Electrochemical impedance of electrolyte/electrode interfaces of lithium-ion rechargeable batteries

Itagaki, Masayuki; Yotsuda, Sachiko; Kobari, Nao; Watanabe, Kunihiro; Kinoshita, Shinichi; Ue, Makoto

doi:10.1016/j.electacta.2005.02.136

Cited by 59 publications

(36 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…R electrode values for Al-and Ta-doped LLZO are comparable (≈100 and ≈50 Ω cm 2 , respectively), whereas R electrode of Nb-doped LLZO is ≈800 Ω cm 2 . [38] Differences in reactivity between all three dopant species are further highlighted when comparing the evolution of the interfacial impedance with time ( Figure 3). Furthermore, despite the highest degree of interfacial Zr reactivity, Al-doped LLZO exhibits very low interfacial impedance (i.e., Nb ≫ Al > Ta), which indicates significant interfacial reactivity is not, in and of itself, a detrimental phenomenon, and may in fact lead to spontaneous stabilization of the interface.…”

Section: Impact Of Reactivity On Interfacial Impedancementioning

confidence: 99%

Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Zhu

Connell

Tepavcevic

et al. 2019

Advanced Energy Materials

261

282

View full text Add to dashboard Cite

materials are a particularly promising class of solid electrolytes for all-solidstate lithium metal batteries, as they are predicted to have a wide electrochemical stability window, [5,6] can be synthesized with very high density (>97%) [7,8] and, through aliovalent doping, can achieve room temperature Li-ion conductivities as high as ≈1.0 mS cm −1 with negligible electronic conductivity. [9] However, significant fundamental issues remain unresolved for garnet-based all-solid-state batteries, including low accessible current densities, [10] the persistence of Li dendrite formation, [11,12] and perhaps most importantly, ambiguities as to whether the interfaces between LLZO and both Li metal [13,14] and high voltage oxide cathodes [15,16] are stable over extended cycling. Indeed, developing deep understanding of the intrinsic reactivity between solid electrolytes and relevant electrode materials is crucial to developing high voltage solidstate batteries with long lifetimes, as the presence of any significant (electro)chemical reactivity will ultimately lead to premature cell failure during extended cycling.Understanding interfacial stability is an especially challenging issue common to all solid-state battery systems due to the inability of many experimental techniques to adequately interrogate the chemical properties of buried interfaces. Such studies are further complicated when one or both materials at the interface are unstable to exposure to air, water, etc., as Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based materials doped with Al, Nb, or Ta to stabilize the Li + -conductive cubic phase are a particularly promising class of solid electrolytes for all-solid-state lithium metal batteries. Understanding of the intrinsic reactivity between solid electrolytes and relevant electrode materials is crucial to developing high voltage solid-state batteries with long lifetimes. Using a novel, surface science-based approach to characterize the intrinsic reactivity of the Li-solid electrolyte interface, it is determined that, surprisingly, some degree of Zr reduction takes place for all three dopant types, with the extent of reduction increasing as Ta < Nb < Al. Significant reduction of Nb also takes place for Nb-doped LLZO, with electrochemical impedance spectroscopy (EIS) of Li||Nb-LLZO||Li symmetric cells further revealing significant increases in impedance with time and suggesting that the Nb reduction propagates into the bulk. Density functional theory (DFT) calculations reveal that Nb-doped material shows a strong preference for Nb dopants toward the interface between LLZO and Li, while Ta does not exhibit a similar preference. EIS and DFT results, coupled with the observed reduction of Zr at the interface, are consistent with the formation of an "oxygen-deficient interphase" (ODI) layer whose structure determines the stability of the LLZO-Li interface.

show abstract

Section: Impact Of Reactivity On Interfacial Impedancementioning

confidence: 99%

Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Zhu

Connell

Tepavcevic

et al. 2019

Advanced Energy Materials

261

282

View full text Add to dashboard Cite

show abstract

“…[5] The next challenge comes from the non-steady state of batteries during impedance measurements. The solution is the development of the non-stationary (4-D) impedance analysis [6][7][8][9][10][11][12][13] which is quickly evaluated and adopted for testing of lithium-ion batteries by Mitsubishi [14,15], and later for studies of other time evolving processes [16,17]. Recently, 4-D impedance analysis was included in the software portfolio of Bio-Logic [18].…”

Section: The Scientistmentioning

confidence: 99%

“…4-D impedance analysis was introduced in the battery testing software and successfully applied in Li-ion battery research [14,15,18], and also for studies of some other time-evolving systems [16,17].…”

Section: Non-stationary (4-d) Impedance Analysismentioning

confidence: 99%

Zdravko Stoynov – the scientist who created new scientific horizons - Review

Vladikova

2020

J. Electrochem. Sci. Eng.

View full text Add to dashboard Cite

<p class="PaperAbstract">This paper is in the memory of the big Bulgarian scientist Professor Zdravko Stoynov. An original and non-standard personality with the spirit of a gentleman, he turned all that he touched into a masterpiece. His innovative thinking which made him one of the world’s leaders in Electrochemical Impedance Spectroscopy, chiseled away at the scientific taboos and created new scientific horizons. Zdravko Stoynov left us an abundant heritage – his spirit, his interminable capacity to wonder, his developments and inventions – all that he has taught us and brought up with. It has no dimensions but rather carries a unique value.</p>

show abstract

“…In addition, there are very few works testing metallic-lithium [20][21][22], while in the case of the graphite anode, there are numerous studies. In the latter case attention is focused on charging/discharging efficiency [23][24][25][26][27][28][29], SEM observations of the graphite surface [8, 14, 23-25, 27, 29-31] and EIS analysis [23,24,29,30,[32][33][34][35].…”

Section: Additivesmentioning

confidence: 99%

Solid electrolyte interphase formation on metallic lithium

Lewandowski

Swiderska‐Mocek

Waliszewski

2012

J Solid State Electrochem

View full text Add to dashboard Cite

Solutions of three salts (LiBF 4 , LiNTf 2 , LiPF 6 ) in N-methyl-2-pyrrolidone (NMP), selected arbitrarily as a reference solvent, were investigated by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy techniques. The lithium surface in contact with LiPF 6 in NMP electrolyte was covered with a protective layer (SEI) which morphology comprise small particles (of ca. 0.2 μm in radius). This salt was selected for further studies. The impedance of the Li|(LiPF 6 in NMP+additive)|Li system was measured immediately after cell assembly and after galvanostatic charging/discharging. Fifteen different additives (10 wt.%) were used. The efficiency of individual additives was evaluated in terms of the Li|electrolyte system resistance (ΔR) or total cell impedance reduction, both deduced from EIS. Some of the additives were able to form the SEI layer and to reduce resistance/impedance of the Li| electrolyte interphase. In such cases, the lithium surface was covered with relatively uniform conglomerates, or regions separated by cracks, of ca. 1-2 μm in dimension.

show abstract

Electrochemical impedance of electrolyte/electrode interfaces of lithium-ion rechargeable batteries

Cited by 59 publications

References 19 publications

Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Zdravko Stoynov – the scientist who created new scientific horizons - Review

Solid electrolyte interphase formation on metallic lithium

Contact Info

Product

Resources

About