High electrochemical performance and lithiation–delithiation phase evolution in CuO thin films for Li-ion storage

Chen, Wenhao; Zhang, Hong; Ma, Zhiyuan; Yang, Bao; Li, Zhicheng

doi:10.1039/c5ta02524a

Cited by 56 publications

(18 citation statements)

References 51 publications

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“…However, at the end of first cycle (delithiation), Cu 4 O 3 was observed to be major phase while Cu 2 O and CuO were minor phase. Cu 4 O 3 has been observed before in thin‐film electrodes by TEM and here we observed Cu 4 O 3 phase in composite electrodes. At the end of delithiation, most of the composite electrodes show reversible Cu 2 O phase rather than Cu 4 O 3 ,, which explains the high capacity reported in the present work.…”

Section: Introductionsupporting

confidence: 85%

Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

et al. 2017

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Conversion materials with high specific capacity are of interest to improve energy density of Li‐ion batteries. Here, we present results concerning hydrothermally synthesized CuO nanoplates that exhibit high specific capacity of 800 and 698 mAh/g at C/2 and 1C rates respectively and 180 mAh/g at a high rate of 30C. The electrodes exhibit high Coulombic efficiencies of about 66% and 60% at C/2 and 1C rate respectively, these are high efficiency values compared to the ones reported in the literature at respective rates. To understand the high performance, ex situ x‐ray diffraction at different states of first discharge/charge is utilized that shine light on the lithiation/delithiation pathways of the CuO nanoplates. Lithiation proceeds through multiple phase transition CuO → Cu4O3 → Cu2O → Cu and it was found that Cu4O3 is reversible at the end of first charge. Cu and residual Cu2O was observed at the end of lithiation along with Li2O and Li2O2 phases. At the end of first charge, Cu4O3 phase along with CuO was observed as a major end‐product with relatively minor concentrations of Cu2O. Cu4O3 as a major constituent observed in composite electrode seems to be the key information that can explain good reversibility and high Coulombic efficiency reported in the present work.

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Section: Introductionsupporting

confidence: 85%

Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

et al. 2017

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“…In terms of the electrochemical reaction characteristics, as the lithium-ion storage electrodes deposited CuO thin film to enlarge the storage properties, the Cu 4 O 3 phase appears. It is found that Cu 4 O 3 plays an important role in the reversible electrochemical reactions that take place during the charging process (Chen et al, 2015). Recently, Wang et al have successfully synthesized Cu 4 O 3 particles for the first time using a facile wet chemical method and investigated the formation mechanism based on a series of control experiments (Wang et al, 2018).…”

Section: Resultsmentioning

confidence: 99%

Solid/liquid-interface-dependent synthesis and immobilization of copper-based particles nucleated by X-ray-radiolysis-induced photochemical reaction

Yamaguchi

Sakurai²,

Okada³

et al. 2020

J Synchrotron Radiat

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X-ray-radiolysis-induced photochemical reaction of a liquid solution enables the direct synthesis and immobilization of nano/micro-scale particles and their aggregates onto a desired area. As is well known, the synthesis, growth and aggregation are dependent on the pH, additives and X-ray irradiation conditions. In this study, it was found that the topography and composition of synthesized particles are also dependent on the types of substrate dipped in an aqueous solution of Cu(COOCH3)2 in the X-ray-radiolysis-induced photochemical reaction. These results are attributed to the fact that a secondary electron induced by the X-ray irradiation, surface or interface on which the particles are nucleated and grown influences the particle shape and composition. This study will shed light on understanding a novel photochemical reaction route induced under X-ray irradiation. The development of this process using the X-ray-radiolysis-induced photochemical reaction in aqueous liquids enables us to achieve the rapid and easy operation of the synthesis, growth and immobilization of special nano/micro-scale complex materials or multifunctional composites.

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“…The Li 2 O signal, observed in both Li-plated and exposed Cu areas, is an indication for reduction of the Cu oxides prior to or during Li plating ( Figures 9 b and 9 d). 33 , 41 The masking of the Cu 2p and O 1s signals of Cu oxides and the negative shift of the Cu 2p peaks were assigned to the lithiation of the Cu oxides ( Figures S15 and S20 ), which could be a possible reason for the thickening of the SEI at 1.4 V. 31 In addition, LiF could be a product of the Cu oxide reduction at 2–1.4 V ( reactions 4 and 5 ). 22 …”

Section: Discussionmentioning

confidence: 99%

Toward an Understanding of SEI Formation and Lithium Plating on Copper in Anode-Free Batteries

et al. 2021

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“Anode-free” batteries present a significant advantage due to their substantially higher energy density and ease of assembly in a dry air atmosphere. However, issues involving lithium dendrite growth and low cycling Coulombic efficiencies during operation remain to be solved. Solid electrolyte interphase (SEI) formation on Cu and its effect on Li plating are studied here to understand the interplay between the Cu current collector surface chemistry and plated Li morphology. A native interphase layer (N-SEI) on the Cu current collector was observed with solid-state nuclear magnetic resonance spectroscopy (ssNMR) and electrochemical impedance spectroscopy (EIS). Cyclic voltammetry (CV) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) studies showed that the nature of the N-SEI is affected by the copper interface composition. An X-ray photoelectron spectroscopy (XPS) study identified a relationship between the applied voltage and SEI composition. In addition to the typical SEI components, the SEI contains copper oxides (Cu x O) and their reduction reaction products. Parasitic electrochemical reactions were observed via in situ NMR measurements of Li plating efficiency. Scanning electron microscopy (SEM) studies revealed a correlation between the morphology of the plated Li and the SEI homogeneity, current density, and rest time in the electrolyte before plating. Via ToF-SIMS, we found that the preferential plating of Li on Cu is governed by the distribution of ionically conducting rather than electronic conducting compounds. The results together suggest strategies for mitigating dendrite formation by current collector pretreatment and controlled SEI formation during the first battery charge.

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High electrochemical performance and lithiation–delithiation phase evolution in CuO thin films for Li-ion storage

Cited by 56 publications

References 51 publications

Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

Solid/liquid-interface-dependent synthesis and immobilization of copper-based particles nucleated by X-ray-radiolysis-induced photochemical reaction

Toward an Understanding of SEI Formation and Lithium Plating on Copper in Anode-Free Batteries

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High electrochemical performance and lithiation–delithiation phase evolution in CuO thin films for Li-ion storage

Cited by 56 publications

References 51 publications

Reversible Cu4O3 Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

Reversible Cu4O3 Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

Solid/liquid-interface-dependent synthesis and immobilization of copper-based particles nucleated by X-ray-radiolysis-induced photochemical reaction

Toward an Understanding of SEI Formation and Lithium Plating on Copper in Anode-Free Batteries

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Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency

Reversible Cu₄O₃ Phase Formation in CuO Nanoplate Anodes for High Capacity and High Coulombic Efficiency