Improved Cycling Performance of Intermetallic Anode by Minimized SEI Layer Formation

Kuwata, Hiroko; Matsui, Masaki; Sonoki, Hidetoshi; Manabe, Yusuke; Imanishi, Nobuyuki; Mizuhata, Minoru

doi:10.1149/2.0951807jes

Cited by 15 publications

(20 citation statements)

References 18 publications

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“…The EQCM result of the LiBH 4 solution quantitatively proves the pseudo-SEI-free model, which we proposed in our previous paper. 31 In the case of LiPF 6 /EC-DEC, the mass increase of the copper electrode begins at a surprisingly high electrode potential of 2.3 V vs. Li during the initial cathodic sweep. The mass increase of the electrode is observed at the same electrode potential we identify the cathodic current peak.…”

Section: Resultsmentioning

confidence: 99%

Effect of Anion Species in Early Stage of SEI Formation Process

Sonoki

Matsui

Imanishi

2019

J. Electrochem. Soc.

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We investigate the early stage of the solid electrolyte interphase (SEI) layer formation process in four electrolyte solutions, using electrochemical quartz crystal microbalance (EQCM) and X-ray photoelectron spectroscopy (XPS). The EQCM result proves that the LiBH 4 in THF solution form a negligible amount of SEI layer. The SEI formation process of the LiPF 6 solution occurs at 2.3 V vs. Li, and the SEI layer continuously grows even during the anodic scan. The electrolyte solutions containing LiTFSA form SEI layer around 1.5 V vs. Li. The XPS study shows that the SEI layer formed at high electrode potential, in the electrolyte containing LiPF 6 forms a dense LiF layer. The LiTFSA solution forms a thick SEI layer containing organic components such as lithium alkyl carbonate or polyether.

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Section: Resultsmentioning

confidence: 99%

Effect of Anion Species in Early Stage of SEI Formation Process

Sonoki

Matsui

Imanishi

2019

J. Electrochem. Soc.

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“…Characteristic absorption peaks in the FTIR spectra (Figure S9) remain unchanged after the introduction of LiNO 3 and CuF 2 , indicating that LiNO 3 additives are readily soluble without any destruction of the solvent structure. However, the intensity of the absorption peaks at 1803 (C=O in EC), 1772 (C=O in DEC), 1196 (C−O in EC), and 1166 cm −1 (C−O in DEC) decrease notably, implying that the concentrations of those organic functional groups is reduced . Therefore, a fraction of solvent molecules participate in the solvation with additional cations or anions, forming a novel solvation structure in LiNO 3 ‐conatining electrolytes.…”

Section: Figurementioning

confidence: 99%

“…[16] Thedissolution chemistry of LiNO 3 in carbonate electrolyte,and its contribution to formation of the SEI, are strongly associated with the solvation structure of electrolytes.Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) techniques,a sw ell as molecular dynamics (MD) simulations,w ere applied to investigate the solvation structure of E-LiNO 3 .Characteristic absorption peaks in the FTIR spectra ( Figure S9) remain unchanged after the introduction of LiNO 3 and CuF 2 ,i ndicating that LiNO 3 additives are readily soluble without any destruction of the solvent structure.H owever,t he intensity of the absorption peaks at 1803 (C = Oi nEC), 1772 (C = OinD EC), 1196 (C À OinE C), and 1166 cm À1 (C À OinDEC) decrease notably,implying that the concentrations of those organic functional groups is reduced. [20] Therefore,afraction of solvent molecules participate in the solvation with additional cations or anions, forming an ovel solvation structure in LiNO 3 -conatining electrolytes.…”

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Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High‐Voltage Lithium Metal Batteries

et al. 2018

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The lithium metal anode is regarded as a promising candidate in next-generation energy storage devices. Lithium nitrate (LiNO ) is widely applied as an effective additive in ether electrolyte to increase the interfacial stability in batteries containing lithium metal anodes. However, because of its poor solubility LiNO is rarely utilized in the high-voltage window provided by carbonate electrolyte. Dissolution of LiNO in carbonate electrolyte is realized through an effective solvation regulation strategy. LiNO can be directly dissolved in an ethylene carbonate/diethyl carbonate electrolyte mixture by adding trace amounts of copper fluoride as a dissolution promoter. LiNO protects the Li metal anode in a working high-voltage Li metal battery. When a LiNi Co Al O cathode is paired with a Li metal anode, an extraordinary capacity retention of 53 % is achieved after 300 cycles (13 % after 200 cycles for LiNO -free electrolyte) and a very high average Coulombic efficiency above 99.5 % is achieved at 0.5 C. The solvation chemistry of LiNO -containing carbonate electrolyte may sustain high-voltage Li metal anodes operating in corrosive carbonate electrolytes.

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“…Fourier Transform Infrared Spectroscopy (FTIR) is a widely used technique that identifies chemical bonds. It is also capable of being used In situ to monitor the changes of SEIs [101] . While FTIR only identifies chemical bonds and is more suitable for organic compounds, X‐ray Photoelectron Spectroscopy (XPS) gives more detailed information about the elemental composition as well as the oxidation state, making it ideal for inorganic components [102] .…”

Section: Characterization Of Artificial Seimentioning

confidence: 99%

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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Improved Cycling Performance of Intermetallic Anode by Minimized SEI Layer Formation

Cited by 15 publications

References 18 publications

Effect of Anion Species in Early Stage of SEI Formation Process

Effect of Anion Species in Early Stage of SEI Formation Process

Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High‐Voltage Lithium Metal Batteries

Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries

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