A 3D Framework with an In Situ Generated Li₃N Solid Electrolyte Interphase for Superior Lithium Metal Batteries

Abstract

The practical application of lithium (Li) metal for next‐generation rechargeable batteries is still hampered by uncontrolled growth of Li dendrite and severe volume change under repeated plating/stripping. Introducing a 3D structure to reserve space for Li storage and inducing uniform plating/stripping by a lithophilic interface layer are effective strategies to solve these problems. Herein, a novel 3D composite Li anode (Fe‐N@SSM‐Li) is constructed via an in situ reaction between Li and lithiophilic Fe2N/Fe3N (Fe‐N) uniformly anchored on a stainless‐steel mesh (SSM). The unique lithiophilic‐conductive structure of the Fe‐N@SSM‐Li can stabilize the Li anode by effectively inducing uniform and dense deposition and confining Li deposition inside the Fe‐N@SSM‐Li to alleviate volume changes. The Fe‐N@SSM‐Li displays a distinguished electrochemical performance, with superior lifespan of 5000, 2250, and 1350 h under 1 mA cm−2/1 mAh cm−2, 5 mA cm−2/3 mAh cm−2, and 20 mA cm−2/3 mAh cm−2 in symmetric cells, respectively. Combined with this highly stable Fe‐N@SSM‐Li, the full cells using LiFePO4 (LFP) and S/C cathodes both show significantly improved electrochemical performances. This work provides a low‐cost and scalable strategy for the construction of high‐efficiency Li anode with a novel 3D structure, offers new insights to the research of Li metal batteries and beyond.

Synergized Interface Engineering and Alloying Strategy for In Situ Construction of a Three-Dimensional Lithiophilic Carbon Skeleton: Motivating High-Performance Lithium Metal Batteries

“…Similarly, R SEI of LiSn@CN@CC symmetric cells also decreased to 66, 50.9, 9.80, and 7.95 Ω during the different cycles. Meanwhile, R SEI of the LiSn@CN@CC symmetric cell is much smaller than that of the Li@CC symmetric cell in each cycle, revealing that the Li 3 N in situ modified micrometer-sized lithium manganate alloy can effectively accelerate the electrochemical reaction with enhanced charge transfer. − …”

Interfacial chemistry regulation using functional frameworks for stable metal batteries

“…[51][52][53] Besides, IOFs can be endowed with various geometries and functional groups via different fabrication methods to facilitate metal deposition and dendrite suppression. 7,[54][55][56] Interfacial modication engineering is regarded as a complicated strategy due to the heterogeneity of mass transport and reactions from the bulk electrolyte to the electrode interface. Decoupling surface reactions and designing target functional frameworks should be systematically correlated to regulate interfacial reactions for stable RMBs.…”

“…51–53 Besides, IOFs can be endowed with various geometries and functional groups via different fabrication methods to facilitate metal deposition and dendrite suppression. 7,54–56…”

Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning

“…Recently, the adoption of electronic blocking layers like LiH, LiF, Li 3 N and organic lithium salts on the surfaces of SIE particles has been observed to increase the critical electrical bias for dendrite growth, enhance ionic conductivity and oxidation stability, and has gained popularity as a promising direction for modifying electrode–SSE pairs. 234–236 Surface coating techniques, such as liquid-phase deposition of nanosized SIEs, 237 lithiophilic metallic 238 or electron-blocking interlayers, 239 electrodeposition, 240 and removal of impurities, 241 have also been explored to address various issues encountered by lithium metal batteries and facilitate intimate contact with SSEs, forming nanoscale electronic/ionic transportation networks for high reversibility capacity and superior rate capability. However, achieving the desired rate performances for fast-charging targets of electric vehicles still poses challenges.…”