Abstract
The traditional electrolyte for lithium-ion batteries is a combination of 1 M LiPF6 with a cyclic carbonate-based solvent (for example, ethylene carbonate). The lack of a suitable alternative solvent has hindered further exploration of new functional electrolytes. Here we design and synthesize a fluorinated cyclic phosphate solvent, 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (TFEP), for use in lithium-ion batteries. Our design rationale is that this solvent molecule has a fused chemical structure of cyclic carbonates that can form a stable solid electrolyte interphase and organic phosphates that can trap hydrogen radicals and prevent combustion. An electrolyte formula composed of 0.95 M LiN(SO2F)2 in TFEP/2,2,2-trifluoroethyl methyl carbonate shows excellent non-flammability with zero self-extinguishing time and enables the highly stable operation of graphite anodes (~0.1 V versus lithium) and high-voltage LiNi0.5Mn1.5O4 cathodes (~4.7 V versus lithium), and thereby outperforms traditional electrolytes. This work opens up new frontiers in electrolyte developments towards safe lithium-ion batteries with higher energy densities.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The datasets generated during and/or analysed during the current study are available from the corresponding author upon reasonable request.
References
Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Li, M., Lu, J., Chen, Z. & Amine, K. 30 Years of lithium-ion batteries. Adv. Mater. 30, 1800561 (2018).
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652 (2008).
Goodenough, J. B. & Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).
Roth, E. P. & Orendorff, C. J. How electrolytes influence battery safety. Electrochem. Soc. Interface 21, 45–49 (2012).
Liu, K. et al. Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries. Sci. Adv. 3, e1601978 (2017).
Sun, Y.-K. et al. Nanostructured high-energy cathode materials for advanced lithium batteries. Nat. Mater. 11, 942 (2012).
Xu, M. Q. et al. Application of cyclohexyl benzene as electrolyte additive for overcharge protection of lithium ion battery. J. Power Sources 184, 427–431 (2008).
Weng, W., Huang, J., Shkrob, I. A., Zhang, L. & Zhang, Z. Redox shuttles with axisymmetric scaffold for overcharge protection of lithium-ion batteries. Adv. Energy Mater. 6, 1600795 (2016).
Rodrigues, M.-T. F. et al. A materials perspective on Li-ion batteries at extreme temperatures. Nat. Energy 2, 17108 (2017).
Zeng, Z. et al. Safer lithium ion batteries based on nonflammable electrolyte. J. Power Sources 279, 6–12 (2015).
Wu, L. et al. A new phosphate-based nonflammable electrolyte solvent for Li-ion batteries. J. Power Sources 188, 570–573 (2009).
Shiga, T., Kato, Y., Kondo, H. & Okuda, C.-a Self-extinguishing electrolytes using fluorinated alkyl phosphates for lithium batteries. J. Mater. Chem. A 5, 5156–5162 (2017).
Wang, X., Yasukawa, E. & Kasuya, S. Nonflammable trimethyl phosphate solvent-containing electrolytes for lithium-ion batteries: I. Fundamental properties. J. Electrochem. Soc. 148, A1058–A1065 (2001).
Gao, D. et al. Ethylene ethyl phosphate as a multifunctional electrolyte additive for lithium-ion batteries. RSC Adv. 5, 17566–17571 (2015).
Wang, X., Yamada, C., Naito, H., Segami, G. & Kibe, K. High-concentration trimethyl phosphate-based nonflammable electrolytes with improved charge–discharge performance of a graphite anode for lithium-ion cells. J. Electrochem. Soc. 153, A135–A139 (2006).
Yamada, Y., Wang, J., Ko, S., Watanabe, E. & Yamada, A. Advances and issues in developing salt-concentrated battery electrolytes. Nat. Energy 4, 269–280 (2019).
Yoshida, K. et al. Oxidative-stability enhancement and charge transport mechanism in glyme–lithium salt equimolar complexes. J. Am. Chem. Soc. 133, 13121–13129 (2011).
Tamura, T. et al. Physicochemical properties of glyme–Li salt complexes as a new family of room-temperature ionic liquids. Chem. Lett. 39, 753–755 (2010).
Wang, J. et al. Fire-extinguishing organic electrolytes for safe batteries. Nat. Energy 3, 22–29 (2017).
Jeong, S.-K., Inaba, M., Iriyama, Y., Abe, T. & Ogumi, Z. Electrochemical intercalation of lithium ion within graphite from propylene carbonate solutions. Electrochem. Solid-State Lett. 6, A13–A15 (2003).
Pappenfus, T. M., Henderson, W. A., Owens, B. B., Mann, K. R. & Smyrl, W. H. Complexes of lithium imide salts with tetraglyme and their polyelectrolyte composite materials. J. Electrochem. Soc. 151, A209–A215 (2004).
Yamada, Y., Takazawa, Y., Miyazaki, K. & Abe, T. Electrochemical lithium intercalation into graphite in dimethyl sulfoxide-based electrolytes: effect of solvation structure of lithium ion. J. Phys. Chem. C 114, 11680–11685 (2010).
Zhang, X. & Devine, T. M. Identity of passive film formed on aluminum in Li-ion battery electrolytes with LiPF6. J. Electrochem. Soc. 153, B344–B351 (2006).
Myung, S.-T., Hitoshi, Y. & Sun, Y.-K. Electrochemical behavior and passivation of current collectors in lithium-ion batteries. J. Mater. Chem. 21, 9891–9911 (2011).
Gallus, D. R. et al. The influence of different conducting salts on the metal dissolution and capacity fading of NCM cathode material. Electrochim. Acta 134, 393–398 (2014).
Tasaki, K., Kanda, K., Nakamura, S. & Ue, M. Decomposition of LiPF6 and stability of PF5 in Li-ion battery electrolytes: density functional theory and molecular dynamics studies. J. Electrochem. Soc. 150, A1628–A1636 (2003).
Lux, S. F. et al. The mechanism of HF formation in LiPF6 based organic carbonate electrolytes. Electrochem. Commun. 14, 47–50 (2012).
Kalhoff, J. et al. Enabling LiTFSI-based electrolytes for safer lithium-ion batteries by using linear fluorinated carbonates as (co)solvent. ChemSusChem 7, 2939–2946 (2014).
Abouimrane, A., Ding, J. & Davidson, I. J. Liquid electrolyte based on lithium bis-fluorosulfonyl imide salt: aluminum corrosion studies and lithium ion battery investigations. J. Power Sources 189, 693–696 (2009).
Krause, L. J. et al. Corrosion of aluminum at high voltages in non-aqueous electrolytes containing perfluoroalkylsulfonyl imides; new lithium salts for lithium-ion cells. J. Power Sources 68, 320–325 (1997).
Yamada, Y. et al. Corrosion prevention mechanism of aluminum metal in superconcentrated electrolytes. ChemElectroChem 2, 1687–1694 (2015).
McOwen, D. W. et al. Concentrated electrolytes: decrypting electrolyte properties and reassessing Al corrosion mechanisms. Energy Environ. Sci. 7, 416–426 (2014).
Zhang, C. et al. Chelate effects in glyme/lithium bis(trifluoromethanesulfonyl)amide solvate ionic liquids, part 2: importance of solvate-structure stability for electrolytes of lithium batteries. J. Phys. Chem. C 118, 17362–17373 (2014).
Matsumoto, K. et al. Suppression of aluminum corrosion by using high concentration LiTFSI electrolyte. J. Power Sources 231, 234–238 (2013).
Zhang, Z. et al. Fluorinated electrolytes for 5 V lithium-ion battery chemistry. Energy Environ. Sci. 6, 1806–1810 (2013).
Wang, Y., Xing, L., Li, W. & Bedrov, D. Why do sulfone-based electrolytes show stability at high voltages? Insight from density functional theory. J. Phys. Chem. Lett. 4, 3992–3999 (2013).
Dahn, J. R. Phase diagram of LixC6. Phys. Rev. B 44, 9170–9177 (1991).
Alvarado, J. et al. A carbonate-free, sulfone-based electrolyte for high-voltage Li-ion batteries. Mater. Today 21, 341–353 (2018).
Suo, L. et al. Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proc. Natl Acad. Sci. USA 115, 1156–1161 (2018).
Zhang, S., Li, A., Zou, J., Lin, L. Y. & Wooley, K. L. Facile synthesis of clickable, water-soluble, and degradable polyphosphoesters. ACS Macro Lett. 1, 328–333 (2012).
Su, C.-C. et al. Functionality selection principle for high voltage lithium-ion battery electrolyte additives. ACS Appl. Mater. Interfaces 9, 30686–30695 (2017).
Aspern, N. V. et al. Fluorinated cyclic phosphorus(iii)-based electrolyte additives for high voltage application in lithium-ion batteries: impact of structure–reactivity relationships on CEI formation and cell performance. ACS Appl. Mater. Interfaces 11, 16605–16618 (2019).
Choi, J. & Manthiram, A. Role of chemical and structural stabilities on the electrochemical properties of layered LiNi1/3Mn1/3Co1/3O2 cathodes. J. Electrochem. Soc. 152, A1714–A1718 (2005).
Doi, T., Masuhara, R., Hashinokuchi, M., Shimizu, Y. & Inaba, M. Concentrated LiPF6/PC electrolyte solutions for 5-V LiNi0.5Mn1.5O4 positive electrode in lithium-ion batteries. Electrochim. Acta 209, 219–224 (2016).
Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).
Dong, Y., Demeaux, J., Zhang, Y. & Lucht, B. L. Improving the performance of graphite/LiNi0.5Mn1.5O4 cells with added N,N-dimethylformamide sulfur trioxide complex. J. Electrochem. Soc. 164, A3182–A3190 (2017).
Sharova, V. et al. Comparative study of imide-based Li salts as electrolyte additives for Li-ion batteries. J. Power Sources 375, 43–52 (2018).
Delp, S. A. et al. Importance of reduction and oxidation stability of high voltage electrolytes and additives. Electrochim. Acta 209, 498–510 (2016).
Acknowledgements
This work was supported by JSPS KAKENHI Specially Promoted Research (no. 15H05701 to A.Y. and no. 19H05459 to E.N.). Q.Z. is grateful to the Japan Society for the Promotion of Sciences (JSPS) for a JSPS Fellowship at The University of Tokyo (no. P18332) and the Grant-in-Aid for JSPS Fellows (no. 18F18332).
Author information
Authors and Affiliations
Contributions
A.Y. and E.N. conceived and directed the project. Q.Z., Y.Y. and R.S. proposed the concept and designed the experiments. Q.Z. performed the experiments and analysed the data. S.K. performed the XPS measurements. Y.L. conducted the DFT calculations. K.K. performed the electrochemical impedance measurements. All the authors contributed to the discussion. Q.Z., Y.Y. and A.Y. wrote the manuscript, and all the authors contributed to editing the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors have submitted a patent on this work with JP application No. 2020-24251.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Figs. 1–20 and Table 1.
Supplementary Video 1
Flammable test for the electrolyte of 1 M LiPF6 in EC/DMC.
Supplementary Video 2
Flammable test for the electrolyte of 0.98 M LiFSI in FEMC.
Supplementary Video 3
Flammable test for the electrolyte of 0.95 M LiFSI in TFEP/FEMC.
Rights and permissions
About this article
Cite this article
Zheng, Q., Yamada, Y., Shang, R. et al. A cyclic phosphate-based battery electrolyte for high voltage and safe operation. Nat Energy 5, 291–298 (2020). https://doi.org/10.1038/s41560-020-0567-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41560-020-0567-z
This article is cited by
-
A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur Batteries
Nano-Micro Letters (2024)
-
Enhanced High-Temperature Cycling Stability of Garnet-Based All Solid-State Lithium Battery Using a Multi-Functional Catholyte Buffer Layer
Nano-Micro Letters (2024)
-
Efficient Fixation of CO2 to Cyclic Carbonates Under Mild Conditions Catalyzed by Deep Eutectic Solvent
Catalysis Letters (2024)
-
Designing electrolytes and interphases for high-energy lithium batteries
Nature Reviews Chemistry (2023)
-
Electrolyte engineering via ether solvent fluorination for developing stable non-aqueous lithium metal batteries
Nature Communications (2023)