Rearrange SEI with artificial organic layer for stable lithium metal anode

Kang, Danmiao; Hart, Noam; Koh, J. C. Y.; Ma, Linge; Liang, Wenbin; Xu, Jing; Sardar, S. A.; Lemmon, John P.

doi:10.1016/j.ensm.2019.06.014

Cited by 77 publications

(61 citation statements)

References 33 publications

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“…30 In addition, even a lithium alkoxide coating was recently reported to greatly improve the cyclability of a lithium anode by preventing dendrite formation. 31 But most importantly, metal alkyl carbonates are known to readily form in the reaction of metal alkoxide with CO 2 . [32][33][34] Here we demonstrate for the rst time the ALD/MLD process of lithium ethylene glycoxide (LiEG), and incorporation of CO 2 into this process to form metal alkyl carbonate species of LiEG.…”

Section: Introductionmentioning

confidence: 99%

CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

2020

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Section: Introductionmentioning

confidence: 99%

CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

2020

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“…The pouch‐type Li|NCMA73 battery with Mg(NO 3 ) 2 additive delivers unprecedented stable cycle performance up to 1300 cycles with a capacity retention of 80% (Figure 3c). Notably, compared with previously reported pouch‐type LMB using carbonate‐based electrolyte ( Table 1 ), [ 20,24–31 ] the proposed strategy manifested great competitiveness in terms of long‐term cycling. Particularly, the positive effect of Mg(NO 3 ) 2 additive was also confirmed in LiPF 6 salt‐based electrolyte (Figure S8, Supporting Information), which is the most commonly used as the salt in commercial LIBs.…”

Section: Resultsmentioning

confidence: 81%

Toward the Sustainable Lithium Metal Batteries with a New Electrolyte Solvation Chemistry

Lee

Hwang

Ming

et al. 2020

Advanced Energy Materials

130

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graphite has been the most commercially successful anode material for LIBs due to its low material cost and reduction potential (≈0.05 V vs Li/Li + ). However, graphite anodes limit the enhancement of energy density and charging rate due to their low theoretical capacity (375 mAh g −1 ) and staged lithium (de) intercalation mechanism, making it difficult to meet the expectation of cutting-edge electronic devices. [5,6] Hence, the development of metallic lithium as an anode is attracting great attention because of its exceptionally high specific capacity (3860 mAh g −1 ), small gravimetric density (0.534 g cm −3 ), and low negative electrochemical potential (−3.040 V vs the standard hydrogen electrode). [7][8][9] Therefore, theoretically, rechargeable batteries using Li metal (LMB) and a nickel-rich NCM cathode can easily surpass the energy density of state-of-the-art commercial LIBs using graphite, thereby achieving the goal of 300-400 Wh kg −1 for LIBs. [10] However, thermodynamic instability between Li metal and electrolyte during the charging process always causes an unavoidable parasitic process, wherein the electrolyte spontaneously reacts with the Li anode to deplete the electrolyte, thicken the solid electrolyte interphase (SEI), and induce dendritic growth of Li, resulting in low Coulombic efficiency (CE), rapid capacity drop, and safety concerns. [7,11,12] To alleviate these weaknesses of LMBs, many efforts, including electrolyte engineering, [4,13,14] use of a 3D host structure, [15,16] and artificial SEI engineering, [17,18] are being widely explored. Among these Herein, a new solvation strategy enabled by Mg(NO 3 ) 2 is introduced, which can be dissolved directly as Mg 2+ and NO 3 − ions in the electrolyte to change the Li + ion solvation structure and greatly increase interfacial stability in Li-metal batteries (LMBs). This is the first report of introducing Mg(NO 3 ) 2 additives in an ester-based electrolyte composed of ternary salts and binary ester solvents to stabilize LMBs. In particular, it is found that NO 3 − efficiently forms a stable solid electrolyte interphase through an electrochemical reduction reaction, along with the other multiple anion components in the electrolyte. The interaction between Li + and NO 3 − and coordination between Mg 2+ and the solvent molecules greatly decreases the number of solvent molecules surrounding the Li + , which leads to facile Li + desolvation during plating. In addition, Mg 2+ ions are reduced to Mg via a spontaneous chemical reaction on the Li metal surface and subsequently form a lithiophilic Li-Mg alloy, suppressing lithium dendritic growth. The unique solvation chemistry of Mg(NO 3 ) 2 enables long cycling stability and high efficiency of the Li-metal anode and ensures an unprecedented lifespan for a practical pouch-type LMB with high-voltage Ni-rich NCMA73 cathode even under constrained conditions.

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“…Organic artificial SEI with various structure and components were also fabricated on Li anode as protection layer. An In situ chemical reaction between some functional groups and metallic Li can form a surface layer with lithiophilic sites to reduce Li depositing overpotential [37–39] . The flexibility of organic Li salts also contributes to the formation of a less fragile artificial SEI layer.…”

Section: Sei Componentsmentioning

confidence: 99%

“…And the rearrangement of SEI structure contributes to a less fragile interphase with high elastic to conform to the volume change of Li anode. Straight chain alcohols and carboxylic acids with carbon number ranging from 2–12 were chosen to form Li alkoxides and Li carboxylates on Li foil [37,38] . And it was found that long carbon chain could increase the lithiophilicity of Li anodes and decrease the surface deposition overpotential simultaneously.…”

Section: Organic Sei Layersmentioning

confidence: 99%

“…Strong interactions between adsorption sites and ions at molecular scale were realized by introducing a quaternized polyethylene terephthalate (q‐PET) interlayer on Li surface (Figure 8). Both lithiophilicity and anionphilicity functional groups worked together to regulate cation distribution and undermine the anion concentration gradient at the same time, contributing to an ultrahigh working current density of 10 mA cm −2 for the Li anode [38] . Furthermore, a highly stable organic interphase was fabricated by introducing trifluoromethyl functional groups as strong electron‐withdrawing sites.…”

Section: Organic Sei Layersmentioning

confidence: 99%

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Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries

Kang

Xiao

Lemmon

2020

Batteries & Supercaps

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Li metal has attracted intense attention due to its high specific capacity, but the dendrite growth during cycling impedes its practical application as a rechargeable anode. To improve the stability of the solid‐electrolyte interphase (SEI) on Li metal is the key to develop Li anode with high safety. In native SEI, inorganics act as fast ion channels and organics play the role of soft base with high flexibility to buffer volume change. However, the SEI with inorganics close to Li surface and organics close to electrolyte always leads to a fragile structure, resulting in repeatedly breaking and growing of the surface layer. Artificial SEI is one of the most effective ways to improve interphase stability and extend the cycle life of Li anode. Inorganics such as Li fluoride, Li nitride, Li phosphate and Li alloys have been widely applied in Li protection. In situ chemical reactions, spin coating and doctor blade coating of organics were also conducted to obtain SEI with high lithiophilic functional groups and high elasticity. To fabricate an ideal artificial SEI, organic and inorganic components should be rearranged as a rational structure to possess synergetic effects with both high flexibility and ionic conductivity. This Minireview summarizes the most recent works on artificial SEI and discusses the electrochemical performance of different components as interphase, aiming to inspire the study on designing and fabricating stable Li anode with robust interphase structure.

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Rearrange SEI with artificial organic layer for stable lithium metal anode

Cited by 77 publications

References 33 publications

CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

Toward the Sustainable Lithium Metal Batteries with a New Electrolyte Solvation Chemistry

Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries

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Rearrange SEI with artificial organic layer for stable lithium metal anode

Cited by 77 publications

References 33 publications

CO2-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

CO2-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

Toward the Sustainable Lithium Metal Batteries with a New Electrolyte Solvation Chemistry

Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries

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CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films

CO₂-based atomic/molecular layer deposition of lithium ethylene carbonate thin films