h i g h l i g h t sChemistry and electrochemistry in lithium-based microbatteries. Recent concept and cell design towards different applications. Future perspectives of microbattery development. a b s t r a c tBatteries employing lithium chemistry have been intensively investigated because of their high energy attributes which may be deployed for vehicle electrification and large-scale energy storage applications. Another important direction of battery research for micro-electronics, however, is relatively less discussed in the field but growing fast in recent years. This paper reviews chemistry and electrochemistry in different microbatteries along with their cell designs to meet the goals of their various applications. The state-of-the-art knowledge and recent progress of microbatteries for emerging micro-electronic devices may shed light on the future development of microbatteries towards high energy density and flexible design.
a low gravimetric density (0.534 g cm −3 ), which is therefore considered as an ideal negative electrode for energy storage systems. Rechargeable Li metal batteries have been extensively studied in the past four decades, especially in the recent years due to an increasing demand for high-energy batteries. [ 1 ] Lithium metal anode is indispensable for the research & development (R&D) of Li metal batteries adopting Lifree cathodes (e.g., MoS 2 , TiS 2 , MnO 2 , V 2 O 5 , etc.) and also has been widely used in the R&D of Li-O 2 and Li-S batteries, which are considered to be the next-generation "beyond Li-ion" energy storage technologies because of their higher theoretical energy densities compared to Li-ion batteries. [ 2 ] However, there are still signifi cant challenges impeding the successful development of Li metal batteries, including the formation and growth of Li dendrites during repeated charge/discharge processes and the low Coulombic effi ciency resulted from the high reactivity of Li metal toward the electrolyte solvents and salt anions.The continuous growth of Li dendrites is undesirable because it may pierce the polymer separator and cause internal short circuit, leading to cell failure and safety issues such as fi re and even explosion. Since Li dendrites mainly form during charging process (Li deposition on anode side) especially at high current densities or C-rates, [ 3 ] the dendrite growth could be largely mitigated or avoided by limiting the charging current density to low-to-medium levels. However, without an effective protecting layer, fresh Li metal anode will be exposed to the liquid electrolyte. The reactions between electrolyte components (i.e., solvent and salt anion) and Li metal continuously occur chemically and electrochemically. This process not only results in serious corrosion to the Li metal anode and rapid increase of the cell impedance but also consumes the electrolyte and leads to cell dry out and early failure of the batteries.Recently, highly concentrated ether-based electrolytes have been reported to be more compatible with Li metal anode [ 4 ] because high concentrations of Li + ions in these electrolytes can facilitate the fast Li deposition/stripping even at high current density conditions. The decreased number of the uncoordinated
Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service-temperature range of lithium (Li)-ion batteries (LIBs). In this study, we report such wide-temperature electrolyte formulations by optimizing the ethylene carbonate (EC) content in the ternary solvent system of EC, propylene carbonate (PC), and ethyl methyl carbonate (EMC) with LiPF salt and CsPF additive. An extended service-temperature range from -40 to 60 °C was obtained in LIBs with lithium nickel cobalt aluminum oxide (LiNiCoAlO, NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room temperature and elevated temperatures were systematically investigated together with the ionic conductivity and phase-transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF in EC-PC-EMC (1:1:8 by wt) with 0.05 M CsPF, which was demonstrated in both coin cells of graphite∥NCA and 1 Ah pouch cells of graphite∥LiNiMnCoO. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the high capacity retention (68%) at -40 °C and C/5 rate, significantly higher than that (20%) of the conventional LIB electrolyte, and the nearly identical stable cycle life as the conventional LIB electrolyte at room temperature and elevated temperatures up to 60 °C.
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