Abstract

The reversible heat in lithium-ion batteries (LIBs) due to entropy change is fundamentally important for understanding the chemical reactions in LIBs and developing proper thermal management strategies. However, the direct measurements of reversible heat are challenging due to the limited temperature resolution of applied thermometry. In this work, by developing an ultra-sensitive thermometry with a differential AC bridge using two thermistors, the noise-equivalent temperature resolution we achieve (±10 μK) is several orders of magnitude higher than previous thermometry applied on LIBs. We directly observe reversible heat absorption of a LIR2032 coin cell during charging with negligible irreversible heat generation and a linear relation between heat generations and currents. The cell entropy changes determined from the reversible heat provide the first verification of the approach of temperature dependent open circuit voltage. Moreover, it is found that the large reversible entropy change can cancel out the irreversible entropy generation at a charging rate as large as C/3.7 and produce a zero-heat-dissipation battery during charging. Our work significantly contributes to fundamental understanding of the entropy changes and heat generations of the chemical reactions in LIBs, and reveals that reversible heat absorption can be an effective way to cool LIBs during charging. Ultra-sensitive thermometry with temperature resolution of 10 μK reveals that batteries absorb heat reversibly during charging. • An ultra-sensitive thermometry with a noise-equivalent resolution of 10 μK. • Observing reversible heat of batteries with negligible irreversible heat generation. • Entropy changes from reversible heat match with that from open circuit voltage. • Batteries generate zero heat with a charging rate of C/3.7

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