Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Venkatraman, S.; Manthiram, Arumugam

doi:10.1016/j.jssc.2004.08.019

Cited by 37 publications

(30 citation statements)

References 35 publications

(60 reference statements)

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“…[ 41,46 ] Due to the incorporation of H + into the oxide layers to form a OHO bonding, the layer stacking sequence of the LRMO‐PAA material could undergo a structural change from O3 to a more stable P3 lattice. [ 46–48 ] In turn, this structural stabilization explains the cause for the protonation reaction taking place between PAA and LRMO. Thought the Li + /H + exchange reaction is negative to Li + storage capacity, the present 10 wt% PAA‐treated sample (LRMO = PAA) without structure change provides only limited Li + /H + exchange, which has little influence on the capacity of LRMO.…”

Section: Resultsmentioning

confidence: 99%

“…[ 41,45 ] However, when increasing the concentration of PAA (50 wt% PAA treatment), a new peak emerged at 19.3° (Figure S4, Supporting Information), which is characteristic of proton insertion into the layered lattice. [ 41,46 ] Due to the incorporation of H + into the oxide layers to form a OHO bonding, the layer stacking sequence of the LRMO‐PAA material could undergo a structural change from O3 to a more stable P3 lattice. [ 46–48 ] In turn, this structural stabilization explains the cause for the protonation reaction taking place between PAA and LRMO.…”

Section: Resultsmentioning

confidence: 99%

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Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Yang

Zhong³

et al. 2020

Advanced Energy Materials

118

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Li‐rich manganese based oxides (LRMOs) are considered an attractive high‐capacity cathode for advanced Li‐ion batteries; however, their poor cyclability and gradual voltage fading have hindered their practical applications. Herein, an efficient and facile strategy is proposed to stabilize the lattice structure of LRMOs by surface modification of polyacrylic acid (PAA). The PAA‐coated LRMO electrode exhibits only 104 mV of the voltage fading after 100 cycles and 88% capacity retention over 500 cycles. The structural stability is attributed to the carboxyl groups in PAA chains reacting with oxygen species on the surface of LRMO to form a uniform and tightly coated film, which significantly suppresses the dissolution of transition metal elements from the cathode materials into the electrolyte. Importantly, a H+/Li+ exchange reaction takes place between the LRMO and PAA, generating a proton‐doped surface layer. Density functional theory calculations and experimental evidence demonstrates that the H+ ions in the surface lattice efficiently inhibit the migration of transition metal ions, leading to a stabilized lattice structure. This surface modification approach may provide a new route to building a stable Li‐rich oxide cathode with high capacity retention and low voltage fading for practical Li‐ion battery applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Yang

Zhong³

et al. 2020

Advanced Energy Materials

118

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“…These results indicate that the GC measurements can also be used for the detection of H 2 gases in any electrode that requires to be analyzed for structural stability1128. However, the focus of the present study is to just measure the evolved oxygen gas from the GC measurement and thereby evaluate the stability of the prepared layered- OLO cathodes.…”

Section: Resultsmentioning

confidence: 99%

An in-situ gas chromatography investigation into the suppression of oxygen gas evolution by coated amorphous cobalt-phosphate nanoparticles on oxide electrode

Gim

Song

Kim

et al. 2016

Sci Rep

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The real time detection of quantitative oxygen release from the cathode is performed by in-situ Gas Chromatography as a tool to not only determine the amount of oxygen release from a lithium-ion cell but also to address the safety concerns. This in-situ gas chromatography technique monitoring the gas evolution during electrochemical reaction presents opportunities to clearly understand the effect of surface modification and predict on the cathode stability. The oxide cathode, 0.5Li2MnO3∙0.5LiNi0.4Co0.2Mn0.4O2, surface modified by amorphous cobalt-phosphate nanoparticles (a-CoPO4) is prepared by a simple co-precipitation reaction followed by a mild heat treatment. The presence of a 40 nm thick a-CoPO4 coating layer wrapping the oxide powders is confirmed by electron microscopy. The electrochemical measurements reveal that the a-CoPO4 coated overlithiated layered oxide cathode shows better performances than the pristine counterpart. The enhanced performance of the surface modified oxide is attributed to the uniformly coated Co-P-O layer facilitating the suppression of O2 evolution and offering potential lithium host sites. Further, the formation of a stable SEI layer protecting electrolyte decomposition also contributes to enhanced stabilities with lesser voltage decay. The in-situ gas chromatography technique to study electrode safety offers opportunities to investigate the safety issues of a variety of nanostructured electrodes.

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“…From the weight loss, and knowing the final products, we could deduce that the formula of the sample is H 3.4 IrO 4 . [17] Having established the structural/physical properties of H 3.4 IrO 4 , we next probe its electrochemical activity versus Li + /Li in nonaqueous media and versus capacitive carbon in aqueous electrolyte. Due to the high redox potential of the H 3 IrO 4 phase, as we will see later, the material oxidizes water hence leading to a reduced H 3+x IrO 4 phase with x being slightly pH dependent.…”

Section: Resultsmentioning

confidence: 99%

Proton Ion Exchange Reaction in Li₃IrO₄: A Way to New H₃₊_xIrO₄ Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

Perez

Beer

Lin

et al. 2018

Advanced Energy Materials

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Progress over the past decade in Li‐insertion compounds has led to a new class of Li‐rich layered oxide electrodes cumulating both cationic and anionic redox processes. Pertaining to this new class of materials are the Li/Na iridate phases, which present a rich crystal chemistry. This work reports on a new protonic iridate phase H3+xIrO4 having a layered structure obtained by room temperature acid‐leaching of Li3IrO4. This new phase shows reversible charge storage properties of 1.5 e− per Ir atom with high rate capabilities in both nonaqueous (vs Li+/Li) and aqueous (vs capacitive carbon) media. It is demonstrated that Li‐insertion in carbonate LiPF6‐based electrolyte occurs through a classical reduction process (Ir5+ ↔ Ir3+), which is accompanied by a well‐defined structural transition. In concentrated H2SO4 electrolyte, this work provides evidence that the overall capacity of 1.7 H+ per Ir results from two additive redox processes with the low potential one showing ohmic limitations. Altogether, the room temperature protonation approach, which can be generalized to various Li‐rich phases containing either 3d, 4d or 5d metals, offers great opportunities for the judicious design of attractive electrode materials.

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Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Cited by 37 publications

References 35 publications

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

An in-situ gas chromatography investigation into the suppression of oxygen gas evolution by coated amorphous cobalt-phosphate nanoparticles on oxide electrode

Proton Ion Exchange Reaction in Li₃IrO₄: A Way to New H₃₊_xIrO₄ Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

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Investigation of the possible incorporation of protons into oxide cathodes during chemical delithiation

Cited by 37 publications

References 35 publications

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

An in-situ gas chromatography investigation into the suppression of oxygen gas evolution by coated amorphous cobalt-phosphate nanoparticles on oxide electrode

Proton Ion Exchange Reaction in Li3IrO4: A Way to New H3+xIrO4 Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

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Proton Ion Exchange Reaction in Li₃IrO₄: A Way to New H₃₊_xIrO₄ Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes