SnSb electrodes for Li-ion batteries: the electrochemical mechanism and capacity fading origins elucidated by using operando techniques

Antitomaso, Philippe; Fraisse, Bernard; Stievano, Lorenzo; Biscaglia, Stéphane; Aymé‐Perrot, David; Girard, Philippe; Sougrati, Moulay Tahar; Monconduit, Laure

doi:10.1039/c6ta10138k

Cited by 33 publications

(24 citation statements)

References 29 publications

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“…This mechanism is very distinct from sodiation process of Sn metal and from the lithiation mechanism of SnSb, for which several intermediate steps involving successive crystalline phase transitions have been reported. 34,39,40 The fact that the nano-confined, amorphous metallic tin phase shows high electrochemical reversibility in this system is in accordance with our previous study in which we highlighted these prerequisites. 41 It is noteworthy that the sodiation reaction of SnSb is often incomplete due to a voltage drop caused by overpotentials arising from kinetic limitations or ohmic resistances which reduces the reversible capacity obtained.…”

Section: Discussionsupporting

confidence: 77%

Elucidating the origin of superior electrochemical cycling performance: new insights on sodiation–desodiation mechanism of SnSb from operando spectroscopy

et al. 2018

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Section: Discussionsupporting

confidence: 77%

Elucidating the origin of superior electrochemical cycling performance: new insights on sodiation–desodiation mechanism of SnSb from operando spectroscopy

et al. 2018

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“…The peaks at 0.45 V, 0.7 V, 0.75 V, and 0.8 V vs. Li/Li + are assigned to the delithiation of Li x Sn alloy to form Sn. The peak at 1 V vs. Li/Li + is ascribed to the dealloying of Sb to form again SnSb 37 . Compared to the CV curve of as-prepared SnSb electrode, the PS- b -PHEA-coated SnSb shows broader peaks and larger surface area under the CV curve.…”

Section: Resultsmentioning

confidence: 99%

Superior Electrochemical Performance of Thin-Film Thermoplastic Elastomer-Coated SnSb as an Anode for Li-ion Batteries

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Dumur

Gigmès

et al. 2019

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The high failure strain of thermoplastic elastomers (TPEs) is a very desirable feature for rechargeable Li-ion batteries by improving the lifetime of high specific capacity anode materials that undergo mechanical fractures induced by large volume variations. In this work, poly(styrene-b-2-hydroxyethyl acrylate) called PS-b-PHEA was synthesized by a nitroxide meditated polymerization method. Owing to the use of a specific polystyrene macroinitiator (SG1), a suitable TPE copolymer with long hydroxyethyl acrylate blocks to ensure good mechanical properties is obtained for the first time. We show that the electrochemical properties of the PS-b-PHEA-coated SnSb anode are drastically improved by suppressing the crack formation at the surface of the electrode. Indeed, electrochemical characterization revealed that a high and stable gravimetric capacity over 100 cycles could be achieved. Moreover, excellent capacity reversibility was achieved when cycled at multiple C-rates and fast kinetics confirming the strong protection role of the polymer. The advanced chemical and mechanical properties of PS-b-PHEA open up promising perspectives to significantly improve the electrochemical performance of all electrodes that are known to suffer from large volume variations.

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“…Lithiation of SnSb (1:1) particles, which is referred to here as the SnSb-50-50-CF sample (vide infra), occurs via the following mechanisms 38 whereas the delithiation occurs via the following stepsScheme 1a summarizes the various phases of SnSb formed during discharge and charge processes, respectively. On full lithiation, SnSb (1:1) converts to mixture of Li 3 Sb and Li x Sn (or Li max Sn, cf.…”

Section: Resultsmentioning

confidence: 99%

“…This is in full accordance with published ex situ and in situ results. 31,38,43 In this context, an investigation of the morphology and microstructure of SnSb-75-25-CF following cycling is studied using SEM and TEM (Figure S9). The retention of the fibrous morphology (Figure S9a) with similar diameter of the carbon fiber composite strongly suggests that the expansion of carbon fiber is small and the particles are well dispersed inside the carbon fibers.…”

Section: Resultsmentioning

confidence: 99%

Probing the Critical Role of Sn Content in SnSb@C Nanofiber Anode on Li Storage Mechanism and Battery Performance

2017

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The minimization of the detrimental effects as a result of the drastic volume changes (few hundred times) occurring during repeated alloying–dealloying of lithium with group IV elements, e.g., tin (Sn), is a major challenge. An important design strategy is to have Sn as a component in a binary compound. SnSb is an important example where the antimony (Sb) itself is redox active at a potential higher than that of Sn. The ability of Sb to alloy with Li reduces the Li uptake amount of Sn in SnSb compared to that in bare Sn. Thus, the volume changes of Sn in SnSb will expectedly be much lower compared to that in bare Sn, leading to greater mechanical stability and cyclability. As revealed recently, the complete reformation of SnSb (for a molar ratio of Sn/Sb = 1:1) during charging is not achieved due to the loss of some fraction of Sn. Thus, the molar concentration of Sn and Sb in SnSb is also absolutely important for the optimization of battery performance. We discuss here SnSb with varying compositions of Sn encapsulated inside an electrospun carbon nanofiber (abbreviated as CF). The carbon-nanofiber matrix not only provides electron transport pathways for the redox process but also provides ample space to accommodate the drastic volume changes occurring during successive charge and discharge cycles. The systematic changes in the chemical composition of SnSb minimize the instabilities in SnSb structure as well as replenish any loss in Sn during repeated cycling. The composition plays a very crucial role, as magnitude of specific capacities and cyclability of SnSb are observed to depend on the variable percentage of Sn. SnSb-75-25-CF, which contains excess Sn, exhibits the highest specific capacity of 550 mAh g –1 after 100 cycles in comparison with pure SnSb (1:1) anode material at a current density of 0.2 A g –1 and shows excellent rate capability over widely varying current densities (0.2–5 A g –1 ).

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SnSb electrodes for Li-ion batteries: the electrochemical mechanism and capacity fading origins elucidated by using operando techniques

Abstract: Operando XRD and Mössbauer spectroscopy to elucidate the mechanism of the SnSb/Li battery.

Cited by 33 publications

References 29 publications

Elucidating the origin of superior electrochemical cycling performance: new insights on sodiation–desodiation mechanism of SnSb from operando spectroscopy

Elucidating the origin of superior electrochemical cycling performance: new insights on sodiation–desodiation mechanism of SnSb from operando spectroscopy

Superior Electrochemical Performance of Thin-Film Thermoplastic Elastomer-Coated SnSb as an Anode for Li-ion Batteries

Probing the Critical Role of Sn Content in SnSb@C Nanofiber Anode on Li Storage Mechanism and Battery Performance

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