Spinel cathodes for advanced lithium ion batteries: a review of challenges and recent progress

Lu, Jin; Lee, Kim Seng

doi:10.1080/10667857.2016.1208957

Cited by 48 publications

(40 citation statements)

References 209 publications

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“…Caballero et al observed an oxidation peak at about 5.1 V and ascribed this peak to the release of oxygen from the spinel framework [72]. According to previous studies [9,17,24,73], the features of the obtained cyclic voltammogram indicates that the as-prepared LNMO exhibited dominantly the disordered structure, which is in accordance to the SAED result.…”

Section: Resultssupporting

confidence: 82%

“…Two pairs of well-resolved, sharp redox peaks were recorded at around 4.7 V vs. Li/Li + , corresponding to the Ni 2+ /Ni 3+ and Ni 3+ /Ni 4+ redox processes [9,70]. The potential difference between the oxidation and the reduction peaks (ΔE p ) for the Ni 2+ /Ni 3+ and Ni 3+ /Ni 4+ redox processes were determined as 0.09 V and 0.10 V, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…As one of the most promising cathode material candidates, LiMn 2 O 4 (LMO) spinel offers advantages such as high rate capability, good safety, low cost and nontoxicity [5,6,7,8,9]. However, a significant challenge posed to the usage of this material is the capacity-fading during cycling, especially at elevated temperature [5,6,7,8,9].…”

Section: Introductionmentioning

confidence: 99%

“…However, a significant challenge posed to the usage of this material is the capacity-fading during cycling, especially at elevated temperature [5,6,7,8,9]. To overcome this challenge, several bi- or trivalent cations, such as Co [10], Ni [11], and Fe [12], have been investigated in their role as dopants to partially substitute the Mn in LMO.…”

Section: Introductionmentioning

confidence: 99%

“…To overcome this challenge, several bi- or trivalent cations, such as Co [10], Ni [11], and Fe [12], have been investigated in their role as dopants to partially substitute the Mn in LMO. Among these materials, the Ni-doped LMO spinels, especially the LiNi 0.5 Mn 1.5 O 4 (LNMO), have been extensively studied [9,13,14]. …”

Section: Introductionmentioning

confidence: 99%

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Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

et al. 2018

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LiNi0.5Mn1.5O4 (LNMO) spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology. In this work, we prepared Ni-doped LiMn2O4 (LMO) spinel via the polyol method. The cycling stability and rate capability of the synthesized material are found to be comparable to the ones reported in literature. Furthermore, its electronic charge transport properties were investigated by local electrical transport measurements on individual particles by means of a nanorobotics setup in a scanning electron microscope, as well as by performing DFT calculations. We found that the scarcity of Mn3+ in the LNMO leads to a significant decrease in electronic conductivity as compared to undoped LMO, which had no obvious effect on the rate capability of the two materials. Our results suggest that the rate capability of LNMO and LMO materials is not limited by the electronic conductivity of the fully lithiated materials.

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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

et al. 2018

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Surface Chemistry of Alkali‐Ion Battery Cathode Materials

Rahman

Lin

2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Layered and spinel transition metal oxides are one of the most technologically important cathode materials for alkali metal ion batteries because of their high energy/power density and excellent electrochemical reversibility. However, similar to many other cathode materials, unstable electrochemical performance on long‐term cycling impacts the cycle life of batteries. Some of the challenges are transition metal dissolution, electrolyte decomposition, surface reconstruction, and chemomechanical breakdown of cathode materials. Most of these degradation phenomena originate from the surface of cathode materials. Owing to different local chemical environments, the surface chemistry of a cathode is distinctively unique from that of the bulk. Even though the surface region of a battery particle only accounts for a small fraction of the entire particle and contributes marginally to the overall capacity, surface‐related chemical and structural transformations can be the major factors in governing the degradation pathway of a cathode material. Herein, we have mechanistically discussed the origin and propagation of these degradation phenomena and their implications in the cycle life of a battery. Moreover, the techniques that mitigate and prevent these degradation pathways are explained. A complete understanding of the instability issues can promote a rational design of stable cathode materials for alkali metal ion batteries.

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Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Shimizu

Cheng

Weaver

et al. 2022

Advanced Energy Materials

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Spinel‐type LiNi0.5Mn1.5O4 (LNMO) is one of the most promising 5 V‐class cathode materials for Li‐ion batteries that can achieve high energy density and low production costs. However, in liquid electrolyte cells, the high voltage causes continuous cell degradation through the oxidative decomposition of carbonate‐based liquid electrolytes. In contrast, some solid‐state electrolytes have a wide electrochemical stability range and can withstand the required oxidative potential. In this work, a thin‐film battery consisting of an LNMO cathode with a solid lithium phosphorus oxynitride (LiPON) electrolyte is tested and their interface before and after cycling is characterized. With Li metal as the anode, this system can deliver stable performance for 600 cycles with an average Coulombic efficiency >99%. Neutron depth profiling indicates a slight overlithiated layer at the interface prior to cycling, a result that is consistent with the excess charge capacity measured during the first cycle. Cryogenic electron microscopy further reveals intimate contact between LNMO and LiPON without noticeable structure and chemical composition evolution after extended cycling, demonstrating the superior stability of LiPON against a high voltage cathode. Consequently, design guidelines are proposed for interface engineering that can accelerate the commercialization of a high voltage cell with solid or liquid electrolytes.

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Spinel cathodes for advanced lithium ion batteries: a review of challenges and recent progress

Cited by 48 publications

References 209 publications

Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

Surface Chemistry of Alkali‐Ion Battery Cathode Materials

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

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