In Situ Atomic Force Microscopy Study of Initial Solid Electrolyte Interphase Formation on Silicon Electrodes for Li-Ion Batteries

Tokranov, Anton; Sheldon, Brian W.; Li, Chunzeng; Minne, S. C.; Xiao, Xingcheng

doi:10.1021/am500363t

Cited by 125 publications

(167 citation statements)

References 68 publications

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“…2016, 6, 1501768 www.MaterialsViews.com www.advenergymat.de wileyonlinelibrary.com At fi rst sight, the large values of SEI thickness might appear surprising (they reach or even overcome the thickness of the pristine electrode). [ 77 ] Therefore, the estimated SEI thickness found on our a-Si:H electrodes are indeed expected to exceed typical values assumed for the SEI layer on carbon electrodes. As a matter of fact, in agreement with the literature, [ 74 ] it has been verifi ed (by in situ optical microscopy, ex situ SEM, and from the analysis of TOF-SIMS profi les) that our 30 nm thick layers do not exhibit cracks upon lithiation/delithiation.…”

Section: Sei Evolutionmentioning

confidence: 63%

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Corte

Caillon

Jordy

et al. 2015

Advanced Energy Materials

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special environment for its characterization appear as steps which in most cases might strongly modify the active material. [ 1 ] Benefi ting from characterization techniques able to analyze the electrodes in situ and in operando therefore appears of uttermost importance for obtaining information of direct relevance regarding the electrode processes. We show in the present work that such pieces of information can be obtained by using in situ Fourier-transform infrared (FTIR) spectroscopy in a suitable geometry, which avoids the traditional limitations associated with this technique and allows for quantitative information to be extracted. [ 2 ] This approach therefore brings significant complementary information to other useful techniques operating in the electrochemical environment, which focus either on electrode materials, such as nuclear magnetic resonance (NMR) [ 3,4 ] or X-ray absorption, diffraction or imaging, [ 5,6 ] or on electrode surfaces, such as scanning probe microscopies. [ 7,8 ] Using infrared spectroscopy at the electrochemical interface has already been attempted in the context of the study of battery electrodes. [9][10][11] The geometry adopted for these studies was however severely limiting the sensitivity, and imposing stringent limitations for the electrochemical conditions (especially in terms of mass-transport limitations), which have direct impact on the obtained results. [ 12 ] Here, we use an alternative approach based on the multiple-internal-refl ection geometry, which allows for benefi ting from an enhanced sensitivity and working in electrochemical conditions similar to those of standard batteries for studying thin-fi lm electrodes. As shown hereafter, such a capability provides useful information of direct relevance for both interfacial and bulk electrode processes.The present study has been devoted to silicon electrodes, studied in a half-cell confi guration against a lithium-metal electrode. Silicon represents an impressive gain in energy density for negative electrodes in Li-ion batteries. One strategy to overcome the poor capacity retention associated with the massive volume expansion of silicon during lithiation is the use of nanosized geometries, for instance, particles, [13][14][15][16] wires, [17][18][19] and tubes. [ 20,21 ] The use of a thin-fi lm geometry also prevents Multiple-internal-refl ection infrared spectroscopy allows for the study of thin-fi lm amorphous silicon electrodes in situ and in operando, in conditions typical of those used in Li-ion batteries. It brings an enhanced sensitivity, and the attenuated-total-refl ection geometry allows for the extraction of quantitative information. When electrodes are cycled in representative electrolytes, the simultaneously recorded infrared spectra give an insight into the solid/electrolyte interphase (SEI) composition. They also unravel the dynamic behavior of this SEI layer by quantitatively assessing its thickness, which increases during silicon lithiation and partially decreases during delithiation. Li-ion solvation ...

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Section: Sei Evolutionmentioning

confidence: 63%

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Corte

Caillon

Jordy

et al. 2015

Advanced Energy Materials

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“…This interpretation is consistent with earlier statements claiming that SEI grows mainly during the initial formation cathodic scan. 10,11,35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 insets. 38 The related distribution of the apparent Young's modulus of the SEI as determined by 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Nanoindentation measurements were conducted with sharp AFM tips and spherical colloidal probes (CPs) on the SEI formed after the first...…”

Section: Electrochemical Formation and Morphological Characterizationmentioning

confidence: 99%

Wet Nanoindentation of the Solid Electrolyte Interphase on Thin Film Si Electrodes

Kuznetsov

Zinn

Zampardi

et al. 2015

ACS Appl. Mater. Interfaces

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The solid electrolyte interphase (SEI) film formed at the surface of negative electrodes strongly affects the performance of a Li-ion battery. The mechanical properties of the SEI are of special importance for Si electrodes due to the large volumetric changes of Si upon (de)insertion of Li ions. This manuscript reports the careful determination of the Young's modulus of the SEI formed on a sputtered Si electrode using wet atomic force microscopy (AFM)-nanoindentation. Several key parameters in the determination of the Young's modulus are considered and discussed, e.g., wetness and roughness-thickness ratio of the film and the shape of a nanoindenter. The values of the Young's modulus were determined to be 0.5-10 MPa under the investigated conditions which are in the lower range of those previously reported, i.e., 1 MPa to 10 GPa, pointing out the importance of the conditions of its determination. After multiple electrochemical cycles, the polymeric deposits formed on the surface of the SEI are revealed, by force-volume mapping in liquid using colloidal probes, to extend up to 300 nm into bulk solution.

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“…The SEI layer does not have mechanical tolerance to endure the large volumetric changes during expansion/contraction of the silicon surface. [8][9][10][11][12][13][14] As a result, the electrolyte decomposes continuously to cover newly exposed surface and increase the thickness of the SEI. In addition to the problems due to the large volume changes, low conductivity of silicon and structural stress owing to phase transformation have also been reported to contribute to capacity fading.…”

mentioning

confidence: 99%

Capacity Fading Mechanisms of Silicon Nanoparticle Negative Electrodes for Lithium Ion Batteries

Yoon

Nguyen

Seo

et al. 2015

J. Electrochem. Soc.

132

126

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A thorough analysis of the evolution of the voltage profiles of silicon nanoparticle electrodes upon cycling has been conducted. The largest changes to the voltage profiles occur at the earlier stages (> 0.16 V vs Li/Li + ) of lithiation of the silicon nanoparticles. The changes in the voltage profiles suggest that the predominant failure mechanism of the silicon electrode is related to incomplete delithiation of the silicon electrode during cycling. The incomplete delithiation is attributed to resistance increases during delithiation, which are predominantly contact and solid electrolyte interface (SEI) resistance. The capacity retention can be significantly improved by lowering delithiation cutoff voltage or by introducing electrolyte additives, which generate a superior SEI. The improved capacity retention is attributed to the reduction of the contact and SEI resistance. Due to increasing demands for lithium ion batteries with higher energy density, several electrode materials capable of improving lithium ion capacity have been investigated. Among them, silicon has been steadily highlighted as one of the most promising materials for negative electrodes due to excellent electrochemical properties; large theoretical specific capacity and low working potential.1 While these properties make silicon an interesting electrode material with promise to bring innovation to energy storage devices, other electrochemical behavior such as cycling performance, coulombic efficiency, and capacity retention are insufficient for commercial batteries. In the context of improving the cycling behavior of silicon electrodes, the mechanism of capacity fade has been investigated extensively. Most reported failure mechanisms are based on problems associated with the large volume change which the silicon particle experiences during lithiation and delithiation. The repeated volume expansion/contraction results in cracking or pulverization of the silicon particles during prolonged cycling.1,3-5 Furthermore, it has been reported that volume contraction of silicon particles upon delithiation is accompanied by loss of electric conductivity of the electrode layer since the contracted silicon particles are poorly connected with surrounding conductive carbon additives and current collector.6,7 The failure of the SEI (solid electrolyte interphase) on the silicon electrode, is another key factor for electrochemical reversibility of lithium ion batteries. The SEI layer does not have mechanical tolerance to endure the large volumetric changes during expansion/contraction of the silicon surface. [8][9][10][11][12][13][14] As a result, the electrolyte decomposes continuously to cover newly exposed surface and increase the thickness of the SEI. In addition to the problems due to the large volume changes, low conductivity of silicon and structural stress owing to phase transformation have also been reported to contribute to capacity fading. 15,16 The widespread approach to overcome the aforementioned failures of volume change is to employ nano-structu...

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In Situ Atomic Force Microscopy Study of Initial Solid Electrolyte Interphase Formation on Silicon Electrodes for Li-Ion Batteries

Cited by 125 publications

References 68 publications

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Wet Nanoindentation of the Solid Electrolyte Interphase on Thin Film Si Electrodes

Capacity Fading Mechanisms of Silicon Nanoparticle Negative Electrodes for Lithium Ion Batteries

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