Improving the rate capability of high voltage lithium-ion battery cathode material LiNi0.5Mn1.5O4 by ruthenium doping

Kiziltas-Yavuz, Nilüfer; Bhaskar, Aiswarya; Dixon, Ditty; Yavuz, Metin; Nikolowski, Kristian; Li, Lü; Eichel, Rüdiger‐A.; Ehrenberg, Helmut

doi:10.1016/j.jpowsour.2014.05.110

Cited by 60 publications

(32 citation statements)

References 33 publications

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“…The LiNi 0.5 Mn 1.5 O 4 and LiNi 0.4 Fe 0.2 Mn 1.4 O 4 materials were synthesized by a citric acid‐assisted sol‐gel method with a final calcination temperature of 1000 °C, which is explained in detail in a previous work 4,5…”

Section: Methodsmentioning

confidence: 99%

“…The reversible processes at voltage plateaus of about 4.7 V against Li/Li + due to the Ni 2+ /Ni 4+ redox couple, results in a high energy density and makes this material a very promising candidate for an application as positive electrode in Li‐ion batteries 2,3. To obtain optimum electrochemical performances, the synthesis of this material has to be performed at high temperatures, for sol‐gel synthesis >800 °C 4,5. However, the high temperature synthesis of LNMO usually results in the formation of impurity phases such as Li z Ni 1– z O due to oxygen loss 1.…”

Section: Introductionmentioning

confidence: 99%

“…Among those, a partial cation substitution of Ni, Mn, or both in LNMO is found to be beneficial for the cycling stability. Fe,2,7–10 Co,2,7,11 Cu,12,13 Cr, [2,7–9,11,14–16] Ru,5,17 Ga,7,9 Mg,18,19 Ti,8 Al,11,13,16 Zr,16 Rh,20,21 and Zn8,12 are the substituting elements that have been used and investigated so far.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Yavuz

Kiziltas-Yavuz

Bhaskar

et al. 2014

Zeitschrift anorg allge chemie

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The cathode materials LiNi 0.5 Mn 1.5 O 4 and LiNi 0.4 Fe 0.2 Mn 1.4 O 4 were synthesized using a citric acid-assisted solgel method with a final calcination temperature of 1000°C. An impurity phase exists in LiNi 0.5 Mn 1.5 O 4 powders, which can be eliminated by substituting some of the Ni 2+ and Mn 4+ ions with Fe 3+ . The substitution of Fe into the spinel structure was confirmed by NMR and Mössbauer spectroscopy. The initial capacity of LiNi 0.4 Fe 0.2 Mn 1.4 O 4 powder synthesized at 1000°C (LNFMO) is slightly higher than that of LiNi 0.5 Mn 1.5 O 4 powder synthesized at 1000°C (LNMO). Addition-* M. Yavuz

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Yavuz

Kiziltas-Yavuz

Bhaskar

et al. 2014

Zeitschrift anorg allge chemie

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“…This intermediate step is necessary as a RuO impurity phase is formed when this mixed oxide step is not applied. A similar synthesis was also performed by Kiziltas-Yavuz et al 25 To obtain well-structured granules of the spinel, a dispersion of the material in water is prepared by grinding in a planetary ball mill for 24 h. The dispersion is then spray dried followed by a final calcination step at 780…”

Section: A6350mentioning

confidence: 99%

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels

Höweling

Stoll

Schmidt

et al. 2017

J. Electrochem. Soc.

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The high voltage LiNi 0.5 Mn 1.5 O 4 spinel suffers from severe capacity fade when cycled against a graphitic anode as well as a relatively low theoretical capacity. Using metallic lithium as counter electrode, the stability is improved and the ability of the spinel structure to host 2 Li eq. can be used to improve the capacity. This leads to a theoretical specific energy of ∼1000 Wh kg −1 . Unfortunately, the cycling of 2 Li eq. involves a phase transition from cubic to tetragonal associated with material degradation. In this work doping is used to improve capacity retention when cycling between 2.0 and 5.0 V. Initial capacities and stabilities are directly dependent on synthesis conditions and doping elements. Therefore, Fe-and Ti-doped spinels are compared with Ru-and Ti-doped spinels and tested at different cycling conditions. The cycling stability can be improved significantly by using reannealed material and by changing the discharge cutoff criteria. Thus a capacity of 190 mAh g −1 is achieved at a rate of C/2 with a capacity retention of ∼92% after 100 cycles. Furthermore, differences in the discharge behavior between the differently treated Ru-and Ti-doped materials are discussed based on the electrochemical behavior, the particle morphology and in-situ XRD analysis. The LiNi 0.5 Mn 1.5 O 4 spinel (LNMO) is a potential candidate for a high-energy cathode material in Li ion batteries. This is due to the high operating voltage of ∼ 4.7 V vs. Li + /Li. 1,2 Regardless of the high voltage the spinel offers a lower specific energy compared with other cathode materials (e.g. Li-rich layered oxides with capacities of ca. 220 -250 mAh g −1 ). 3-5However, the ability to host an additional lithium on the 16c octahedral sites 6,7 when a lithium metal anode is used, leads to an increased specific energy. The theoretical capacity increases up to 294 mAh g −1 and a theoretical energy of around 1000 Wh kg 9,10 Furthermore the trivalent manganese is Jahn-Teller active and cycling is accompanied by a strong Jahn-Teller-distortion.7,9 The c-axis parameter is increased by ∼6% while the a-and b-axis parameters shrink by ca. 0.6% leading to a phase transition from cubic to tetragonal symmetry. 11,12 The loss of manganese and the mechanical strain due to the phase transition lead to a severe capacity fade. Therefore, stable cycling of 2 Li eq. in the LNMO\\Li metal system is not possible.In order to enhance the electrochemical stability of spinel cathode materials several studies use various elements as dopants (e.g. Cr, Fe, Ga;13 Fe, Cu, Al, Mg; 14C r, Fe, Co, Ga; 15 Ti 16 ). In many publications the positive influence of Fe-and/or Ti-doping on the electrochemical stability of LNMO has been shown. 13,14,[16][17][18][19][20] Another promising doping element is Ruthenium. It has also been investigated as dopant in previous studies for the manganese spinel 21 and the LNMO spinel. 22-25It leads to an increased rate capability due to a higher electronic conductivity as well as faster lithium diffusion. However, except from z E-mai...

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“…Since current anode materials possess working potentials fairly close to the potential of lithium metal, the focus is on the development of high voltage cathode materials [1]. Up to now, the most promising development in high voltage cathode are represented by nickel-doped Mn spinel LiNi 0.5 Mn 1.5 O 4 [2][3][4][5][6] and Co-based poly-anion oxides [7,8]. At the same time, high-voltage materials demonstrate substantial performance fade and electrochemical stability problems.…”

Section: Introductionmentioning

confidence: 99%

Silicon nanowires used as the anode of a lithium-ion battery

Prosini¹,

Rufoloni²,

Rondino³

et al. 2015

AIP Conference Proceedings

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In this paper the synthesis and characterization of silicon nanowires to be used as the anode of a lithiumion battery cell are reported. The nanowires were synthesized by CVD and characterized by SEM. The nanostructured material was used as an electrode in a lithium cell and its electrochemical properties were investigated by galvanostatic charge/discharge cycles at C/10 rate as a function of the cycle number and at various rates as a function of the charge current. The electrode was then coupled with a LiFePO 4 cathode to fabricate a lithium-ion battery cell and the cell performance evaluated by galvanostatic charge/discharge cycles.

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Improving the rate capability of high voltage lithium-ion battery cathode material LiNi0.5Mn1.5O4 by ruthenium doping

Cited by 60 publications

References 33 publications

Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels

Silicon nanowires used as the anode of a lithium-ion battery

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Improving the rate capability of high voltage lithium-ion battery cathode material LiNi0.5Mn1.5O4 by ruthenium doping

Cited by 60 publications

References 33 publications

Influence of Iron on the Structural Evolution of LiNi0.4Fe0.2Mn1.4O4 during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Iron on the Structural Evolution of LiNi0.4Fe0.2Mn1.4O4 during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi0.5Mn1.5O4Spinels

Silicon nanowires used as the anode of a lithium-ion battery

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Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Iron on the Structural Evolution of LiNi_0.4Fe_0.2Mn_1.4O₄ during Electrochemical Cycling Investigated by in situ Powder Diffraction and Spectroscopic Methods

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels