Electrochemical and 119Sn Mössbauer study of sulfospinels as anode materials for lithium-ion batteries

Dedryvère, Rémi; Olivier‐Fourcade, J.; Jumas, Jean‐Claude; Denis, S.; Lavela, Pedro; Tirado, J.L.

doi:10.1016/s0013-4686(00)00564-8

Cited by 9 publications

(9 citation statements)

References 22 publications

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“…The recharge up to 3 V corresponds to a reversible capacity of 520 mAh/g, that can reach 620 mAh/g in the compound CulnSnS4 (tx = 0.5). Three areas have been assigned to the different electrochemical processes observed [6,7]. Area 1 (up to ca.…”

Section: Resultsmentioning

confidence: 99%

“…Sulfide compounds with spinel-related structure such as CuM0.sSnl.5S 4 (M = Fe, Co) [3,4] or InzSno.sS4 [5] have been investigated and the mechanisms of lithium insertion discussed. In recent papers, we have shown the interest of copper, indium and tin sulfospinels of general formula Cu0.5+~Inzs_3c~Sn2~S4 (0 < ~ < 0.5), which display reversible capacities up to 600 mAh/g with however a relatively high capacity fading during cycling [6,7]. We have shown by X-ray and neutron diffraction that lithium insertion induces a transformation from the spinel phase into a rocksalt-related phase at the beginning of the insertion, coming with the reduction of Sn TM into Sn H and Cu I into Cu ~ and the formation of metallic copper.…”

Section: Introductionmentioning

confidence: 99%

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Physical investigation of the mechanisms of lithium insertion in sulfides as anode materials for lithium-ion batteries

Dedryvère¹,

Olivier‐Fourcade²,

Jumas³

2000

Ionics

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Abstract. Electrochemical and chemical lithium insertion (via n-butyllithium) were carried out on a family of spinel phases of the CuzS-InzSa-SnS2 system. Electrochemical measurements have revealed great reversible capacities and the possible use of these materials as negative electrodes in lithium-ion batteries, ll9Sn Mrssbauer spectroscopy, 7Li NMR and S K edge EXAFS spectroscopy were carried out to characterize the mechanisms of lithium insertion. This study has shown the formation of lithium-metal alloys finely dispersed in an amorphous lithium sulfide matrix at low potentials. A model is proposed to explain the great capacities observed in these materials.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Physical investigation of the mechanisms of lithium insertion in sulfides as anode materials for lithium-ion batteries

Dedryvère¹,

Olivier‐Fourcade²,

Jumas³

2000

Ionics

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“…Therefore, sulfide compounds of a spinelrelated structure are very interesting host materials since the presence of a great number of empty sites in the structure is particularly favorable for incorporation of guest ions and allows a three-dimensional insertion. 10,11 As a typical defect spinel structured material, b-In 2 S 3 is used as an n-type semiconductor with a band gap of 2-2.45 eV, 12 and is a rare case of an ordered crystalline material with a large amount of vacancies. 13 According to its specific optoelectronic, 14 photoconductive, 15 and optical properties, 13 b-In 2 S 3 has shown important applications for solar cells, 16 photocatalysts, 17 and phosphors for lighting.…”

Section: Introductionmentioning

confidence: 99%

Improved electrode performance of mesoporous β-In2S3 microspheres for lithium ion batteries using carbon coated microspheres

Liu

2011

J. Mater. Chem.

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“…As part of an ongoing effort to determine the scope and generality of CDI reactions as the basis for positive electrodes in Li-ion type batteries, we decided to revisit the chemistry of Cu-based thiospinel phases, because previous authors − have reported some Li-driven copper extrusion without exploring its outcome upon subsequent charges/discharges. In this paper, we report results regarding CuM 2 S 4 /electrolyte/Li cells (where M = Ti, Cr) with special attention to the interplay between Li + and Cu + ions during electrochemical redox processes.…”

Section: Introductionmentioning

confidence: 99%

Copper Extrusion/Reinjection in Cu-Based Thiospinels by Electrochemical and Chemical Routes

et al. 2006

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The electrochemical reactivity of CuTi 2 S 4 and CuCr 2 S 4 spinel samples toward Li was studied over a wide range of voltages. Their electrochemical behavior can be decomposed into two steps. For less than two inserted lithium, we emphasized a Li-driven electrochemical displacement reaction that led to the extrusion of copper from lithium, leading to the rocksalt-type structure phases Li 2 Ti 2 S 4 and Li 2-x Cu 0.3 Cr 2 S 4 , whereas conversion reactions were observed beyond x ) 2. These conversion reactions were shown to have a large rechargeable uptake and release of Li + ions (7 per formula unit) that rapidly fade on cycling. Regarding the Cu extrusion, we demonstrated that this process is reversible for the Ti-based spinel upon oxidation through a chemically assisted electrochemical process. For the Cr-based system, a new phase LiCu 0.7 Cr 2 S 4 was evidenced to form on oxidation. This difference is explained in terms of band structure considerations and d-sp redox chemistry. Chemical reinjection of Cu into Ti 2 S 4 forming the single phase Cu x Ti 2 S 4 (0 < x < 1) from the reaction of Ti 2 S 4 powders with an aqueous CuSO 4 ‚nH 2 O solution is also reported. It is shown that traces of H 2 S coming from the slight chemical instability of Ti 2 S 4 in water are necessary for initiating the chemical reinjection reaction to form Cu x Ti 2 S 4 .

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Electrochemical and 119Sn Mössbauer study of sulfospinels as anode materials for lithium-ion batteries

Cited by 9 publications

References 22 publications

Physical investigation of the mechanisms of lithium insertion in sulfides as anode materials for lithium-ion batteries

Physical investigation of the mechanisms of lithium insertion in sulfides as anode materials for lithium-ion batteries

Improved electrode performance of mesoporous β-In2S3 microspheres for lithium ion batteries using carbon coated microspheres

Copper Extrusion/Reinjection in Cu-Based Thiospinels by Electrochemical and Chemical Routes

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