Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.; Sallis, Shawn; Kwon, Deok‐Hwang; Shi, Tan; Yang, Wanli; McCloskey, Bryan D.; Ceder, Gerbrand

doi:10.1038/s41467-017-01115-0

Cited by 219 publications

(288 citation statements)

References 42 publications

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“…The increase in Li-gettering by F at higher Li-excess levels indicates that fluorine doping may not increase Li capacity within a given voltage window even in the case where fluorine incorporates into the bulk lattice, even though fluorination is beneficial for other properties such as stability on cycling and obtainable metal-redox capacity. 5,6,21 Thus, in broad terms, in a disordered rocksalt oxyfluoride material, one may expect a reduction in accessible Li capacity equal to 0.4-0.8 Li per F in the discharged cathode material.…”

Section: Accessibility Of LI On Chargingmentioning

confidence: 99%

“…The 19 F NMR spectra collected for ST-LMVF20, MR-LMVF20 and LR-LMVF20, shown in Fig. 2b, 6 In addition, some of our ongoing work on related paramagnetic cation-disordered oxyfluorides indicates that observable paramagnetic 19 F NMR signals can be assigned to F nuclei surrounded by 6 Li in their first coordination shell, with paramagnetic species (here Mn and V) in their second and/or third metal coordination shells (see ESI, † Fig. S2a in Lee et al 6 for a schematic diagram of coordination shells).…”

Section: Electrochemical Design and Performancementioning

confidence: 99%

“…6,8,11 The recently realized Mn 2+/4+ couple avoids this limitation while providing high capacity at a high average voltage. 21 However, as the low-valence of the discharged Mn 2+ requires a source of charge compensation, previous reports have mixed the active Mn with redox-inactive elements, as well as fluorine.…”

Section: Introductionmentioning

confidence: 99%

“…Fluorination is an efficient route for introducing Li-excess, which is necessary for both Li percolation in disordered rocksalts, and high Li capacity. Fluorine doping has also been reported to reduce oxygen loss, improve capacity retention, 6 and increase transition metal oxidation potential through the inductive effect. 21 As shown here, fluorine also increases the extraction voltage of Li by strongly binding some of the Li directly bonded to F. This trend rationalizes the behavior of previously reported oxyfluorides, with between 0.2 and 0.4 Li reported to be inaccessible at moderate voltages in Li 2 VO 2 F, even when starting from an as-synthesized VO 2 F endpoint.…”

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confidence: 99%

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

Kitchaev¹,

Lun

Richards³

et al. 2018

Energy Environ. Sci.

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130

182

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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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Section: Accessibility Of LI On Chargingmentioning

confidence: 99%

Section: Electrochemical Design and Performancementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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

Kitchaev¹,

Lun

Richards³

et al. 2018

Energy Environ. Sci.

Self Cite

130

182

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“…However, the cell based on 80LiNiO 2 ·20Li 2 SO 4 exhibited a limited capacity of ≈150 mAh g −1 . [41,42] Although a high capacity was achieved, the cycle performance of the cell using the active material with the high Ni content was not sufficiently high. The disordered rock-salt-type crystal has been regarded as the electrochemically inactive due to the limitation of lithium-ionic migration pathway in the structure.…”

Section: Effect Of the Ni Content In Nmc On The Charge-discharge Perfmentioning

confidence: 99%

Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Nagao

Sakuda

Hayashi

et al. 2019

Adv Materials Inter

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typical organic liquid electrolytes. [1][2][3] Although the safety and reliability of batteries can be potentially improved by utilizing solid electrolytes instead of liquid electrolytes, there are still several challenges in sulfide-type all-solidstate batteries, such as H 2 S generation and chemical reaction with active materials. [4][5][6][7] On the other hand, oxide-type all-solid-state batteries have been regarded as one of the leading candidates to overcome these problems owing to the high chemical and electrochemical stabilities of oxide electrolytes. Despite the merits, the construction of all-oxide solid-state batteries is quite difficult owing to the lack of deformability of the typical crystalline oxide electrolytes, which leads to a poor contact between the active material and solid electrolyte particles. [8] Therefore, high-temperature sintering is required to achieve a good contact. Even if a good contact is achieved, unfavorable chemical reactions between the active material and solid electrolyte might proceed at the high temperature, leading to generation of a highly resistive layer. [9,10] Therefore, formation of an excellent electrode/ electrolyte interface without high-temperature sintering is important for the operation of all-oxide solid-state batteries. In order to achieve a good formability in oxide electrolytes, we have focused on materials with lower melting points such as Li 3 BO 3 . [11] A mechanochemically prepared Li 3 BO 3 glass electrolyte exhibited a relatively high conductivity of 10 −7 S cm −1 at room temperature and good formability. In addition, we previously developed ductile oxide glass-ceramic electrolytes of the pseudobinary system Li 3 BO 3 -Li 2 SO 4 . The Li 2.9 B 0.9 S 0.1 O 3.1 (90Li 3 BO 3 ·10Li 2 SO 4 (mol%)) glass-ceramic electrolyte exhibited a high conductivity of ≈10 −5 S cm −1 at room temperature. [12,13] A good contact with electrode active materials was successfully achieved simply by pressing at room temperature, which was enabled by the excellent formability of the electrolyte.Crystalline materials such as layered, [14,15] spinel, [16] and olivine [17] structures have been utilized as positive electrode materials in typical lithium-ion and all-solid-state batteries. Amorphous materials are also candidates for electrode materials, which generally exhibit higher conductivities than those of the All-solid-state batteries attract significant attention owing to their potential to realize an energy storage system with high safety and energy density. In this paper, a mechanochemical synthesis of novel amorphous positive electrode materials of the Ni-rich LiNi 1−x−y Mn x Co y O 2 (NMC)-Li 2 SO 4 system suitable for oxide-type all-solid-state batteries is reported. Through the mechanochemical treatment with Li 2 SO 4 , excellent formabilities of the electrode materials as those of ductile solid electrolytes are obtained. Owing to the deformability of the active material, a good electrode/electrolyte interface is provided simply by pressing at room temperature. In all...

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Next‐Generation Cobalt‐Free Cathodes – A Prospective Solution to the Battery Industry's Cobalt Problem*

Muralidharan¹,

Self²,

Nanda³

et al. 2022

Transition Metal Oxides for Electrochemical Energy Storage

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Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

Cited by 219 publications

References 42 publications

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

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

Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Next‐Generation Cobalt‐Free Cathodes – A Prospective Solution to the Battery Industry's Cobalt Problem*

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Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

Cited by 219 publications

References 42 publications

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

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

Amorphous Ni‐Rich Li(Ni1−x−yMnxCoy)O2–Li2SO4 Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries

Next‐Generation Cobalt‐Free Cathodes – A Prospective Solution to the Battery Industry's Cobalt Problem*

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Amorphous Ni‐Rich Li(Ni₁₋_x₋_yMn_xCo_y)O₂–Li₂SO₄ Positive Electrode Materials for Bulk‐Type All‐Oxide Solid‐State Batteries