Controlling Residual Lithium in High‐Nickel (&gt;90 %) Lithium Layered Oxides for Cathodes in Lithium‐Ion Batteries

Seong, Won Mo; Cho, Kwang‐Hwan; Park, Ji Won; Park, Hyeokjun; Eum, Donggun; Lee, Myeong Hwan; Kim, Il‐seok Stephen; Lim, Jongwoo; Kang, Kisuk

doi:10.1002/ange.202007436

Cited by 6 publications

(6 citation statements)

References 48 publications

(53 reference statements)

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“…38,40 This theoretical and experimental η charge discrepancy is due to the potential required to decompose the side product of lithium carbonate (including Li 2 CO 3 ) formed during discharge, which has been detected as the main side product of many transition metal oxides (including Co 3 O 4 ). 45,46 The decomposition voltage of lithium carbonate is about 4.0−4.5 V (vs RHE) in experiment, 46,47 which corresponds to η charge ≈ 1−1.5 V in Li−air batteries. Therefore, in order to decrease the large η charge (toward Li−air batteries) observed in realistic battery prototypes, it is more important to deal with the formation of the side product lithium carbonate rather than the decomposition of Li 2 O 2 on the Co 3 O 4 cathode.…”

Section: ■ Introductionmentioning

confidence: 98%

Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte

Jiang

Rappe

2021

J. Phys. Chem. C

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The lithium−air battery, a powerful competitor to replace the traditional lithium-ion battery, has attracted increasing attention due to its extremely high theoretical energy density. However, its development is limited by the cathode and electrolyte properties, which should include high stability, conductivity, and electrocatalytic properties in oxygen-rich environments. Here, we employ a systematic first-principles study of Li−O 2 discharge and charge reactions on the Co 3 O 4 -based cathode with the assistance of dimethyl sulfoxide (DMSO) electrolyte. The structure, stability, and electronic properties of different surface reconstructions of the Co 3 O 4 (100) facet are investigated. In addition, the mechanisms and thermodynamic overpotentials of multi-step reactions between Li + /e − and O 2 are provided, where lithium suboxide products (Li 2 O 2 or Li 3 O 2 ) are formed on the different Co 3 O 4 (100) terminations. The solvation shell of Li + components in explicit DMSO solvent is investigated through ab initio molecular dynamics simulations. In general, we find that the Co 3 O 4 (100)-O (oxidized) surface is the most stable one under standard conditions, and the stable Li + solvation structure is found in a tetrahedral Li(DMSO) 4 + shell in the DMSO-based electrolyte. Moreover, in the system of the Co 3 O 4 (100)-O cathode and DMSO electrolyte, the solution model pathway is energetically favorable for the Li−O 2 discharge reaction. It provides a low constant overpotential of 0.17 V during a long-term discharging process, thus causing the final toroid Li 2 O 2 formation on the cathode. During the charging process, an overpotential of 0.36 V is required to rapidly decompose Li 2 O 2 .

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Section: ■ Introductionmentioning

confidence: 98%

Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte

Jiang

Rappe

2021

J. Phys. Chem. C

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“…Recently, studies of the dry coating process of high-Ni layered oxides have been extensively conducted to mitigate these issues. 16,17,28 However, the formation and removal mechanisms of each of the LiOH and Li 2 CO 3 species on high-Ni layered oxides have rarely been studied. Preparing the analyte in water for titration to determine the residual lithium content is accompanied by leaching of Li from high-Ni layered cathode materials.…”

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confidence: 99%

Unraveling the Intricacies of Residual Lithium in High-Ni Cathodes for Lithium-Ion Batteries

et al. 2021

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High-nickel layered oxide cathodes suffer seriously from the formation of residual lithium on the surface, which causes notorious issues, such as slurry gelation and gas evolution. Due to the use of water for the titration to determine the residual lithium content, certain practical issues remain unresolved. We present here, for the first time, a thorough study of residual lithium that reveals the following. (1) Li 2 CO 3 impurity in lithium raw materials contributes to an increase in residual lithium in high-Ni cathodes after synthesis. (2) LiOH formed due to a leaching of Li from high-Ni cathodes during analyte preparation in water exaggerates the LiOH content in residual lithium (employing a new titration method). (3) A dry cobalt hydroxide coating on high-Ni cathodes not only effectively reduces residual lithium content but also leads to the formation of a Co-rich concentration gradient layer on the surface that suppresses Li leaching when in contact with water.

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“…Coatings that preemptively convert residual Li 2 O, which is the precursor for surface residual Li impurities, into more stable compounds will inevitably reduce CO 2 production from Li 2 CO 3 . [36,71] This is promising, as the reduction in surface residual Li will also enhance the manufacturability of high-Ni electrodes by minimizing gelation during the slurry casting process. On the other hand, certain coatings are also known to chemically scavenge HF or form well-known beneficial electrolyte additives like LiPO 2 F 2 .…”

Section: Gas Evolution From the Cathode With Various Dopants And Surf...mentioning

confidence: 99%

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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Controlling Residual Lithium in High‐Nickel (>90 %) Lithium Layered Oxides for Cathodes in Lithium‐Ion Batteries

Cited by 6 publications

References 48 publications

Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte

Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte

Unraveling the Intricacies of Residual Lithium in High-Ni Cathodes for Lithium-Ion Batteries

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

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Controlling Residual Lithium in High‐Nickel (>90 %) Lithium Layered Oxides for Cathodes in Lithium‐Ion Batteries

Cited by 6 publications

References 48 publications

Mechanistic Study of the Li–Air Battery with a Co3O4 Cathode and Dimethyl Sulfoxide Electrolyte

Mechanistic Study of the Li–Air Battery with a Co3O4 Cathode and Dimethyl Sulfoxide Electrolyte

Unraveling the Intricacies of Residual Lithium in High-Ni Cathodes for Lithium-Ion Batteries

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

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Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte

Mechanistic Study of the Li–Air Battery with a Co₃O₄ Cathode and Dimethyl Sulfoxide Electrolyte