Lithium Rich Composition of Li2RuO3and Li2Ru1-xIrxO3Layered Materials as Li-Ion Battery Cathode

Sarkar, Shaibal K.; Mahale, Pratibha; Mitra, Sagar

doi:10.1149/2.030406jes

Cited by 35 publications

(29 citation statements)

References 33 publications

(44 reference statements)

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“…22 However, the electrochemical properties upon cycling under various voltage ranges have not been sufficiently studied for Li 2 RuO 3 and its related solid solutions. 14,[25][26][27][28] Evaluating the electrochemical properties under various (dis)charge voltage ranges is crucial to obtain design guidelines on how to optimize the performance of electrode materials. In this study, the electrochemical properties upon cycling under various charge cut-off voltages and the phase transition behaviors in the initial and second cycles are investigated for Li 2 RuO 3 and Li 2 Mn 0.4 Ru 0.6 O 3 (x = 0.6; hereafter denoted as LMR) showing the largest capacity and good cyclability among Li 2 Mn 1¹x Ru x O 3 system and their relationship to local structure change are discussed.…”

Section: /Rumentioning

confidence: 99%

Relationship between Cyclic Properties and Charge-discharge Condition for Li2Mn0.4Ru0.6O3 and Li2RuO3

et al. 2015

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Capacity and voltage retentions upon subsequent cycles for Li 2 RuO 3 and Li 2 Mn 0.4 Ru 0.6 O 3 (LMR) under various cutoff voltages have been investigated. The change in average and local structures upon electrochemical cycling were examined by ex-situ XRD and Ru L 3 -edge XANES measurements, and the relationship between the cyclic capabilities and the structural changes is discussed. The deteriorations of discharge capacity and average discharge voltage in the subsequent cycles of LMR with a charge cut-off voltage of 4.8 V vs. Li/Li + are remarkably smaller than that with the voltage of 4.2 V. Moreover, LMR exhibits higher average discharge voltage than Li 2 RuO 3 under a charge cut-off voltage of 4.8 V. The phase transition behavior of LMR was not similar to Li 2 RuO 3 upon electrochemical cycling. Ru L 3 -edge XANES spectra measurements reveal that RuO 6 octahedra in LMR charged at 4.2 V are much distorted. The local structure of RuO 6 octahedra is associated with the cyclic capability of LMR and Li 2 RuO 3 .

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Section: /Rumentioning

confidence: 99%

Relationship between Cyclic Properties and Charge-discharge Condition for Li2Mn0.4Ru0.6O3 and Li2RuO3

et al. 2015

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“…109,110 It has recently been reported that Li 2 MO 3 containing two types of TM elements with different oxidation states (ex: Li 2 M1 3+ M2 5+ O 3 ) is electrochemically active and exhibits interesting properties. 29,111,112 Among these LLCs, Li 4 FeSbO 6 offered a more detailed understanding of the oxygen participation during redox reactions. 30,113 Based on the variation of the redox behavior depending on cutoff voltages (Figure 21a), the authors determined that there are three types of redox centers: reversible redox reactions of TMs (Fe 3+ /Fe 4+ ), Fe 4+ and O 2 n− , respectively.…”

Section: Llcs Containing Heavy Atomsmentioning

confidence: 99%

Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries

Hong

Gwon

Jung

et al. 2015

J. Electrochem. Soc.

150

122

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The exceptionally high gravimetric capacity of lithium-excess layered cathodes (LLCs) has generated interest in their use in lithiumion batteries (LIBs) for high-capacity applications. Their unique electrochemical and structural properties are responsible for this high capacity, which exceeds the theoretical redox capability of transition metal oxides and have been intensively investigated. However, various fundamental and practical challenges must be overcome before LLCs can be successfully commercialized. The structure of pristine LLCs, which varies with the composition and type of transition metal species used, remains unclear. In addition, the structure continuously changes during electrochemical cycling, which further complicates its understanding. In this review, we discuss the current understanding of LLCs, including their pristine structures, redox chemistries, and structural evolution during cycling, and suggest future research directions to address the critical issues.There has been a recent upsurge of interest in overcoming the current energy density limitation of lithium-ion batteries (LIBs) to address the pressing demand from the electric vehicle and large-scale energy storage system industries. 1-3 As one of the key components of LIBs that govern their performance, cathode materials that are capable of delivering a high energy density have been extensively sought after. 4-16 Although some currently used cathode materials possess a high theoretical capacity (C th ), i.e., LiCoO 2 (LCO, C th = 274 mAh g −1 ), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (NCM, C th = 278 mAh g −1 ), LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA, C th = 279 mAh g −1 ), LiMn 2 O 4 (LMO, C th = 148 mAh g −1 ), and LiFePO 4 (LFP, C th = 170 mAh g −1 ), the practically usable capacity remains at 100-180 mAh g −1 , as shown in Figure 1, which is insufficient for future applications. As an alternative high-energy cathode, lithium-excess layered cathodes (LLCs) have been intensively studied in recent years. 6-10 Whereas the aforementioned cathode materials, LCO, NCM, NCA, and LFP, have a lithium-to-transition metal (TM) ratio of unity, LLCs have a lithiumto-TM ratio exceeding 1, indicating the possible utilization of more than one Li in the chemical formula unit, which would substantially increase C th . However, the utilization of the excess Li requires an additional redox active center in the material, and most M 4+ /M 5+ (M = Mn, Fe, Co, or Ni) redox reactions occur at a high potential beyond the electrochemical stability window of electrolytes; thus, the "lithium-excess" strategies did not appear suitable for achieving high capacity. Nevertheless, most reported LLCs exhibit exceptionally high reversible capacities exceeding 250 mAh g −1 , which far surpass the C th values calculated based on the redox capabilities of the TM ions.This unique property of LLCs and their consequent high capacities have attracted significant attention from the community, and extensive investigations have been conducted accordingly. These investigations primarily focused ...

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“…Doping the oxide lattice has demonstrated to be a more facile way to modify the structural properties and to improve the cycling stability/voltage maintenance of LROs. To date, several attempts based on single cation doping have been reported . For example, the Mitra group demonstrated the capacity and cycling stability of LRO were enhanced by introducing an Ir dopant .…”

Section: Introductionmentioning

confidence: 99%

“…To date, several attempts based on single cation doping have been reported . For example, the Mitra group demonstrated the capacity and cycling stability of LRO were enhanced by introducing an Ir dopant . The Im group discovered the Ti 4+ doping led to the improved cycle stability and rate performance of LROs .…”

Section: Introductionmentioning

confidence: 99%

“…[30][31][32][33][34][35][36][37][38][39][40][41][42] For example, the Mitra group demonstrated the capacity and cycling stability of LRO were enhanced by introducing an Ir dopant. 32 The Im group discovered the Ti 4+ doping led to the improved cycle stability and rate performance of LROs. 33 This group also found that a low content of Co 3+ is sufficient to achieve high Li insertion/extraction reversibility in LROs.…”

Section: Introductionmentioning

confidence: 99%

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A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

et al. 2019

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Summary Lithium‐rich layered oxides (LRLOs) are highly attractive cathode materials for next‐generation lithium‐ion batteries because of their high reversible capacity, but poor cycle performance and voltage decay are two main problems that strongly limit their practical applications. These challenges also apply to the Ru‐based LRLOs of Li2RuO3. The Li2RuO3 cathode material is highly attractive because of their high conductivity and favourable electrochemical reaction kinetics. To overcome the problems associated with Li2RuO3, in contrast to normal single atom doping, here, we propose a Na, Cr co‐doping strategy with the design of Li2−xNaxRu0.95Cr0.05O3 (x = 0, 0.02, 0.06, and 0.1) series materials. Cr doping increases capacity, and Na doping suppresses voltage decay. As a result, the discharge capacity of the optimal Li1.98Na0.02Ru0.95Cr0.05O3 sample over 240 mAh/g after 50 charge‐discharge cycles at 0.2 C is maintained, and the capacity retention reaches a value of 80.5% compared with 69.1% for the undoped Li2RuO3. The value of the voltage decay in the Li1.98Na0.02Ru0.95Cr0.05O3 sample is 125 mV after 100 cycles at a rate of 1 C, and the voltage decay is 188.4 mV for the undoped Li2RuO3. This finding will expand the scope for designing novel layered electrodes with excellent performance.

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Lithium Rich Composition of Li₂RuO₃and Li₂Ru_1-xIr_xO₃Layered Materials as Li-Ion Battery Cathode

Cited by 35 publications

References 33 publications

Relationship between Cyclic Properties and Charge-discharge Condition for Li<sub>2</sub>Mn<sub>0.4</sub>Ru<sub>0.6</sub>O<sub>3</sub> and Li<sub>2</sub>RuO<sub>3</sub>

Relationship between Cyclic Properties and Charge-discharge Condition for Li<sub>2</sub>Mn<sub>0.4</sub>Ru<sub>0.6</sub>O<sub>3</sub> and Li<sub>2</sub>RuO<sub>3</sub>

Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries

A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

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