Introducing 4<i>s</i>–2<i>p</i> Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium‐Ion Batteries

Liang, Gemeng; Olsson, Emilia; Zou, Jinshuo; Wu, Zhibin; Li, Jingxi; Lu, Cheng‐Zhang; D’Angelo, Anita M.; Johannessen, Bernt; Thomsen, Lars; Cowie, Bruce C. C.; Peterson, Vanessa K.; Cai, Qiong; Guo, Zaiping

doi:10.1002/anie.202201969

Cited by 40 publications

(38 citation statements)

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“…We do not doubt that some point defects of the oxygen lattice can exist in LNMO and we also assume that the substitution of Mn(IV) by trivalent ions like Fe(III) [ 26 ] or Ga(III) [ 53 ] might favor quantitative oxygen defect formation. However, we want to emphasize that oxygen defects are clearly not directly related to the Mn(III) content in LNMO materials.…”

Section: Discussionmentioning

confidence: 99%

On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

Stüble

Mereacre

Geßwein

et al. 2023

Advanced Energy Materials

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A characteristic advantage over state-of-the-art Ni-rich cathode active materials such as LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM-622) or LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM-811) is that LNMO is cobalt free and the redox capacity of nickel is used in its entirety. The latter could become more important considering rising nickel prices. Based on realistic full cell capacities of 120 mAh g −1 for LNMO and 170 mAh g −1 for the NCM materials, 43.8 Ah per mol Ni is obtained for LNMO, whereas NCM-622 and NCM-811 only yield 27.5 and 20.7 Ah mol −1 , respectively. The specific energy density of LNMO vs. graphite full cells is likewise highly competitive. For LNMO, up to 464 Wh kg −1 are expected, which exceeds the energy densities of corresponding NCM-622 and NCM-811 cells, yielding 416 and 448 Wh kg −1 , respectively. [2] Despite these favorable features, commercialization of LNMO cathode materials never succeeded. Up to date, it was not possible to build competitive cells with graphite anodes, as the degradation of these full cells has not been brought under control. [3,4] The problem, however, is not the stability of LNMO itself, but the dissolution and disproportionation of Mn(III) from LNMO, which leads to continuous decomposition reactions on the anode side and ongoing loss of cyclable lithium. [3,5,6] LNMO is nevertheless a very stable cathode material, which does not tend to decompose or release oxygen during cycling. [7] There is scientific consensus that LNMO crystallizes as an ordered or disordered spinel phase in the space groups P4 3 32 or Fd3m, respectively, or as intermediate, partial ordered phases. The term "order" refers to the distribution of transition metal cations on the octahedral sites of the spinel structure. In the ordered structure, Mn and Ni predominantly occupy the Wyckoff positions 12d and 4a, while in the disordered structure, they are statistically distributed over the 16c octahedral site. [8,9] Whether an LNMO material is predominantly ordered or disordered is commonly associated with the calcination temperature. Temperatures below 730 °C are reported to favor the formation of the ordered phase, whereas at higher temperatures disordered crystal structures are reported to occur. [10] LNMO phases with the composition LiNi 0.5 Mn 1.5 O 4 , where Mn is Mn(IV) exclusively, are reported to be obtained by calcining LNMO materials at 700 °C. [11] Increasing calcination temperatures however, lead to a partial reduction of Mn(IV) to Mn(III), which becomes obvious from an increasing Mn 3+ /Mn 4+ LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode active materials for lithium-ion batteries have been investigated for over 20 years. Despite all this effort, it has not been possible to transfer their favorable properties into applicable, stable battery cells. To make further progress, the research perspective on these spinel type materials needs to be updated and a number of persisting misconceptions on LNMO have to be overcome. Therefore, the current knowledge on LNMO is summarized and controversial points are addressed by detaile...

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Section: Discussionmentioning

confidence: 99%

On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

Stüble

Mereacre

Geßwein

et al. 2023

Advanced Energy Materials

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“…36,37 Surprisingly, the unoccupied octahedral sites of LNMO can store extra Li + , thus forming spinel-related Li 2 Ni 0.5 Mn 1.5 O 4 (L 2 NMO). 5,6,40,41 Fig. 1c shows the charge-discharge curve of the LikLNMO half-cell and a schematic diagram of the reversible phase transition between LNMO and L 2 NMO.…”

Section: Resultsmentioning

confidence: 99%

“…Anode-free lithium metal batteries (AF-LMBs) can maximize the energy density of rechargeable batteries. [1][2][3][4][5][6] However, the AF-LMBs suffer from rapid lithium stock loss and poor cycle life, due to the poor reversibility of lithium plating/stripping on the anode. [7][8][9] Many approaches have been applied to overcome these limitations, and some promising results have been achieved.…”

Section: Introductionmentioning

confidence: 99%

Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li₂Ni_0.5Mn_1.5O₄spinel cathode

Chen

Chiang

et al. 2023

Chem. Sci.

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“…Notably, now that a different degree of localization for s, p, d, and f orbitals is acknowledged by the public, engineering gradient orbital coupling is shining in the near future. [ 188–190 ]…”

Section: Comparison Of Various Field‐assisted Electrocatalysismentioning

confidence: 99%

Field‐assisted electrocatalysts spark sulfur redox kinetics: From fundamentals to applications

Zhang

et al. 2023

Interdisciplinary Materials

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The chief culprit impeding the commercialization of lithium–sulfur (Li–S) batteries is the parasitic shuttle effect and restricted redox kinetics of lithium polysulfides (LiPSs). To circumvent these key stumbling blocks, incorporating electrocatalysts with rational electronic structure modulation into sulfur cathode plays a decisive role in vitalizing the higher electrocatalytic activity to promote sulfur utilization efficiency. Breaking the stereotype of contemporary electrocatalyst design kept on pretreatment, field‐assisted electrocatalysts offer strategic advantages in dynamically controllable electrochemical reactions that might be thorny to regulate in conventional electrochemical processes. However, the highly interdisciplinary field‐assisted electrochemistry puzzles researchers for a fundamental understanding of the ambiguous correlations among electronic structure, surface adsorption properties, and catalytic performance. In this review, the mechanisms, functionality explorations, and advantages of field‐assisted electrocatalysts including electric, magnetic, light, thermal, and strain fields in Li–S batteries have been summarized. By demonstrating pioneering work for customized geometric configuration, energy band engineering, and optimal microenvironment arrangement in response to decreased activation energy and enriched reactant concentration for accelerated sulfur redox kinetics, cutting‐edge insights into the holistic periscope of charge‐spin‐orbital‐lattice interplay between LiPSs and electrocatalysts are scrutinized, which aspires to advance the comprehensive understanding of the complex electrochemistry of Li–S batteries. Finally, future perspectives are provided to inspire innovations capable of defeating existing restrictions.

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Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium‐Ion Batteries

Cited by 40 publications

References 40 publications

On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li₂Ni_0.5Mn_1.5O₄spinel cathode

Field‐assisted electrocatalysts spark sulfur redox kinetics: From fundamentals to applications

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Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium‐Ion Batteries

Cited by 40 publications

References 40 publications

On the Composition of LiNi0.5Mn1.5O4 Cathode Active Materials

On the Composition of LiNi0.5Mn1.5O4 Cathode Active Materials

Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li2Ni0.5Mn1.5O4spinel cathode

Field‐assisted electrocatalysts spark sulfur redox kinetics: From fundamentals to applications

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On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

On the Composition of LiNi_0.5Mn_1.5O₄ Cathode Active Materials

Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li₂Ni_0.5Mn_1.5O₄spinel cathode