Integrated Materials xLi[sub 2]MnO[sub 3]⋅(1−x)LiMn[sub 1/3]Ni[sub 1/3]Co[sub 1/3]O[sub 2] (x=0.3, 0.5, 0.7) Synthesized

Amalraj, Francis; Kovacheva, D.; Talianker, M.; Zeiri, Leila; Grinblat, Judith; Leifer, Nicole; Goobes, Gil; Markovsky, Boris; Aurbach, Doron

doi:10.1149/1.3463782

Cited by 192 publications

(155 citation statements)

References 30 publications

(55 reference statements)

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“…Amalraj et al, synthesized xLi 2 MnO 3 :(1-x)LiMn 0.33 Ni 0.33 Co 0.33 O 2 (x = 0.3, 0.5 and 0.7) using self-combustion reaction in solution containing metal nitrates and sucrose. 53 Cycling performance, rate capability and impedance evolution of the electrodes were investigated. Structural changes occurring due to cycling were evaluated by XRD, Raman spectroscopy and 7 Li magic angle spinning NMR techniques.…”

Section: 51mentioning

confidence: 99%

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Penki

Duraisamy

Kishore

et al. 2016

J. Electrochem. Soc.

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A porous layered composite of Li 2 MnO 3 and LiMn 1/3 Ni 1/3 Fe 1/3 O 2 (composition: Li 1.2 Mn 0.53 Ni 0.13 Fe 0.13 O 2 ) is prepared by reverse microemulsion method employing tri-block co-polymer, F068 as a soft-polymer template. The Co-free composite is studied as a cathode material for Li-ion battery. Several samples are prepared by heating the precursor in the temperature range between 500 and 900 • C. The N 2 adsorption/desorption studies reveal that the product samples possess mesoporosity with broadly distributed pores around 15-50 nm diameter. Pore volume and surface area decrease by increasing the temperature of preparation. Charge-discharge, cycling and rate capability are investigated. The discharge capacity of the sample prepared at 900 • C is about 170 mAh g −1 at a specific current of 25 mA g −1 with a good cycling stability. A value of 140 mAh g −1 is obtained at the end of 50 charge-discharge cycles. Discharge capacity of 91 mAh g −1 is obtained at a specific current of 206 mA g −1 . A high rate capacity of the composite is attributed to its porous nature. Research activities on lithium-ion batteries have increased in the recent past because of their attractive energy density. [1][2][3] In an extended range of applications, they are successful in small sizes at present and anticipated to be useful in large sizes for applications such as electric vehicles. Although the energy density of the present Li-ion batteries is the greatest among rechargeable batteries, future requirements such as electric vehicle applications require still greater energy density. The next generation Li-ion batteries, thus, need novel electrode materials which can provide greater discharge capacity than the present materials. Compounds with a high atomic ratio of extractable lithium to transition metal are expected to provide high discharge capacity values. Li 2 MnO 3 belongs to this category of materials.4 Li 2 MnO 3 is a layered oxide similar to LiCoO 2 and its formula can also be presented as Li (Li 0.33 was reported at a specific current of 30 mA g −1 in the potential range between 1.5 and 4.8 V. 33,34 In addition to the high discharge capacity, an electrode material needs to possess high rate capability for the purpose of fast charge or/and discharge. Porous materials are expected to possess high rate capability because the electrolyte can creep into particles and enhance the contact area. 35 As a result, the material can withstand an enhanced specific current during charge-discharge cycling. Furthermore, the electrode material can tolerate volume expansion and contraction that may occur during charge-discharge processes. To the best of authors' knowledge, there are only few reports available on the synthesis of porous composites of Li 2 MnO 3 . A porous composite of Li 2 MnO 3 with nanoplate morphology was prepared via colloidal crystal template of poly(methyl methacrylate) beads. The porous composite was better in electrochemical properties in relation to the nonporous composite. 36,37 Investigations on high capa...

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Section: 51mentioning

confidence: 99%

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Penki

Duraisamy

Kishore

et al. 2016

J. Electrochem. Soc.

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“…18,19,24,[26][27][28][29][30][31] Raman microscopy offers high spatial resolution (< 1μm 3 ), large field of view, and chemical specificity, making it an ideal tool to investigate both the pristine material and composite battery electrodes. 32,33 Nonetheless, there are significant differences in the spectra reported for LMR-NMC oxides, as well as ambiguity in the interpretation of the vibrational modes.…”

Section: -6mentioning

confidence: 99%

“…9,[17][18][19][20][21][22][23][24][25] In particular, several groups have applied Raman microscopy to understand the structure and structural evolution of lithium-rich, manganese-rich TM oxides of nickel, manganese, and cobalt (hereafter LMR-NMC). 18,19,24,[26][27][28][29][30][31] Raman microscopy offers high spatial resolution (< 1μm 3 ), large field of view, and chemical specificity, making it an ideal tool to investigate both the pristine material and composite battery electrodes. 32,33 Nonetheless, there are significant differences in the spectra reported for LMR-NMC oxides, as well as ambiguity in the interpretation of the vibrational modes.…”

mentioning

confidence: 99%

Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes

Ruther

Callender

Zhou

et al. 2014

J. Electrochem. Soc.

121

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Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2 MnO 3 · (1-x)LiMO 2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this study, Raman microscopy is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. The results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets. Lithium-manganese-rich TM oxides form as the integrated structure of two layered phases: xLi 2 MnO 3 with C2/m space group symmetry and (1-x)LiMO 2 (M = Co, Mn, Ni, Fe, Cr) with R3m space group symmetry. While the exact structure of lithium-rich TM oxides has been the subject of much debate, a number of recent studies conclude that the material forms as the composite of these two distinct phases with nanoscale domains of Li 2 MnO 3 and LiMO 2 character. 1-6The intense interest in lithium excess cathodes stems from the potential to deliver very large reversible capacities (>200 mAh g −1 ) when charged beyond 4.5 V vs. Li 0 /Li + . 7 Part of the capacity derives from electrochemical activation of the Li 2 MnO 3 component at voltages beyond 4.4 V. Two mechanisms have been proposed for this activation. The dominant mechanism appears to be the simultaneous removal of lithium and oxygen to form a composition similar to MnO 2 . [8][9][10][11] Protons from electrolyte decomposition may also exchange for lithium. This secondary mechanism becomes more significant at higher temperature.12-14 Despite the promise of lithium rich TM oxides to deliver very high capacities, one significant limitation remains the large voltage and capacity fade observed upon extended electrochemical cycling. 15,16 A number of studies have attempted to link structural changes in lithium-rich TM oxides with electrochemical stability and cycling behavior.9,17-25 In particular, several groups have applied Raman microscopy to understand the structure and structural evolution of lithium-rich, manganese-rich TM oxides of nickel, manganese, and cobalt (hereafter LMR-NMC). 18,19,24,[26][27][28][29][30][31] Raman microscopy offers high spatial resolution (< 1μm 3 ), large field of view, and chemical specificity, making it an ideal tool to investigate both the pristine material and comp...

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“…Moreover, this reaction was found to be reversible by the appearance of corresponding oxidation peak in the following charge. [ 28,36 ] The broad oxidation peak appearing in the potential range of 3. [ 16 ] In case of all the composite systems, the CV curves show features of both the parent LNMO and the LIR components.…”

Section: Cyclic Voltammetrymentioning

confidence: 99%

Synthesis and Characterization of High‐Energy, High‐Power Spinel‐Layered Composite Cathode Materials for Lithium‐Ion Batteries

Bhaskar

Krueger²,

Siozios³

et al. 2014

Advanced Energy Materials

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the LiNi 0.5 Mn 1.5 O 4 material is intensively investigated due to its high-voltage electrochemical activity, excellent rate capability as well as cycling stability. [2][3][4][5][6][7] LiNi 0.5 Mn 1.5 O 4 exists mainly in two crystallographic structures according to the oxygen stoichiometry in the material. [ 2,[8][9][10] The cation-ordered spinel (space group P 4 3 32) which is oxygen-stoichiometric, contains all the Mn ions in their tetravalent form. [ 11 ] At the same time in the cation-disordered structure (space group Fd 3 m) , in addition to the tetravalent Mn species, some of the Mn ions exist in the trivalent form as a result of oxygen deficiency from the crystal lattice. [ 12 ] This is mainly associated with the synthesis temperature. According to Pasero et al. [ 10 ] when the synthesis temperature exceeds ≈650 °C, the structure of LiNi 0.5 Mn 1.5 O 4 transforms gradually from the cationordered to cation-disordered. In the cation-ordered structure, the only electrochemically active species is Ni 2+ . The electrochemical reaction takes place at ≈4.7 V with two plateaus corresponding to Ni 2+ / Ni 3+ and Ni 3+ /Ni 4+ reactions, respectively. [ 2,12 ] Meanwhile, in the cation-disordered structure, a slight electrochemical activity is observed around 4.0 V versus Li/Li + as a result of Mn 3+ /Mn 4+ electrochemical reaction. [ 12 ] However, this material offers only a theoretical capacity of ≈148 mAh g −1 in the usual cycling voltage range 3.5-5.1 V. [ 13 ] It is possible to intercalate a second Li + into the material at voltage <3.0 V which in turn increases the capacity delivered. [ 1,14 ] For this purpose a Li excess electrode must be used as the counter electrode during cycling. Moreover, this process is believed to induce Jahn-Teller distortion of the structure due to the existence of excessive amount of Mn 3+ which in turn results in an average oxidation state of Mn less than +3.5. [ 1,14,15 ] The layered lithium-rich (Li-rich) materials with a general composition x Li 2 MnO 3 · (1 -x ) LiMO 2 (M = Mn, Co, Ni) are known to deliver capacities >250 mAh g −1 when cycled within the voltage range 2.0-4.8 V. [ 16 ] This material has a complex structure which is reported either as composites with nanodomains of Li 2 MnO 3 -and LiMO 2 -like features or as their solid solutions. [17][18][19][20] The powder diffraction patterns of this material

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Integrated Materials xLi[sub 2]MnO[sub 3]⋅(1−x)LiMn[sub 1/3]Ni[sub 1/3]Co[sub 1/3]O[sub 2] (x=0.3, 0.5, 0.7) Synthesized

Cited by 192 publications

References 30 publications

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes

Synthesis and Characterization of High‐Energy, High‐Power Spinel‐Layered Composite Cathode Materials for Lithium‐Ion Batteries

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