Mechano-Electrochemical Stochastics in High-Capacity Electrodes for Energy Storage

Barai, Pallab; Mukherjee, Partha P.

doi:10.1149/2.01191606jes

Cited by 33 publications

(26 citation statements)

References 68 publications

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“…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. An enlarged SEM image of the severely fractured particle no.…”

Section: Resultsmentioning

confidence: 91%

“…35 Hence it is important to correctly understand the mechanism behind the formation of surface cracks to explain these discrepancies in the published experimental results. Computational modeling of volume expansion in Si indicates that there exist two different mechanisms of microcrack formation within two-phase lithiated Si active particles: 20,21,36 i) Transport of lithium occurs via a two-phase diffusion process, which gives rise to very large concentration gradient induced load at the two-phase interface boundary. ii) Large volume expansion during lithiation causes the lithium rich phase to move outward along the radial direction resulting in generation of tensile stress at the particle surface.…”

Section: Journal Of the Electrochemical Society 163 (14) A3022-a3035mentioning

confidence: 99%

“…9,15,19 Also, due to the high volume expansion of the lithiated phase, outward movement of the surface of the active particle induces tensile stress in the outer reacted region that can open cracks at the surface. 9,20,21 Almost no strain rate sensitivity is predicted, or observed experimentally, in Si since no appreciable compositional gradient evolves and the reaction follows the same evolutionary pathway regardless of lithiation rate.9,22 Fracture in alternative systems, such as Ge, Al, SnO 2 , ZnO, and Sn has been experimentally investigated by similar techniques, which have yielded differing results. 9,13,14,17,[23][24][25] For example, Si, Ge, and Sn fracture in distinct manners at different length scales, despite the fact that their reaction mechanism is quite similar.…”

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confidence: 99%

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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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Section: Resultsmentioning

confidence: 91%

Section: Journal Of the Electrochemical Society 163 (14) A3022-a3035mentioning

confidence: 99%

mentioning

confidence: 99%

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

Barai

Huang

Dillon

et al. 2016

J. Electrochem. Soc.

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“…Detailed illustration of the lattice spring methodology amalgamating large deformation has been provided in Barai et al 40,41 The salient features of this framework are summarized here along with the modifications required to incorporate surface film mechanics.…”

Section: Methodsmentioning

confidence: 99%

“…29,34 Lattice spring model based high volume expansion modeling has been shown to replicate the deformation of silicon and tin electrodes. 40,41 However, there are no detailed numerical analyses investigating the effect of the diffusion mechanism on fracture tendencies inside silicon particle with surface film mimicking solid electrolyte interphase or secondary phase layer.In this work, we have extended the computational methodology developed in our group 40,41 to analyze and contrast the effect of the diffusion mechanism on the fracture methodology inside silicon active material with a surface film. Lithiation of crystalline silicon via two-phase diffusion process has been reported to cause large strain inhomogeneity between lithium rich and lithium poor phase exacerbating fracture.…”

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confidence: 99%

Mechanistic Analysis of Mechano-Electrochemical Interaction in Silicon Electrodes with Surface Film

Verma

Mukherjee

2017

J. Electrochem. Soc.

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High-capacity anode materials for lithium-ion batteries, such as silicon, are prone to large volume change during lithiation/delithiation which may cause particle cracking and disintegration, thereby resulting in severe capacity fade and reduction in cycle life. In this work, a stochastic analysis is presented in order to understand the mechano-electrochemical interaction in silicon active particles along with a surface film during cycling. Amorphous silicon particles exhibiting single-phase lithiation incur lower amount of cracking as compared to crystalline silicon particles exhibiting two-phase lithiation for the same degree of volumetric expansion. Rupture of the brittle surface film is observed for both amorphous and crystalline silicon particles and is attributed to the large volumetric expansion of the silicon active particle with lithiation. The mechanical property of the surface film plays an important role in determining the amount of degradation in the particle/film assembly. A strategy to ameliorate particle cracking in silicon active particles is proposed. Lithium ion battery (LIB) technology has become the prevalent energy storage and supply system for portable electronics.1 In recent years, the application of LIBs is extending to large scale applications such as electric vehicles, 2-4 commercial aircrafts 5,6 and grid energy storage. 7,8 The widespread usage of LIBs in high energy and power applications is predicated on robust improvement of energy and power densities afforded by the LIB which is directly correlated with the anode 9,10 and cathode 11,12 active materials utilized. Current commercial batteries use graphite 13 as anode and lithium cobalt oxide/lithium nickel manganese cobalt oxide 14,15 as cathode material. Graphite exhibits a maximum specific capacity of 372 mAh/g graphite while the current cathode materials are limited to a maximum of 200 mAh/g AM . These chemistries have been utilized in electric vehicle batteries, however, the low capacity necessitates use of bulky and expensive battery packs to power the vehicle which form the major impediment to commercialization of electric vehicles.Extensive efforts have been invested in identifying high capacity anode and cathode materials for usage in next generation lithium ion batteries.10 Silicon has been the focus of several researchers as an anode material owing to its high theoretical specific capacity of 4200 mAh/g Si , approximately ten times that of graphite. [16][17][18] This high capacity is a result of large lithium intercalation ability of silicon as compared to graphite; a silicon atom can intercalate a maximum of 4.4 atoms of lithium (Li 4.4 Si) while graphite can accommodate a maximum of 1 lithium atom per graphite molecule (LiC 6 ).17 However, experimental analysis of silicon anode lithium ion battery has revealed much lower capacities (∼75% of the theoretical capacity) during initial cycles 19 as well as rapid capacity degradation with charge-discharge cycling. Capacity fade of the order of 20% is observed within the first...

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A Model for Diffusion and Immobilization of Lithium in SiOC Nanocomposite Anodes

Stein

Vranković

Graczyk‐Zajac

et al. 2017

JOM

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Mechano-Electrochemical Stochastics in High-Capacity Electrodes for Energy Storage

Cited by 33 publications

References 68 publications

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

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

Mechanistic Analysis of Mechano-Electrochemical Interaction in Silicon Electrodes with Surface Film

A Model for Diffusion and Immobilization of Lithium in SiOC Nanocomposite Anodes

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