Rechargeable Li-metal batteries using high-voltage cathodes can deliver the highest possible energy densities among all electrochemistries. However, the notorious reactivity of metallic lithium as well as the catalytic nature of high-voltage cathode materials largely prevents their practical application. Here, we report a non-flammable fluorinated electrolyte that supports the most aggressive and high-voltage cathodes in a Li-metal battery. Our battery shows high cycling stability, as evidenced by the efficiencies for Li-metal plating/stripping (99.2%) for a 5 V cathode LiCoPO4 (~99.81%) and a Ni-rich LiNi0.8Mn0.1Co0.1O2 cathode (~99.93%). At a loading of 2.0 mAh cm−2, our full cells retain ~93% of their original capacities after 1,000 cycles. Surface analyses and quantum chemistry calculations show that stabilization of these aggressive chemistries at extreme potentials is due to the formation of a several-nanometre-thick fluorinated interphase.
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This work was supported by the US Department of Energy (DOE) under award no. DEEE0008202 and DEEE0008200. The support of the Maryland NanoCenter and its AIM Lab is acknowledged. The authors thank K. Pupek and G. Krumdick for providing one of the fluorinated solvents, and B. Dunn for constructive discussions.
Supplementary Figures 1–39; Supplementary Tables 1–3; Supplementary Notes 1–2
Flammable test for the electrolyte of 1 M LiFSI-DME
Flammable test for the electrolyte of 1 M LiPF6-EC/DMC
Flammable test for the electrolyte of 1 M LiPF6-FEC/DMC
Flammable test for the electrolyte of 1 M LiPF6-FEC/FEMC/HFE
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Nature Chemistry (2019)
Nature Communications (2019)
Dendrite-free sandwiched ultrathin lithium metal anode with even lithium plating and stripping behavior
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