LFP cathodes were synthesized from 80% LFP powders (MTI Kejing Group), 10% super P carbon blacks, and 10% PVDF binder. The three components were fully mixed in N-methyl-2-pyrrolidone (Peking Reagent Modern Oriental Technology Development), and the resultant slurry was coated on aluminum foil using a doctor blade. The electrodes were dried for 48 hours before use. The LFP cathode foil was punched for a 60 mm by 40 mm pouch cell. The typical active material loading was about 5.0 mg cm−2. Commercial Li metal foils with the thickness of 50 μm were purchased from China Energy Lithium Co. Ltd.

The carbonate-based electrolytes were 1.0 M LiPF6 dissolved in EC/DEC (1:1 in volume) without other additives. The ether-based electrolytes were 1.0 M Li bis(trifluoromethane-sulfonyl)imide DOL/DME. The electrolytes used in Li | Cu cells in Fig. 4A were DOL/DME with 5.0 weight % lithium nitrate (LiNO3), while other ether-based electrolytes were used without any additives. The liquid electrolytes used in all batteries were 7.0 μl cm−2. Li | Li symmetric coin cells and Li | Cu cells were assembled with 2032 coin-type cells. Lithium was plated and stripped for 2 hour per cycle in Li | Li cells and for 2 hours per cycle in Li | Cu cells. In Li | Cu cells, the capacity of 0.5 mAh cm−2 Li was deposited on bare copper substrate and set to be totally stripped in one cycle. All batteries were assembled in an Ar-filled glove box with O2 and H2O content below 0.5 parts per million. The interfacial resistance was tested via electrochemical impedance spectroscopy measurement (0.1 × 106 Hz) with a Solartron 1470E electrochemical workstation. The LFP pouch cells were cycled in a galvanostatic mode with a voltage range of 2.5 to 3.8 V.

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