Operation of Layered LiCoO<sub>2</sub> to Higher Voltages with a Localized Saturated Electrolyte

Adamo, J. Brandon; Su, Laisuo; Manthiram, Arumugam

doi:10.1021/acsami.2c22786

Cited by 7 publications

(3 citation statements)

References 40 publications

(103 reference statements)

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“…This assumption for Co is based upon the voltage curves for high‐voltage LiCoO 2 relative to LiNiO 2 . [ 64 ] Remarkably, similar Ni oxidation states of 3.93 + , 3.93 + , 3.93 + , and 3.88 + are calculated for, respectively, LNO, NC‐95, NA‐95, and NM‐95. In fact, gas evolution from all nine cathodes is found to initiate at Ni oxidation states of ≈3.85 + .…”

Section: Mitigation Strategies For the Suppression Of Gas Evolutionmentioning

confidence: 53%

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Sim,

Manthiram

2024

Advanced Energy Materials

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Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO2, O2, and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.

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Section: Mitigation Strategies For the Suppression Of Gas Evolutionmentioning

confidence: 53%

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Sim,

Manthiram

2024

Advanced Energy Materials

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“…In both steps, the sample was naturally cooled down to room temperature where the ramping rate was 5 °C min −1 . [69] Materials Characterization: The structural and morphological analyses of the cathodes and Cu foils were achieved by XRD (Rigaku Miniflex 600, Cu K𝛼 target, 𝜆 = 1.54 Å) and SEM (FEI Quanta 650 ESEM). The XRD patterns were collected between 10°and 80°with a step size of 0.02°and scan rate of 4°min −1 .…”

Section: Methodsmentioning

confidence: 99%

“…In both steps, the sample was naturally cooled down to room temperature where the ramping rate was 5 °C min −1 . [ 69 ]…”

Section: Methodsmentioning

confidence: 99%

Effect of Electrochemical Pre‐Lithiation on Layered Oxide Cathodes for Anode‐Free Lithium‐metal Batteries

Vanaphuti,

Su,

Manthiram

2023

Small Methods

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Due to high energy density and lower manufacturing cost, anode‐free lithium‐metal batteries (AFLMBs) are attracting increasing attention. The challenges for developing them lie in inferior Coulombic efficiency and short cycle life due to the highly reactive lithium metal. Herein, an electrochemical pre‐lithiation strategy is applied to layered oxide cathodes, specifically LiNiO2 and LiCoO2, aiming to provide an additional lithium source and understand the effect on the cathode structure for AFLMBs. The mechanism for accommodating the excess Li depends on the structural stability of the cathodes where LiNiO2 forms lithiated Li2NiO2 with the excess lithium in the crystalline lattice while the excess lithium in LiCoO2 forms a Li2O phase. More importantly, an optimal amount of Li excess is necessary to maintain decent cycle stability and specific capacity in AFLMB, with 40% excess Li for LiNiO2 and 150% for LiCoO2. While the pre‐lithiation process causes particle pulverization depending on the amount of Li excess, LiCoO2 offers a much better cycle performance than LiNiO2 with a promising capacity retention of 80% after 300 cycles in AFLMB (vs 76% after 100 cycles for 40% Li excess in LiNiO2). This study provides a promising avenue for developing tailor‐made layered oxide cathodes for AFLMBs.

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Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte

Darga,

Manthiram

2024

Adv Funct Materials

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Sodium layered oxide cathodes can uniquely benefit from the existing lithium‐ion battery industry as sodium‐ion batteries gain traction as a potential low‐cost, drop‐in replacement. However, achieving relevant energy density with a suitable cycle life remains a challenge for sodium layered oxides. At high operating potentials, several competing degradation mechanisms prevent P2‐type Na2/3Ni1/3Mn2/3O2 (≈550 Wh kg−1) from achieving meaningful cycle life—with bulk structural instability and surface reactivity being the primary retractors. Herein, the issue of particle cracking is addressed through detailed synthesis methods of “single‐crystal” materials. By comparison to a polycrystalline baseline, the single‐crystal materials quantify the capacity loss due to isolation of active material caused by intergranular particle cracking. The single crystal materials are then employed in cells with an advanced, “localized saturated electrolyte” (LSE) to demonstrate the magnitude of capacity loss due to electrolyte decomposition at the cathode surface. Mitigation of the surface reactivity through the LSE electrolyte effectively demonstrates the elevated importance of surface reactivity at high voltages despite the onset of egregious particle cracking. This work aims to guide future research into understanding molten‐salt assisted syntheses and advance the debate on surface versus bulk degradation.

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Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Cited by 7 publications

References 40 publications

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Effect of Electrochemical Pre‐Lithiation on Layered Oxide Cathodes for Anode‐Free Lithium‐metal Batteries

Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte

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Operation of Layered LiCoO2 to Higher Voltages with a Localized Saturated Electrolyte

Cited by 7 publications

References 40 publications

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Effect of Electrochemical Pre‐Lithiation on Layered Oxide Cathodes for Anode‐Free Lithium‐metal Batteries

Deconstructing the High Voltage Degradation Mechanisms in Na2/3Ni1/3Mn2/3O2 with Single Crystals and Advanced Electrolyte

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Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte