Regulating the Inner Helmholtz Plane for Stable Solid Electrolyte Interphase on Lithium Metal Anodes

Abstract

The stability of a battery is strongly dependent on the feature of solid electrolyte interphase (SEI). The electrical double layer forms prior to the formation of SEI at the interface between the Li metal anode and the electrolyte. The fundamental understanding on the regulation of the SEI structure and stability on Li surface through the structure of the electrical double layer is highly necessary for safe batteries. Herein, the interfacial chemistry of the SEI is correlated with the initial Li surface adsorption electrical double layer at the nanoscale through theoretical and experimental analysis. Under the premise of the constant solvation sheath structure of Li + in bulk electrolyte, a trace amount of lithium nitrate (LiNO 3 ) and copper fluoride (CuF 2 ) were employed in electrolytes to build robust electric double layer structures on a Li metal surface. The distinct results were achieved with the initial competitive adsorption of bis(fluorosulfonyl)imide ion (FSI − ), fluoride ion (F − ), and nitrate ion (NO 3 − ) in the inner Helmholtz plane. As a result, Cu−NO 3 − complexes are preferentially adsorbed and reduced to form the SEI. The modified Li metal electrode can achieve an average Coulombic efficiency of 99.5% over 500 cycles, enabling a long lifespan and high capacity retention of practical rechargeable batteries. The as-proposed mechanism bridges the gap between Li + solvation and the adsorption about the electrode interface formation in a working battery.

A Sodiophilic Interphase‐Mediated, Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

“…To solve these problems, significant progress has been achieved recently by applying various strategies, including an artificial solid‐electrolyte interphase (SEI), electrolyte additives, solid‐state electrolytes, and nanostructured Na anodes . Generally, these strategies mainly concentrate on the already formed Na plating morphology, that is, Na dendrites, yet few involve the initial Na deposition behavior, including the nucleation.…”

“…Therefore,Nadendrites and their related issues have severely hindered the practical applications of sodium-metal batteries (SMBs), [4,5] fore xample,s odium-air batteries [2,6] and roomtemperature sodium-sulfur batteries. [7] To solve these problems,s ignificant progress has been achieved recently by applying various strategies,including an artificial solid-electrolyte interphase (SEI), [8,9] electrolyte additives, [10,11] solid-state electrolytes, [12,13] and nanostructured Na anodes. [14,15] Generally,t hese strategies mainly concentrate on the already formed Na plating morphology,t hat is, Na dendrites,y et few involve the initial Na deposition behavior, including the nucleation.…”

Recent progress on biomass‐derived ecomaterials toward advanced rechargeable lithium batteries

“…Oriented material designs have been deemed as one of effective strategies to address the aforementioned challenges and promote the development of advanced lithium (Li) batteries for practical application. [9][10][11][12][13][14][15] Naturally biomass materials always exist in the form of biological macromolecules or carbohydrate compounds in plant or animal cells, which endow themselves with diverse microstructures, complex compositions, and abundant functional groups. These unique physicochemical properties offer an emerging opportunity to compatible with high-energy advanced lithium batteries.…”

A Sodiophilic Interphase‐Mediated, Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

“…[1][2][3] Unfortunately,t he formation of Na dendrites caused by inhomogeneous deposition will decrease the utilization of reactive Na with poor cyclic stability,a nd more importantly,r esult in at hreat of internal short circuit towards thermal runaway and fire hazards (Figure 1a). [7] To solve these problems,s ignificant progress has been achieved recently by applying various strategies,including an artificial solid-electrolyte interphase (SEI), [8,9] electrolyte additives, [10,11] solid-state electrolytes, [12,13] and nanostructured Na anodes. [7] To solve these problems,s ignificant progress has been achieved recently by applying various strategies,including an artificial solid-electrolyte interphase (SEI), [8,9] electrolyte additives, [10,11] solid-state electrolytes, [12,13] and nanostructured Na anodes.…”

“…Therefore,Nadendrites and their related issues have severely hindered the practical applications of sodium-metal batteries (SMBs), [4,5] fore xample,s odium-air batteries [2,6] and roomtemperature sodium-sulfur batteries. [7] To solve these problems,s ignificant progress has been achieved recently by applying various strategies,including an artificial solid-electrolyte interphase (SEI), [8,9] electrolyte additives, [10,11] solid-state electrolytes, [12,13] and nanostructured Na anodes. [14,15] Generally,t hese strategies mainly concentrate on the already formed Na plating morphology,t hat is, Na dendrites,y et few involve the initial Na deposition behavior, including the nucleation.…”