Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Zhang, Xiaoyu; Jiang, Wenjun; Mauger, A.; Qilu,; Giligny, François; Julien, C.

doi:10.1016/j.jpowsour.2009.09.029

Cited by 374 publications

(274 citation statements)

References 45 publications

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“…Although it is generally accepted that the capacity of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 arises from the Ni 2+ /Ni 3+ /Ni 4+ redox centers within the 3-4 V operating window, the contribution of the Mn 3+ /Mn 4+ and Co 3+ /Co 4+ redox couples to this capacity is also reported. [30][31][32][33] In this work, we report a Li-rich Li 1+x MO 2 (xLi 2 MO 3 •(1-x)(Li 5/6 Ni 1/6 )(Li 1/6 Ni 1/6 Mn 1/3 Co 1/3 )O 2 composite material, M = Li, Ni, Mn, Fe) that is Co free. We study its electrochemical performance and function, determining the phase evolution of the active phase (Li 5/6 Ni 1/6 )(Li 1/6 Ni 1/6 Mn 1/3 Co 1/3 )O 2 using operando neutron powder diffraction (NPD).…”

Section: Introductionmentioning

confidence: 87%

“…This cation mixing can complicate the electrochemical function of the cathode as the active Li intercalation layer (3b site) contains inactive Ni which may lower capacity and block Li diffusion. 30,41 Nevertheless, it is the inactive Ni in this layer which is expected to increase structural stability and the subsequent cycling performance. @ taken from refinement results using the NPD data.…”

Section: Methodsmentioning

confidence: 99%

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Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Pang

Kalluri

Peterson

et al. 2014

Phys. Chem. Chem. Phys.

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The development of cathode materials with high capacity and cycle stability is essential to emerging electricvehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wet-chemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b). We find Ni2+/Ni3+/Ni4+ to be the active redox-center of the cathode with lithiation/delithiation occurring via a solid-solution reaction where the lattice responds approximately linearly with cycling, differing to that observed for iso-structural commercial cathodes with a lower level of cation mixing. The composite cathode has ∼75% active material and delivers an initial dischargecapacity of ∼103 mA h g-1 with a reasonable capacity retention of ∼84.4% after 100 cycles. Notably, the electrochemically-active component possesses a capacity of ∼139 mA h g-1, approaching that of the commercialized LiCoO2 and Li(Ni1/3Mn1/3Co1/3)O2 materials. Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ∼80% less change in its stacking-axis than for LiCoO2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials. The development of cathode materials with high capacity and cycle stability is essential to emerging electric-vehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li 1+x MO 2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wetchemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ~ 80% less change in its stacking-axis than for LiCoO 2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials.

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Section: Introductionmentioning

confidence: 87%

Section: Methodsmentioning

confidence: 99%

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Pang

Kalluri

Peterson

et al. 2014

Phys. Chem. Chem. Phys.

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“…Moreover, the increased c-lattice parameter in the K-LMN sample provides a direct evidence for the enlargement of Li layer spacing, which would cause a substantially higher Li + diffusivity [28]. The c/a and I (003) /I (104) values of K-LMN are also higher than LMN sample, implying a more well-defined layered structure and a lower level of cation disordering after K doping into the pristine material [29][30][31]. These two peaks can be well assigned to K 2p 1/2 and K 2p 3/2 as previous reports [36,37].…”

Section: å (K-lmn) This Observation Is In Agreement With Previous Rementioning

confidence: 90%

Host Structural Stabilization of Li1.232Mn0.615Ni0.154O2 through K-Doping Attempt: toward Superior Electrochemical Performances

Zheng

Guo

Zhong

et al. 2016

Electrochimica Acta

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. Host structural stabilization of Li1.232Mn0.615Ni0.154O2 through K-doping attempt: toward superior electrochemical performances. Electrochimica Acta, 188 336-343.Host structural stabilization of Li1.232Mn0.615Ni0.154O2 through Kdoping attempt: toward superior electrochemical performances Abstract Lithium-rich layered cathodes are known famously for its superior capacity over traditional layered oxides but trapped for lower initial coulombic efficiency, poorer rate capability and worse cyclic stability in spite of diverse attempts. Herein, a new K-stabilized Li-rich layered cathode synthesized through a simple oxalate coprecipitation is reported for its super electrochemical performances. Compared with pristine Li-rich layered cathode, K-stabilized one reaches a higher initial coulombic efficiency of 87% from 76% and outruns for 94% of capacity retention and 244 mAh g-1 of discharge capacity at 0.5C after 100 cycles. Moreover, 133 mAh g-1 of discharge capacity can be delivered even charged at 10C showing a highly-improved rate capability. X-ray diffraction and electrochemical impedance spectroscopy tests show that enlarged Li slab layer caused by K+ accommodation can provide facile Li+ diffusion paths and facilitate Li+ migration from the crystal lattice. As a consequence, the introduction of K+ in the host layered structure can inhibit the detrimental spinel structure growth during cycling. Therefore, the K-stabilized Li-rich layered materials can be considered to be an attractive alternative to meet with the higher power and energy density demands of advanced lithium-ion battery.Keywords structural, stabilization, li1, 232mn0, 615ni0, k, host, doping, performances, attempt, toward, superior, electrochemical, 154o2 Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsZheng, Z., Guo, X., Zhong, Y., Hua, W., Shen, C., Chou, S. & Yang, X. (2016 As a consequence, the introduction of K + in the host layered structure can inhibit the detrimental spinel structure growth during cycling. Therefore, the K-stabilized Li-rich layered materials can be considered to be an attractive alternative to meet with the higher power and energy density demands of advanced lithium-ion battery.

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“…LiNi 0.33 Mn 0.33 Co 0.33 O 2 -layered powders were prepared using the co-precipitation method described elsewhere [27] by a hydroxide route, for which transition-metal hydroxide and lithium carbonate were starting materials. Using a lithium excess η = Li/M ratio of 1.05 the sample shows low cationic mixing Ni 2+ (3b) < 2%.…”

Section: Synthesis and Characterizationsmentioning

confidence: 99%

Olivine-Based Blended Compounds as Positive Electrodes for Lithium Batteries

et al. 2016

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Blended cathode materials made by mixing LiFePO 4 (LFP) with LiMnPO 4 (LMP) or LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) that exhibit either high specific energy and high rate capability were investigated. The layered blend LMP-LFP and the physically mixed blend NMC-LFP are evaluated in terms of particle morphology and electrochemical performance. Results indicate that the LMP-LFP (66:33) blend has a better discharge rate than the LiMn 1´y Fe y PO 4 with the same composition (y = 0.33), and NMC-LFP (70:30) delivers a remarkable stable capacity over 125 cycles. Finally, in situ voltage measurement methods were applied for the evaluation of the phase evolution of blended cathodes and gradual changes in cell behavior upon cycling. We also discuss through these examples the promising development of blends as future electrodes for new generations of Li-ion batteries.

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Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Cited by 374 publications

References 45 publications

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Host Structural Stabilization of Li1.232Mn0.615Ni0.154O2 through K-Doping Attempt: toward Superior Electrochemical Performances

Olivine-Based Blended Compounds as Positive Electrodes for Lithium Batteries

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Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Cited by 374 publications

References 45 publications

Electrochemistry and structure of the cobalt-free Li1+xMO2(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li1+xMO2(M = Li, Ni, Mn, Fe) composite cathode

Host Structural Stabilization of Li1.232Mn0.615Ni0.154O2 through K-Doping Attempt: toward Superior Electrochemical Performances

Olivine-Based Blended Compounds as Positive Electrodes for Lithium Batteries

Contact Info

Product

Resources

About

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode