Electric and Magnetic Properties of LiMn2O4- and Li2MnO3-Type Oxides

Massarotti, Vincenzo; Capsoni, Doretta; Bini, Marcella; Chiodelli, Gaetano; Azzoni, C. B.; Mozzati, Maria Cristina; Палеари, А.

doi:10.1006/jssc.1997.7349

Cited by 85 publications

(66 citation statements)

References 25 publications

(29 reference statements)

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“…It was observed that the line shape and broadening are mainly related to the presence of non stoichiometric Li-rich spinel phase [2,3,14]. A detailed analysis of the XRD pattern was obtained by considering an effective non-stoichiometry of the spinel phase in addition to the diffraction effects of Li 2 Mn0 3 , in order to determine the phase abundance and composition in the samples from the Rietveld refinement procedure.…”

Section: Resultsmentioning

confidence: 99%

“…Samples were prepared from starting reacting mixtures Mn0/Li 2 C0 3 [2,3] with lithium cationic fraction, x, ranging between 0 and 0.67. The mixtures were previously treated 1 hour at 1073 K (heating rate 5 K/min) to decompose the carbonate and then 0932-0784 / 98 / 0900-0771 $ 06.00 © Verlag der Zeitschrift für Naturforschung, Tübingen • www.znaturforsch.com On 01.01.2015 it is planned to change the License Conditions (the removal of the Creative Commons License condition "no derivative works").…”

Section: Methodsmentioning

confidence: 99%

“…valence states [2][3][4][5]. The magnetic properties of these compounds depend on the Mn oxidation state which may be influenced by a change of the Li cationic fraction.…”

Section: +mentioning

confidence: 99%

“…Some controversy exists in the literature [2,[7][8][9] on the magnetic susceptibility of the stoichiometric LiMn 2 0 4 which shows a sample dependent behaviour, particularly at low temperature. The spread of results may arise from differences in the preparation methods, which can easily introduce unwanted spurious phases [10].…”

Section: +mentioning

confidence: 99%

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Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Azzoni

Mozzati

Палеари³

et al. 1998

Zeitschrift Für Naturforschung A

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Magnetic susceptibility measurements and electron paramagnetic resonance spectra of samples prepared from the reactive system Mn0/Li 2 C0 3 with different starting Li cationic fraction x are analyzed, taking into account the structural and compositional information provided by x-ray diffraction. Parent phases, as Mn 2 0 3 , Mn 3 0 4 and Li 2 Mn0 3 , arise together with the lithium-manganese spinel as a result of Li-deficiency or Li-excess with respect to the x = 0.33 composition pertinent to the stoichiometric LiMn 2 0 4 spinel. The data show that the spinel phase can sustain a partial Li-Mn substitution in the cation sites, according to compositional models described, for x > 0.33, by Lii +y Mnit 3y Mnf+ 2y 0 4 (Li-rich spinel) and, for x < 0.33, by Lii_| J/ |Mn^|Mn^| y |Mnfi| I/ |0 4 (Li-poor spinel). Paramagnetic resonance data of the Li-poor spinel phase are analyzed to discuss the possible oxidation state of Mn in the tetrahedral site.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…valence states [2][3][4][5]. The magnetic properties of these compounds depend on the Mn oxidation state which may be influenced by a change of the Li cationic fraction.…”

Section: +mentioning

confidence: 99%

Section: +mentioning

confidence: 99%

See 2 more Smart Citations

Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Azzoni

Mozzati

Палеари³

et al. 1998

Zeitschrift Für Naturforschung A

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“…It undergoes at ϳ290 K a structural phase transition attributed either to a partial charge ordering 2 or a cubictetragonal structural phase transition driven by a cooperative Jahn-Teller distortion mechanism around the Mn 3ϩ cation sites. 3 That transition renders the material unsuitable as a cathode because of a poor cycling performance. Li substitution on the Mn site gives rise to an increase in Mn 4ϩ concentration and subsequently a decrease in Mn 3ϩ concentration.…”

mentioning

confidence: 99%

Li mobility in the battery cathode materialLix[Mn1.96Li
Kaiser
¹
,
Verhoeven
²
,
Gubbens
³

et al. 2000
Phys. Rev. B
27
4
29
0
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The battery cathode materials Li x ͓Mn 1.96 Li 0.04 ͔O 4 with xϭ1 and 0.2 were studied by the zero-field muonspin-relaxation technique. Both materials have a magnetic transition below T M Ӎ25 K. At high temperature, above Tϭ230 K, a large decrease of the width of the static field distribution at the muon site is found for Li͓Mn 1.96 1 In combination with carbonaceous anodes these materials form excellent rechargeable batteries. Their principle is based on the transport of Li ions, which shuttle back and forth between the insertion electrodes. A battery is recharged by an external voltage causing a flow of Li ϩ ions to the anode, where they intercalate and are stored for later use. The backflow of Li ϩ ions between the anode and cathode generates the power of the battery. The battery operates between the xϭ0.2 ͑''charged''͒ and xϭ1 ͑''empty''͒ states, provided that y is small, i.e., 0Ͻyр0.06. x refers to the occupation probability of the regular Li 8a sites.In LiMn 2 O 4 (xϭ1,yϭ0) equal amounts of Mn 3ϩ and Mn 4ϩ ions are present. This compound is a hopping electronic conductor in which electrons move between adjacent Mn sites. It undergoes at ϳ290 K a structural phase transition attributed either to a partial charge ordering 2 or a cubictetragonal structural phase transition driven by a cooperative Jahn-Teller distortion mechanism around the Mn 3ϩ cation sites.3 That transition renders the material unsuitable as a cathode because of a poor cycling performance. Li substitution on the Mn site gives rise to an increase in Mn 4ϩ concentration and subsequently a decrease in Mn 3ϩ concentration. This leads to an increased stability of the cubic spinel structure as shown by a recent powder neutron-diffraction study, which did not detect for Li͓Mn 1.96 Li 0.04 ͔O 4 any structural phase transition from room temperature down to 4.2 K. 4The thermal variation of the lattice parameter is far less than 1% in this temperature range. 7 The size of the grains is ϳ25 m as shown from scanning electron microscopy. Flame atomic adsorption spectroscopy indicated that the amount of elements present in the samples is correct. Furthermore, the powders were analyzed by the Jaeger and Vetter titration method in order to determine the Mn valency.8 It was found that the Mn valencies are 3.55 and 3.96 for x ϭ1 and xϭ0.2, respectively. These values are in the expected range.The SR technique uses the positive muon as a local magnetic probe. The polarized muons are implanted into the sample where their polarization evolves in the local magnetic field until they decay ͑the muon lifetime is 2.2 s). The decay positron is emitted preferentially along the muon spin direction. By collecting several million positrons as function of the evolution time, one can construct the time dependence of the muon spin polarization which, in turn, reflects the distribution of the magnetic field at the muon site. Since the kinetic energy of the positrons is relatively large, they pass easily through sample, cryostat or furnace to the detectors.

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Recent Progress and Challenges of Li‐Rich Mn‐Based Cathode Materials for Solid‐State Lithium‐Ion Batteries

Huang,

Liu,

Chen

et al. 2024

Advanced Materials

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Li‐rich Mn‐based (LRM) cathode materials, characterized by their high specific capacity (>250 mAh g−¹) and cost‐effectiveness, represent promising candidates for next‐generation lithium‐ion batteries. However, their commercial application is hindered by rapid capacity degradation and voltage fading, which can be attributed to transition metal migration, lattice oxygen release, and the toxicity of Mn ions to the anode solid electrolyte interphase (SEI). Recently, the application of LRM cathode in all‐solid‐state batteries (ASSBs) has garnered significant interest, as this approach eliminates the liquid electrolyte, thereby suppressing transition metal crosstalk and solid–liquid interfacial side reactions. This review first examines the historical development, crystal structure, and mechanisms underlying the high capacity of LRM cathode materials. It then introduces the current challenges facing LRM cathode and the associated degradation mechanisms and proposes solutions to these issues. Additionally, it summarizes recent research on LRM materials in ASSBs and suggests strategies for improvement. Finally, the review discusses future research directions for LRM cathode materials, including optimized material design, bulk doping, surface coating, developing novel solid electrolytes, and interface engineering. This review aims to provide further insights and new perspectives on applying LRM cathode materials in ASSBs.

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Electric and Magnetic Properties of LiMn2O4- and Li2MnO3-Type Oxides

Cited by 85 publications

References 25 publications

Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Li mobility in the battery cathode materialLix[Mn1.96Li
Kaiser
¹
,
Verhoeven
²
,
Gubbens
³

et al. 2000
Phys. Rev. B
27
4
29
0
View full text Add to dashboard Cite

Recent Progress and Challenges of Li‐Rich Mn‐Based Cathode Materials for Solid‐State Lithium‐Ion Batteries

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Electric and Magnetic Properties of LiMn2O4- and Li2MnO3-Type Oxides

Cited by 85 publications

References 25 publications

Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Evidence of a Cationic Substitution Domain in Lithium-Manganese Spinels

Li mobility in the battery cathode materialLix[Mn1.96LiKaiser1, Verhoeven2, Gubbens3 et al. 2000Phys. Rev. B274290View full textAdd to dashboardCite

Recent Progress and Challenges of Li‐Rich Mn‐Based Cathode Materials for Solid‐State Lithium‐Ion Batteries

Contact Info

Product

Resources

About

Li mobility in the battery cathode materialLix[Mn1.96Li
Kaiser
¹
,
Verhoeven
²
,
Gubbens
³

et al. 2000
Phys. Rev. B
27
4
29
0
View full text Add to dashboard Cite