The effect of 3d substitutions in the manganese sublattice on the electrical and electrochemical properties of manganese spinel

Molenda, Janina; Marzec, J.; Świerczek, Konrad; Pałubiak, D.; Ojczyk, W.; Ziemnicki, M.

doi:10.1016/j.ssi.2004.01.069

Cited by 49 publications

(26 citation statements)

References 15 publications

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“…Molenda et al, have studied the conductivity properties of LiNi x Mn 2 À x O 4 recently[31]. They reported that the unequal 16d sites occupancy of Mn 3+ and Mn 4+ in LiNi x Mn 2 À x O 4 decreases the electrons hopping rate between the cations, and cannot be fully compensated by the Ni cations.…”

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confidence: 99%

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

et al. 2006

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confidence: 99%

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

et al. 2006

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“…The electrical conductivity of the as-prepared LNMO was thus determined as (1.1 ± 0.8) × 10 −4 S/cm, which is about one order of magnitude higher than the electrical conductivity values of LNMO materials reported in the literature (1.7 × 10 −5 − 3.2 × 10 −6 S/cm) [24,25,26]. The difference between the electrical conductivity values from this work compared with those reported in the literature is due to the different measurement setups.…”

Section: Resultsmentioning

confidence: 68%

“…It exhibited an electrical conductivity of (1.3 ± 1.0) ×·10 −3 S/cm, which was about one order of magnitude higher than the electrical conductivity of the individual LNMO particles. Previous work revealed that the electronic conduction mechanism in both LMO and LNMO materials is small-polaron hopping [26,64]. As the polaron states are localized at the Mn 3+ sites, the electronic conductivity of the materials is assumingly determined mainly by the Mn 3+ content in the material.…”

Section: Resultsmentioning

confidence: 99%

“…However, most of the electrical investigations conducted so far are bulk measurements, such as four-probe AC measurements or impedance spectroscopy (IS) measurements, on pressed pellets [26,27]. To densify the pellets, sintering at high temperature is generally required, which can influence the crystallographic structure of LNMO and/or result in formation of secondary phases [28,29].…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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

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“…7,8 To make structurally and electrochemically stable spinel LiMn 2 O 4 , the manganese (Mn) ion substituted with Ti, Cr, Fe, Co, Ni, Al and Mg were explored. 7,[9][10][11][12][13] Even though layered and spinel transition metal oxides are extensively studied for Li ion battery applications, there is an existence of crystal structural problems while on charging to higher voltage where the electrolyte is unstable due to evolution of oxygen from de-lithiated transition metal oxide framework. To address this problem, more research focus on lithium containing metal phosphate LiFePO 4 , LiMnPO 4 , Li 3 V 2 (PO 4 ) 3 etc.…”

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Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Satyanarayana¹,

Rao²,

Pralong³

et al. 2016

J. Electrochem. Soc.

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Li-insertion studies were performed on V 4 O 3 (PO 4 ) 3 that belongs to the libscombite/lazulite family. Availability of multiple oxidation states and vacancies in crystal structure allows for the insertion of more than 7 lithium ions per formula unit. We will show that in the voltage window of 1-4 V vs. Li + /Li, 6.0 Li-ions could be inserted leading to a reversible capacity of 195 mAh/g at a C/5 rate. A structural transformation is observed from ex-situ XRD patterns after the insertion of 2 lithium at 2.4 V vs. Li + /Li, consistent with the available crystallographic sites in the structure. Interestingly we show that from this phase Li 2 V 4 O 3 (PO 4 ) 3 , further lithium insertion lead to an amorphous material but the structure is completely recovered on charge. Layered hexagonal transition metal oxides LiMO 2 (here, M = Co, Mn, Ni, Fe, Cr) have been extensively studied for commercial Li-ion secondary battery applications.1,2 The substitution of Ni and Mn in LiCoO 2 results in composition of LiNi 1/3 Mn 1/3 Co 1/3 O 2 is proven to be a promising cathode material.3-6 Spinel LiMn 2 O 4 has shown more interest due to less toxic nature of Mn, but lagged in the competition for next generation cheap energy storage device in presence of manganese dissolution in electrolyte and structural instability. 7,8 To make structurally and electrochemically stable spinel LiMn 2 O 4 , the manganese (Mn) ion substituted with Ti, Cr, Fe, Co, Ni, Al and Mg were explored. 7,9-13 Even though layered and spinel transition metal oxides are extensively studied for Li ion battery applications, there is an existence of crystal structural problems while on charging to higher voltage where the electrolyte is unstable due to evolution of oxygen from de-lithiated transition metal oxide framework. To address this problem, more research focus on lithium containing metal phosphate LiFePO 4 , LiMnPO 4 , Li 3 V 2 (PO 4 ) 3 etc.14-16 have been explored as thermally stable electrode materials. Indeed, the bonding of oxygen to phosphorous stabilize the structure from oxygen evolution, differently to layered transition metal oxides whereas oxygen evolution occurs at high charge voltages.17,18 But the energy obtained for these materials is low compared to metal oxide materials due to its high molecular weight. To compensate the energy density of metal polyanionic materials, the number of electrons transferred per unit formula has to increase through oxidation or reduction of transition metal ions vs. ExperimentalFor the synthesis route of V 4 O 3 (PO 4 ) 3 , we use the same route that was described by E. Benser and co-workers 32 in which stoichiometric amounts of homemade precursors VO 2 , VPO 4 , and (VO) 2 P 2 O 7 are placed in a carbon coated evacuated quart tube at 800• C for the period of five days.The X-ray diffraction pattern was recorded in the 2θ scale range of 10-120• , Cu Kα as X-ray source using BRUKER (D8) diffractometer and Co Kα as X-ray source using PAN analytical diffractometer. Rietveld refinement was carried out using FULLPROF so...

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The effect of 3d substitutions in the manganese sublattice on the electrical and electrochemical properties of manganese spinel

Cited by 49 publications

References 15 publications

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

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

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

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The effect of 3d substitutions in the manganese sublattice on the electrical and electrochemical properties of manganese spinel

Cited by 49 publications

References 15 publications

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

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

Reversible Li Insertion Studies on V4O3(PO4)3as High Energy Storage Material for Li-Ion Battery Applications

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Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications