Ion Transport Kinetics in Low‐Temperature Lithium Metal Batteries

Abstract

The deployment of rechargeable batteries is crucial for the operation of advanced portable electronics and electric vehicles under harsh environment. However, commercial lithium‐ion batteries using ethylene carbonate electrolytes suffer from severe loss in cell energy density at extremely low temperature. Lithium metal batteries (LMBs), which use Li metal as anode rather than graphite, are expected to push the baseline energy density of low‐temperature devices at the cell level. Albeit promising, the kinetic limitations of standard cell chemistries under subzero operation condition inevitably hamper the cyclability of LMBs, resulting in a severe decline in plating/stripping reversibility and short‐circuit hazards due to the dendritic growth. Such performance degradation becomes more pronounced with decreasing temperature, ascribing to sluggish ion transport kinetics during charging/discharging processes which includes Li+ solvation/desolvation, ion transport through bulk electrolyte, as well as ion diffusion within solid electrolyte interphase and bulk electrode materials at low temperature. In this review, the critical limiting factors and challenges for low‐temperature ion transport behaviors are systematically reviewed and discussed. The strategies to enhance Li+ transport kinetics in electrolytes, electrodes, and electrolyte/electrode interface are comprehensively summarized. Finally, perspective on future research direction of low‐temperature LMBs toward practical applications is proposed.

Lithium-ion batteries for low-temperature applications: Limiting factors and solutions

“…Low ambient temperature causes a significant cell resistance and polarization, leading to a lower state of charge (SOC, defined in %, where 100% means the maximum number of Li + that can be fully reversibly intercalated or de-intercalated in the applied voltage region) of electrodes, and causing a significant decrease of the capacity and faster degradation upon continuous cycling [28,29]. The increased resistance at low temperatures is believed to be mainly associated with the changed migration behavior of Li + at each battery component, including electrolyte, electrodes, and electrode-electrolyte interphases [21,26]. Being a Li + conducting medium, high-freezing-point electrolyte remains the main rate-limiting factor for different LIB systems at low temperatures.…”

“…Piao et al focused more on heating techniques and thermal management to control the external reaction temperature [21]. The most recent reviews dissected the Li + transport/diffusion in electrolyte, solid electrode and their interphase, temperature-dependent limitating factors and challenges of lithium batteries, and offered their strategies to make an improvement [22][23][24][25][26][27].…”

Guiding Principles for the Design of Artificial Interface Layer for Zinc Metal Anode

“…The speed of ion transport in the interfacial layer is the key to uniform deposition, which affects the overall performance of Zn metal anode. [18] Some studies have shown that dendrite growth is inhibited when electrolytes with higher ionic conductivity and higher migration number are used. [15a,19] Uneven deposition is the beginning of a vicious cycle and dendrites growth.…”

Tailored Solvation and Interface Structures by Tetrahydrofuran‐Derived Electrolyte Facilitates Ultralow Temperature Lithium Metal Battery Operations

“…The implementation of small amount of FEC in the solvation structure increases ion carrier concentration and Li + transport channels in the SEI, as creating more inorganic compounds and grain boundaries [2b,14] . Therefore, sufficient Li + flux in the bulk electrolyte and fast charge‐transfer in the SEI, being inherent in this electrolyte design, are effective to resolve the low‐temperature limiting factor of the LMA [5a,10] . With these properties of our LHCE, the LMA could obtain substantially improved Li deposition morphology and plating/stripping stability from room temperature (RT) to −40 °C.…”