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Auteur : Grafiati
Publié le 11 septembre 2023

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1

Shirazimoghadam, Yasaman, Abdel El kharbachi, Yang Hu, Thomas Diemant, Georginan Melinte et Maximilian Fichtner. « (Digital Presentation) Recent Development of the Cobalt Free and Lithium Rich Manganese Based Disordered Rocksalt Oxyfluorides As a Cathode Material for Lithium Ion Batteries ». ECS Meeting Abstracts MA2022-01, no 2 (7 juillet 2022) : 365. http://dx.doi.org/10.1149/ma2022-012365mtgabs.

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Recently, new types of cation disordered rocksalt (DRS) have been reported which show good reversibility. In our study we combined the strategy of using high-valent cations with partial substitution of fluorine for oxygen anions in disordered rocksalt-structure phase to achieve optimal Mn2+/Mn4+ double-redox reaction in the composition system Li2MnxTi1-xO2F (1/3 ≤ x ≤ 1). we synthesized 4 different compositions (Li2MnIIIO2F, Li2MnII 1/3MnIII 1/3TiIV 1/3O2F, Li2MnII 1/2TiIV 1/2O2F and Li2MnII 1/3TiIII 1/3TiIV 1/3O2F). Two of them were synthesized for the first time, Li2MnII 1/3MnIII 1/3TiIV 1/3O2F and Li2Mn II 1/3TiIII 1/3TiIV 1/3O2F. By studying the electrochemical properties of different compounds we found that Ti+4 in the structure keeps Mn at the second state of charge, thus enabling a double redox reaction of Mn2+/Mn4+. By investigating the electrochemical properties of all samples we found that the sample with the composition Li2Mn2/3Ti1/3O2F showed the best electrochemical properties with initial high discharge capacity of 227 mAh g-1 in the voltage window of 1.5-4.3 V and 82% of capacity retentionafter 100 cycles. However, fluorination might lead to several issues such as synthesis limitation, lithium diffusion issues due to preferable strong Li-F bonds, etc. thus, two more different samples based on the Li2Mn2/3Ti1/3O2F composition were synthesized and their properties were investigated (Li1.5MnII 1/3MnIII 1/3TiIV 1/3O2F0.5 and Li1.25MnII 1/3MnIII 1/3TiIV 1/3O2F0.25) in order to find the proper amount of fluorine in the structure which promises the electrochemical behavior. In the following the effect of fluorine on lithium diffusion was investigated by ex-situ Raman studies. These studies shed light on the diffusion pathways of lithium ions during charge and discharge process. The structural characteristics are examined using X-ray diffraction patterns, Rietveld refinement, energy-dispersive X-ray spectroscopy and scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The oxidation states and charge transfer mechanism are also studied further using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy in which the results approve the double redox mechanism of Mn2+/Mn4+ in agreement with Mn-Ti structural charge compensation. The findings pave the way for designing high capacity electrode materials with multi-electron redox reactions. References: [1]: Chen, R.; Ren, S.; Knapp, M.; Wang, D.; Witter, R.; Fichtner, M.; Hahn, H., Disordered Lithium‐Rich Oxyfluoride as a Stable Host for Enhanced Li+ Intercalation Storage. Advanced Energy Materials 2015, 5, (9), 1401814. [2]: Lee, J.; Kitchaev, D. A.; Kwon, D.-H.; Lee, C.-W.; Papp, J. K.; Liu, Y.-S.; Lun, Z.; Clément, R. J.; Shi, T.; McCloskey, B. D., Reversible Mn 2+/Mn 4+ double redox in lithium-excess cathode materials. Nature 2018, 556, (7700), 185-190.
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Marinova, Delyana, Mariya Kalapsazova, Zlatina Zlatanova, Liuda Mereacre, Ekaterina Zhecheva et Radostina Stoyanova. « Lithium Manganese Sulfates as a New Class of Supercapattery Materials at Elevated Temperatures ». Materials 16, no 13 (3 juillet 2023) : 4798. http://dx.doi.org/10.3390/ma16134798.

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To make supercapattery devices feasible, there is an urgent need to find electrode materials that exhibit a hybrid mechanism of energy storage. Herein, we provide a first report on the capability of lithium manganese sulfates to be used as supercapattery materials at elevated temperatures. Two compositions are studied: monoclinic Li2Mn(SO4)2 and orthorhombic Li2Mn2(SO4)3, which are prepared by a freeze-drying method followed by heat treatment at 500 °C. The electrochemical performance of sulfate electrodes is evaluated in lithium-ion cells using two types of electrolytes: conventional carbonate-based electrolytes and ionic liquid IL ones. The electrochemical measurements are carried out in the temperature range of 20–60 °C. The stability of sulfate electrodes after cycling is monitored by in-situ Raman spectroscopy and ex-situ XRD and TEM analysis. It is found that sulfate salts store Li+ by a hybrid mechanism that depends on the kind of electrolyte used and the recording temperature. Li2Mn(SO4)2 outperforms Li2Mn2(SO4)3 and displays excellent electrochemical properties at elevated temperatures: at 60 °C, the energy density reaches 280 Wh/kg at a power density of 11,000 W/kg. During cell cycling, there is a transformation of the Li-rich salt, Li2Mn(SO4)2, into a defective Li-poor one, Li2Mn2(SO4)3, which appears to be responsible for the improved storage properties. The data reveals that Li2Mn(SO4)2 is a prospective candidate for supercapacitor electrode materials at elevated temperatures.
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Susai, Francis Amalraj, Michael Talianker, Jing Liu, Rosy, Tanmoy Paul, Yehudit Grinblat, Evan Erickson et al. « Electrochemical Activation of Li2MnO3 Electrodes at 0 °C and Its Impact on the Subsequent Performance at Higher Temperatures ». Materials 13, no 19 (1 octobre 2020) : 4388. http://dx.doi.org/10.3390/ma13194388.

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This work continues our systematic study of Li- and Mn- rich cathodes for lithium-ion batteries. We chose Li2MnO3 as a model electrode material with the aim of correlating the improved electrochemical characteristics of these cathodes initially activated at 0 °C with the structural evolution of Li2MnO3, oxygen loss, formation of per-oxo like species (O22−) and the surface chemistry. It was established that performing a few initial charge/discharge (activation) cycles of Li2MnO3 at 0 °C resulted in increased discharge capacity and higher capacity retention, and decreased and substantially stabilized the voltage hysteresis upon subsequent cycling at 30 °C or at 45 °C. In contrast to the activation of Li2MnO3 at these higher temperatures, Li2MnO3 underwent step-by-step activation at 0 °C, providing a stepwise traversing of the voltage plateau at >4.5 V during initial cycling. Importantly, these findings agree well with our previous studies on the activation at 0 °C of 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2 materials. The stability of the interface developed at 0 °C can be ascribed to the reduced interactions of the per-oxo-like species formed and the oxygen released from Li2MnO3 with solvents in ethylene carbonate–methyl-ethyl carbonate/LiPF6 solutions. Our TEM studies revealed that typically, upon initial cycling both at 0 °C and 30 °C, Li2MnO3 underwent partial structural layered-to-spinel (Li2Mn2O4) transition.
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Liu, Guang, Hui Xu, Zhongheng Wang et Sa Li. « Operando electrochemical fluorination to achieve Mn4+/Mn2+ double redox in a Li2MnO3-like cathode ». Chemical Communications 58, no 20 (2022) : 3326–29. http://dx.doi.org/10.1039/d1cc06865b.

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The drastic changes (Li2MnO3→Li1.67MnO2.1F0.2) in the first cycle of Li2MnO3-like through oxygen release (O2−→O2) and in operando F-doping, activated a two-electron redox of Mn4+/2+ with a capacity of 326 mA h g−1.
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5

Pulido, Ruth, Nelson Naveas, Raúl J. Martin-Palma, Fernando Agulló-Rueda, Victor R. Ferró, Jacobo Hernández-Montelongo, Gonzalo Recio-Sánchez, Ivan Brito et Miguel Manso-Silván. « Phonon Structure, Infra-Red and Raman Spectra of Li2MnO3 by First-Principles Calculations ». Materials 15, no 18 (8 septembre 2022) : 6237. http://dx.doi.org/10.3390/ma15186237.

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The layer-structured monoclinic Li2MnO3 is a key material, mainly due to its role in Li-ion batteries and as a precursor for adsorbent used in lithium recovery from aqueous solutions. In the present work, we used first-principles calculations based on density functional theory (DFT) to study the crystal structure, optical phonon frequencies, infra-red (IR), and Raman active modes and compared the results with experimental data. First, Li2MnO3 powder was synthesized by the hydrothermal method and successively characterized by XRD, TEM, FTIR, and Raman spectroscopy. Secondly, by using Local Density Approximation (LDA), we carried out a DFT study of the crystal structure and electronic properties of Li2MnO3. Finally, we calculated the vibrational properties using Density Functional Perturbation Theory (DFPT). Our results show that simulated IR and Raman spectra agree well with the observed phonon structure. Additionally, the IR and Raman theoretical spectra show similar features compared to the experimental ones. This research is useful in investigations involving the physicochemical characterization of Li2MnO3 material.
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Kuganathan, Navaratnarajah, Efstratia Sgourou, Yerassimos Panayiotatos et Alexander Chroneos. « Defect Process, Dopant Behaviour and Li Ion Mobility in the Li2MnO3 Cathode Material ». Energies 12, no 7 (7 avril 2019) : 1329. http://dx.doi.org/10.3390/en12071329.

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Lithium manganite, Li2MnO3, is an attractive cathode material for rechargeable lithium ion batteries due to its large capacity, low cost and low toxicity. We employed well-established atomistic simulation techniques to examine defect processes, favourable dopants on the Mn site and lithium ion diffusion pathways in Li2MnO3. The Li Frenkel, which is necessary for the formation of Li vacancies in vacancy-assisted Li ion diffusion, is calculated to be the most favourable intrinsic defect (1.21 eV/defect). The cation intermixing is calculated to be the second most favourable defect process. High lithium ionic conductivity with a low activation energy of 0.44 eV indicates that a Li ion can be extracted easily in this material. To increase the capacity, trivalent dopants (Al3+, Co3+, Ga3+, Sc3+, In3+, Y3+, Gd3+ and La3+) were considered to create extra Li in Li2MnO3. The present calculations show that Al3+ is an ideal dopant for this strategy and that this is in agreement with the experiential study of Al-doped Li2MnO3. The favourable isovalent dopants are found to be the Si4+ and the Ge4+ on the Mn site.
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Chennakrishnan, Sandhiya, Venkatachalam Thangamuthu, Akshaya Subramaniyam, Viknesh Venkatachalam, Manikandan Venugopal et Raju Marudhan. « Synthesis and characterization of Li2MnO3 nanoparticles using sol-gel technique for lithium ion battery ». Materials Science-Poland 38, no 2 (1 juin 2020) : 312–19. http://dx.doi.org/10.2478/msp-2020-0026.

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AbstractNanoparticles of Li2MnO3 were fabricated by sol-gel method using precursors of lithium acetate and manganese acetate, and citric acid as chelating agent in the stoichiometric ratio. TGA/DTA measurements of the sample in the regions of 30 °C to 176 °C, 176 °C to 422 °C and 422 °C to 462 °C were taken to identify the decomposition temperature and weight loss. The XRD analysis of the sample indicates that the synthesized material is monoclinic crystalline in nature and the calculated lattice parameters are 4.928 Å (a), 8.533 Å (b), and 9.604 Å (c). The surface morphology, particle size and elemental analysis of the samples were observed using SEM and EDAX techniques and the results confirmed the agglomeration of nanoparticles and, as expected, Li2MnO3 composition. Half cells of Li2MnO3 were assembled and tested at C/10 rate and the maximum capacity of 27 mAh/g was obtained. Charging and discharging processes that occurred at 3 V and 4 V were clearly observed from the cyclic voltammetric experiments. Stability of the electrodes was confirmed by the perfect reversibility of the anodic and cathodic peak positions observed in the cyclic voltammogram of the sample. The Li2MnO3 nanoparticles exhibit excellent properties and they are suitable for cathode materials in lithium ion batteries.
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8

Mogashoa, Tshidi, Raesibe Sylvia Ledwaba et Phuti Esrom Ngoepe. « Analysing the Implications of Charging on Nanostructured Li2MnO3 Cathode Materials for Lithium-Ion Battery Performance ». Materials 15, no 16 (18 août 2022) : 5687. http://dx.doi.org/10.3390/ma15165687.

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Capacity degradation and voltage fade of Li2MnO3 during cycling are the limiting factors for its practical use as a high-capacity lithium-ion battery cathode. Here, the simulated amorphisation and recrystallisation (A + R) technique is used, for generating nanoporous Li2MnO3 models of different lattice sizes (73 Å and 75 Å), under molecular dynamics (MD) simulations. Charging was carried out by removing oxygen and lithium ions, with oxygen charge compensated for, to restrain the release of oxygen, resulting in Li2−xMnO3−x composites. Detailed analysis of these composites reveals that the models crystallised into multiple grains, with grain boundaries increasing with decreasing Li/O content, and the complex internal microstructures depicted a wealth of defects, leading to the evolution of distorted cubic spinel LiMn2O4, Li2MnO3, and LiMnO2 polymorphs. The X-ray diffraction (XRD) patterns for the simulated systems revealed peak broadening in comparison with calculated XRD, also, the emergence of peak 2Θ ~ 18–25° and peak 2Θ ~ 29° were associated with the spinel phase. Lithium ions diffuse better on the nanoporous 73 Å structures than on the nanoporous 75 Å structures. Particularly, the Li1.00MnO2.00 shows a high diffusion coefficient value, compared to all concentrations. This study shed insights on the structural behaviour of Li2MnO3 cathodes during the charging mechanism, involving the concurrent removal of lithium and oxygen.
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Kadhum, Samah Abd, et Zainab Raheem Muslim. « Synthesis and Characterization of Li2MnO3 Using Sol-gel Technique ». NeuroQuantology 20, no 5 (18 mai 2022) : 808–12. http://dx.doi.org/10.14704/nq.2022.20.5.nq22238.

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Li2MnO3 nanoparticles were prepared using the Sol-Gel method and characterized by XRD, AFM, SEM, TGA and DSC with major peaks (18.81°), (37.10°) and (44.76°) using AfM, the average diameter of the nanoparticles was (45.71 nm). SEM was used to assess the surface morphology; The micropicture showed homogeneous spherical formations with particle sizes ranging from 2 to 4 meters. Thermal analysis was determined by TGA and DSC results showed a thermal stability from 500 to 750, indicating development of the phase. Li2MnO3 nanoparticles display excellent properties and are suitable as cathode materials in lithium-ion batteries.
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Zhuravlev, Victor D., Sergei I. Shchekoldin, Stanislav E. Andrjushin, Elena A. Sherstobitova, Ksenia V. Nefedova et Olga V. Bushkova. « Electrochemical Characteristics and Phase Composition of Lithium­Manganese Oxide Spinel with Excess Lithium Li1+xMn2O4 ». Electrochemical Energetics 20, no 3 (2020) : 157–70. http://dx.doi.org/10.18500/1608-4039-2020-20-3-157-170.

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The paper presents the results of the study of phase composition and electrochemical performance of lithium­manganese oxide spinel with excess lithium of nominal composition of Li1+xMn2O4 obtained by solidphase method. It was established that samples with x = 0.1 and 0.2 were composite materials with LiMn2O4 being the basic phase and Li2MnO3 being the impurity (3 and 7 mas.%, respectively) also comprising trace amounts of MnO2. The composite material with 3% of Li2MnO3 (x = 0.1) retained 80–90% of the initial specific capacity after 300 charge­discharge cycles at C/2, while single­phase stoichiometric spinel LiMn2O4 retained less than 70–75%.
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Ren, Xiao Dong, Jian Jun Liu et Wen Qing Zhang. « Strain Effect on the Electrochemical Properties of Li2MnO3 Cathode Material : A First Principles Calculation ». Key Engineering Materials 519 (juillet 2012) : 147–51. http://dx.doi.org/10.4028/www.scientific.net/kem.519.147.

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The strain effect on the properties of Li2MnO3 cathode material is investigated by means of first principles method. The intercalation potential decreases with the strains at the extent of about 0.1V. The strain effect on the intercalation potential is anisotropic with the strain perpendicular to the host layer brings the largest decrease to the potential. Additionally, the tensile paralleling to the host layer can also open up the migrating pathway of lithium in the transition metal layer. The strain effect on the anomalously large charging capacity of Li2MnO3 stabilized LiMO2 (M = Mn, Ni, Co, etc.) solid solution system is also evaluated from the two factors.
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Vu, Ngoc Hung, Van-Duong Dao, Hong Ha Thi Vu, Nguyen Van Noi, Dinh Trinh Tran, Minh Ngoc Ha et Thanh-Dong Pham. « Hydrothermal Synthesis of Li2MnO3-Stabilized LiMnO2 as a Cathode Material for Li-Ion Battery ». Journal of Nanomaterials 2021 (11 juillet 2021) : 1–6. http://dx.doi.org/10.1155/2021/9312358.

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Herein, we reported the composite structure of LiMnO2 and Li2MnO3 as a low-cost and environmentally benign cathode material. This composite with the main phase of LiMnO2 (90%) was synthesized by hydrothermal method at 220°C from LiOH and Mn(CH3COO)2 precursors. The obtained nanosized LiMnO2-LiMnO3 cathode material exhibits a high capacity of 265 mAh g-1 at C/10. The incorporation of Li2MnO3 into the LiMnO2 phase could stabilize the structure, leading to the improved cycle stability of the cathode. The capacity retention of the cathode was 93% after 80 cycles at C/2. Our results facilitate a potential strategy for developing high-performance cathode materials based on the Li-Mn-O system.
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Guerrini, Niccoló, Liyu Jin, Juan G. Lozano, Kun Luo, Adam Sobkowiak, Kazuki Tsuruta, Felix Massel, Laurent-Claudius Duda, Matthew R. Roberts et Peter G. Bruce. « Charging Mechanism of Li2MnO3 ». Chemistry of Materials 32, no 9 (14 avril 2020) : 3733–40. http://dx.doi.org/10.1021/acs.chemmater.9b04459.

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Riou, A., A. Lecerf, Y. Gerault et Y. Cudennec. « Etude structurale de Li2MnO3 ». Materials Research Bulletin 27, no 3 (mars 1992) : 269–75. http://dx.doi.org/10.1016/0025-5408(92)90055-5.

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Wang, Lian-Bang, He-Shan Hu, Wei Lin, Qing-Hong Xu, Jia-Dong Gong, Wen-Kui Chai et Chao-Qi Shen. « Electrochemically Inert Li2MnO3 : The Key to Improving the Cycling Stability of Li-Rich Manganese Oxide Used in Lithium-Ion Batteries ». Materials 14, no 16 (23 août 2021) : 4751. http://dx.doi.org/10.3390/ma14164751.

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Lithium-rich manganese oxide is a promising candidate for the next-generation cathode material of lithium-ion batteries because of its low cost and high specific capacity. Herein, a series of xLi2MnO3·(1 − x)LiMnO2 nanocomposites were designed via an ingenious one-step dynamic hydrothermal route. A high concentration of alkaline solution, intense hydrothermal conditions, and stirring were used to obtain nanoparticles with a large surface area and uniform dispersity. The experimental results demonstrate that 0.072Li2MnO3·0.928LiMnO2 nanoparticles exhibit a desirable electrochemical performance and deliver a high capacity of 196.4 mAh g−1 at 0.1 C. This capacity was maintained at 190.5 mAh g−1 with a retention rate of 97.0% by the 50th cycle, which demonstrates the excellent cycling stability. Furthermore, XRD characterization of the cycled electrode indicates that the Li2MnO3 phase of the composite is inert, even under a high potential (4.8 V), which is in contrast with most previous reports of lithium-rich materials. The inertness of Li2MnO3 is attributed to its high crystallinity and few structural defects, which make it difficult to activate. Hence, the final products demonstrate a favorable electrochemical performance with appropriate proportions of two phases in the composite, as high contents of inert Li2MnO3 lower the capacity, while a sufficient structural stability cannot be achieved with low contents. The findings indicate that controlling the composition through a dynamic hydrothermal route is an effective strategy for developing a Mn-based cathode material for lithium-ion batteries.
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Zhou, Yun Long, Zhi Biao Hu, Chen Hao Zhao, Li Yan et Kai Yu Liu. « Facile Preparation and Electrochemical Performances of LiMn2O4/Li1.2(Mn0.56Ni0.16Co0.08)O2 Blend Cathode Materials for Lithium Ion Battery ». Materials Science Forum 852 (avril 2016) : 805–10. http://dx.doi.org/10.4028/www.scientific.net/msf.852.805.

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The blend cathode materials LiMn2O4/Li1.2(Mn0.56Ni0.16Co0.08)O2 have been successfully prepared by the physical mixing of commercial Li2MnO4 and self-prepared Li1.2(Mn0.56Ni0.16Co0.08)O2 nanoparticles. The structures, morphologies and electrochemical performances are characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), Cyclic Voltammetry (CV) and charge-discharge test, and the results show that the good mass ratio of Li2MnO4 and Li1.2(Mn0.56Ni0.16Co0.08)O2 is 50:50. Therein, the nanosized Li1.2Ni0.16Co0.08Mn0.56O2 uniformly adhere on the surface of Li2MnO4 micro structure, and occupy the gap of Li2MnO4 particles, which can effectively elevate the tap density of Li1.2(Mn0.56Ni0.16Co0.08)O2 nanoparticles. As lithium ion battery cathode, the 50:50 sample reveals an initial discharge capacity of 265.4 mAh/g with negligible irreversible capacity loss at current density of 0.1C within 2.0-4.8 V, and retain 89.2% after 20 cycles.
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Yu, Zhiyong, Jishen Hao, Wenji Li et Hanxing Liu. « Enhanced Electrochemical Performances of Cobalt-Doped Li2MoO3 Cathode Materials ». Materials 12, no 6 (13 mars 2019) : 843. http://dx.doi.org/10.3390/ma12060843.

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Co-doped Li2MoO3 was successfully synthesized via a solid phase method. The impacts of Co-doping on Li2MoO3 have been analyzed by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) measurements. The results show that an appropriate amount of Co ions can be introduced into the Li2MoO3 lattices, and they can reduce the particle sizes of the cathode materials. Electrochemical tests reveal that Co-doping can significantly improve the electrochemical performances of the Li2MoO3 materials. Li2Mo0.90Co0.10O3 presents a first-discharge capacity of 220 mAh·g−1, with a capacity retention of 63.6% after 50 cycles at 5 mA·g−1, which is much better than the pristine samples (181 mAh·g−1, 47.5%). The enhanced electrochemical performances could be due to the enhancement of the structural stability, and the reduction in impedance, due to the Co-doping.
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Abulikemu, Aierxiding, Shenghan Gao, Toshiyuki Matsunaga, Hiroshi Takatsu, Cédric Tassel, Hiroshi Kageyama, Takashi Saito et al. « Partial cation disorder in Li2MnO3 obtained by high-pressure synthesis ». Applied Physics Letters 120, no 18 (2 mai 2022) : 182404. http://dx.doi.org/10.1063/5.0088023.

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While atomic disorder has provided a paradigm shift in crystalline materials because of unusual atomic arrangements and functional response, “partial” disorder is scarcely reported until now. We discovered partial cation disorder in Li2MnO3 with fewer stacking faults, which was synthesized under high pressure. Mn and Li atoms in a Mn2/3Li1/3O2 layer disorder while Li atoms in a Li layer order. Magnetization and specific heat measurements indicate a long-range antiferromagnetic (AF) order below 35 K. The irreversibility observed in the magnetization data and the hump observed for the specific heat data suggest the coexistence of an AF order and a partial magnetic disorder. Neutron diffraction measurements reveal that the coexisted state is formed instead of the Néel AF state that has previously been reported for conventional Li2MnO3. These results indicate that high pressure makes a breakthrough to introduce partial disorder within crystals and designs not only a unique magnetic structure but also other physical properties.
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Xiao, Ruijuan, Hong Li et Liquan Chen. « Density Functional Investigation on Li2MnO3 ». Chemistry of Materials 24, no 21 (novembre 2012) : 4242–51. http://dx.doi.org/10.1021/cm3027219.

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Nazario-Naveda, Renny, Segundo Rojas-Flores, Luisa Juárez-Cortijo, Moises Gallozzo-Cardenas, Félix N. Díaz, Luis Angelats-Silva et Santiago M. Benites. « Effect of x on the Electrochemical Performance of Two-Layered Cathode Materials xLi2MnO3–(1−x)LiNi0.5Mn0.5O2 ». Batteries 8, no 7 (29 juin 2022) : 63. http://dx.doi.org/10.3390/batteries8070063.

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In our study, the cathodic material xLi2MnO3–(1−x)LiNi0.5Mn0.5O2 was synthesized by means of the co-precipitation technique. The effect of x (proportion of components Li2MnO3 and LiNi0.5Mn0.5O2) on the structural, morphological, and electrochemical performance of the material was evaluated. Materials were structurally characterized using X-ray diffraction (XRD), and the morphological analysis was performed using the scanning electron microscopy (SEM) technique, while charge–discharge curves and differential capacity and impedance spectroscopy (EIS) were used to study the electrochemical behavior. The results confirm the formation of the structures with two phases corresponding to the rhombohedral space group R3m and the monoclinic space group C2/m, which was associated to the components of the layered material. Very dense agglomerations of particles between 10 and 20 µm were also observed. In addition, the increase in the proportion of the LiNi0.5Mn0.5O2 component affected the initial irreversible capacity and the Li2MnO3 layer’s activation and cycling performance, suggesting an optimal chemical ratio of the material’s component layers to ensure high energy density and long-term durability.
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Robertson, Alastair D., et Peter G. Bruce. « Mechanism of Electrochemical Activity in Li2MnO3 ». Chemistry of Materials 15, no 10 (mai 2003) : 1984–92. http://dx.doi.org/10.1021/cm030047u.

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Strobel, Pierre, et Bernadette Lambert-Andron. « Crystallographic and magnetic structure of Li2MnO3 ». Journal of Solid State Chemistry 75, no 1 (juillet 1988) : 90–98. http://dx.doi.org/10.1016/0022-4596(88)90305-2.

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Jiang, Jin He. « Synthesis of Spinel Li2MnO3 and its Ion-Exchange Property for Li+ ». Advanced Materials Research 554-556 (juillet 2012) : 860–63. http://dx.doi.org/10.4028/www.scientific.net/amr.554-556.860.

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Compound [Li2MnO3], a spinel-type metal compound, was prepared by a solid state reaction crystallization method. The results showed that the Li+ extraction/insertion be progressed mainly by an ion-exchange mechanism. Results of column test indicated, that the exchange capacity obtained from tests for Li+ in 0.1mol/L HNO3 solution is 7.0 mmol•g-1.It had a memorial ion-sieve property for Li+
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Hibble, S. J., I. D. Fawcett et A. C. Hannon. « Structure of Two Disordered Molybdates, Li2MoIVO3 and Li4Mo3 IVO8, from Total Neutron Scattering ». Acta Crystallographica Section B Structural Science 53, no 4 (1 août 1997) : 604–12. http://dx.doi.org/10.1107/s0108768197003844.

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The structures of the disordered lithium molybdates Li2MoO3 and Li4Mo3O8 have been investigated using total neutron scattering from polycrystalline powders. Rietveld analysis of the Bragg scattering is used to determine the average structures. Shortcomings in this method of analysis are demonstrated by comparing the total correlation function, T(r), determined from total neutron scattering, with those calculated from the structures determined from Rietveld analysis. Much more satisfactory models for these materials are derived from the structurally related ordered material LiZn2Mo3O8, using information from Mo K-edge extended X-ray absorption fine-structure spectroscopy (EXAFS). These models include metal–metal-bonded Mo3O13 clusters [d(Mo—Mo) = 2.58 Å in Li2MoO3 and 2.56 Å in Li4Mo3O8] not present in the average structure determined from Rietveld analysis [d(Mo—Mo) = 2.88 Å in Li2MoO3]. In contrast to EXAFS studies neutron diffraction yields information on all the pair correlations in the material, not merely those involving molybdenum, and allows, for example, the location of lithium. Remaining discrepancies between our models and the experimental T(r)'s give an insight into the disorder in the two materials.
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25

Qi, Yue, Christine James, Tridip Das, Jason D. Nicholas, Leah Nation et Brian W. Sheldon. « (Invited) Computing the Anisotropic Chemical Strain in Non-Stoichiometric Oxides for Solid Oxide Fuel Cell and Li-Ion Battery Applications ». ECS Meeting Abstracts MA2018-01, no 32 (13 avril 2018) : 1940. http://dx.doi.org/10.1149/ma2018-01/32/1940.

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Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. By combining density functional theory (DFT) calculations and elastic dipole tensor theory, it is readily to predict the long-range chemical strain tensor and the chemical expansion coefficient tensor induced by dilute point defects in a crystal structure. First, we demonstrate that, even in cubic CeO2-δ, both the short-range deformation surrounding an oxygen vacancy and the long-range chemical strain (or the expansion coefficient) are anisotropic. The origin of this anisotropy is the charge disproportionation between the four cerium atoms surrounding each oxygen vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen vacancy is formed. While the short-range deformation agrees with experimentally determined Ce-O bond lengths, the predicted maximum and average chemical strains successfully bound the variety of CeO2-δ chemical strain behavior previously reported in the literature. Normally, since there are six possible disproportionation configurations, the average chemical strain is isotropic. Only under an external bias, such as an applied electric field, the chemical strain can be oriented to show the anisotropic effect. This successfully explained the giant electrostriction effect reported in doped and un-doped CeO2-δ. Next, we show strains induced by coupled vacancies in layered Li-intercalation compounds for battery applications. Li2MnO3 was investigated as Li-excess intercalation compounds containing Li2MnO3 need to be “activated” to deliver the high capacity. This activation process during the first delithiation cycle at a high voltage is believed to introduce oxygen vacancies into the system. Due to the large amount Li vacancy generated, a large number of defect configurations were sampled and the average chemical strain induced by Li vacancy concentration is obtained by Boltzmann average. Previously, we have demonstrated that it is energetically favorable to create a Li-O-Li vacancy dumbbell structure (VLi - VO - VLi) in Li2MnO3. The chemical strain of the vacancy dumbbell structure is smaller than the sum of the chemical strain of one Vo and two VLis. The chemical expansion coefficient averaged for the polycrystalline samples and the experimentally measured stress change provided a novel method to in situ track the irreversible chemical changes in Li-excess cathode materials.
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KUMADA, Nobuhiro, Suguru MURAMATSU, Nobukazu KINOMURA et Fumio MUTO. « Deintercalation of Li2MoO3 ». Journal of the Ceramic Society of Japan 96, no 1120 (1988) : 1181–85. http://dx.doi.org/10.2109/jcersj.96.1181.

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Lim, Jinsub, Jieh Moon, Jihyeon Gim, Sungjin Kim, Kangkun Kim, Jinju Song, Jungwon Kang, Won Bin Im et Jaekook Kim. « Fully activated Li2MnO3 nanoparticles by oxidation reaction ». Journal of Materials Chemistry 22, no 23 (2012) : 11772. http://dx.doi.org/10.1039/c2jm30962a.

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Robertson, Alastair D., et Peter G. Bruce. « The origin of electrochemical activity in Li2MnO3 ». Chemical Communications, no 23 (24 octobre 2002) : 2790–91. http://dx.doi.org/10.1039/b207945c.

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Lei, C. H., J. G. Wen, M. Sardela, J. Bareño, I. Petrov, S. H. Kang et D. P. Abraham. « Structural study of Li2MnO3 by electron microscopy ». Journal of Materials Science 44, no 20 (8 août 2009) : 5579–87. http://dx.doi.org/10.1007/s10853-009-3784-1.

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Li, Zhe, Kai Zhu, Yu Hui Wang, Gang Li, Gang Chen, Hong Chen, Ying Jin Wei et Chun Zhong Wang. « Electrochemical Properties of Li-Riched Li[Li0.2Co0.4Mn 0.4]O2 Cathode Material for Lithium Ion Batteries ». Advanced Materials Research 347-353 (octobre 2011) : 3658–61. http://dx.doi.org/10.4028/www.scientific.net/amr.347-353.3658.

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The Li[Li0.2Co0.4Mn0.4]O2 cathode material was prepared by a sol-gel method. The X-ray diffraction (XRD) spectroscopic showed that the material was a solid solution of LiCoO2 and Li2MnO3. The material showed a reversible discharge capacity of 155.6 mAhg−1 in the voltage window of 2.0-4.3 V after percharge to 4.6 V. While the material cycled in the same voltage window without precharge could only deliver capacity of 77.6 mAhg−1. This high capacity was attributed to the loss of oxygen and structural rearrangement in the precharge process.
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Wang, Yu Hui, Zhe Li, Kai Zhu, Gang Li, Ying Jin Wei, Gang Chen et Chun Zhong Wang. « Low-Temperature Performance of the Li[Li0.2Co0.4Mn0.4]O2 Cathode Material Studied for Li-Ion Batteries ». Advanced Materials Research 347-353 (octobre 2011) : 3662–65. http://dx.doi.org/10.4028/www.scientific.net/amr.347-353.3662.

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The Li[Li0.2Co0.4Mn0.4]O2 cathode material was prepared by a sol-gel method. Combinative X-ray diffraction (XRD) studies showed that the material was a solid solution of LiCoO2 and Li2MnO3. The material showed a reversible discharge capacity of 155.0 mAhg−1 at -20 °C, which is smaller than that at room temperature (245.5 mAhg−1). However, the sample exhibited capacity retention of 96.3 % at -20 °C, only 74.2 % at 25 °C. The good electrochemical cycle performance at low temperature was due to the inexistence of Mn3+ in the material.
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32

Torres-Castro, L., R. S. Katiyar et A. Manivannan. « Structural and Electrochemical Studies of Rhodium Substituted Li2MnO3 ». ECS Transactions 69, no 18 (28 décembre 2015) : 23–32. http://dx.doi.org/10.1149/06918.0023ecst.

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Koyama, Yukinori, Isao Tanaka, Miki Nagao et Ryoji Kanno. « First-principles study on lithium removal from Li2MnO3 ». Journal of Power Sources 189, no 1 (avril 2009) : 798–801. http://dx.doi.org/10.1016/j.jpowsour.2008.07.073.

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Zhang, Xianke, Shaolong Tang et Youwei Du. « Synthesis and magnetic properties of antiferromagnetic Li2MnO3 nanoribbons ». Physics Letters A 375, no 36 (août 2011) : 3196–99. http://dx.doi.org/10.1016/j.physleta.2011.07.008.

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Wang, Z. Q., Y. C. Chen et C. Y. Ouyang. « Polaron states and migration in F-doped Li2MnO3 ». Physics Letters A 378, no 32-33 (juin 2014) : 2449–52. http://dx.doi.org/10.1016/j.physleta.2014.06.025.

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36

Rana, Jatinkumar, Joseph K. Papp, Zachary Lebens-Higgins, Mateusz Zuba, Lori A. Kaufman, Anshika Goel, Richard Schmuch et al. « Quantifying the Capacity Contributions during Activation of Li2MnO3 ». ACS Energy Letters 5, no 2 (27 janvier 2020) : 634–41. http://dx.doi.org/10.1021/acsenergylett.9b02799.

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37

Boulineau, A., L. Croguennec, C. Delmas et F. Weill. « Structure of Li2MnO3 with different degrees of defects ». Solid State Ionics 180, no 40 (29 janvier 2010) : 1652–59. http://dx.doi.org/10.1016/j.ssi.2009.10.020.

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Phillips, P. J., H. Iddir, R. Benedek, D. P. Abraham et R. F. Klie. « Imaging and Spectroscopy of Pristine and Cycled Li2MnO3 ». Microscopy and Microanalysis 20, S3 (août 2014) : 494–95. http://dx.doi.org/10.1017/s143192761400419x.

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Park, Sang-Ho, Yuichi Sato, Jae-KooK Kim et Yun-Sung Lee. « Powder property and electrochemical characterization of Li2MnO3 material ». Materials Chemistry and Physics 102, no 2-3 (avril 2007) : 225–30. http://dx.doi.org/10.1016/j.matchemphys.2006.12.008.

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Quesne-Turin, Ambroise, Delphine Flahaut, Germain Salvato Vallverdu, Laurence Croguennec, Joachim Allouche, François Weill, Michel Ménétrier et Isabelle Baraille. « Surface reactivity of Li2MnO3 : Structural and morphological impact ». Applied Surface Science 542 (mars 2021) : 148514. http://dx.doi.org/10.1016/j.apsusc.2020.148514.

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Ruther, Rose E., Hemant Dixit, Alan M. Pezeshki, Robert L. Sacci, Valentino R. Cooper, Jagjit Nanda et Gabriel M. Veith. « Correlating Local Structure with Electrochemical Activity in Li2MnO3 ». Journal of Physical Chemistry C 119, no 32 (31 juillet 2015) : 18022–29. http://dx.doi.org/10.1021/acs.jpcc.5b03900.

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Ozkendir, O. Murat, Messaoud Harfouche, Intikhab Ulfat, Çiğdem Kaya, Gultekin Celik, Sule Ates, Sevda Aktas, Hadi Bavegar et Tugba Colak. « Boron activity in the inactive Li2MnO3 cathode material ». Journal of Electron Spectroscopy and Related Phenomena 235 (août 2019) : 23–28. http://dx.doi.org/10.1016/j.elspec.2019.06.011.

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Wang, Fangwei, Xiyang Li Li, Lunhua He, Rui Wang Wang, Xiaoqing He, Lin Gu, Hong Li et Liquan Chen. « Atomic structure of Li2-xMnO3studied by neutron diffraction and STEM ». Acta Crystallographica Section A Foundations and Advances 70, a1 (5 août 2014) : C142. http://dx.doi.org/10.1107/s205327331409857x.

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Li2MnO3 is an important cathode material with extra high capacity (>300mAh g-1 for the first charge process). The exact charge-discharge mechanism and the structure evolution still remain controversial. Here the atomic structures of Li2MnO3 after partial delithiation and lithiation are investigated by neutron powder diffraction and spherical aberration-corrected scanning transmission electron microscopy (STEM). Neutron diffraction experiments are performed on Li2-xMnO3 (x=0, 0.25) in a bulk level. It can be found that the volume of the unit cell almost keeps constant, while the lattice constants in the a, b direction increases after the chemical delithiation, but the c direction decreases. For the delithiated compound Li1.75MnO3, the Li occupancies are 0.7(+-0.3), 0.9(+-0.1) for the 2c and 4h sites, respectively, resulting in the Li-concentration of 1.75(+-0.27), while the 2b sites are fully occupied. Furhtermore, the isotropic thermal vibration factors of the 2c and 4h Li atoms are considerably larger than that of the 2b Li atoms, also seemingly implying the feasible delithiation of Li atoms at the 2c and 4h sites in the Li-O layer. It is interesting to note that the thermal factor of Mn atoms is slightly larger than O atoms, which probably means that the Mn atoms are more mobile than O atoms. The STEM results suggest that the Li ions can be extracted both from the LiMn2 planes and Li planes, and the Mn ions can move reversibly in the (110) plane during delithiation and lithiation.
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James, Christine, Yan Wu, Brian Sheldon et Yue Qi. « Computational Analysis of Coupled Anisotropic Chemical Expansion in Li2-XMnO3-δ ». MRS Advances 1, no 15 (2016) : 1037–42. http://dx.doi.org/10.1557/adv.2016.48.

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ABSTRACTDuring the activation and charge process, vacancies are generated in the Li2MnO3 component in lithium-rich layered cathode materials. The chemical expansion coefficient tensor associated with oxygen vacancies, lithium vacancies and a Li-O vacancy pair were calculated for Li2-xMnO3-δ. The chemical expansion coefficient was larger for oxygen vacancies than for lithium vacancies in most directions. Additionally, the chemical expansion coefficient for a Li-O vacancy pair was shown to not be a linear sum of the chemical expansion coefficients of the two vacancy types, suggesting that the oxygen vacancies and lithium vacancies in Li2-XMnO3-δ exhibit a coupling effect.
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Kataoka, R., N. Taguchi, T. Kojima, N. Takeichi et T. Kiyobayashi. « Improving the oxygen redox stability of NaCl-type cation disordered Li2MnO3 in a composite structure of Li2MnO3 and spinel-type LiMn2O4 ». Journal of Materials Chemistry A 7, no 10 (2019) : 5381–90. http://dx.doi.org/10.1039/c8ta11807h.

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Zhang, Shiwei, Jianchuan Wang, Ting Lei, Xu Li, Yuling Liu, Fangyu Guo, Jun Wang et al. « First-principles study of Mn antisite defect in Li2MnO3 ». Journal of Physics : Condensed Matter 33, no 41 (5 août 2021) : 415201. http://dx.doi.org/10.1088/1361-648x/ac16f6.

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Arachi, Yoshinori, Kentarou Hinoshita et Yoshiyuki Nakata. « Effect of CuO on the Electrochemical Activity of Li2MnO3 ». ECS Transactions 41, no 29 (16 décembre 2019) : 1–7. http://dx.doi.org/10.1149/1.3696677.

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Singh, Gurpreet, R. Thomas, Arun Kumar et R. S. Katiyar. « Electrochemical Behavior of Cr- Doped Composite Li2MnO3-LiMn0.5Ni0.5O2Cathode Materials ». Journal of The Electrochemical Society 159, no 4 (2012) : A410—A420. http://dx.doi.org/10.1149/2.059204jes.

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Torres-Castro, Loraine, Jifi Shojan, Christian M. Julien, Ashfia Huq, Chetan Dhital, Mariappan Parans Paranthaman, Ram S. Katiyar et Ayyakkannu Manivannan. « Synthesis, characterization and electrochemical performance of Al-substituted Li2MnO3 ». Materials Science and Engineering : B 201 (novembre 2015) : 13–22. http://dx.doi.org/10.1016/j.mseb.2015.07.006.

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Kan, Yongchun, Yuan Hu, Jason Croy, Yang Ren, Cheng-Jun Sun, Steve M. Heald, Javier Bareño, Ira Bloom et Zonghai Chen. « Formation of Li2MnO3 investigated by in situ synchrotron probes ». Journal of Power Sources 266 (novembre 2014) : 341–46. http://dx.doi.org/10.1016/j.jpowsour.2014.05.032.

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