Origin of the Ni/Mn ordering in high-voltage spinel LiNi0.5Mn1.5O4: The role of oxygen vacancies and cation doping

Chen, Yuyang; Sun, Yang; Huang, Xuejie

doi:10.1016/j.commatsci.2016.01.005

Cited by 59 publications

(42 citation statements)

References 42 publications

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“…This finding is in agreement with the dQ/dV plots. There are two sources of Mn 3+ ; one source of Mn 3+ is oxygen deficiency [24], resulting in Mn 3+ , while another is the substitution of Ga 3+ for Ni 2+ in which quite a few portions of Mn 4+ should transform into Mn 3+ to maintain charge neutrality. However, the disproportionation reaction of Mn 3+ that occurs in the electrolyte is not conducive to structural stability.…”

Section: Resultsmentioning

confidence: 99%

Enhancement of the electrochemical performance of the spinel structure LiNi0.5-xGaxMn1.5O4 cathode material by Ga doping

Lan

et al. 2018

Nanoscale Res Lett

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A sol-gel method was adopted to obtain LiNi0.5-xGaxMn1.5O4 (x = 0, 0.04, 0.06, 0.08, 0.1) samples. The effect of Ga doping on LiNi0.5Mn1.5O4 and its optimum content were investigated, and the electrochemical properties at room temperature and at a high temperature were discussed. The structural, morphological, and vibrational features of LiNi0.5-xGaxMn1.5O4 (x = 0, 0.04, 0.06, 0.08, 0.1) compounds were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The XRD results demonstrate that all samples have a disordered spinel structure with a space group of Fd3m, and Ga doping restrains the formation of the LixNi1-xO secondary phase. FT-IR analysis reveals that Ga doping increases the degree of cation disorder. The SEM results reveal that all samples possess a fine spinel octahedron crystal. The electrochemical performance of the samples was investigated by galvanostatic charge/discharge tests, dQ/dV plots, and electrochemical impedance spectroscopy (EIS). The LiNi0.44Ga0.06Mn1.5O4 sample with the optimum content shows a superior rate performance and cycle stability after Ga doping, especially at a high discharge rate and high temperature. In addition, the LiNi0.44Ga0.06Mn1.5O4 sample retained 98.3% of its initial capacity of 115.7 mAhg−1 at the 3 C discharge rate after 100 cycles, whereas the pristine sample delivered a discharge capacity of 87.3 mAhg−1 at 3 C with a capacity retention of 80% at the 100th cycle. Compared with the pristine material, the LiNi0.44Ga0.06Mn1.5O4 sample showed a high capacity retention from 74 to 98.4% after 50 cycles at a 1 C discharge rate and 55 °C.

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Section: Resultsmentioning

confidence: 99%

Enhancement of the electrochemical performance of the spinel structure LiNi0.5-xGaxMn1.5O4 cathode material by Ga doping

Lan

et al. 2018

Nanoscale Res Lett

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“…While both forms are spinels, and exhibit discharge plateaus at 4.7 V due to the presence of the Ni 2+/4+ redox couple, the space group of the stoichiometric form is a cation ordered P4 3 32 and that of the nonstoichiometric form is a cation disordered Fd‐3m . In the cation ordered form, nickel‐centered octahedra are isolated from one another by manganese‐centered octahedra, and nickel and manganese adopt +2 and +4 oxidation states, respectively . In the disordered form, oxygen vacancies stabilize nickel aggregated structures, a process correlated with oxidation of nickel to +3 and reduction in manganese to +3 .…”

Section: Introductionmentioning

confidence: 99%

“…In the cation ordered form, nickel‐centered octahedra are isolated from one another by manganese‐centered octahedra, and nickel and manganese adopt +2 and +4 oxidation states, respectively . In the disordered form, oxygen vacancies stabilize nickel aggregated structures, a process correlated with oxidation of nickel to +3 and reduction in manganese to +3 . The Mn 3+ presence is thought to favor improvements in high rate charge/discharge cycling and increases in electrical conductivity …”

Section: Introductionmentioning

confidence: 99%

Interfacial reaction during co‐sintering of lithium manganese nickel oxide and lithium aluminum germanium phosphate

Deiner

Howell

Koenig

et al. 2019

Int J Applied Ceramic Tech

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Understanding interface evolution during co-sintering of solid Li-ion conducting electrolytes and Li-metal oxide cathodes is crucial to development of solid state batteries. In this work, X-ray photoelectron spectroscopy, X-ray diffraction (XRD), and thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) document changes at the lithium manganese nickel oxide (LMNO)/lithium aluminum germanium phosphate interface during sintering. Measurements are performed as a function of sintering gas environment (air vs N 2 ). Upon sintering, manganese is reduced from +4 to a mixture of +4, +3, and +2, while nickel is oxidized from +2 to a mixture of +2 and +3. The Mn 2+ species does not arise when LMNO is sintered alone. XRD identifies formation of new chemical phases, LiGe 0.5 M 0.5 PO 4 (where M = Mn 3+ or Ni 3+ ), AlPO 4 , and NiMn 2 O 4 , also not observed when LMNO is sintered alone. The emergence of resistive interfacial phases may offset the increase in conductivity expected when Mn 3+ is formed. |DEINER Et al.

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“…The cations (usually metals) occupy 1/8 of the tetrahedral sites and 1/2 of the octahedral sites, with 32 O 2− ions in the unit cell. The spinel structure is interesting because it may contain vacancies as a regular part of the crystal . For example, if magnetite, Fe 3+ (Fe 2+ Fe 3+ )O 4 , is slowly oxidized, Fe 2+ will turn into Fe 3+ .…”

Section: Introductionmentioning

confidence: 99%

Effective hydrogen productions from propane steam reforming over spinel-structured metal-manganese oxide redox couple catalysts

et al. 2017

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Summary In this study, redox couple metal components (M═Mn) were introduced in a catalyst design. Main catalytic components (M═Fe, Co, Ni, or Cu) were combined with Mn, resulting in spinel‐structured M2MnO4 for applications to the propane steam reforming reaction as catalysts. Hydrogen selectivity and propane conversions over spinel‐structured 30.0 wt% M2MnO4 loaded on 70.0 wt% γ‐Al2O3 support were comparable. The Ni2MnO4/Al2O3 exhibited extremely stable catalytic performance for 3 recycling tests. Catalytic activities decreased in the order Ni2MnO4/Al2O3 > Co2MnO4/Al2O3 > Fe2MnO4/Al2O3 > Cu2MnO4/Al2O3 > Mn2O3/Al2O3. A mechanism for propane steam reforming over M2MnO4 was suggested, and it was found that the catalytic performance for the reforming reaction was closely related to the stability of metal oxidation states via Mn oxide assistance. Furthermore, this study suggested that the Mn oxide delivered oxygen to the main catalytic active site, in particular the Ni component, leading to the rapid cracking and oxidation of C3H8, C2H4, and CH4, and increased hydrogen production.

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Origin of the Ni/Mn ordering in high-voltage spinel LiNi0.5Mn1.5O4: The role of oxygen vacancies and cation doping

Cited by 59 publications

References 42 publications

Enhancement of the electrochemical performance of the spinel structure LiNi0.5-xGaxMn1.5O4 cathode material by Ga doping

Enhancement of the electrochemical performance of the spinel structure LiNi0.5-xGaxMn1.5O4 cathode material by Ga doping

Interfacial reaction during co‐sintering of lithium manganese nickel oxide and lithium aluminum germanium phosphate

Effective hydrogen productions from propane steam reforming over spinel-structured metal-manganese oxide redox couple catalysts

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