Trace level doping of lithium-rich cathode materials

Lengyel, Miklos; Shen, Kuan-Yu; Lanigan, Deanna; Martin, Jonathan; Zhang, Xiaofeng; Axelbaum, Richard L.

doi:10.1039/c5ta07764h

Cited by 22 publications

(12 citation statements)

References 27 publications

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“…This result indicates a larger degree of separation of the Li 2 MnO 3 and LiCoO 2 phases 44 as well as crystals with larger domain sizes crystals than the S-LMO material. Generally, lithium rich layered oxide materials often form a composite structure in terms of a phase separation between their Li 2 MnO 3 and LiCoO 2 components 4,45,46 . This result indicates that the crystal structures of the Li 2 MnO 3 and LiCoO 2 phases in the two materials are very similar and that their phase separation behaviors are significantly different.…”

Section: Resultsmentioning

confidence: 99%

Structural and Electrochemical Kinetic Properties of 0.5Li2MnO3∙0.5LiCoO2 Cathode Materials with Different Li2MnO3 Domain Sizes

Kaewmala

Limphirat

Yordsri

et al. 2019

Sci Rep

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Lithium rich layered oxide xLi2MnO3∙(1−x)LiMO2 (M = Mn, Co, Ni, etc.) materials are promising cathode materials for next generation lithium ion batteries. However, the understanding of their electrochemical kinetic behaviors is limited. In this work, the phase separation behaviors and electrochemical kinetics of 0.5Li2MnO3∙0.5LiCoO2 materials with various Li2MnO3 domain sizes were studied. Despite having similar morphological, crystal and local atomic structures, materials with various Li2MnO3 domain sizes exhibited different phase separation behavior resulting in disparate lithium ion transport kinetics. For the first few cycles, the 0.5Li2MnO3∙0.5LiCoO2 material with a small Li2MnO3 domain size had higher lithium ion diffusion coefficients due to shorter diffusion path lengths. However, after extended cycles, the 0.5Li2MnO3∙0.5LiCoO2 material with larger Li2MnO3 domain size showed higher lithium ion diffusion coefficients, since the larger Li2MnO3 domain size could retard structural transitions. This leads to fewer structural rearrangements, reduced structural disorders and defects, which allows better lithium ion mobility in the material.

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Section: Resultsmentioning

confidence: 99%

Structural and Electrochemical Kinetic Properties of 0.5Li2MnO3∙0.5LiCoO2 Cathode Materials with Different Li2MnO3 Domain Sizes

Kaewmala

Limphirat

Yordsri

et al. 2019

Sci Rep

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“…[13][14][15] Both cation and anion doping such as Mg, Mo, F were also designed to mitigate the capacity and voltage decay through the altering of electronic structure and the suppression of structural degradation. [16][17][18] Heat treatment and re-lithiation on cycled LRLO materials were also studied to recover the capacity and voltage decay after electrochemical cycling through the recovery of the honeycomb ordering in the TM layer. [19,20] Besides the modification on active materials, many cell components have also been optimized for high-voltage operation such as the binder and conductive agents.…”

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confidence: 99%

Elucidating the Effect of Borate Additive in High‐Voltage Electrolyte for Li‐Rich Layered Oxide Materials

Shimizu

et al. 2022

Advanced Energy Materials

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high energy density LIBs is increasing. [2] Lithium-rich layered oxide (LRLO) as a high-energy cathode material has attracted many interests due to its large specific capacity (over 300 mAh g −1 ). [3,4] Accompanied by Li extraction/insertion during charge and discharge, LRLO experiences not only the transition metal (TM) redox but also the oxygen redox which contributes a large portion to its high capacity. [5,6] Despite its high capacity, the practical deployment of LRLO is hindered by voltage fade and capacity decay during electrochemical cycling. [7,8] These two issues are correlated to the activation of oxygen redox at high voltage (>4.5 V versus Li + /Li 0 ), which leads to surface and structure degradation during cycling, such as the formation of oxygen vacancies and irreversible oxygen loss, [8,9] the migration and the dissolution of TM, [10,11] the formation of spinel-like phase, [4] and the accumulation of microstrain. [12] Intensive materials modification efforts have been devoted to addressing the capacity and voltage decay issues in LRLO. Surface coating with oxides or fluorides such as Al 2 O 3 and AlF 3 was applied to reduce the oxygen release and protect the surface from acidic species in the electrolyte. [13][14][15] Both cation and anion doping such as Mg, Mo, F were also designed to mitigate the capacity and voltage decay through the altering of electronic structure and the suppression of structural degradation. [16][17][18] Heat treatment and re-lithiation on cycled LRLO materials were also studied to recover the capacity and voltage decay after electrochemical cycling through the recovery of the honeycomb ordering in the TM layer. [19,20] Besides the modification on active materials, many cell components have also been optimized for high-voltage operation such as the binder and conductive agents. [21] However, the compatibility of the electrolyte with the charged state of LRLO is often neglected in the literature. The activation step ubiquitously seen in anionic redox materials occurs at 4.5 V versus Li + / Li 0 . For the commonly used carbonate-based liquid electrolytes, when the voltage is pushed above this limit (4.5 V), the electrolytes decompose through the following processes: carbonatebased organic solvents such as ethylene carbonate (EC) oxidize and decompose at high voltage, accompanied by dehydrogenation reaction as the protons attached to the carbon in the carbonate solvents are dissociated. [22] The protons may further Lithium-rich layered oxides (LRLO) have attracted great interest for high-energyLi-ion batteries due to their high theoretical capacity. However, capacity decay and voltage fade during the cycling impede the practical application of LRLO. Herein, the use of lithium bis-(oxalate)borate (LiBOB) as an electrolyte additive is reported to improve the cycling stability in high voltage LRLO/graphite full cells. The cell with LiBOB-containing electrolyte delivers 248 mAh g −1 initial capacity and shows no capacity decay after 70 cycles as well as 95.5% retention after 150 c...

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“…97 Doping may alter the electronic structure of the material, enhance the materials' c-lattice parameter to improve rate-capabilities and act as a pillar to stabilize the structure of the material. [96][97][98][99] Our group has explored doping of Li-rich materials with Al 3+ , performed during self-combustion synthesis. 96 Figure 8A depicts an EDX line scan of an Al-doped, Li-rich Li 1.2 Ni 0.16 Mn 0.56 O 2 particle, showing uniform Al distribution.…”

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confidence: 99%

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

Erickson

Schipper

Penki

et al. 2017

J. Electrochem. Soc.

158

103

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Electrodes prepared from lithium-rich (Li-rich) xLi 2 MnO 3 ·(1-x)LiNi a Co b Mn c O 2 materials (a + b + c = 1) show extremely high discharge capacities, arising from excess Li + present in their Li 2 MnO 3 component, and the ability to reversibly store charge with O 2− anions. These electrodes suffer serious voltage and capacity fading however, due to the migration of transition metals to the Li-layer at advanced states of charging, partial structural layered-to-spinel transformation and other reasons. In this focus paper, the current understanding of the above materials is summarized, briefly concluding with attempts by our groups to mitigate the voltage and capacity fade of these electrodes.

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Trace level doping of lithium-rich cathode materials

Abstract: Lithium ion batteries have revolutionized portable electronics and have the potential to electrify the transportation sector.

Cited by 22 publications

References 27 publications

Structural and Electrochemical Kinetic Properties of 0.5Li2MnO3∙0.5LiCoO2 Cathode Materials with Different Li2MnO3 Domain Sizes

Structural and Electrochemical Kinetic Properties of 0.5Li2MnO3∙0.5LiCoO2 Cathode Materials with Different Li2MnO3 Domain Sizes

Elucidating the Effect of Borate Additive in High‐Voltage Electrolyte for Li‐Rich Layered Oxide Materials

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

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