Mitigating the capacity and voltage decay of lithium-rich layered oxide cathodes by fabricating Ni/Mn graded surface

Li, Feng; Wang, Yangyang; Gao, Shilun; Hou, Peiyu; Zhang, Lianqi

doi:10.1039/c7ta07659b

Cited by 42 publications

(25 citation statements)

References 56 publications

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Section: Composition Tailoringmentioning

confidence: 99%

“…This full-Li-gradient LRM cathode displayed a specific density of 808 Wh kg −1 after 100 cycles at 1C, with a low release of oxygen gas and low consumption of the electrolyte. Li et al [156] prepared a Ni/Mn-graded LRM cathode material by a coprecipitation route combined with solid-state reactions, in which the nickel content increased gradually, while the manganese content decreased continuously from the core to the surface, as shown in Figure 17f. Compared with the pristine LRMs, the Ni/Mn-graded LRM cathode exhibited enhanced electrochemical performances, which are attributed to the nickel-increased surface, suppressed phase transition from layered to spinel/rock-salt phases, and inhibited side reactions on the CEI.…”

Section: Composition Tailoringmentioning

confidence: 99%

mentioning

confidence: 99%

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Challenges and Recent Advances in High Capacity Li‐Rich Cathode Materials for High Energy Density Lithium‐Ion Batteries

et al. 2021

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mismatch between the cathode and anode materials (the cathode capacity is nearly an order of magnitude smaller than the anode capacity) has seriously hindered the development of LIBs. [2] Li-rich cathode materials have been regarded as one of the most promising candidates for next-generation cathode materials for rechargeable LIBs owing to their prominent specific capacity. For instance, in Li-rich Mn-based (LRM) cathode materials with the chemical formula xLi 2 MnO 3 ⋅(1 -x)LiTMO 2 (TM = Ni, Mn, Co, etc.), when x = 0.5, in the form of Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 , the theoretical capacity of the LRM cathode reaches over 250 mA h g −1 for 1 Li + extraction, and ≈378 mA h g −1 for 1.2 Li + extraction. [3] Furthermore, LRM cathodes reduce the use of expensive Co and have the advantages of low cost, environmental friendliness, and high thermal stability. However, LRM cathode materials have inherent issues, such as low initial Coulombic efficiency (ICE), poor rate capacity, and serious voltage fading, which inhibit their further practical applications. [4] These issues need to be immediately addressed to eliminate range and safety anxiety in the electric consumption market. The development of state-of-the-art characterization techniques has brought new understandings of the origins of these problems. [5] In this case, considerable progress has been made in the evolution of LRM cathode structures and its various reaction mechanisms during long-time cycles, the electrochemical activity of anions, and other aspects. In addition, significant advances have also been made in the novel modification methods for promoting the electrochemical performances of LRM cathode materials as well as other branches of Li-rich cathode materials. Herein, we present a comprehensive review of the recent challenges and prospects in high-capacity Li-rich cathode materials. This paper aims to offer a global and critical perspective on Lirich cathode materials for LIBs, as shown in Figure 1, including an in-depth evaluation of degradation mechanisms, the prevailing modification methods and development trends, application, and future opportunities for LRM electrode materials in full-cells and future solid-state batteries. We intend to provide perspectives on the practical development and application of Li-rich cathode materials have attracted increasing attention because of their high reversible discharge capacity (>250 mA h g −1 ), which originates from transition metal (TM) ion redox reactions and unconventional oxygen anion redox reactions. However, many issues need to be addressed before their practical applications, such as their low kinetic properties and inefficient voltage fading. The development of cutting-edge technologies has led to cognitive advances in theory and offer potential solutions to these problems. Herein, a recent in-depth understanding of the mechanisms and the frontier electrochemical research progress of Li-rich cathodes are reviewed. In addition, recent advances associated with various strategies to promot...

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Section: Composition Tailoringmentioning

confidence: 99%

Section: Composition Tailoringmentioning

confidence: 99%

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Challenges and Recent Advances in High Capacity Li‐Rich Cathode Materials for High Energy Density Lithium‐Ion Batteries

et al. 2021

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“…Note that, Sample III shows a very slow voltage decay with only 0.004 V per cycle in this study. Careful observation shows that as the cycle period increases, the voltage attenuation becomes more and more slow, which is superior to the previous reports [39–41], indicating that sodium doping could suppress the phase transition from layered structure to spinel phase and thereby improve the voltage decay during cycles [42].…”

Section: Resultsmentioning

confidence: 57%

Enhanced electrochemical properties of sodium‐doped lithium‐rich manganese‐based cathode materials

Fang

Zhu

Hua

et al. 2021

Materialwissenschaft Werkst

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In this work, sodium has been successfully doped into the layered lithium‐rich manganese‐based cathode material through melt impregnation. The as‐prepared samples are characterized by multiple techniques of x‐ray diffraction, scanning electron microscopy, transmission electron microscopy, x‐ray photoelectron spectroscopy and the electrochemical measurements. The results show that sodium doping hardly changes the layered structure and surface morphology of pristine sample. The sample particles of sodium‐doped materials exhibit polygonal shape similar to prism. The sodium‐doped material possesses high rate performance and good cycling stability, and the initial charge and discharge capacity reaches 340.2 mA h g−1 and 249.0 mA h g−1 at a current density of 20 mA g−1, respectively. The initial coulombic efficiency of the first cycle is 73 %. After running 100 repeated cycles at 40 mA g−1 and 100 mA g−1, the discharge capacity could still be maintained at about 230.0 mA h g−1 and 220.0 mA h g−1, respectively. Moreover, the voltage attenuation is effectively suppressed during charging/discharging cycles.

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“…The electrode fabrication procedures may be referred to previous reports. [ 68,69 ] Briefly, the mass loading of P2‐type active oxides was ≈3.0 mg cm −2 . Sodium metal was used as anode in half cell.…”

Section: Methodsmentioning

confidence: 99%

Boosting the Redox Kinetics of High‐Voltage P2‐Type Cathode by Radially Oriented {010} Exposed Nanoplates for High‐Power Sodium‐Ion Batteries

Fan

Hou

et al. 2021

Small Structures

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High‐voltage P2‐type cathode with large capacity, high air stability, and low cost has attracted extensive attention. However, large ionic radius of Na+ and Na+/vacancy ordering result in low reaction kinetics and poor high‐rate capability. Herein, cobalt‐doped hierarchical structure assembled by radially oriented {010} exposed nanoplates is developed. With radially oriented grains infiltrating from surface to interior, all the {010} exposed surfaces are electrochemically active planes, and Na+ ions diffuse directly into electrolyte without passing through grain boundaries, building up 3D transfer channels. The trivalent cobalt substitution suppresses unwanted Na+/vacancy ordering and increases energy barrier of the phase transition from P2‐ to O2‐type oxide. These synergetic effects remarkably boost the redox kinetics of high‐voltage P2‐type cathode. Consequently, a large reversible capacity of 112 mAh g−1 is achieved even at 20 C, indicating excellent high‐rate capability. The absence of P2–O2 phase transition also gives rise to superior cycling stability, maintaining a capacity retention of 85% after 200 cycles. In addition, full cells composed of this hierarchical P2‐type cathode and hard carbon anode deliver high energy‐ and power‐densities. These achievements offer a new insight into boosting redox kinetics of P2‐ and O3‐type layered cathodes for high‐power sodium‐ion batteries.

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Mitigating the capacity and voltage decay of lithium-rich layered oxide cathodes by fabricating Ni/Mn graded surface

Abstract: A Ni/Mn-graded surface is proposed to suppress the unwanted phase transformations and side-reactions of high-energy lithium-rich layered oxide cathodes, and thus to mitigate their capacity and voltage decay.

Cited by 42 publications

References 56 publications

Challenges and Recent Advances in High Capacity Li‐Rich Cathode Materials for High Energy Density Lithium‐Ion Batteries

Challenges and Recent Advances in High Capacity Li‐Rich Cathode Materials for High Energy Density Lithium‐Ion Batteries

Enhanced electrochemical properties of sodium‐doped lithium‐rich manganese‐based cathode materials

Boosting the Redox Kinetics of High‐Voltage P2‐Type Cathode by Radially Oriented {010} Exposed Nanoplates for High‐Power Sodium‐Ion Batteries

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