A study on the interior microstructures of working Sn particle electrode of Li-ion batteries by in situ X-ray transmission microscopy

Chao, Sung-Chieh; Yen, Yu-Chan; Song, Yen‐Fang; Chen, Yiming; Wu, Hung-Chun; Wu, Nae‐Lih

doi:10.1016/j.elecom.2009.12.002

Cited by 133 publications

(68 citation statements)

References 15 publications

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“…However, the lithiation and delithiation reactions (Snþ4.4Li þ þ4.4e À 2Li 4.4 Sn) are accompanied by a large volume change [7][8][9], which lead to the pulverization of the particles and the electrical disconnection of the electrode. This is the major reason for the poor cycle life of metallic Sn, which hampers the application in lithium-ion batteries [10,11]. Sn particles are usually prepared in nanoscale in order to improve the rate capability, since nanoscale metallic has high activity and short pathway for Li þ transport.…”

Section: Introductionmentioning

confidence: 99%

Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries

Liang

Zhu

Lian

et al. 2011

Journal of Solid State Chemistry

140

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Section: Introductionmentioning

confidence: 99%

Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries

Liang

Zhu

Lian

et al. 2011

Journal of Solid State Chemistry

140

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“…9,26,35 There exist several studies where X-ray tomography imaging techniques revealed the presence of surface cracks within Sn active particles during the first lithiation process. 44,62 In the present analysis, surface cracks during the lithiation process have been captured by a combination of large volume expansion and two phase lithiation process. 21 To demonstrate the similarity between the experimentally observed surface cracks and computationally predicted crack fronts, a direct comparison is provided in Figures 3a and 3b.…”

Section: Resultsmentioning

confidence: 99%

“…There exist several experimentally observed in situ X-ray and electron microscopy imaging based evidences that lithiation in Sn particles occur through two-phase diffusion process. 35,43,44 Extremely slow lithiation of Sn reveals the presence of multiple lithium-tin phases, 45,46 but during lithiation only two phases are observed at a time. For more accurate estimation of the lithiation process, all the individual phases must be taken into consideration.…”

Section: Experimental and Modeling Detailsmentioning

confidence: 99%

Mechano-Electrochemical Interaction Gives Rise to Strain Relaxation in Sn Electrodes

Barai

Huang

Dillon

et al. 2016

J. Electrochem. Soc.

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Tin (Sn) anode active particles were electrochemically lithiated during simultaneous imaging in a scanning electron microscope. Relationships among the reaction mechanism, active particle local strain rate, particle size, and microcrack formation are elucidated to demonstrate the importance of strain relaxation due to mechano-electrochemical interaction in Sn-based electrodes under electrochemical cycling. At low rates of operation, due to significant creep relaxation, large Sn active particles, of size 1 μm, exhibit no significant surface crack formation. Microcrack formation within Sn active particles occurs due to two different mechanisms: (i) large concentration gradient induced stress at the two-phase interface, and (ii) high volume expansion induced stress at the surface of the active particles. From the present study, it can be concluded that majority of the microcracks evolve at or near the particle surface due to high volume expansion induced tension. Concentration gradient induced damage prevails near the center of the active particle, though significantly smaller in magnitude. Comparison with experimental results indicates that at operating conditions of C/2, even 500 nm sized Sn active particles remain free from surface crack formation, which emphasizes the importance of creep relaxation. A phase map has been developed to demonstrate the preferred mechano-electrochemical window of operation of Sn-based electrodes. High energy-density lithium-ion batteries use intercalation of lithium into solid active particles as the primary mechanism of energy storage.1 Traditional electrochemical systems used to store energy through surface reactions, which was a major barrier against achieving high specific capacity.2 Insertion and extraction of the secondary species during charge and discharge must occur through minimal irreversible change in the structure of the solid electrode material. Mitigation of mechanisms responsible for degradation of storage capacity is necessary for long-term battery cycling with good capacity retention. 3Most of the commercially available lithium ion batteries use electrode active materials (graphite as anode and lithium-cobalt-oxide/lithiumnickel-manganese-cobalt-oxide/lithium-manganese-oxide as cathode) that store lithium ions through intercalation mechanism.4,5 During lithiation and delithiation processes, these active materials experience very small strain and associated structural change, which results in capacity retention over many cycles. 6,7 However, the specific capacity of the intercalation materials is limited due to the weight of the atomic framework. Alloying anodes have received significant attention, as high capacity alternatives to intercalation anodes, due to their relatively high specific capacity (e.g. 3579 mAh g −1 for Li in Si).3 To accommodate Li atoms, this material undergoes a large volume expansion that can lead to particle failure. 8,9 Even small volume expansion cathode materials (such as, LiCoO 2 and LiFePO 4 ) experiences mechanical failure due to anisot...

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“…For example, the expansion and contraction of active electrode materials can cause SEI and particle fracture on the micro scale [14,15], whereas the same chemo-mechanical forces can result in severe delamination and electrical isolation of the bulk electrode [5,16]. The authors and others have led work over the past 5 years in the application of X-ray tomography to explore these materials both ex-situ [14,[17][18][19][20][21] and in-situ [14,15,22,23]. Additional work using tomography and radiography to characterize cell architecture during failure [22] and post mortem [24,25] as well as to understand the role of safety features [26][27][28] help to build a comprehensive understanding of the role of each component in driving device degradation and failure.…”

Section: *Manuscript Text (With Figures and Captions Embedded) -Cleanmentioning

confidence: 99%

Multi-scale 3D investigations of a commercial 18650 Li-ion battery with correlative electron- and X-ray microscopy

Gelb

Finegan

Brett

et al. 2017

Journal of Power Sources

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In the present study, a commercial 18650 Li-ion cylindrical cell is investigated with nondestructive 3D X-ray microscopy across a range of length scales, beginning with a survey of the entire cell and non-destructively enlarging a smaller section. Active materials are extracted from a disassembled cell and imaging performed using a combination of sub-micron X-ray microscopy and 2D scanning-electron microscopy, which point toward the need for multi-scale analysis in order to accurately characterize the cell. Furthermore, a small section is physically isolated for 3D nano-scale X-ray microscopy, which provides a measurement of porosity and enables the effective diffusivity and 3-dimensional tortuosities to be calculated via computer simulation. Finally, the 3D X-ray microscopy data is loaded into a correlative microscopy environment, where a representative sub-surface region is identified and, subsequently, analyzed using electron microscopy and energy-dispersive X-ray spectroscopy. The results of this study elucidate the microstructural characteristics and potential degradation mechanisms of a commercial NCA battery and, further, establish a technique for extracting the Bruggeman exponent for a real-world microstructure using correlative microscopy. IntroductionThere is considerable and growing research interest in Li-ion batteries driven largely by an increase in dependence on energy storage solutions, for applications ranging from mobile electronics to stationary power supplies and electric vehicles [1][2][3]. In the coming years, increasingly demanding applications from mW to MW, will require advanced Li-ion batteries to operate under extremes of temperature, rate, and pressure. Li-ion batteries are expected to deliver high performance, over long lifetimes, at a reduced cost as compared to existing solutions. With growing dependence on Li-ion technologies, in particular due to the growing popularity of hybrid-and fully-electric vehicles [2], it is of paramount importance to understand how batteries 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 61 62 63 64 65 perform, age, and degrade under real-world conditions [4,5]. Recent high profile failures have emphasized the need to better understand these processes [6][7][8]. *Manuscript text (with figures and captions embedded) -clean Click here to view linked ReferencesThere are a range of Li-ion battery architectures commercially available, such as pouch, prismatic, and spiral wound cells; by far the most common geometry is the 18650 cell, which has found diverse applications from consumer electronics [9] to aerospace equipment [10] and automotive power trains [11]. While the chemistry within these cells may vary, there are common components across most available commercial cells: the functional cell comprises two porous electrodes, electrically isolated by a porous separ...

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A study on the interior microstructures of working Sn particle electrode of Li-ion batteries by in situ X-ray transmission microscopy

Cited by 133 publications

References 15 publications

Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries

Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries

Mechano-Electrochemical Interaction Gives Rise to Strain Relaxation in Sn Electrodes

Multi-scale 3D investigations of a commercial 18650 Li-ion battery with correlative electron- and X-ray microscopy

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