A Lithium Metal Anode Surviving Battery Cycling Above 200 °C

Abstract

Lithium (Li) metal electrode cannot endure elevated temperature (e.g., >200 °C) with the regular battery configuration due to its low melting point (180.5 °C) and high reactivity, which restricts its application in high‐temperature Li metal batteries for energy storage and causes safety concerns for regular ambient‐temperature Li metal batteries. Herein, this work reports a Li5B4/Li composite featuring a 3D Li5B4 fibrillar framework filled with metallic Li, which maintains its initial structure at 325 °C in Ar atmosphere without leakage of the liquid Li. The capillary force caused by the porous structure of the Li4B5 fibrillar framework, together with its lithiophilic surface, restricts the leakage of liquid metallic Li and enables good thermal tolerance of the Li5B4/Li composite. Thus, it can be facilely operated for rechargeable high‐temperature Li metal batteries. Li5B4/Li electrodes are coupled with a garnet‐type ceramic electrolyte (Li6.5La3Zr0.5Ta1.5O12) to fabricate symmetric cells, which exhibit stable Li stripping/plating behaviors with low overpotential of ≈6 mV at 200 °C using a regular sandwich‐type cell configuration. This work affords new insights into realizing a stable Li metal anode for high‐temperature Li metal batteries with a simple battery configuration and high safety, which is different from traditional molten‐salt Li metal batteries using a pristine metallic Li anode.

LixCu alloy nanowires nested in Ni foam for highly stable Li metal composite anode

“…In our group, a series of dual-phase Li-rich alloy composites including Li-Ca [50], Li-Zn [51], and Li-Cu [52] have been prepared via a thermal infusion method, where the phase-segregation process leads to a Li alloy phase as a 3D scaffold dispersed in the matrix of Li metal phase. Recently, Li-rich alloys such as Li-B [53], Li-Si [54], Li-Ag [55], Li-Mg [56], and Li-Sn [57] have also been reported by other groups, showing highly improved electrochemical performance. Taking the Li-Cu dualphase alloy composite as an example, the Li x Cu alloy nanowires with a diameter of about 100 nm and a length approaching centimeter scale can self-assemble into a randomly aligned network that is subsequently used as the 3D skeleton to alleviate the volume change and regulate Li stripping/plating behaviors.…”

Insights on “nitrate salt” in lithium anode for stabilized solid electrolyte interphase

“…Metallic lithium (Li) has been regarded as one of the most promising anodes for next-generation rechargeable batteries owing to its highest theoretical specific capacity (3860 mA h g -1 ) and lowest electrochemical potential (-3.04 V vs. standard hydrogen electrode). [1][2][3][4][5] However, the huge volume fluctuations, together with the high reactivity of metallic Li, can result in repeated cracking/ reformation of solid electrolyte interphase (SEI) and serious side reactions with electrolyte during the Li plating/stripping processes, thus leading to nonuniform Li plating/stripping behavior, low Coulombic efficiency (CE), short lifespan, and even safety hazards. [6][7][8] This process continuously consumes active Li and electrolyte, accompanied by quick SEI and dead Li accumulation.…”

Dendrite‐free lithium and sodium metal anodes with deep plating/stripping properties for lithium and sodium batteries

“…However, due to the uncontrolled volume changes and dendrite growth of Li and Na metal anodes under the repeated charge/discharge processes, the applications of Li/Na metal anodes for rechargeable batteries still remain doubtful, because the continuous growth of dendrites at the metal anodes can lead to capacity fade, low Columbic efficiency (CE), thermal runaway, short circuit, and even fire 4 . To deal with these issues, two strategies have been put forward, one is to engineer the interface between metal anode and electrolyte, and the other is to optimize the anode structure by using an artificial host or innovative electrode substrate 5–8 . Although many efforts have been made to construct dendrite‐free metal anodes, their long‐term cycling stability could only be achieved under the relatively low current densities (<1 mA cm −2 ) and areal capacities (<1 mAh cm −2 ), which cannot satisfy the application requirements, especially for electric vehicles and energy storage stations.…”

“…4 To deal with these issues, two strategies have been put forward, one is to engineer the interface between metal anode and electrolyte, and the other is to optimize the anode structure by using an artificial host or innovative electrode substrate. [5][6][7][8] Although many efforts have been made to construct dendrite-free metal anodes, their longterm cycling stability could only be achieved under the relatively low current densities (<1 mA cm −2 ) and areal capacities (<1 mAh cm −2 ), which cannot satisfy the application requirements, especially for electric vehicles and energy storage stations. In an effort to develop highperformance metal anodes for metal batteries, threedimensional (3D) structures have been largely used as the substrates for the current collector.…”