Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries

Hy, Sunny; Liu, Haodong; Zhang, Minghao; Qian, Danna; Hwang, Bing‐Joe; Meng, Ying Shirley

doi:10.1039/c5ee03573b

Cited by 305 publications

(246 citation statements)

References 250 publications

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“…147 Recently, positrode materials with high operating potential of ~4.7 V vs. Li + /Li, such as LiNi0.5Mn1.5O4, LiMPO4 (M=Mn, Co, V), Li2MPO4F (M=Ni, Co) and Lirich layer oxides, xLi2MnO3• (1-x) LiMeO2 (Me=Mn, Co, Ni), have been investigated extensively. 148,149 However, a major difficulty in using these positrode materials is the anodic instability of conventional carbonate-based organic electrolytes at operating potentials over 4.5 V. 127,150,151 It was shown that the conventional EC-based electrolyte was not stable around 4.5 V, resulting in severe oxidative decomposition into a resistive and unstable surface film of inorganic Li salts and organic carbonates in the positrode, and deterioration of the cycling performance. Moreover, the transition-metal ions could catalyse the oxidation reaction and accelerate the decomposition of electrolytes at potentials higher than 4.5 V, leading to rapid capacity fading.…”

Section: High Voltage Electrolytesmentioning

confidence: 99%

Electrolytes for electrochemical energy storage

Xia

et al. 2017

Mater. Chem. Front.

213

114

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A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription.For more information, please contact eprints@nottingham.ac.uk Journal NameThis journal is © The Royal Society of Chemistry 20xxJ. Name., 2013, 00, 1-3 | 1 Electrolyte is a key component of electrochemical energy storage (EES) devices and its properties greatly affect the energy capacity, rate performance, cyclability and safety of all EES devices. This article offers a critical review of recent progresses and challenges in electrolyte research and development particularly for supercapacitors and supercapatteries, recharegable batteries (such as lithium-ion and sodium-ion batteries), and redox flow batteries (including fuel cells in a broad sense). The review will focus on liquid electrolytes, particularly aqueous and organic electrolytes, ionic liquids and molten salts. Influences of electrolyte properties on the performances of different EES devices are discussed in detail.

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Section: High Voltage Electrolytesmentioning

confidence: 99%

Electrolytes for electrochemical energy storage

Xia

et al. 2017

Mater. Chem. Front.

213

114

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“…High-valence multi-electron couples spanning the average oxidation states of V typically require additional anion redox for high energy density, which is accompanied by irreversibility due to oxygen loss and surface densification. 9,11,16,22,23 Finally, while the high-voltage Ni…”

Section: Introductionmentioning

confidence: 99%

Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes

Kitchaev¹,

Lun

Richards³

et al. 2018

Energy Environ. Sci.

134

188

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The discovery of facile Li transport in disordered, Li-excess rocksalt materials has opened a vast new chemical space for the development of high energy density, low cost Li-ion cathodes. We develop a strategy for obtaining optimized compositions within this class of materials, exhibiting high capacity and energy density as well as good reversibility, by using a combination of low-valence transition metal redox and a high-valence redox active charge compensator, as well as fluorine substitution for oxygen.Furthermore, we identify a new constraint on high-performance compositions by demonstrating the necessity of excess Li capacity as a means of counteracting high-voltage tetrahedral Li formation, Li-binding by fluorine and the associated irreversibility. Specifically, we demonstrate that 10-12% of Li capacity is lost due to tetrahedral Li formation, and 0.4-0.8 Li per F dopant is made inaccessible at moderate voltages due to Li-F binding. We demonstrate the success of this strategy by realizing a series of high-performance disordered oxyfluoride cathode materials based on Mn 2+/4+ and V 4+/5+ redox. Broader contextElectrochemical energy storage is a key component of modern energy systems, providing portable power to devices ranging from personal electronics to electric vehicles, and enabling grid-scale mitigation of the fluctuating availability of renewable energy sources. The central role of energy storage systems motivates the search for, and optimization of, low-cost, environmentally-benign materials which can reversibly provide high energy density. Cathode materials, which are presently the performance-limiting components in state-of-the-art Li-ion batteries, have been traditionally limited to Ni and Co-based layered oxides. The recent discovery of Li-percolation in disordered rocksalts has expanded the structural space of materials which may serve as a Li-ion electrode, while the demonstration of Mn 2+/4+ cathode electrochemistry and disordered rocksalt fluorination has opened to door to the use of cheap, environmentally-friendly chemistries. Here, we build on these demonstrations to derive optimization rules for designing disordered rocksalt oxyfluoride cathodes and provide an example of an optimized series of cathode materials.

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“…12,13 Despite the promise of large capacities, unfortunately, a decade long research effort in commercializing LR-NMCs has remained unsuccessful because the extra capacity comes with undesirable practical drawbacks, such as voltage fade, voltage hysteresis, and poor rate capability. [14][15][16] Firstly, irreversible voltage fade diminishes energy density upon cycling and * Electrochemical Society Member.…”

mentioning

confidence: 99%

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

Assat

Delacourt

Corte

et al. 2016

J. Electrochem. Soc.

143

199

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Li-rich layered oxides, e.g. Li [Li 0.20 Ni 0.13 Mn 0.54 Co 0.13 ]O 2 (LR-NMC), lead high energy density Li-ion battery cathodes, thanks to the reversible redox of oxygen anions that boost charge storage capacity. Unfortunately, their commercialization has been stalled by practical issues (i.e. voltage hysteresis, poor rate capability, and voltage fade) and hence it is necessary to investigate whether these problems are intrinsically inherent to anionic redox and its structural consequences. To this end, the 'model' Li-rich layered oxide Li 2 Ru 0.75 Sn 0.25 O 3 (LRSO) is here used as a fertile test-bed for scrutinizing the effects of cationic and anionic redox independently since they are neatly isolated at low and high potentials, respectively. Through an arsenal of electrochemical techniques, we demonstrate that voltage hysteresis is triggered by anionic redox and grows progressively with deeper oxidation of oxygen in conjunction with the deterioration of both interfacial charge-transfer kinetics and bulk diffusion coefficient. We equally show that this anionic-driven poor kinetics keeps deteriorating further with cycling and we also find that voltage fades faster if oxygen is kept oxidized for longer. Our findings, which are in fact harsher for LR-NMC, convey caution that anionic redox risks practical problems; hence, when chasing larger capacities with this class of materials, we encourage considering real-world applications.

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Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries

Abstract: The Li-excess layered oxide compound is one of the most promising positive electrode materials for next generation batteries exhibiting high capacities of >300 mA h g−1 due to the unconventional participation of the oxygen anion redox in the charge compensation mechanism.

Cited by 305 publications

References 250 publications

Electrolytes for electrochemical energy storage

Electrolytes for electrochemical energy storage

Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

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