Abstract
Traditional Li-ion intercalation chemistry into graphite anodes exclusively utilizes the cointercalation-free or cointercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfactory cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in situ synthesis of t-GIC in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GIC (b-GIC) and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional cointercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles, even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10 000 cycles. Full cells coupled with a layered cathode display remarkable cycling stability upon a 15 min charging and excellent rate capability even at −40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach for achieving fast-charging and low-temperature batteries.
Original language | English |
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Pages (from-to) | 16764-16774 |
Number of pages | 11 |
Journal | Journal of the American Chemical Society |
Volume | 146 |
Issue number | 24 |
DOIs | |
State | Published - Jun 19 2024 |
Funding
The work was supported by the USDA AFRI Foundational and Applied Program (grant number 2020-67021-31139), the Sun Grant program of the National Institute of Food and Agriculture (NIFA), USDA, USA, and the Institute for Critical Technology and Applied Science at Virginia Tech. The material characterization experiments were partly supported by the IMSE (Institute of Materials Science and Engineering) at Washington University in Saint Louis (WUSTL). P.B. acknowledges the faculty startup support from WUSTL, a gift fund from TSVC, and the National Science Foundation grant (award no. 1934122). P.S. acknowledges the fellowship support from the McDonnell International Scholars Academy at WUSTL. F.S. acknowledges the National Science Foundation grant (award no. 2239690). This research used electron microscopy resources of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. FTIR performed at the ORNL was financially supported by Dr Imre Gyuk from the Energy Storage Program, Office of Electricity, Department of Energy. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We appreciate CAMP (Cell Analysis, Modeling, and Prototyping) for supplying graphite powder and electrodes. We also appreciate Qian Wang for the TGA measurement.