Shop for assistance with the in situ Raman cell design. D.S. also thanks Dr Michael J. Counihan and Michael Pence for helping with the in situ Raman cell setup and experiments. The computational part of this work was carried out was supported in part through computational resources and services provided by the Institute for Cyber-Enabled Research at Michigan State University.
Publisher Copyright:
© 2022 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited.
PY - 2022/10
Y1 - 2022/10
N2 - Na-ion batteries (NIBs) are proposed as a promising candidate for beyond Li-ion chemistries, however, a key challenge associated with NIBs is the inability to achieve intercalation in graphite anodes. This phenomenon has been investigated and is believed to arise due to the thermodynamic instability of Na-intercalated graphite. We have recently demonstrated theoretical calculations showing it is possible to achieve thermodynamically stable Na-intercalated graphene structures with a fluorine surface modifier. Here, we present experimental evidence that Na+ intercalation is indeed possible in fluorinated few-layer graphene (F-FLG) structures using cyclic voltammetry (CV), ion-sensitive scanning electrochemical microscopy (SECM) and in situ Raman spectroscopy. SECM and Raman spectroscopy confirmed Na+ intercalation in F-FLG, while CV measurements allowed us to quantify Na-intercalated F-FLG stoichiometries around NaC14-18. These stoichiometries are higher than the previously reported values of NaC186 in graphite. Our experiments revealed that reversible Na+ ion intercalation also requires a pre-formed Li-based SEI in addition to the surface fluorination, thereby highlighting the critical role of SEI in controlling ion-transfer kinetics in alkali-ion batteries. In summary, our findings highlight the use of surface modification and careful study of electrode-electrolyte interfaces and interphases as an enabling strategy for NIBs.
AB - Na-ion batteries (NIBs) are proposed as a promising candidate for beyond Li-ion chemistries, however, a key challenge associated with NIBs is the inability to achieve intercalation in graphite anodes. This phenomenon has been investigated and is believed to arise due to the thermodynamic instability of Na-intercalated graphite. We have recently demonstrated theoretical calculations showing it is possible to achieve thermodynamically stable Na-intercalated graphene structures with a fluorine surface modifier. Here, we present experimental evidence that Na+ intercalation is indeed possible in fluorinated few-layer graphene (F-FLG) structures using cyclic voltammetry (CV), ion-sensitive scanning electrochemical microscopy (SECM) and in situ Raman spectroscopy. SECM and Raman spectroscopy confirmed Na+ intercalation in F-FLG, while CV measurements allowed us to quantify Na-intercalated F-FLG stoichiometries around NaC14-18. These stoichiometries are higher than the previously reported values of NaC186 in graphite. Our experiments revealed that reversible Na+ ion intercalation also requires a pre-formed Li-based SEI in addition to the surface fluorination, thereby highlighting the critical role of SEI in controlling ion-transfer kinetics in alkali-ion batteries. In summary, our findings highlight the use of surface modification and careful study of electrode-electrolyte interfaces and interphases as an enabling strategy for NIBs.
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U2 - 10.1149/1945-7111/ac9c33
DO - 10.1149/1945-7111/ac9c33
M3 - Article
AN - SCOPUS:85141896616
SN - 0013-4651
VL - 169
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
IS - 10
M1 - 106522
ER -