Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

Li, Bimei; Yuan, Zhongzhi; Xu, Ying; Liu, Jincheng

doi:10.1016/j.electacta.2016.09.071

Cited by 16 publications

(10 citation statements)

References 23 publications

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“…Another bottleneck limiting further application of Li-SOCl 2 batteries is their low-rate discharge performances. In recent decades, molecular catalysts such as transition metal-phthalocyanine complexes ,− have been employed in Li-SOCl 2 systems with the aim of enhancing electron transfer and/or avoiding radical dimerization during discharging. However, the challenge remains as the rate-determining step of discharge is unchanged.…”

Section: Introductionmentioning

confidence: 99%

Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Chen,

Li,

et al. 2023

J. Am. Chem. Soc.

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Li-SOCl 2 batteries possess ultrahigh energy densities and superior safety features at a wide range of operating temperatures. However, the Li-SOCl 2 battery system suffers from poor reversibility due to the sluggish kinetics of SOCl 2 reduction during discharging and the oxidation of the insulating discharge products during charging. To achieve a high-power rechargeable Li-SOCl 2 battery, herein we introduce the molecular catalyst I 2 into the electrolyte to tailor the charging and discharging reaction pathways. The as-assembled rechargeable cell exhibits superior power density, sustaining an ultrahigh current density of 100 mA cm −2 during discharging and delivering a reversible capacity of 1 mAh cm −2 for 200 cycles at a current density of 2 mA cm −2 and 6 mAh cm −2 for 50 cycles at a current density of 5 mA cm −2 . Our results reveal the molecular catalystmediated reaction mechanisms that fundamentally alter the rate-determining steps of discharging and charging in Li-SOCl 2 batteries and highlight the viability of transforming a primary high-energy battery into a high-power rechargeable system, which has great potential to meet the ever-increasing demand of energy-storage systems.

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Section: Introductionmentioning

confidence: 99%

Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Chen,

Li,

et al. 2023

J. Am. Chem. Soc.

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“…[1][2][3][4] It is widely used in civil meter, petroleum exploration, wireless network, military weapon, and medical equipment. [5][6][7][8] The cathodes of the batteries generally adopt the porous carbon. Porous carbon not only has excellent conductivity, but also is beneficial to ease the immersion of the electrolyte and support more cathodic products.…”

mentioning

confidence: 99%

Enhanced Nucleation of LiCl during Lithium Battery Discharging with Carbon Nanotubes Supported Nitrogen-Rich Manganese Phthalocyanine Catalysts

Zhu

Liu

et al. 2020

J. Electrochem. Soc.

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Large-size LiCl particles deposited on the carbon cathode of lithium thionyl chloride battery during discharge are mainly limited by the sluggish kinetics, decreasing the voltage platform and service life. In this work, the carbon nanotubes supported nano-sized nitrogen-rich manganese phthalocyanine composites (MnTAP/CNTs) were prepared by in situ solid phase synthesis as catalysts. The effect of reaction kinetics of the battery with/without catalysts on nucleation process of LiCl particles is investigated. After discharge, the surface of the carbon cathode with MnTAP/CNTs displays LiCl particles approximately 200 nm, which is only a fifth of the size without catalysts. Moreover, a large number of nano LiCl particles appear inside compared to the catalyst free. The fast reaction kinetics of SOCl 2 with MnTAP/CNTs is favorable for the nucleation of LiCl particles. Meanwhile, the electrolyte resistance, the surface film resistance and the charge transfer resistance of the battery are reduced to approximately 57%, and the discharge time and voltage platform are 15.6 min and 0.2 V higher than that without catalysts.

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“…[1][2][3] In fact, however, the energy of Li-SOCl 2 battery is far below the theoretical value, which seriously hinders its wide application. 4 Later the researchers 5 found that reduction occurred when SOCl 2 was adsorbed by the porous carbon cathode: 2SOCl 2 + 4e − → S + SO 2 + 4Cl − . The porous carbon cathode material can be used as both a carrier for SOCl 2 and a catalyst for the reduction reaction of SOCl 2 .…”

mentioning

confidence: 99%

“…And the soluble transition metal macrocyclic compounds catalysts are deposited at the anode surface by migration, which usually increase the corrosion rate of the lithium anode thus make the anode protective film thicker limiting its practical application. 5 N-doped carbon is then used as a highly efficient electrocatalyst in lithium cells, where N-doped carbon is obtained by thermal decomposition of carbonaceous materials mixed with nitrogen-containing precursors. 13,14 Zheng et al 15 introduced pyrolyzed N-doped carbon materials, confirming the presence of carbon structural defects and the creation of new active sites after N doping.…”

mentioning

confidence: 99%

Highly Efficient and Non-Precious Metal for the Li-SOCl₂ Battery Using Nitrogen Doped Carbon Supported Cu Nanoparticles

Du¹,

Guan²,

Liu³

et al. 2019

J. Electrochem. Soc.

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For lithium thionyl chloride batteries, the catalytic activity of the cathode material plays a crucial role in its electrochemical performance. In this paper, a poly (1-vinyl-3-methylimidazolium dicyanamide) ionic liquid (PIL) is selected as precursor to support CuO nanoparticles, and an efficient, non-precious metal nitrogen doped carbon supported Cu nanoparticles (N-C@Cu) composite material is designed and prepared for the lithium thionyl chloride battery cathode catalyst. X-ray diffraction (XRD) and high-resolution transmission electron microscope (HRTEM) verified that the supported CuO nanoparticles is reduced to Cu via carbon which formed from the thermally decompose of PIL. X-ray photoelectron spectroscopy (XPS) images confirm the existence of nitrogen doped carbon and Cu nanoparticles. Raman spectroscopy also demonstrate that the interaction between Cu and N-C provides more active sites. The N-C@Cu composite catalyst exhibits excellent activity in the reduction process of thionyl chloride, as can be seen from the materials display characteristics of lower discharge over-potential, and improved electron transfer of its rate-determining step. The rate performance, operating voltage and discharge capacity are all improved.

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Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

Cited by 16 publications

References 23 publications

Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Enhanced Nucleation of LiCl during Lithium Battery Discharging with Carbon Nanotubes Supported Nitrogen-Rich Manganese Phthalocyanine Catalysts

Highly Efficient and Non-Precious Metal for the Li-SOCl₂ Battery Using Nitrogen Doped Carbon Supported Cu Nanoparticles

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Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

Cited by 16 publications

References 23 publications

Transforming a Primary Li-SOCl2 Battery into a High-Power Rechargeable System via Molecular Catalysis

Transforming a Primary Li-SOCl2 Battery into a High-Power Rechargeable System via Molecular Catalysis

Enhanced Nucleation of LiCl during Lithium Battery Discharging with Carbon Nanotubes Supported Nitrogen-Rich Manganese Phthalocyanine Catalysts

Highly Efficient and Non-Precious Metal for the Li-SOCl2 Battery Using Nitrogen Doped Carbon Supported Cu Nanoparticles

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Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Transforming a Primary Li-SOCl₂ Battery into a High-Power Rechargeable System via Molecular Catalysis

Highly Efficient and Non-Precious Metal for the Li-SOCl₂ Battery Using Nitrogen Doped Carbon Supported Cu Nanoparticles