Direct Observation of Inhomogeneous Solid Electrolyte Interphase on MnO Anode with Atomic Force Microscopy and Spectroscopy

Zhang, Jie; Wang, Rui; Yang, Xiaocheng; Lü, Wei; Wu, Xiaodong; Wang, Xiaoping; Li, Hong; Chen, Liwei

doi:10.1021/nl300570d

Cited by 173 publications

(194 citation statements)

References 21 publications

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“…This method was firstly introduced to study the SEI of MnO anode. 63 The scheme of the measurement is shown in Figure 16. The deformation of the SEI is represented by δ. F is the force of the tip acted on the surface.…”

Section: Early Researches On Si-based Anode Materialsmentioning

confidence: 99%

Review—Nano-Silicon/Carbon Composite Anode Materials Towards Practical Application for Next Generation Li-Ion Batteries

Luo

Liu

Zheng

et al. 2015

J. Electrochem. Soc.

Self Cite

298

186

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Among many candidates, silicon anode materials have been considered as one of the most promising materials for the next generation Li-ion batteries to replace widely used graphite anode materials, due to its high capacity, abundant source, environmental friendly and potential low cost. However, practical applications of silicon anode materials are still quite challenge due to large volume change and serious interfacial side reactions. Many strategies have been purposed and evaluated over last two decades. It seems that SiO x , Si-M alloy and nano-Si/C composite are more promising materials. In this review, scientific and technological problems and possible solutions of nano-Si/C composite anode for Li-ion batteries are summarized.Lithium-ion batteries have the advantages of high energy density, good rate capability, long cycle life, low self-discharge rate. [1][2][3][4] Since the first commercial application in the portable electronic devices market in 1991, 5 three generations of Li-ion batteries have been developed, as listed in Figure 1.The energy density of commercial Li-ion batteries has been improved from 90 Wh kg −1 to 245 Wh kg −1 . 6 (note: a prototype of 30 Ah Li-ion battery using Si-based anode material and Ni-riched cathode material achieved 330 Wh kg −1 , as claimed by Hitachi Chemical in November 18, 2014, Japanese Battery Symposium). The applications of lithium-ion batteries have been extended to many emerging markets, including electric bikes and vehicles, large scale energy storage, back-up power sources and power tools. 7 For most of applications, the energy densities of the advanced Li-ion batteries are still far from satisfactory. The calls for battery revolutionary have been heard every day.According to theoretical energy density calculations based on thermodynamic data, 6 the rechargeable batteries using metallic lithium as anode could achieve the highest energy densities for electrochemical energy storage devices, as shown in Figure 2. 8,9 Currently, metallic lithium anodes in nonaqueous batteries suffer from the formation of lithium dendrites and holes, growth of the instable solid electrolyte interphase (SEI) and exhaustion of electrolyte caused by the side reactions. Great efforts are needed to solve these problems. 10 In view of short term targets, it is more practical to develop the third generation Li-ion batteries, in which Si-based materials are used in anodes.Silicon is the most attractive choice as anode material in lithiumion batteries to replace graphite. It has a theoretical capacity of 4200 mAh g −1 for forming Li 22 Si 5 and 3580 mAh g −1 for forming Li 15 Si 4 , 11,12 which is 10 times higher than 350-365 mAh g −1 of commercial graphitic anode materials. Si is environmental friendly and has abundant source and low cost for precursors. However, after 20 years R&D, it is realized that the use of the high capacity Si-based anode materials is still very difficult in full Li-ion batteries. In this short review, the main scientific and technoligical problems of the nano-Si/C compo...

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Section: Early Researches On Si-based Anode Materialsmentioning

confidence: 99%

Review—Nano-Silicon/Carbon Composite Anode Materials Towards Practical Application for Next Generation Li-Ion Batteries

Luo

Liu

Zheng

et al. 2015

J. Electrochem. Soc.

Self Cite

298

186

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“…[7][8][9][10][11] The Poisson ratio of the anisotropic SEI is likely to be between 0.5 and 0.25, which is typical for polymeric composite materials. 24 We used the modification of Bilodeau 25 for the four-sided pyramid indenter for the numerical fitting of the force-indentation data obtained with AFM tip…”

Section: Theoretical Basismentioning

confidence: 99%

“…Similar values with large scattering were also found at different states of charge. 7 Ex-situ indentation of dried SEI on silicon electrodes was conducted by Weadock et al 8 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 28 differences in SEI thickness between Si and graphite electrodes are consistent with literature, 2…”

Section: Electrochemical Formation and Morphological Characterizationmentioning

confidence: 99%

“…[4][5][6] In addition, AFM-based methods can provide information about the mechanical properties of the SEI, such as the Young´s modulus. [7][8][9][10][11] However, probing thin films by indentation is challenging and special attention must be paid to address several important aspects, e.g. morphology or surface properties such as roughness and adhesiveness to minimize errors and obtain reliable results.…”

Section: Introductionmentioning

confidence: 99%

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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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“…[19][20][21] In carbon anodes, the SEI layer prevents further decomposition of the electrolyte by hindering electron transport from the electrode to the electrolyte, and by blocking the travel of solvent molecules to the active surface of the anode, where they can react with lithium ions and electrons. 25 In silicon anodes, i.e., the huge volume expansion of the anode creates cracks in the SEI layer and generates new surfaces which are freshly exposed to the electrolyte.…”

mentioning

confidence: 99%

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

Benitez

Seminario

2017

J. Electrochem. Soc.

114

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Understanding the transport properties of the solid electrolyte interphase (SEI) is a critical piece in the development of lithium ion batteries (LIB) with better performance. We studied the lithium ion diffusivity in the main components of the SEI found in LIB with silicon anodes and performed classical molecular dynamics (MD) simulations on lithium fluoride (LiF), lithium oxide (Li 2 O) and lithium carbonate (Li 2 CO 3 ) in order to provide insights and to calculate the diffusion coefficients of Li-ions at temperatures in the range of 250 K to 400 K, which is within the LIB operating temperature range. We find a slight increase in the diffusivity as the temperature increases and since diffusion is noticeable at high temperatures, Li-ion diffusion in the range of 1300 K to 1800 K was also studied and the diffusion mechanisms involved in each SEI compound were analyzed. We observed that the predominant mechanisms of Li-ion diffusion included vacancy assisted and knock-off diffusion in LiF, direct exchange in Li 2 O, and vacancy and knock-off in Li 2 CO 3 . Moreover, we also evaluated the effect of applied electric fields in the diffusion of Li-ions at room temperature. The continuous demand for smart phones, tablets and other mobile devices has enormously promoted the improvement of Li-ion batteries. Moreover, volatile oil prices, pollution and climate change concerns have further increased the need for energy storage devices for renewable energies and electric vehicles. The latter applications require batteries with even higher energy density, better cycle life, better power performance, lower cost and improved safety.1 Therefore, improving and increasing the fundamental scientific knowledge of lithium ion batteries is essential for their continual advancement.A key component in lithium ion batteries is the solid electrolyte interphase (SEI) film. The SEI film is a thin passivating layer that is initially formed, on both anode and cathode surfaces, from the reduction of the electrolyte during the first charging/discharging cycles. [2][3][4][5][6][7][8][9] It consists of a mixture of inorganic and organic products, such as LiF, Li 2 O and LiCO 3 , and (CH 2 OCO 2 Li) 2 , ROCO 2 Li and ROLi, where R is an organic group such as CH 2 , CH 3 , CH 2 CH 2 , CH 2 CH 3 , CH 2 CH 2 CH 3 that depends on the electrolyte solvent.10-24 Proposed structure models suggest that a dense layer of inorganic products is found near the electrode (inner layer) followed by a porous organic layer near the electrolyte/SEI interface (outer layer). [19][20][21] In carbon anodes, the SEI layer prevents further decomposition of the electrolyte by hindering electron transport from the electrode to the electrolyte, and by blocking the travel of solvent molecules to the active surface of the anode, where they can react with lithium ions and electrons. 25 In silicon anodes, i.e., the huge volume expansion of the anode creates cracks in the SEI layer and generates new surfaces which are freshly exposed to the electrolyte. 26 In both carbon and si...

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Direct Observation of Inhomogeneous Solid Electrolyte Interphase on MnO Anode with Atomic Force Microscopy and Spectroscopy

Cited by 173 publications

References 21 publications

Review—Nano-Silicon/Carbon Composite Anode Materials Towards Practical Application for Next Generation Li-Ion Batteries

Review—Nano-Silicon/Carbon Composite Anode Materials Towards Practical Application for Next Generation Li-Ion Batteries

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

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

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