Copper Selenide as a New Cathode Material based on Displacement Reaction for Rechargeable Magnesium Batteries

Tashiro, Yuta; Taniguchi, Kouji; Miyasaka, Hitoshi

doi:10.1016/j.electacta.2016.05.202

Cited by 92 publications

(76 citation statements)

References 38 publications

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“…The reversibility of conversion reaction could be well‐explained by hard and soft acids and bases theory. Since X 2 n − anion is bonded with bivalent Mg 2+ ion (hard acid), using soft X 2 n − anions (such as S 2− and Se 2− ) is expected to weaken the Mg—X bonds, and thus could improve the reversibility of conversion reaction . However, selection of M element is also of great significance.…”

Section: Introductionmentioning

confidence: 99%

“…A soft acid M 2 m + cation (such as Cu + ) would have a relatively stronger interaction with X n − anion and assist the dissociation of discharge product (Mg n X m ). For example, Cu 2 S and Cu 2 Se, which are combinations of soft‐acid cation (Cu + ) and soft‐base anion (S 2− and Se 2− ), show superior Mg‐storage performances as conversion cathodes . Therefore, a promising conversion cathode could be a combination of soft anions and soft cations.…”

Section: Introductionmentioning

confidence: 99%

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A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics

Zhang

Shen

et al. 2019

Energy Tech

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Rechargeable Mg batteries are attractive candidates for large‐scale energy storage batteries with high safety due to the low‐cost and non‐dendritic metallic Mg anode. However, exploring high‐performance cathode materials is blocking their development. Herein, a high‐rate rechargeable Mg battery is established with a AgCl cathode, delivering a high reversible capacity of 70.3 mAh g−1 at 100 mA g−1, an outstanding rate capability of 32.6 mAh g−1 at 1000 mA g−1, and a superior long‐term cyclability over 500 cycles. Further investigation of the mechanism demonstrates that a conversion reaction takes place between AgCl and metallic Ag0 for the cathode. The solid‐state Mg2+ diffusion coefficient is as high as 8.1 × 10−11 cm2 s−1, which would be the reason for the high rate capability. The current study reveals significant insights to select promising Mg‐storage conversion cathodes by a combination of soft anions and soft transition‐metal cations.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics

Zhang

Shen

et al. 2019

Energy Tech

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“…[12,13] Only several cathodes, for example, Cheverel phase, [4] layered TiS 2 , [14] thiospinel Ti 2 S 4 , [15] covellite CuS, [16] β-CuSe 2 , [17] and MgMSiO 4 olivine compounds (M = Fe, Co, and Ni), [2] display reversible Mg-ion storage properties. In following sections, we show how the microsized and high-capacity selenium electrode exhibits highly reversible magnesiation/de-magnesiation properties along with largely elongated cycling stabilities.…”

Section: Resultsmentioning

confidence: 99%

Self‐Established Rapid Magnesiation/De‐Magnesiation Pathways in Binary Selenium–Copper Mixtures with Significantly Enhanced Mg‐Ion Storage Reversibility

Zhang

Chen

et al. 2017

Adv Funct Materials

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“…It is worth noting that the S 2¹ sublattice of MgS is an fcc lattice similar to that of c-Cu 2¹x S. This situation implies that the reaction of c-Cu 2¹x S with Mg ions is ascribed to be of a displacement type wherein Mg 2+ ions diffuse into the S 2¹ sublattice of c-Cu 2¹x S to form MgS with the same fcc S 2¹ sublattice ( Figure S5), as observed in an Mg battery with the β-Cu 2 Se cathode. 15 Concomitantly, Cu + ions with high mobility are extruded from the S 2¹ sublattice and Cu metal appeared after a reduction reaction. An inverse reaction, i.e., exchanging Mg 2+ ions with Cu + ions, should accompany an oxidation reaction in the charging process.…”

Section: ¹1mentioning

confidence: 99%

“…Recently, based on the displacement reaction, we reported that β-Cu 2 Se is suitable as a cathode material for rechargeable Mg batteries. 15 In the discharge process for this material, Mg 2+ ions diffuse to the face-centered cubic (fcc) sublattice composed of Se 2¹ anions (i.e. a Se 2¹ sublattice) to induce a position displacement of Cu + ions that are reduced to Cu 0 (i.e., Cu metal) at the outside of the lattice, leading to the formation of MgSe (+2Cu 0 ).…”

mentioning

confidence: 99%

The Effect of Anion-sublattice Structure on the Displacement Reaction in Copper Sulfide Cathodes of Rechargeable Magnesium Batteries

2017

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Copper sulfides (Cu 2¹x S, where x denotes position defects) with different structures of the S 2¹ sublattice, such as cubic digenite and hexagonal chalcocite, have been investigated as cathode materials for magnesium (Mg) batteries. Rechargeable performance is only achieved using a cubic digenite cathode; however, using hexagonal chalcocite cathode yields poor rechargeable performance. The face-centered cubic S 2¹ sublattice in cubic digenite, which enables Cu + and Mg 2+ ions to be displaced from each other without causing the lattice to collapse, could play a key role in improving the performance of rechargeable cathodes.Keywords: Rechargeable magnesium battery | Anion-sublattice structure | Copper sulfide cathodeCurrently, a rechargeable lithium (Li)-ion battery is one of the key systems for energy storage.1,2 However, the growing demand for reduced cost and safety in energy storage for largescale applications has motivated the development of secondary batteries using non-Li cations. For this purpose, a magnesium (Mg) battery is one of the promising alternatives owing to its relatively high stability of magnesium metal upon air exposure and high terrestrial abundance. Despite their promising characteristics, the development of Mg batteries has been slow. In fact, although relevant materials have been extensively researched, only a limited number of transition metal compounds have been found as suitable materials for the insertion-type cathode of rechargeable Mg batteries. 312 One of the reasons for this is that Mg 2+ ions travel through the electrodes too slowly. This is due to the bivalent nature of Mg 2+ ions and their highly stable coordination with hard Lewis bases, as per the hard and soft Lewis acids and bases (HSAB) theory. 13 A new type of cathode materials should be developed for Mg batteries other than the insertion-type one.One promising approach is to research materials that enable the displacement reaction, which is a type of conversion reaction found in the study of Li-ion batteries.14 In this reaction, the insertion of guest cations induces the displacement and extrusion of transition metal cations from the original lattice sites, while maintaining the sublattice of anions. In this situation, the energy barrier caused by lattice strains should be suppressed such that the exchange of cations proceeds more smoothly in the reaction process than in most conversion reactions that require a reconstruction of the anion sublattice. Recently, based on the displacement reaction, we reported that β-Cu 2 Se is suitable as a cathode material for rechargeable Mg batteries. 15 In the discharge process for this material, Mg 2+ ions diffuse to the face-centered cubic (fcc) sublattice composed of Se 2¹ anions (i.e. a Se 2¹ sublattice) to induce a position displacement of Cu + ions that are reduced to Cu 0 (i.e., Cu metal) at the outside of the lattice, leading to the formation of MgSe (+2Cu 0 ). Importantly, the Se 2¹ sublattice in MgSe also has an fcc structure. This result suggested that a key factor for suc...

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Copper Selenide as a New Cathode Material based on Displacement Reaction for Rechargeable Magnesium Batteries

Cited by 92 publications

References 38 publications

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics

Self‐Established Rapid Magnesiation/De‐Magnesiation Pathways in Binary Selenium–Copper Mixtures with Significantly Enhanced Mg‐Ion Storage Reversibility

The Effect of Anion-sublattice Structure on the Displacement Reaction in Copper Sulfide Cathodes of Rechargeable Magnesium Batteries

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Copper Selenide as a New Cathode Material based on Displacement Reaction for Rechargeable Magnesium Batteries

Cited by 92 publications

References 38 publications

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg2+ Diffusion Kinetics

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg2+ Diffusion Kinetics

Self‐Established Rapid Magnesiation/De‐Magnesiation Pathways in Binary Selenium–Copper Mixtures with Significantly Enhanced Mg‐Ion Storage Reversibility

The Effect of Anion-sublattice Structure on the Displacement Reaction in Copper Sulfide Cathodes of Rechargeable Magnesium Batteries

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A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics

A High‐Rate Rechargeable Mg Battery Based on AgCl Conversion Cathode with Fast Solid‐State Mg²⁺ Diffusion Kinetics