Copper oxide cathodes for lithium organic electrolyte batteries

Podhájecký, P.; Scrosati, B.

doi:10.1016/0378-7753(85)80095-1

Cited by 23 publications

(6 citation statements)

References 4 publications

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“…The plateaus in the discharge profiles suggest a two-phase reaction mechanism, whereby growth of a new phase occurred at the expense of the initial phase, and not a single-phase reaction (i.e., lithiation in the form of solid solution). Also, as the brochantite particle size decreased, the discharge profiles became flatter, which is similar to what has been observed for particle size reduction in CuSO 4 • 5H 2 O 12 and CuO conversion electrodes, 19 indicating improved kinetics. At higher depths of discharge, the voltage followed a sloped profile from 1.5 to 1 V. This is similar to the sloped profile observed in Cu 2 O, which has been attributed to formation of Li 2 O and Cu 0 2 .…”

supporting

confidence: 84%

“…The values of the discharge potentials can be explained by the induction effect . For instance, the discharge voltage of brochantite is higher than that for CuO (1.35 V) , and Cu 2 O (1.5 V) but lower than that for CuSO 4 ·5H 2 O (3.2 V) . The discharge voltage for brochantite is slightly higher than that for copper oxides due to the presence of the more ionic sulfate and hydroxyl groups, but its lower number of sulfate anions gives it a lower voltage than for copper sulfate.…”

mentioning

confidence: 97%

“…In contrast, CuO electrodes show much better reversibility and form only small 3 nm particles at the end of discharge, which may be attributed to the lower mobility of O 2– anions and Cu cations in CuO preventing large Cu dendrite formation. Despite the better cycling characteristics in CuO, its discharge potential of ∼1.35 V versus Li/Li + is too low for its application as a cathode and too high to be used as an anode in lithium-ion battery applications.…”

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confidence: 99%

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Electrochemical Properties of Nanostructured Copper Hydroxysulfate Mineral Brochantite upon Reaction with Lithium

Zhao¹,

Yang²,

Miller

et al. 2013

Nano Lett.

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Cu-containing conversion electrodes have received much study as high capacity electrodes for lithium-ion batteries, but many suffer from poor reversibility. The electrochemical properties of the copper hydroxysulfate compound, Cu4(OH)6SO4, more commonly known as the mineral brochantite and as a patina constituent on the Statue of Liberty, were investigated. Nanostructured brochantite was synthesized using precipitation and microwave-assisted hydrothermal reactions and evaluated in half-cells with Li metal counter electrodes. Reversible capacities >400 mAh/g corresponding to the 2 electron reduction of Cu(2+) and discharge potential of 1.8 V versus Li/Li(+) were observed in brochantite with a nanoplate morphology. Detailed characterization using X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy was performed to better understand the conversion process.

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confidence: 84%

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confidence: 97%

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confidence: 99%

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Electrochemical Properties of Nanostructured Copper Hydroxysulfate Mineral Brochantite upon Reaction with Lithium

Zhao¹,

Yang²,

Miller

et al. 2013

Nano Lett.

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“…For this study we chose copper oxide (CuO) as electrode material, as it is considered as an attractive electrode material for LIBs and SIBs due to its low cost, environmental friendliness and high theoretical capacity (674 mAh g –1 ) ,,,,− and as it has already been applied in primary cells. − Table summarizes some general characteristics of the CuO electrode reaction with Na and Li. However, due to the issues discussed above, the electrode reaction is much more complex and requires detailed characterization.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Degradation Processes of CuO as Conversion Electrode for Sodium-Ion Batteries: An Electrochemical Study Combined with Pressure Monitoring and DEMS

et al. 2017

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Copper oxide (CuO) can be used as electrode material for lithium-ion and sodium-ion batteries; however, the path toward application for rechargeable systems is still long. This is mainly related to the complex nature of the electrode reaction and to aging mechanisms that are not well understood, especially in the case of sodium. The main subject of this paper is to compare the electrode reaction of CuO in lithium (CuO/Li) and sodium (CuO/Na) half-cells and to study side reactions in the CuO/Na system by means of differential electrochemical mass spectrometry (DEMS) and in situ pressure monitoring during galvanostatic cycling (PMGC). Electrode processes have been studied at different current densities and temperatures. In CuO/Li cells, CuO and Cu 2 O form during charging, their respective fraction depending on the current density. In case of CuO/Na, Cu 2 O is always the charging product although oxidation to CuO can be temporarily achieved by increasing the temperature to 50 °C. The difference between both CuO/Na and CuO/Li is related to the electrode volume expansion/shrinkage during cycling. Differences in the temporal evolution of electrode surface films are followed by electrochemical impedance spectroscopy (EIS). For the CuO/Na system, PMGC and DEMS studies reveal a periodic release of gaseous side products as a result of a slow but likely continuous electrolyte degradation. This degradation is due to the repeated formation of a surface film (discharge) and its partial dissolution (charge) accompanied by the release of H 2 and CO 2 . The degradation processes fade during cycling but remain dynamic. This means that a long cycle life of CuO electrodes in sodium-ion batteries can likely be only achieved by employing some excess electrolyte.

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“…In this study, we focus on the surface film formation and cell reaction of the conversion reaction between CuO thin films with lithium and sodium, respectively. CuO has been chosen, as it has been already applied in primary cells − and is currently also studied as thin film material for solar cells. Some of the authors have extended experience in preparing such films by sputtering methods. , …”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanism and Surface Film Formation of Conversion Materials for Lithium- and Sodium-Ion Batteries: An XPS Case Study on Sputtered Copper Oxide (CuO) Thin Film Model Electrodes

et al. 2016

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Charge storage based on conversion reactions is a promising concept to store electrical energy. Many studies have been devoted to conversion reactions with lithium; however, still many scientific questions remain due to the complexity of the reaction mechanism combined with surface film formation. Replacing lithium by sodium is an attractive approach to widen the scope of conversion reactions and to study whether the increase in ion size changes the reaction mechanisms and whether the cell performance benefits or worsens. In this study, we use thin film electrodes as a additive-free model system to study the conversion reaction of CuO with sodium (CuO/Na) by means of electrochemical methods, microscopy, and X-ray photoelectron spectroscopy. The reaction mechanism and film formation are being discussed. Some important differences to the analogue lithium-based system (CuO/Li) are found. Whereas CuO has been reported as charge product in CuO/Li cells, charging is incomplete in the case of CuO/Na and only Cu2O is formed. As an important finding, oxygen appears to be redox active and Na2O2 forms during charging from Na2O. Moreover, surface film formation due to electrolyte decomposition is much more severe as compared to CuO/Li. Depth profiling is used to probe the inner composition of the surface film, revealing a much thicker surface film with more inorganic components as compared to the lithium system. It is also found that the surface film disappears to a large extent during charging.

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Copper oxide cathodes for lithium organic electrolyte batteries

Cited by 23 publications

References 4 publications

Electrochemical Properties of Nanostructured Copper Hydroxysulfate Mineral Brochantite upon Reaction with Lithium

Electrochemical Properties of Nanostructured Copper Hydroxysulfate Mineral Brochantite upon Reaction with Lithium

Kinetics and Degradation Processes of CuO as Conversion Electrode for Sodium-Ion Batteries: An Electrochemical Study Combined with Pressure Monitoring and DEMS

Reaction Mechanism and Surface Film Formation of Conversion Materials for Lithium- and Sodium-Ion Batteries: An XPS Case Study on Sputtered Copper Oxide (CuO) Thin Film Model Electrodes

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