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1
Wang, Yihong, Ning Li, Duanyun Cao, Yuefeng Su, and Feng Wu. "Synthesis of High-capacity and High-rate Intergrown Cathodes for Lithium-ion Batteries." Journal of Physics: Conference Series 2563, no. 1 (August 1, 2023): 012014. http://dx.doi.org/10.1088/1742-6596/2563/1/012014.
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Abstract Nowadays, general energy storage and electric vehicles urgently need to develop advanced lithium-ion batteries (LIB) with high specific energy and low cost, and one of the great challenges is to invent cheap cathode materials. Manganese-based cathode materials have been widely studied due to the low prices and high reserves of precursors, such as lithium-rich manganese-based (LMR) and Mn-based disordered rock-salt (DRX) cathodes. Inspired by the concept of layered-layered intergrown structure in LMR, we design a spinel-rock salt intergrown nano-composite. The as-developed cathode (Li1.7Ni0.12Mn1.48O4) shows a partially intergrown structure of spinel- and DRX-phases. Most importantly, the material enables the combination of the structural and electrochemical merits of the individual spinel and rock-salt phases, and it yields ultrahigh-capacity in comparison with the LMR or DRX and displays outstanding rate performance. It is hoped this novel intergrown cathode with low cost can inspire the design of advanced cathode for LIB.
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Tan, T. Q., S. P. Soo, A. Rahmat, J. B. Shamsul, Rozana A. M. Osman, Z. Jamal, and M. S. Idris. "A Brief Review of Layered Rock Salt Cathode Materials for Lithium Ion Batteries." Advanced Materials Research 795 (September 2013): 245–50. http://dx.doi.org/10.4028/www.scientific.net/amr.795.245.
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Nowadays, many researchers have been studying on the layered rock salt-type structure as cathode materials for the lithium ion batteries. LiCoO2is the most commonly used cathode material but Co is costly and toxic. Thus, alternative cathode materials which are cheaper, safer and having higher capacity are required. Replacing Co with Ni offered higher energy density battery but it raised interlayer mixing or cation disorder that impedes electrochemical properties of batteries. This paper has reviewed some recent research works that have been done to produce better and safer cathode materials from the structural perspective.
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Malovanyy, Sergiy. "CATHODE MATERIALS OF ROCK SALT DERIVATIVE STRUCTURES FOR SODIUM-ION SECONDARY POWER SOURCES." Ukrainian Chemistry Journal 85, no. 9 (October 16, 2019): 44–57. http://dx.doi.org/10.33609/0041-6045.85.9.2019.44-57.
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The rechargeable lithium-ion batteries have been dominating the portable electronic market for the past two decades with high energy density and long cycle-life. However, applications of lithium-ion batteries in large-scale stationary energy storage are likely to be limited by the high cost and availability of lithium resources. The room temperature Na-ion secondary battery have received extensive investigations for large-scale energy storage systems (EESs) and smart grids lately due to similar chemistry of “rocking-chair” sodium storage mechanism, lower price and huge abundance. They are considered as an alternative to lithium-ion batteries for large-scale applications, bringing an increasing research interests in materials for sodium-ion batteries. Although there are many obstacles to overcome before the Na-ion battery becomes commercially available, recent research discoveries corroborate that some of the cathode materials for the Na-ion battery have indeed advantages over its Li-ion competitors. Layered oxides are promising cathode materials for sodium ion batteries because of their high theoretical capacities. In this publication, a review of layered oxides (NaxMO2, M = V, Cr, Mn, Fe, Co, Ni, and a mixture of 2 or 3 elements) as a Na-ion battery cathode is presented. O3 and P2 layered sodium transition metal oxides NaxMO2 are a promising class of cathode materials for Na secondary battery applications. These materials, however, all suffer from capacity decline when the extraction of Na exceeds certain capacity limits. Understanding the causes of this capacity decay is critical to unlocking the potential of these materials for battery applications. Single layered oxide systems are well characterized not only for their electrochemical performance, but also for their structural transitions during the cycle. Binary oxides systems are investigated in order to address issues regarding low reversible capacity, capacity retention, operating voltage, and structural stability. Some materials already have reached high energy density, which is comparable to that of LiFePO4. On the other hand, the carefully chosen elements in the electrodes also largely determine the cost of SIBs. Therefore, earth abundant-based compounds are ideal candidates for reducing the cost of electrodes. Among all low-cost metal elements, cathodes containing iron, chromium and manganese are the most representative ones. The aim of the article is to present the development of Na layered oxide materials in the past as well as the state of the art today.
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Si, Zheng, Baozhao Shi, Jin Huang, Ye Yu, You Han, Jinli Zhang, and Wei Li. "Titanium and fluorine synergetic modification improves the electrochemical performance of Li(Ni0.8Co0.1Mn0.1)O2." Journal of Materials Chemistry A 9, no. 14 (2021): 9354–63. http://dx.doi.org/10.1039/d1ta00124h.
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Ti4+ and F− co-dopants expand the lattice spacing of Ni-rich cathode materials and form ultra-thin rock salt phases on the surface of the cathode, thereby improving the electrochemical performance of lithium-ion batteries.
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Chen, Dongchang, and You Wang. "Revealing Hidden Structural Anisotropy in Cation-Disordered Rock Salts." ECS Meeting Abstracts MA2022-02, no. 3 (October 9, 2022): 255. http://dx.doi.org/10.1149/ma2022-023255mtgabs.
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Cation disordered rock salts (DRX), a new class of cathode materials for Li ion batteries, have attracted lots of attention in recent years, due to their fascinatingly simple cubic structure, highly diverse composition, and great electrochemical performance. As cations in DRX are randomly distributed in a long-range, how the cations (Li and transition metal) are arranged in a shorter range is an intriguing question for the community of cathode materials research. In this work, we study the vibrational structure of a series of DRXs with well controlled compositions and revealed significant anisotropy of cation arrangements. Based on the results, we propose a scheme that describes how the structural anisotropy could exist in rock salt structures but shows an overall cubic Fm-3m diffraction pattern. Furthermore, we raise a model of Li transport based on the scheme we proposed, which complements the theory of Li percolation in DRX. The electrochemical behavior of the cathodes used in the study supports the model.
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Nanda, Jagjit, and Ethan Self. "Cobalt and Nickel Free Disorder Rock Salt Cathodes – Recent Developments." ECS Meeting Abstracts MA2022-02, no. 2 (October 9, 2022): 107. http://dx.doi.org/10.1149/ma2022-022107mtgabs.
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Disordered Li-excess rock salt (DRX) cathodes are a promising class of high capacity (and voltage) cathodes for next-generation Li-ion batteries. Compared to conventional Li-ion cathodes which are generally restricted to Co/Ni-based compositions with specific cation ordering, DRX materials have a wide compositional design space based on earth abundant metals such as Mn, Ti, Mo, Al, Zr, V, and Nb. Furthermore, Li-rich oxyfluoride DRX cathodes have demonstrated specific energies up to 1,000 Wh/kg which exceeds that of state-of-the-art layered LiNixMnyCo1-x-yO2 (NMC) cathodes (~700 Wh/kg). Despite such scientific advancements, widespread adoption of DRX cathodes has been hindered by several technical challenges. First, most of the high fluorine content DRX compositions are synthesized using mechano-chemical synthesis that has inherent limitation in scalability and maintaining a uniform particle-size and morphology. Further, DRX compositions have about 3-4 order lower electronic conductivity compared to layered cathodes requiring a high carbon loading in the electrode (up to 25%) compromising energy density. The focus of this talk will be on developing alternate synthesis method for Li-Mn rich DRX compositions. Specifically solid-state and sol-gel synthesis methods to produce DRX cathodes with the nominal composition Li1.2Mn0.4+xTi0.4-xO2-xFx (x = 0-0.3). Detailed advanced characterization (i.e., neutron total scattering and electron microscopy) and modelling efforts (i.e., Reverse Monte Carlo simulations) to understand how SRO impacts cathode performance will be presented. Different choice of precursors based on thermodynamic and kinetic consideration that minimizes formation of LiF impurity phases will be proposed. Acknowledgment This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725
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Schweidler, Simon, Sören L. Dreyer, Ben Breitung, and Torsten Brezesinski. "Acoustic Emission Monitoring of High-Entropy Oxyfluoride Rock-Salt Cathodes during Battery Operation." Coatings 12, no. 3 (March 18, 2022): 402. http://dx.doi.org/10.3390/coatings12030402.
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High-entropy materials with tailorable properties are receiving increasing interest for energy applications. Among them, (disordered) rock-salt oxyfluorides hold promise as next-generation cathodes for use in secondary batteries. Here, we study the degradation behavior of a high-entropy oxyfluoride cathode material in lithium cells in situ via acoustic emission (AE) monitoring. The AE signals allow acoustic events to be correlated with different processes occurring during battery operation. The initial cycle proved to be the most acoustically active due to significant chemo-mechanical degradation and gas evolution, depending on the voltage window. Irrespective of the cutoff voltage on charge, the formation and propagation of cracks in the electrode was found to be the primary source of acoustic activity. Taken together, the findings help advance our understanding of the conditions that affect the cycling performance and provide a foundation for future investigations on the topic.
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Li, Zongchang, Zhihao Zhang, Baojun Huang, Huanwen Wang, Beibei He, Yansheng Gong, Jun Jin, and Rui Wang. "Improved Cycling Performance of Cation-Disordered Rock-Salt Li1.2Ti0.4Mn0.4O2 Cathode through Mo-Doping and Al2O3-Coating." Coatings 12, no. 11 (October 23, 2022): 1613. http://dx.doi.org/10.3390/coatings12111613.
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Cation-disordered rock-salt cathode material is a promising material for next-generation lithium-ion batteries due to their extra-high capacities. However, the drawbacks of large first-cycle irreversible capacity loss, severe capacity decay, and lower discharge voltage have undoubtedly hindered their application in commercial systems. In this study, cation doping (Mo4+) and atomic layer deposition (ALD) techniques were used to synthetically modify the Li1.2Ti0.4Mn0.4O2 (LTMO) material to improve the cycling stability. First, the optimal Mo-doped sample (Mo01) with the best electrochemical performance among the different doping amounts was selected for further study. Second, the selected sample was subsequently coated with an Al2O3 layer by the ALD technique to further optimize its electrochemical performance. Results show that the LTMMO/24Al2O3 sample, under optimal conditions, could obtain a specific discharge capacity of up to 228.4 mAh g−1 after 30 cycles, which is much higher than that of the unmodified LTMO cathode material. Our work has provided a new possible solution to address some of the capacity fading issues related to the cation-disordered rock-salt cathode materials.
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Nanda, Jagjit. "Design Framework for Cobalt and Ni-Free High-Capacity Lithium-Ion Cathodes." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 361. http://dx.doi.org/10.1149/ma2022-012361mtgabs.
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Growing demand for Lithium-ion batteries for electric transportation and grid-scale storage will inevitably put resource constraints in terms of availability of key critical battery materials such as cobalt, nickel, lithium, and graphite. Specifically limited global reserve of elements such as cobalt and nickel will lead to severe supply chain issues driving the cost and contributing to market uncertainty. Given such scenario, there has been a significant effort in the global research community to develop high performance battery materials derived from relatively earth abundant elements. The talk will highlight ongoing research at PI’s Laboratory and collaborators on developing cobalt-free disorder rock salt (DRX) cathodes for next generation Li-ion. Most practical Li-ion cathode materials have well-ordered structures (e.g., spinel, layered, olivine), while the DRX compounds do not require any cation ordering. Instead, Li transport is achieved by percolation through a cation-disordered within the dense crystalline rock salt structure. Since DRX compounds do not necessitate a layered structure, they do not necessarily require cobalt metal and can be synthesized from an extremely wide variety of common metals, including Ti, Mn, Ni, Al, Nb, Mo, V, Zr, etc. Therefore, such class of materials provides plenty of chemical options for cathode design for Li-ion. Another key enabling aspect for this class of cathodes is the role of fluorine in stabilizing the high voltage oxygen redox and capacity retention. The talk will focus specifically on synthesis and structural design of Li-Mn-Ti-OF based DRX compositions and pathways for improving high voltage redox and stability. This work performed at Oak Ridge National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725
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Baur, Christian, Ida Källquist, Johann Chable, Jin Hyun Chang, Rune E. Johnsen, Francisco Ruiz-Zepeda, Jean-Marcel Ateba Mba, et al. "Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes." Journal of Materials Chemistry A 7, no. 37 (2019): 21244–53. http://dx.doi.org/10.1039/c9ta06291b.
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Lee, Jinhyuk. "(Digital Presentation) Particle Size and Transition-Metal Chemistry Determine the Impact of Li-Excess on Disordered Rock-Salt Li-Ion Cathode Materials." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2616. http://dx.doi.org/10.1149/ma2022-0272616mtgabs.
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The development of Co-free Li-excess disordered rock-salt (DRX) cathodes (e.g., Li1.2Mn0.4Ti0.4O2) for Li-ion batteries and interpretation through the percolation theory of Li diffusion have directed researchers to consider “Li-excess” (x > 1.1 in Li x TM 2-x O 2 ; TM = transition metal) as being essential to achieving high performance [1]. While the percolation theory provided an important insight into Li-transport in DRX materials, it leaves a critical impression that those DRXs without Li-excess will not deliver high capacity and thus are unsuitable as Li-ion cathode materials. However, the majority of DRX materials are made into pulverized nanoparticles whose small particle sizes (diameter < 150 nm) should render Li transport easy to achieve even with slow intrinsic Li diffusivity, making us question if Li-excess is necessary for designing DRX cathodes [2]. Moreover, the introduction of Li-excess requires a high degree of oxygen redox (along with TM-redox) in the materials to store electrons during cycling, leading to various O-redox-related side reactions (e.g., O-loss) that trigger fast capacity/voltage loss. In this presentation, we show that Li-excess is not necessary for some DRX-cathodes demonstrated by Li1.05Mn0.90Nb0.05O2 (M90) and Li1.20Mn0.60Nb0.20O2 (M60), which both deliver high capacity (>250 mAh/g) regardless of their Li-excess level [3]. By contextualizing this finding within the broader space of DRX materials and confirming with DFT calculations, we reveal that the percolation effect is not crucial at the nanoparticle scale, which most DRX materials developed so far have assumed by having the pulverized nanoparticle morphology [2]. Instead, Li-excess is required to decrease the charging voltage of certain DRX cathodes, which otherwise would experience difficulties in charging due to their very high TM-redox potential. Our findings show the double roles of Li-excess – modifying the cathode voltage and improving Li diffusion – that must be simultaneously considered to understand the necessity of Li-excess for high-capacity DRX cathodes. [1] J. Lee & G. Ceder et al., Science 343, 519-522 (2014) [2] H. Li & J. Lee et al., Joule 6, 53-91 (2022) [3] J. Lee & J. Li et al., Adv. Energy Mater., 2100204 (2021)
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Hu, Y., V. Thoréton, C. Pirovano, E. Capoen, C. Bogicevic, N. Nuns, A. S. Mamede, G. Dezanneau, and R. N. Vannier. "Oxide diffusion in innovative SOFC cathode materials." Faraday Discuss. 176 (2014): 31–47. http://dx.doi.org/10.1039/c4fd00129j.
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Oxide diffusion was studied in two innovative SOFC cathode materials, Ba2Co9O14 and Ca3Co4O9+δ derivatives. Although oxygen diffusion was confirmed in the promising material Ba2Co9O14, it was not possible to derive accurate transport parameters because of an oxidation process at the sample surface which has still to be clarified. In contrast, oxygen diffusion in the well-known Ca3Co4O9+δ thermoelectric material was improved when calcium was partly substituted with strontium, likely due to an increase of the volume of the rock salt layers in which the conduction process takes place. Although the diffusion coefficient remains low, interestingly, fast kinetics towards the oxygen molecule dissociation reaction were shown with surface exchange coefficients higher than those reported for the best cathode materials in the field. They increased with the strontium content; the Sr atoms potentially play a key role in the mechanism of oxygen molecule dissociation at the solid surface.
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Antipov, Evgeny V., Nellie R. Khasanova, and Stanislav S. Fedotov. "Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries." IUCrJ 2, no. 1 (January 1, 2015): 85–94. http://dx.doi.org/10.1107/s205225251402329x.
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To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4)n−and F−] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications.
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Tahmasebi, Mohammad H., and M. N. Obrovac. "Quantitative Measurement of Compositional Inhomogeneity in NMC Cathodes by X-ray Diffraction." Journal of The Electrochemical Society 170, no. 8 (August 1, 2023): 080519. http://dx.doi.org/10.1149/1945-7111/acefff.
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A novel XRD analysis technique is described for quantitatively measuring compositional inhomogeneity in Li[NixMnyCoz]O2 (NMC) cathode materials and NMC precursors. Single-phase rock salt precursors with varying degrees of compositional inhomogeneity were prepared by grinding mixtures of Ni, Mn and Co oxides for different times and then heating. These precursors were then heated with lithium to form cathode materials. A modified Williamson-Hall analysis was used to measure the degree of compositional inhomogeneity in the precursors and the final NMC materials. This analysis showed that precursors made with low grinding times had higher compositional inhomogeneity and that this compositional inhomogeneity was amplified in the final NMC, leading to interlayer mixing and poor electrochemical performance. Higher precursor grinding times lead to more compositionally homogeneous NMC, while even higher compositional homogeneity was achieved by NMC made from conventional hydroxide precursors, with correspondingly improved electrochemical performance. The ability described here to measure the degree of compositional homogeneity in NMC precursors and NMC cathode materials by simple XRD measurements presents a powerful tool for the research and development of NMC and other cathode materials.
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Yu, Zhaozhe, Qilin Tong, Yan Cheng, Ping Yang, Guiquan Zhao, Huacheng Li, Weifeng An, Dongliang Yan, Xia Lu, and Bingbing Tian. "Enabling 4.6 V LiNi0.6Co0.2Mn0.2O2 cathodes with excellent structural stability: combining surface LiLaO2 self-assembly and subsurface La-pillar engineering." Energy Materials 2, no. 5 (2022): 37. http://dx.doi.org/10.20517/energymater.2022.42.
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Although Ni-rich layered materials with the general formula LiNi1-x-yCoxMnyO2 (0 < x, y < 1, NCM) hold great promise as high-energy-density cathodes in commercial lithium-ion batteries, their practical application is greatly hampered by poor cyclability and safety. Herein, a LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode modified with a surface self-assembling LiLaO2 coating and subsurface La pillars demonstrates stabilized cycling at 4.6 V. The LiLaO2-coated NCM622 benefits from the suppression of interfacial side reactions, which relieves the layer-to-rock salt phase transformation and therefore improves the capacity retention under high voltages. Moreover, the La dopant, as a pillar in the NCM622 lattice, plays a dual role in expanding the c lattice parameter to enhance the Li-ion diffusion capability, as well as suppressing Ni antisite defect formation upon cycling. Consequently, the dual-modified NCM622 cathode exhibits an initial Coulombic efficiency of over 85% and a high capacity of over 200 mAh g-1 at 0.1 C. A specific capacity of 188 mAh g-1 with a capacity retention of 76% is achieved at 1 C after 200 cycles within a voltage range of 3.0-4.6 V. These findings lay a solid foundation for the materials design and performance optimization of high-energy-density cathodes for Li-ion batteries.
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Shirazi Moghadam, Yasaman, Sirshendu Dinda, Abdel El Kharbachi, Georgian Melinte, Christian Kübel, and Maximilian Fichtner. "Structural and Electrochemical Insights from the Fluorination of Disordered Mn-Based Rock Salt Cathode Materials." Chemistry of Materials 34, no. 5 (February 17, 2022): 2268–81. http://dx.doi.org/10.1021/acs.chemmater.1c04059.
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Su, Yuefeng, Yongqing Yang, Lai Chen, Yun Lu, Liying Bao, Gang Chen, Zhiru Yang, et al. "Improving the cycling stability of Ni-rich cathode materials by fabricating surface rock salt phase." Electrochimica Acta 292 (December 2018): 217–26. http://dx.doi.org/10.1016/j.electacta.2018.09.158.
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Kamel, M., M. Abdel-Hafiez, A. Hassan, M. Abdellah, T. A. Abdel-Baset, and A. Hassen. "Optical, magnetic, thermodynamic, and dielectric studies of the disordered rock salt Li1.3Nb0.3Fe0.4O2 cathode for Li-ion batteries." Journal of Applied Physics 131, no. 15 (April 21, 2022): 155103. http://dx.doi.org/10.1063/5.0084684.
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While most studies in disordered rock salt cathode materials focus on synthesis and electrochemical investigation, detailed investigations on their optical and thermodynamic properties are a matter of interest. Here, we report on complementary measurements of transient absorption spectroscopy, thermodynamic, and dielectric properties for Li1.3Nb0.3Fe0.4O2 (LNFO) disordered rock salt Li-excess. The structure was studied using powder x-ray diffraction and scanning electron microscopy, which showed the fine crystallization of LNFO. The ultra-fast laser spectroscopy is used to study the dynamics of charge carriers and electron–phonon coupling in the system. Our thermodynamic measurements have revealed a magnetically ordered phase with small spontaneous magnetization. The dielectric properties of LNFO illustrate high permittivity with losses at low frequencies. Furthermore, the behavior of the dielectric modulus and AC conductivity vs temperature and frequency were discussed.
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Cheng, Tao, Zhongtao Ma, Run Gu, Riming Chen, Yingchun Lyu, Anmin Nie, and Bingkun Guo. "Cracks Formation in Lithium-Rich Cathode Materials for Lithium-Ion Batteries during the Electrochemical Process." Energies 11, no. 10 (October 11, 2018): 2712. http://dx.doi.org/10.3390/en11102712.
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The lithium-rich Li[Li0.2Ni0.13Mn0.54Co0.13]O2 nanoplates were synthesized using a molten-salt method. The nanoplates showed an initial reversible discharge capacity of 233 mA·h·g−1, with a fast capacity decay. The morphology and micro-structural change, after different cycles, were studied by a scanning electron microscope (SEM) and transmission electron microscopy (TEM) to understand the mechanism of the capacity decay. Our results showed that the cracks generated from both the particle surface and the inner, and increased with long-term cycling at 0.1 C rate (C = 250 mA·g−1), together with the layered to spinel and rock-salt phase transitions. These results show that the cracks and phase transitions could be responsible for the capacity decay. The results will help us to understand capacity decay mechanisms, and to guide our future work to improve the electrochemical performance of lithium-rich cathode materials.
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Flannagin, Megan, Hernando Gonzalez Malabet, and George J. Nelson. "Characterization of Low Cobalt Cathode Degradation Using Distribution of Relaxation Times Analysis." ECS Meeting Abstracts MA2022-02, no. 3 (October 9, 2022): 256. http://dx.doi.org/10.1149/ma2022-023256mtgabs.
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High-capacity cathode materials with reduced or eliminated cobalt usage are being pursued for lithium-ion batteries (LIB) due to environmental and humanitarian issues in the cobalt supply chain. Consequently, increased nickel content and reduced cobalt content results in faster cell degradation. A connection between morphological and chemical changes within the cathode microstructure, charge cut-off voltage, and operating temperature has been developed through a combination of cycling conditions, X-ray Diffraction (XRD), and Distribution of Relaxation Times (DRT) analysis. Low cobalt half-cell batteries were fabricated with Li(Ni0.8Mn0.1Co0.1)O2 (NMC811) active material and tested under high cut-off voltage (4.3V), low cut-off voltage (4.0V), high temperature (60°C), and ambient temperature (25°C). XRD analysis of high cut-off voltage samples show a presence of NiOx crystalline structure, a low diffusivity rock-salt phase. To further understand the electrochemical changes due to the appearance of the rock-salt phase, DRT analysis was conducted on the electrochemical impedance spectra taken after formation of the solid electrolyte interphase (SEI) and after cycling. DRT analysis is becoming a preferred method of analysis due to the fact that electrochemical processes, like solid-state diffusion, cathode electrolyte interphase (CEI), and SEI formation, show up at characteristic frequencies, allowing for interpretation of changes that are often not visible within typical impedance plots. Prior to cycling, the primary contribution was initially found to be from the CEI and SEI. At low cut-off voltage cycling conditions, ambient temperature cycling showed that the contribution shifted from the CEI to diffusion resistance, but changes within the SEI and CEI were still detected. High temperature cycling conditions within the low cut-off voltage samples showed that the diffusion resistance again increased and the contributions from the CEI and SEI decreased. At high cut-off voltage cycling conditions, ambient temperature cycling showed that diffusion was becoming the main contribution but changes due to the CEI were still evident. High temperature cycling conditions in the high cut-off voltage samples showed that the mechanism was completely taken over by diffusion, due to the lithium transport being limited by the rock-salt phase or electrolyte degradation. XRD patterns confirmed that the rock-salt phase was beginning to form within the low cut-off voltage high temperature cycling condition, but in much lower intensity than that of the high cut-off voltage condition. This observation clearly shows that the diffusion mechanism, which hinders intercalation and deintercalation, is driven by the formation of the non-conductive rock-salt phase. While primarily influenced by cut-off voltage, elevated temperature may also contribute to this degradation mechanism. The combination of different electrochemical and microstructural characterization techniques supports this observation and demonstrate that DRT analysis is an effective method to better understand the driving mechanisms behind battery degradation.
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Zheng, Yu, and Perla B. Balbuena. "Electrolyte Deprotonation Stimulates Phase Transition of Ni-Rich Cathodes in Na-Ion Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 509. http://dx.doi.org/10.1149/ma2022-024509mtgabs.
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Sodium-ion batteries (SIBs) are considered as a promising alternative to lithium-ion batteries (LIBs), Since they are composed of naturally abundant elements, cheaper and larger scale battery modules can be assembled. However, due to their similar electrochemical mechanisms, their practical utilization is hindered by high reactivity of conventional carbonate electrolytes with electrode materials leading to the capacity fading over repeated charging cycles. To overcome this obstacle, localized high concentration electrolytes (LHCEs) are used as an effective approach to maintain localized solvation structure of active electrolyte salts by using hydrofluoroether as diluents. Earlier studies are mainly focusing on the interactions between electrolytes with anode materials. Little was known about the electrochemical reactions of LHCEs on SIB cathode. In this work, we examined the reactivities of carbonate electrolytes and LHCEs on NaNiO2 surfaces. Ab initio molecular dynamics simulations showed that carbonate electrolytes involve more dehydrogenation reactions than LHCEs. The proton-transfer reactions between electrolyte molecules and cathode surface oxygens cause the formation of hydroxyl (-OH) groups, which leads to reduction of neighboring surface nickel atoms from Ni3+ to Ni2+. As cathode surface gets desodiated, more proton-transfer reactions were observed and Ni migrations from transition metal layer to Na layer were also identified. Consequently, it results in the oxygen loss of NaNiO2 which accelerates the layered-rock salt phase transition of bulk cathodes.
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Rocca, Riccardo, Mauro Francesco Sgroi, Bruno Camino, Maddalena D’Amore, and Anna Maria Ferrari. "Disordered Rock-Salt Type Li2TiS3 as Novel Cathode for LIBs: A Computational Point of View." Nanomaterials 12, no. 11 (May 27, 2022): 1832. http://dx.doi.org/10.3390/nano12111832.
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The development of high-energy cathode materials for lithium-ion batteries with low content of critical raw materials, such as cobalt and nickel, plays a key role in the progress of lithium-ion batteries technology. In recent works, a novel and promising family of lithium-rich sulfides has received attention. Among the possible structures and arrangement, cubic disordered Li2TiS3 has shown interesting properties, also for the formulation of new cell for all-solid-state batteries. In this work, a computational approach based on DFT hybrid Hamiltonian, localized basis functions and the use of the periodic CRYSTAL code, has been set up. The main goal of the present study is to determine accurate structural, electronic, and spectroscopic properties for this class of materials. Li2TiS3 precursors as Li2S, TiS2, and TiS3 alongside other formulations and structures such as LiTiS2 and monoclinic Li2TiS3 have been selected as benchmark systems and used to build up a consistent and robust predictive scheme. Raman spectra, XRD patterns, electronic band structures, and density of states have been simulated and compared to available literature data. Disordered rock-salt type Li2TiS3 structures have been derived via a solid solution method as implemented into the CRYSTAL code. Representative structures were extensively characterized through the calculations of their electronic and vibrational properties. Furthermore, the correlation between structure and Raman fingerprint was established.
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Chen, Hao, Li Xiao, Pengcheng Liu, Han Chen, Zhimei Xia, Longgang Ye, and Yujie Hu. "Rock Salt-Type LiTiO2@LiNi0.5Co0.2Mn0.3O2 as Cathode Materials with High Capacity Retention Rate and Stable Structure." Industrial & Engineering Chemistry Research 58, no. 40 (August 28, 2019): 18498–507. http://dx.doi.org/10.1021/acs.iecr.9b03276.
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Doeff, Marca M. "(Invited) Thermal Properties of NMC Cathode Materials." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 378. http://dx.doi.org/10.1149/ma2022-012378mtgabs.
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NMC (LiNixMnyCozO2; x+y+z»1) materials deliver high capacity and excellent performance when used as cathodes in lithium-ion batteries. Increasing demand for higher energy density and concerns about the cost and ethics of using cobalt have prompted battery manufacturers to use Ni-rich formulations such as LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Mn0.1Co0.1O2 (NMC811). The thermal stability of (partially) delithiated NMCs is known to decrease with increasing Ni content, however, so that scenarios of fires and other safety events become more distinct possibilities. To investigate the thermal properties of Ni-rich NMCs, we prepared partially and fully delithiated Ni-rich NMCs corresponding to various states-of-charge by chemical methods. We then studied the bulk and surface properties of these materials as they were heated or after they were heated, using a variety of ex situ and in situ synchrotron methods to understand the chemical changes that occur. Of particular concern are reactions that result in release of oxygen. Heated materials progress through a series of bulk structural changes from layered to spinel to rock salt as temperatures rise. Transition temperatures depend on both lithium and nickel content, with bulk changes evident at temperatures as low as 150°C. Surface-sensitive techniques such as soft X-ray absorption spectroscopy (sXAS) indicate that subtle changes that lead to oxygen release can happen well below these temperatures. The thermal behavior of the Ni-rich materials is very complex, and involves lattice transformation, transition metal migration and valence change and lithium redistribution. Moreover, these changes are dependent upon primary particle size, with smaller particles reacting at lower temperatures than larger ones. These observations suggest that materials can be engineered (through primary particle size manipulation, for example) to improve thermal robustness, and therefore, safety and reliability of lithium-ion batteries.
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Celasun, Yagmur, Jean-François Colin, Sébastien Martinet, Anass Benayad, and David Peralta. "Lithium-Rich Rock Salt Type Sulfides-Selenides (Li2TiSexS3−x): High Energy Cathode Materials for Lithium-Ion Batteries." Materials 15, no. 9 (April 22, 2022): 3037. http://dx.doi.org/10.3390/ma15093037.
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Lithium-rich disordered rocksalt Li2TiS3 offers large discharge capacities (>350 mAh·g−1) and can be considered a promising cathode material for high-energy lithium-ion battery applications. However, the quick fading of the specific capacity results in a poor cycle life of the system, especially when liquid electrolyte-based batteries are used. Our efforts to solve the cycling stability problem resulted in the discovery of new high-energy selenium-substituted materials (Li2TiSexS3−x), which were prepared using a wet mechanochemistry process. X-ray diffraction analysis confirmed that all compositions were obtained in cation-disordered rocksalt phase and that the lattice parameters were expanded by selenium substitution. Substituted materials delivered large reversible capacities, with smaller average potentials, and their cycling stability was superior compared to Li2TiS3 upon cycling at a rate of C/10 between 3.0–1.6 V vs. Li+/Li.
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Llewellyn, Alice V., Andrew S. Leach, Isabella Mombrini, Alessia Matruglio, Jiecheng Diao, Chun Tan, Thomas M. M. Heenan, et al. "Understanding the Degradation Mechanisms of Lithium Ion Batteries Using in-Situ Multi-Scale Diffraction Techniques." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 177. http://dx.doi.org/10.1149/ma2022-012177mtgabs.
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Advanced Li-ion batteries adopting new cathode chemistries are required for the successful widespread transition to electric vehicles (EVs) and renewable energy sources, aiming for high energy density, long cycle life, and good rate capability. Commercial candidates for EV batteries include Ni-rich Li(NixMnyCo1−x-y)O2 (NMC) cathodes, with Ni:Mn:Co ratios of 8:1:1 (NMC811) and higher. These are favored because of their high specific capacity (~ 200 mAh g-1)and reduced cobalt content. Despite all of the advantages, these materials suffer from a range of degradation modes, many of which are associated with the redox and crystallographic behavior at high states of charge. In particular, Ni-rich cathodes suffer from several limitations, such as rapid capacity fade in comparison to NMC stoichiometries with lower Ni content. In addition, they also have a lower onset voltage for oxygen release and subsequent surface reconstruction leading to the formation of spinel and rock salt phases which impede (de)lithiation and therefore the achievable capacity of the cell.1 Crystallographic properties of electrode materials are intrinsically linked to the electrochemical performance of the cell. NMC materials suffer from anisotropic changes in the crystal structure during cycling which induces strain and leads to issues such as crack formation, expediting degradation. One method to tackle capacity fade is to switch to single-crystal morphologies (particle size 1-3 μm) which have better mechanical stability than conventional polycrystalline morphologies (secondary agglomerate particles ~ 10 μm made up of primary particles which are 100 nm – 1 μm in size) and have less propensity to form extensive rock-salt layers. It is thought that the single-crystal morphology helps to reduce stress in the material as the anisotropic stress in polycrystalline cathodes is concentrated at grain boundaries. However, there is still a limited understanding of the subtle mechanistic differences between the two materials during cycling.2 A multi-scale approach is required to gain a more comprehensive understanding of the degradation mechanisms at play and how they initiate and propagate. In this work, synchrotron diffraction methods were employed at the crystal, particle and cell scale using a variety of techniques including in-situ Bragg Coherent Diffraction Imaging (BCDI), 3D-XRD and operando high-resolution XRD. Intra-particle, inter-particle and electrode level heterogeneities were observed during cycling, both in pristine and aged samples. It is believed that these heterogeneities accelerate the loss of performance at the cell level by inducing crack formation which can then be observed in X-ray computed tomography data acquired in simultaneous lab studies. The overarching goal of these investigations is to add to the understanding of complex degradation mechanisms for Ni-rich layered transition metal oxide cathodes, ultimately aiding in the informed development of future battery electrode materials. References: 1] Xu, C. et al., Phase Behaviour during Electrochemical Cycling of Ni‐Rich Cathode Materials for Li‐Ion Batteries. Adv. Energy Mater. 2021, 11, 2003404. 2] Yin, S. et al., Fundamental and solutions of microcracks in Ni-rich layered oxide cathode materials of lithium-ion batteries. Nano Energy, 2021, 83, 105854.
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Lian, Fang, Yan Li, Yang Hu, Sheng Wen Zhong, Li Hua Xu, and Qing Guo Liu. "Rate Capability Fade of 18650 Li-Ion Cells." Key Engineering Materials 368-372 (February 2008): 290–92. http://dx.doi.org/10.4028/www.scientific.net/kem.368-372.290.
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The rate capability of 18650 lithium-ion cells was studied in the paper. The experimental results showed that the reversible capacity declined to 89.5, 85.8 and 81.2% of the initial capacity after 300 cycles at discharge rate of 0.5, 1 and 2C, respectively. The XRD and SAED analysis indicated that at a high current density partial positive electrode material LiCoO2 transformed gradually from well-layered structure to rock salt cubic crystal. Upon the cycling, the degradation of cathode materials’ structure and much thicker negative film on anode electrode surface contributed to the rate capability fade.
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Fan, Xiaojian, Qianwan Qin, Dongming Liu, Aichun Dou, Mingru Su, Yunjian Liu, and Jun Pan. "Synthesis and electrochemical performance of Li3NbO4-based cation-disordered rock-salt cathode materials for Li-ion batteries." Journal of Alloys and Compounds 797 (August 2019): 961–69. http://dx.doi.org/10.1016/j.jallcom.2019.05.163.
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Lee, Hayeon, Woosung Choi, Wontae Lee, Jae‐Hyun Shim, Young‐Min Kim, and Won‐Sub Yoon. "Rock Salt Cathodes: Impact of Local Separation on the Structural and Electrochemical Behaviors in Li 2 MoO 3 LiCrO 2 Disordered Rock‐Salt Cathode Material (Adv. Energy Mater. 3/2021)." Advanced Energy Materials 11, no. 3 (January 2021): 2170011. http://dx.doi.org/10.1002/aenm.202170011.
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Suzuki, Kosuke, Yuji Otsuka, Kazushi Hoshi, Hiroshi Sakurai, Naruki Tsuji, Kentaro Yamamoto, Naoaki Yabuuchi, et al. "Magnetic Compton Scattering Study of Li-Rich Battery Materials." Condensed Matter 7, no. 1 (December 28, 2021): 4. http://dx.doi.org/10.3390/condmat7010004.
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The redox process in a lithium-ion battery occurs when a conduction electron from the lithium anode is transferred to the redox orbital of the cathode. Understanding the nature of orbitals involved in anionic as well as cationic redox reactions is important for improving the capacity and energy density of Li-ion batteries. In this connection, we have obtained magnetic Compton profiles (MCPs) from the Li-rich cation-disordered rock-salt compound LixTi0.4Mn0.4O2 (LTMO). The MCPs, which involved the scattering of circularly polarized hard X-rays, are given by the momentum density of all the unpaired spins in the material. The net magnetic moment in the ground state can be extracted from the area under the MCP, along with a SQUID measurement. Our analysis gives insight into the role of Mn 3d magnetic electrons and O 2p holes in the magnetic redox properties of LTMO.
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Roy, Indrani, and Jordi Cabana. "Investigation of the Redox Activity in Mn-Based Oxyfluorides." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 305. http://dx.doi.org/10.1149/ma2022-012305mtgabs.
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Li-ion batteries offer excellent electrochemical performance, are widely used in vehicle electrification and portable devices, and have huge potential for grid storage applications. Their electrochemical behavior relies primarily on transition metal oxide cathodes. In a recent development, Mn has been used in Li-rich cathode materials with a cationic disordered rock-salt (DRX) structure [1,2]. These Mn-based DRX materials are promising candidates for next-generation Li-ion battery cathodes because of their large energy densities and basic favorable features of Mn, such as sustainability. Along with the use of Mn in a DRX structure, substitution of some of the oxygen by fluorine imparts improved cyclability [1-6]. It has been proposed that Li-site distribution played an important role in the initial capacity of these materials and the metal-redox capacity and reversibility was improved by fluorination [5,6]. However, the contribution of the different ions to this improvement has not been fully elucidated. Fluorine and oxygen have different bonding interactions with transition metals, raising the question of how they may comparatively participate in redox compensation. To address this question and determine the role of a mixture of anions in improving the energy density in such cathode materials, we conducted a deep dive into Li2MnO2F as a model cathode material [6]. We interrogated the covalent interaction between the oxygen 2p states, fluorine 2p states, and the transition metal 3d orbitals, and their respective contribution to the charge compensation mechanism using X-ray absorption spectroscopy (XAS). XAS allowed us to resolve the role of both oxygen and fluorine in the electrochemical activity and how covalent interactions are affected by redox, both in extent and in their reversibility. References: Gerbrand Ceder et. al. "The Configurational Space of Rocksalt‐Type Oxides for High‐Capacity Lithium Battery Electrodes." Advanced Energy Materials 4, no. 13 (2014): 1400478. Lee, Jinhyuk et.al. "Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries." science 343, no. 6170 (2014): 519-522. Freire, Melanie et. al. "A new active Li-Mn–O compound for high energy density Li-ion batteries." Nature materials 15, no. 2 (2016): 173-177. Reed, J., G. Ceder, and A. Van Der Ven. "Layered-to-spinel phase transition in Li x MnO2." Electrochemical and Solid-State Letters 4, no. 6 (2001): A78. Lee, Jinhyuk, et al. "Reversible Mn 2+/Mn 4+ double redox in lithium-excess cathode materials." Nature 556, no. 7700 (2018): 185-190. 7/8 Lun, Zhengyan, et al. "Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes." Chem 6, no. 1 (2020): 153-168.
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Antipov, Evgeny, and Nellie Khasanova. "Impact of Crystallography on Design of Cathode Materials for Li-ion Batteries." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C20. http://dx.doi.org/10.1107/s2053273314099793.
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Ninety percent of the energy produced today come from fossil fuels, making dramatically negative impact on our future due to rapid consumption of these energy sources, ecological damage and climate change. This justifies development of the renewable energy sources and concurrently efficient large storage devices capable to replace fossil fuels. Li-ion batteries have originally been developed for portable electronic devices, but nowadays new application niches are envisaged in electric vehicles and stationary energy storages. However, to satisfy the needs of these rapidly growing applications, Li-ion batteries require further significant improvement of their properties: capacity and power, cyclability, safety and cost. Cathode is the key part of the Li-ion batteries largely determining their performance. Severe requirements are imposed on a cathode material, which should provide fast reversible intercalation of Li-ions at redox potential close to the upper boundary of electrolyte stability window, possess relatively low molecular weight and exhibit small volume variation upon changing Li-concentration. First generation of the cathode materials for the Li-ion batteries based on the spinel (LiM2O4, M – transition metal) or rock-salt derivatives (LiMO2) has already been widely commercialised. However, the potential to further improve the performance of these materials is almost exhausted. The compounds, containing lithium and transition metal cations together with different polyanions (XmOn)p- (X=B, P, S, Si), are now considered as the most promising cathode materials for the next generation of the Li-ion batteries. Covalently-bonded structural frameworks in these compounds offer long-term structural stability, which is essential for good cyclability and safety. Further advantages are expected from combining different anions (such as (XO4)p- and F- ) in the anion sublattice, with the hope to enhance the specific energy and power of these materials. Various fluoride-phosphates and fluoride-sulphates have been recently discovered, and some of them exhibit attractive electrochemical performance. An overview of the research on the cathode materials for the Li-ion batteries will be presented with special emphasis on crystallography as a guide towards improved properties important for practical applications.
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Wang, Han, Tong Zhou, Yong Wang, Wei Zhang, and Linsen Li. "Stabilizing Lattice Oxygen in Slightly Li-Enriched Nickel Oxide Cathodes Toward High-Energy Batteries." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2559. http://dx.doi.org/10.1149/ma2022-0272559mtgabs.
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LiNiO2 (LNO, 100% Ni) is an old material first identified in the early 1990s (as a higher-capacity and lower-cost alternative to LiCoO2) but has yet to fulfill its potential. Despite intense research efforts for more than two decades, LNO still exhibits rapid capacity loss during cycling and poor thermal stability (1-3). The traditional LNO is generally prepared by solid-state reactions and recognized as Li-deficient Li1-yNi1+yO2 (4). Ex situ characterizations indicated that the performance degradation originates from the detrimental phase transition (layered to rock-salt structure) during electrochemical cycling (5-7), which is closely related to the lattice-oxygen release during charge (8, 9). To improve the performance of LNO, the structure is commonly modified by lattice doping or surface coating, which have led to improved cycle stability but at the cost of capacity loss (10). Meanwhile, these modification approaches failed to address the lattice oxygen instability, as the O2 release was still detected for the doped or surface-coated layered cathodes (11, 12). Here, we demonstrate an Li-enrichment strategy to produce a trigonal-structured layered Li-enriched LNO (Li1.04Ni0.96O2, LR-LNO) with a slight excess of Li to occupy the Ni sites, which is a possible phase according to the Li-Ni-O phase diagram but has never been experimentally synthesized (Figure 1). LR-LNO (Figure 1) enables a combination of a high specific energy density of 904 Wh kg-1, outstanding cyclability (~80% capacity retention after 400 cycles in full cells versus 35 cycles for LNO), and significantly enhanced thermal stability (>70 °C increase in thermal-runaway temperature over LNO). We further designed a double-tilt electrochemical liquid cell inside a transmission electron microscope (TEM) to track the local structural changes at the surface of individual particles during galvanostatic cycling (Figure 2), revealing the performance-enhancing mechanism behind the slight change in the material composition. Excess Li ions in the Ni layer promoted intralayer migration of Ni ions during delithiation in LR-LNO, generating vacancy clusters to trap the electrochemically oxidized molecular O2 in the near-surface lattice. Consequently, the oxygen redox reaction became highly reversible, and the detrimental layered-to-rock-salt phase transition are effectively inhibited, thus improving the structural reversibility of LR-LNO during cycling and the thermal stability.Our results provide a composition fine-tuning strategy to produce highly-reversible cathodes for high energy-density, low-cost and safe batteries. Beyond batteries, the double-tilt operando TEM technique will facilitate studies into complex phase transitions in a wide range of materials. Figure 1 Pristine structure and outstanding performance of LR-LNO References M. M. Thackeray, K. Amine, Layered Li–Ni–Mn–Co oxide cathodes. Nature Energy 6, 933-933 (2021). A. Manthiram, J. B. Goodenough, Layered lithium cobalt oxide cathodes. Nature Energy 6, 323-323 (2021). K. Turcheniuk, D. Bondarev, V. Singhal, G. Yushin, Ten years left to redesign lithium-ion batteries. Nature 559, 467-470 (2018). J.-H. Kim, K.-J. Park, S. J. Kim, C. S. Yoon, Y.-K. Sun, A method of increasing the energy density of layered Ni-rich Li[Ni1−2xCoxMnx]O2 cathodes (x = 0.05, 0.1, 0.2). Journal of Materials Chemistry A 7, 2694-2701 (2019). C. S. Yoon, D.-W. Jun, S.-T. Myung, Y.-K. Sun, Structural stability of LiNiO2 cycled above 4.2 V. ACS Energy Lett. 2, 1150-1155 (2017). D.-W. Jun, C. S. Yoon, U.-H. Kim, Y.-K. Sun, High-energy density core-shell structured Li[Ni0.95Co0.025Mn0.025]O2 cathode for lithium-ion batteries. Chem. Mater. 29, 5048-5052 (2017). C. S. Yoon, M. H. Choi, B. B. Lim, E. J. Lee, Y.-K. Sun, Review—high-capacity Li[Ni1-xCox/2Mnx/2]O2 (x = 0.1, 0.05, 0) cathodes for next-generation Li-ion battery. J. Electrochem. Soc. 162, A2483-A2489 (2015). N. Li et al., Unraveling the cationic and anionic redox reactions in a conventional layered oxide cathode. ACS Energy Lett. 4, 2836-2842 (2019). S. S. Zhang, Problems and their origins of Ni-rich layered oxide cathode materials. Energy Storage Materials 24, 247-254 (2020). M. Bianchini, M. Roca-Ayats, P. Hartmann, T. Brezesinski, J. Janek, There and back again-the journey of LiNiO2 as a cathode active material. Angew. Chem., Int. Ed. 58, 10434-10458 (2019). N. Li et al., Correlating the phase evolution and anionic redox in Co-Free Ni-Rich layered oxide cathodes. Nano Energy 78, (2020). F. Strauss et al., Li2ZrO3-Coated NCM622 for Application in Inorganic Solid-State Batteries: Role of Surface Carbonates in the Cycling Performance. ACS applied materials & interfaces 12, 57146-57154 (2020). Figure 1
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Geng, Fushan, Bei Hu, Chao Li, Chong Zhao, Olivier Lafon, Julien Trébosc, Jean-Paul Amoureux, Ming Shen, and Bingwen Hu. "Anionic redox reactions and structural degradation in a cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 cathode material revealed by solid-state NMR and EPR." Journal of Materials Chemistry A 8, no. 32 (2020): 16515–26. http://dx.doi.org/10.1039/d0ta03358h.
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The cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 is studied by solid-state NMR and electron paramagnetic resonance (EPR) spectroscopy during the first cycle. The anionic redox and structural degradation mechanism are discussed.
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Fujiwara, Yoshiya, Yoshiyuki Morita, Hiroshi Ogasa, Fumika Fujisaki, and Akihiro Kushima. "Role of Ni, Mn and Co in Layered Rock Salt Cathode Materials for Li-Ion Battery: A DFT Study." ECS Meeting Abstracts MA2020-02, no. 1 (November 23, 2020): 61. http://dx.doi.org/10.1149/ma2020-02161mtgabs.
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Idris, Mohd Sobri. "The Existing of Oxygen Nonstoichiometry in Complex Lithium Oxides." Advanced Materials Research 795 (September 2013): 438–40. http://dx.doi.org/10.4028/www.scientific.net/amr.795.438.
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The possibility of oxygen deficiency in lithium-based complex oxides particularly for layered rock salt structures has little attention in the literature, in spite of the importance of these materials as potential lithium battery cathodes. This paper briefly reviewed the existing of oxygen non-stoichiometry in complex lithium oxides and their effect to perfomance of cathodes in lithium ion batteries.
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Nakamura, Hitoshi. "(Digital Presentation) Synthesis and Properties of Llithium Iron Phosphate Cathode Materials without Carbon Coating with High-Rate Property." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 366. http://dx.doi.org/10.1149/ma2022-012366mtgabs.
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Lithium iron (ferrium) phosphate (LFP) use iron as a transition metal, so there is lower resource risk. And because of tolerant to overcharging, they have excellent safety and durability. Lithium-ion secondary batteries using LFP have become widely used as main power sources for EVs and ESSs in recent years. Originally, LFP has higher bulk resistance than other layered rock salt-based positive materials, so that carbon-coating was applied to surface of LFP particles. This idea was extremely effective in putting LFP into practical use. However, the use of the carbon coat has led disadvantage of high cost despite the use of cheaper iron because the manufacturing process increases. We report that we have developed LFP that has extremely high-rate charge and discharge performance even though it does not have carbon coating. Figure 1
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Källquist, Ida, Andrew J. Naylor, Christian Baur, Johann Chable, Jolla Kullgren, Maximilian Fichtner, Kristina Edström, Daniel Brandell, and Maria Hahlin. "Degradation Mechanisms in Li2VO2F Li-Rich Disordered Rock-Salt Cathodes." Chemistry of Materials 31, no. 16 (June 3, 2019): 6084–96. http://dx.doi.org/10.1021/acs.chemmater.9b00829.
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Ou, Limin, Shengheng Nong, Ruoxi Yang, Yaoying Li, Jinrong Tao, Pan Zhang, Haifu Huang, et al. "Multi-Role Surface Modification of Single-Crystalline Nickel-Rich Lithium Nickel Cobalt Manganese Oxides Cathodes with WO3 to Improve Performance for Lithium-Ion Batteries." Nanomaterials 12, no. 8 (April 12, 2022): 1324. http://dx.doi.org/10.3390/nano12081324.
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Compared with the polycrystalline system, the single-crystalline ternary cathode material has better cycle stability because the only primary particles without grain boundaries effectively alleviate the formation of micro/nanocracks and retain better structural integrity. Therefore, it has received extensive research attention. There is no consistent result whether tungsten oxide acts as doping and/or coating from the surface modification of the polycrystalline system. Meanwhile, there is no report on the surface modification of the single-crystalline system by tungsten oxide. In this paper, multirole surface modification of single-crystalline nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O2 by WO3 is studied by a simple method of adding WO3 followed by calcination. The results show that with the change in the amount of WO3 added, single-crystalline nickel-rich ternary cathode material can be separately doped, separately coated, and both doped and coated. Either doping or coating effectively enhances the structural stability, reduces the polarization of the material, and improves the lithium-ion diffusion kinetics, thus improving the cycle stability and rate performance of the battery. Interestingly, both doping and coating (for SC-NCM622-0.5%WO3) do not show a more excellent synergistic effect, while the single coating (for SC-NCM622-1.0%WO3) after eliminating the rock-salt phase layer performs the most excellent modification effect.
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Morimoto, Sayaka, Yuta Kanai, Masahiko Yoshiki, Mitsuhiro Oki, and Ryosuke Yagi. "(Digital Presentation) Accelerated Degradation Mechanism of Ni-Rich Ncm Cathode Materials at High and Low Voltage Range Combined Cycling for Li-Ion Batteries." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 382. http://dx.doi.org/10.1149/ma2022-012382mtgabs.
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Lithium-ion batteries are widely used as power sources in electric buses, railways, ferries, and other mass transportation systems. To meet the energy needs of these infrastructure systems, it is important to realize battery control that enables high-energy operation for long periods of time. The high-capacity Ni-rich cathode material NCM811 (LiNi0.8Co0.1Mn0.1O2) has attracted research interest as a candidate high-energy-density cathode material. However, NCM811 has been reported to have some degradation problems, especially when operating at potential above 4.2 V versus Li/Li+1).Furthermore, the safety of NCM811 becomes compromised with time. Therefore, understanding the aging mechanism and predicting battery aging behavior are required for effective battery control. We have found that operating NCM811 cathodes at the combination of the potential higher than 4.2 V and lower potential less than 3.6 V that accelerates aging, leading to substantial capacity loss and increased resistance. However, aging was mitigated when NCM811 batteries were operated at a higher or lower potential range. Electrochemical and chemical analyses were performed to clarify the aging mechanism. We prepared 1-Ah LTO/NCM811 pouch cells. Charge/discharge cycling tests were carried out using various state-of-charge (SOC) ranges (SOC0-100%, SOC20-100%, and SOC0-70%) at a 3C rate at 65°C. When the cell was charged at SOC100% and SOC0%, the cathode potential was set to above 4.2 V and to below 3.6 V. The capacity retention and DC resistance (DCR: SOC50%, 0.2 sec) for these cells are shown in Figure1a. The capacity retention of the cell after 1000 cycles at SOC0-100% cycling test was about 75% for the initial capacity. However, a high capacity retention of 93% was obtained at SOC20-100% cycling, despite the cell was charged at SOC100% of 1000 times. The capacity retention of SOC0-70% cycling was nearly 100%. DCR increased 2.5-times after 1000 cycles at SOC0-100% cycling, which was higher increase than that of SOC20-100% cycling and SOC0-70% cycling. To clarify the mechanism, the cathode was removed from the deteriorated pouch cells and its electrochemical properties were investigated using a three-electrode glass beaker cell. The cell was assembled using the cathode and lithium metal as a counter electrode, and a reference electrode was also prepared. The lithium-diffusion coefficient of NCM811 at the time of preparation and after 1000 cycles was measured using the galvanostatic intermittent titration technique method. In the case of a NCM811 cathode operated at SOC0-100% for 1000 cycles, there was little change for the lithium-diffusion coefficient of x < 0.8 in LixNi0.8Co0.1Mn0.1O2, but that of x > 0.8 decreased to less than 1/10. Changes in the crystal structure of the NCM811 particle surface were analyzed by scanning transmission electron microscopy–electron energy loss spectroscopy (STEM-EELS). The thickness of the surface structural change layer was calculated from the EELS spectrum. Also, the thickness and composition of surface film was analyzed by hard X-ray photoelectron spectroscopy (HAX-PES). This measurement was performed at the SPring-8 synchrotron radiation facility. From the STEM-EELS analyses, in the case of SOC0-100% cycling, the surface crystal structure of NCM811 changed from the layered type to the rock-salt or spinel-layer type. The thickness of this transition layer increased by 7 nm compared from beginning. In the case of SOC0-70% cycling, the thickness increased by only 2 nm. It is expected that the cathode operated above 4.2 V at SOC0-100% cycling. From the HAX-PES analysis, the film thickness increased by 20 nm from the initial condition after SOC0-100% cycling. But, after SOC20-100% cycling and SOC0-70% cycling, the film thickness increased was suppressed than that. Based on the results of these analyses, we proposed the following model. In the first step, the structure change of NCM811 was accelerated at high potential. As the rock-salt layer disturbed lithium diffusion, the diffusional resistance increased and the capacity during discharge decreased. In the second step, when NCM811 subjected to a higher potential was discharged to a lower potential, the lithium can’t be intercalated smoothly at the surface x > 0.8 in LixNi0.8Co0.1Mn0.1O2. As a result, the lithium near the surface reacts with electrolyte, forming a film on the NCM811 surface. As the lithium was consumed by the film-growth reaction, the cathode operating potential increased, which accelerated the first step mechanism. The combination of the first and second steps accelerated aging. But this aging can be minimized by controlling the operating voltage. Understanding of the aging mechanism will enable accurate prediction of deterioration. [1]F. Friedrich, B. Strehle, etc, Journal of The Electrochemical Society, 166, A3760-A3774 (2019) Figure 1
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Chen, Dongchang, Wang Hay Kan, and Guoying Chen. "Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes." Advanced Energy Materials 9, no. 31 (July 11, 2019): 1901255. http://dx.doi.org/10.1002/aenm.201901255.
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Ahn, Juhyeon, and Guoying Chen. "(Invited) High-Energy Mn-Rich Disordered Rocksalt Cathodes." ECS Meeting Abstracts MA2022-02, no. 1 (October 9, 2022): 35. http://dx.doi.org/10.1149/ma2022-02135mtgabs.
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In recent years, cation-disordered Li-excess rocksalts (DRX) have emerged as a promising new class of high-energy cathode materials for lithium-ion batteries. [1] Aside from the desirable Co-free chemistry, these compounds offer exceptionally large charge storage capacities by utilizing the redox reactions of both cationic transition-metals and anionic oxygen in the lattice. While early research focused on DRX oxides, which met with significant challenges in voltage stability and capacity retention upon cycling [2-3], recent studies shifted towards oxyfluorides with a substantial level of F substitution. It was found that incorporating F into the anionic sublattice can reduce oxygen gas release, impedance rise and capacity fade, consequently improving cathode cycling stability. [4-5] To this end, developing synthesis methods to incorporate large F content in the lattice as well as designing and optimizing oxyfluoride chemistry for both high energy density and cycling stability are imperative. While high F substitution levels (up to 30-40 at.%) in DRX have been achieved through mechanochemical synthesis, the method has limitations in industrial application due to poor scalability. Solid-state synthesis, on the other hand, are readily scalable and often offers drop-in replacement in materials processing. In this presentation, we show our recent effort in developing calcination-based fluorination approach to achieve high-level fluorination of Mn-redox-active DRX materials. [6] The unique behavior of capacity rise upon cycling of a new class of Mn-rich DRX oxyfluoride cathodes will be reported. Our understanding in how chemistry can impact local and long-range structures and their evolution during electrochemical cycling will also be presented, as well as perspectives on future directions in DRX development. References Lee, J.; Urban, A.; Li, X.; Su, D.; Hautier, G.; Ceder, G. Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries. Science 2014, 343, 519. Yabuuchi, N.; Takeuchi, M.; Nakayama, M.; Shiiba, H.; Ogawa, M.; Nakayama, K.; Ohta, T.; Endo, D.; Ozaki, T.; Inamasu, T.; Sato, K.; Komaba, S., High-Capacity Electrode Materials for Rechargeable Lithium Batteries: Li3NbO4-based System with Cation-Disordered Rocksalt Structure. Natl. Acad. Sci. 2015, 112, 7650. Chen, D.; Kan, W. H.; Chen, G. Understanding Performance Degradation in Cation-Disordered Rock-Salt Oxide Cathodes. Energy Mater. 2019, 9, 1901255. Lee, J.; Papp, J. K.; Clément, R. J.; Sallis, S.; Kwon, D.-H.; Shi, T.; Yang, W.; McCloskey, B. D.; Ceder, G. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials. Commun. 2017, 8, 981. Lun, Z.; Ouyang, B.; Kitchaev, D. A.; Clément, R. J.; Papp, J. K.; Balasubramanian, M.; Tian, Y.; Lei, T.; Shi, T.; McCloskey, B. D.; Lee, J.; Ceder, G. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. Energy Mater. 2018, 9,1802959. Ahn, J.; Chen, D.; Chen, G.. A Fluorination Method for Improving Cation-Disordered Rocksalt Cathode Performance. Energy Mater. 2020, 10, 2001671.
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Mishchenko, Kseniya V., Maria A. Kirsanova, Arseny B. Slobodyuk, Anna A. Krinitsyna, and Nina V. Kosova. "Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure." Chimica Techno Acta 9, no. 3 (August 4, 2022): 20229310. http://dx.doi.org/10.15826/chimtech.2022.9.3.10.
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According to the extensive studies in the field of high-energy cathode materials for lithium-ion batteries (LIBs), Mn-based oxyfluorides Li1.2Mn0.6+0.5yNb0.2–0.5yO2–yFy with Li-excess and cation-disordered rock-salt structure capable of reversible cationic and anionic redox reactions are among the most promising candidates. In this work, a series of Mn-based oxyfluorides with y = 0.05, 0.10, 0.15 were obtained using mechanochemically assisted solid-state synthesis with different cooling rates. Transmission electron microscopy, electron paramagnetic spectroscopy (EPR) and nuclear magnetic resonance spectroscopy (NMR) show that increasing the amount of fluorine promotes local ordering in crystals with the formation of isolated clusters of Mn3+–O2––Mn4+ that interrupt lithium diffusion. The occurrence of local ordering depends on the conditions of synthesis and affects electrochemistry. It was found that more clusters are formed in slowly cooled samples than in quenched ones. The best electrochemical characteristics with reversible capacity of 150 mAh·g–1 at room temperature were demonstrated by the Li1.2Mn0.65Nb0.15O0.90F0.10 sample obtained by quenching.
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Diaz-Lopez, Maria, Philip A. Chater, Yves Joly, Olivier Proux, Jean-Louis Hazemann, Pierre Bordet, and Valerie Pralong. "Correction: Reversible densification in nano-Li2MnO3 cation disordered rock-salt Li-ion battery cathodes." Journal of Materials Chemistry A 8, no. 25 (2020): 12833. http://dx.doi.org/10.1039/d0ta90126a.
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Correction for ‘Reversible densification in nano-Li2MnO3 cation disordered rock-salt Li-ion battery cathodes’ by Maria Diaz-Lopez et al., J. Mater. Chem. A, 2020, 8, 10998–11010, DOI: 10.1039/d0ta03372c.
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Idris, M. Sobri, and A. R. West. "The Effect on Cathode Performance of Oxygen Non-Stoichiometry and Interlayer Mixing in Layered Rock Salt LiNi0.8Mn0.1Co0.1O2-δ." Journal of The Electrochemical Society 159, no. 4 (2012): A396—A401. http://dx.doi.org/10.1149/2.037204jes.
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Méndez-Román, J. Arnaldo. "Energy boost confirmed in Li-rich disordered rock-salt oxyfluoride cathodes." MRS Bulletin 46, no. 7 (July 2021): 561. http://dx.doi.org/10.1557/s43577-021-00146-9.
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Soo, S. P., M. S. Idris, Rozana A. M. Osman, and A. Rahmat. "The Effect of Synthesis Temperature on Interlayer Mixing in Layered Rock Salt Cathode Materials LiNi0.7Mn0.1Co0.2O2 for Li-Ion Batteries Application." Materials Science Forum 819 (June 2015): 155–60. http://dx.doi.org/10.4028/www.scientific.net/msf.819.155.
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The interlayer mixing of layered rock salt cathode materials LiNi0.7Mn0.1Co0.2O2 that prepared by mixed hydroxide method at various temperatures (750-950°C) has been studied. X-ray Diffraction (XRD) was used to determine a suitable temperature range to obtain the fully reacted sample. Phase of pure sample was obtained at high temperature above 850°C. The results of XRD show that the LiNi0.7Mn0.1Co0.2O2 samples are iso-structural with α-NaFeO2 with space group of R-3m.The sample that heated at 900°C exhibits a well-ordered and lower cation mixed layered structure than others. Rietveld refinement using XRD data was used to determine the amount of interlayer mixing vary as a function of temperature. Refinements data showed that the interlayer mixing varies depend upon the synthesis temperature and the optimum temperature to prepare LiNi0.7Mn0.1Co0.2O2 with the lowest amount of interlayer mixing was 900°C.
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Quintelier, Matthias, Tyché Perkisas, Romy Poppe, Maria Batuk, Mylene Hendrickx, and Joke Hadermann. "Determination of Spinel Content in Cycled Li1.2Ni0.13Mn0.54Co0.13O2 Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction." Symmetry 13, no. 11 (October 20, 2021): 1989. http://dx.doi.org/10.3390/sym13111989.
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Among lithium battery cathode materials, Li1.2Ni0.13Mn0.54Co0.13O2 (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially ascribed to transition metal cation migration, which involves the local transformation of the honeycomb layered structure to spinel-like nano-domains. Determination of the honeycomb layered/spinel phase ratio from powder X-ray diffraction data is hindered by the nanoscale of the functional material and the domains, diverse types of twinning, stacking faults, and the possible presence of the rock salt phase. Determining the phase ratio from transmission electron microscopy imaging can only be done for thin regions near the surfaces of the crystals, and the intense beam that is needed for imaging induces the same transformation to spinel as cycling does. In this article, it is demonstrated that the low electron dose sufficient for electron diffraction allows the collection of data without inducing a phase transformation. Using calculated electron diffraction patterns, we demonstrate that it is possible to determine the volume ratio of the different phases in the particles using a pair-wise comparison of the intensities of the reflections. Using this method, the volume ratio of spinel structure to honeycomb layered structure is determined for a submicron sized crystal from experimental three-dimensional electron diffraction (3D ED) and precession electron diffraction (PED) data. Both twinning and the possible presence of the rock salt phase are taken into account. After 150 charge–discharge cycles, 4% of the volume in LR-NMC particles was transformed irreversibly from the honeycomb layered structure to the spinel structure. The proposed method would be applicable to other multi-phase materials as well.
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Li, Yang, Liubin Ben, Hailong Yu, Wenwu Zhao, Xinjiang Liu, and Xuejie Huang. "Stabilizing the (003) Facet of Micron-Sized LiNi0.6Co0.2Mn0.2O2 Cathode Material Using Tungsten Oxide as an Exemplar." Inorganics 10, no. 8 (August 3, 2022): 111. http://dx.doi.org/10.3390/inorganics10080111.
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The structural stability of layered LiNi1-x-yCoxMnyO2 cathode materials is critical for guaranteeing their excellent electrochemical cycling performance, particularly at elevated temperatures. However, the notorious H2–H3 phase transition along with associated large changes in the c-axis or (003) facet is the fundamental origin of the anisotropic and abrupt change in the unit cell and the degradation of the cycling performance. In this study, we coat micron-sized LiNi0.6Co0.2Mn0.2O2 (NCM) with tungsten oxide via atomic layer deposition and investigate the atomic-to-microscopic structures in detail via advanced characterization techniques, such as Cs-corrected scanning transmission electron microscopy. The results reveal that coated tungsten oxide is predominately accumulated on the (003) facet of NCM, with the migration of a small amount of W6+ into this facet, resulting in a reduction of Ni3+ to Ni2+ and the formation of a rock-salt-like structure on the surface. The electrochemical cycling performance of tungsten-oxide-coated NCM is significantly improved, showing a capacity retention of 86.8% after 300 cycles at 55 °C, compared to only 69.4% for the bare NCM. Through further structural analysis, it is found that the initial tungsten-oxide-coating-induced (003) facet distortion effectively mitigates the expansion of the c-lattice during charge, as well as oxygen release from the lattice, resulting in a lowered strain in the cathode lattices and a crack in the cathode particles after prolonged cycling.
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Zhang, Hanlei, Brian M. May, Jon Serrano-Sevillano, Montse Casas-Cabanas, Jordi Cabana, Chongmin Wang, and Guangwen Zhou. "Facet-Dependent Rock-Salt Reconstruction on the Surface of Layered Oxide Cathodes." Chemistry of Materials 30, no. 3 (January 18, 2018): 692–99. http://dx.doi.org/10.1021/acs.chemmater.7b03901.
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