A synergistic “cascade” effect in copper zinc tin sulfide nanowalls for highly stable and efficient lithium ion storage

Chiu, Jian-Ming; Chou, Tsu‐Chin; Wong, Deniz; Lin, Yen-Chih; Shen, Chung‐Hua; Hy, Sunny; Hwang, Bing‐Joe; Tai, Yian; Wu, Heng‐Liang; Chen, Li‐Chyong; Chen, Kuei‐Hsien

doi:10.1016/j.nanoen.2017.12.020

Cited by 26 publications

(31 citation statements)

References 41 publications

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“…The proposed “buffer” role of Li 2 S is well reported,,, however to our knowledge no studies of the effect of continued formation and deformation of this Li 2 S have been carried out. In fact, standard testing procedures in existing studies of CAMs involve simply extended cycling over the entire voltage, encompassing all mechanisms/processes ,,,. The lower stability of the 3.9–2.5 V cell here indicates that this standard procedure is not optimum for extracting maximum capacity, and may in fact be significantly underestimating the capacity retention capabilities of CAMs.…”

Section: Resultsmentioning

confidence: 92%

“…Based on the presence of multiple plateaus in the first delithiation, and a large change in electrochemical characteristics between the 1 st and 2 nd cycles,,, it was concluded that the individual metal sulfides (Cu 2 S, ZnS and SnS 2 ) rather than CZTS, were formed at this stage. In subsequent lithiations, the conversion process in Equation (3) therefore separates into Equations (6), (7) and :

true C u_{2} S + 2 L i \to 2 C u + L i_{2} S

true S n S_{2} + 4 L i \to S n + 2 L i_{2} S

true Z n S + 2 L i \to Z n + L i_{2} S

…”

Section: Resultsmentioning

confidence: 99%

“…It has also been proposed that these ternary/quaternary systems provide even greater accommodation of volume expansion and enhanced conductivity when compared with binary analogues ,. Materials based on this formulation, such as CuSnS 3 ,, Cu 3 BiS 3 , CuSbS 2 ,, CuInZnS and Cu 2 ZnSnS 4 have demonstrated multiple reversible lithiation steps, with measured capacities up to 1,400 mAh g −1 …”

Section: Introductionmentioning

confidence: 99%

“…The contributions of the various lithiation/delithiation processes in a CAM are not typically analyzed individually but rather the sum total of gravimetric capacity is solely reported. This means that valuable insights into the sources of capacity, and the causes of capacity degradation under extended cycling, are therefore overlooked ,,. These insights would prove useful in the design of new, more stable materials which maximize usable energy density.…”

Section: Introductionmentioning

confidence: 99%

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Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

2018

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Here we report an interesting observation on anode materials for lithium ion batteries that undergo combined conversion and alloying lithiation processes during cycling (CAMs). These materials are generating interest as low cost and high capacity alternatives to graphite. We find that common testing protocols (CTPs) are unsuitable for assessment of CAMs due to their distinct multi‐step lithiation characteristics. CTPs involve reporting total gravimetric capacity in a half‐cell configuration alone (opposite Li foil), without individual analysis of each process; energy density and the problems associated with wide discharge voltages are not addressed. Through isolating the individual lithiation processes of a model system (Cu2ZnSnS4), we determine that the conversion processes are highly unstable, whereas the alloying processes exhibit remarkable capacity retention. We demonstrate that inclusion of the conversion processes in cycling actually reduced full cell energy density when compared with alloying alone. This indicates that CTPs may well underestimate the stability of CAMs. It is apparent that the true advantage of CAMs lies in the synergistic combination of the capacity of the alloying portion, and the stability provided by the uncycling Li2S buffer material. Finally, we prescribe a set of testing protocols for a meaningful assessment of new CAMs.

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Section: Resultsmentioning

confidence: 92%

true C u_{2} S + 2 L i \to 2 C u + L i_{2} S

true S n S_{2} + 4 L i \to S n + 2 L i_{2} S

true Z n S + 2 L i \to Z n + L i_{2} S

…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

2018

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“…[1,2] Transition metal oxides (TMOs) and sulfides (TMSs) have triggered much interesti nt he last decadea sc ompetitive alternatives to replacet he graphite anode,o wing to their high theoretical capacities and abundance. [3][4][5][6][7][8][9][10][11][12][13][14][15][16] Although effective nanoengineering strategies for morphological and structuralc ontrol and coupling with carbon materials have been developed, [3][4][5][6][7][8][9] their rate capability still suffers from low electrical conductivity ands luggish lithium inter-calation-deintercalation kinetics. The lithium storage mechanism of conversion reaction and alloying, which result in inevitable volumec hanges, also hindert he application of TMOs and TMSs and certainly shorten cycling life.…”

Section: Introductionmentioning

confidence: 99%

VS₄‐Decorated Carbon Nanotubes for Lithium Storage with Pseudocapacitance Contribution

Wang

Zang

et al. 2019

ChemSusChem

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The application of metal oxides and sulfides for lithium‐ion batteries (LIBs) is hindered by the limited Li+ diffusion kinetics and inevitable structural damage. Pseudocapacitance for electrochemical lithium storage provides an effective and competitive solution for developing electrode materials with large capacity, high rate capability, and stability. Herein, a composite composed of VS4 nanoplates tightly bound to carbon nanotubes (VS4/CNTs) is developed to demonstrate pseudocapacitance‐assisted lithium storage. The texture of the assembled VS4 nanoplates supplies efficient electrolyte/ion diffusion, as well as exposed surface for pseudocapacitive behavior. The effective coupling between VS4 and CNTs ensures fast electron transfer and high stability. The VS4/CNTs anode exhibits high capacity of 1144 mAh g−1 at 0.1 A g−1, superior cycling stability (capacity retention of 100 % at 1 A g−1 after 400 cycles), and good rate capability. The pseudocapacitive behavior plays an important role in determining the excellent electrochemical properties, contributing to the increased charge rate and reaching as high as 42 % of the total charge at a scan rate of 1 mV s−1. This study demonstrates the potential application of metal sulfides with pseudocapacitive contribution in LIBs.

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A Passionfruit‐Like Carbon‐Confined Cu₂ZnSnS₄ Anode for Ultralong‐Life Sodium Storage

Sun

Zhang

et al. 2021

Advanced Energy Materials

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Recent years have witnessed the flourish of lithium-ion batteries (LIBs) in the energy storage markets, ranging from smart vehicles to portable electronic devices. This is because LIBs feature a long cycling lifetime and prominent energy densities. Nevertheless, the limited lithium sources on the earth impose restrictions on the application of LIBs in our daily life. [1] As a next-generation alternative energy storage system to LIBs, sodium-ion batteries (SIBs) have received considerable attention, owing to the natural abundance of Na sources and more importantly their similar energy storage mechanisms to LIBs. [2] However, the ionic radius of a Na + ion (1.02 Å) is larger than that of a Li + ion (0.76 Å), resulting in the huge volume expansion and sluggish electrochemical reaction kinetics during the SIB charge/discharge process. [3] To develop and configure highperformance SIBs, the design of highly stable SIB anode materials is thus of great significance.Recently, various 2D materials (e.g., MXenes, MXene composites, [4] metal-organic frameworks and their derivatives) [5] and 3D ones (e.g., carbon materials) [6] have been explored as the SIB anode candidates. Besides them, transition metal sulfides (TMSs) have been frequently applied, owing to their chemical/ structural stability, low cost, and eco-friendliness. [7] The open architectures of TMSs also provide the facilitations in ionic mobility for the insertion/desertion and diffusion of Na + ions. Such a reaction mechanism in the TMSs has been revealed as a multistep process, including conversion and alloying/dealloying reactions. These reactions guarantee the outstanding theoretical capacities and relatively considerable redox reversibility that is benefited from the weak MS bonds. During the long-term cycling, the conversion reaction in TMSs (MS 2 + 4Na + → M + 2Na 2 S) inevitably leads to severe volume expansion of the TMS anodes. Their drastic construction collapses and thus sharp decays of the capacities occur. It is also known that the alloying-dealloying process at a lower redox potential followed by the conversion reaction always depends upon the alloy formation ability of sodium and metal. [8] However, owing to the poor electrical conductivity, drastic volume changes, and sluggish sodium diffusion kinetics, the limited cycling lifespan and inferior cycling performance of TMSs, these SIBs are still far from what is expected for their scale-up production.The sodium-ion battery (SIB) is one of the new generation of electrochemical energy storage devices, although its life-time needs to be improved. To assemble an SIB with an ultralong life-time, passionfruit-like Cu 2 ZnSnS 4 nanoparticles confined with nitrogen-doped carbon (CZTS@C) are synthesized. As an alternative anode for an SIB, the CZTS@C anode exhibits a reversible capacity of 461 mA h g −1 at a current density of 50 mA g −1 after 140 charge/ discharge cycles and excellent cycling stability (e.g., a capacity of 146 mA h g −1 at 4 A g −1 even after 1000 charge/discharge cycles). Such high pe...

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A synergistic “cascade” effect in copper zinc tin sulfide nanowalls for highly stable and efficient lithium ion storage

Cited by 26 publications

References 41 publications

Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

VS₄‐Decorated Carbon Nanotubes for Lithium Storage with Pseudocapacitance Contribution

A Passionfruit‐Like Carbon‐Confined Cu₂ZnSnS₄ Anode for Ultralong‐Life Sodium Storage

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A synergistic “cascade” effect in copper zinc tin sulfide nanowalls for highly stable and efficient lithium ion storage

Cited by 26 publications

References 41 publications

Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

Common Battery Anode Testing Protocols Are Not Suitable for New Combined Alloying and Conversion Materials

VS4‐Decorated Carbon Nanotubes for Lithium Storage with Pseudocapacitance Contribution

A Passionfruit‐Like Carbon‐Confined Cu2ZnSnS4 Anode for Ultralong‐Life Sodium Storage

Contact Info

Product

Resources

About

VS₄‐Decorated Carbon Nanotubes for Lithium Storage with Pseudocapacitance Contribution

A Passionfruit‐Like Carbon‐Confined Cu₂ZnSnS₄ Anode for Ultralong‐Life Sodium Storage