Synthesis and characterization of 5 V insertion material of Li[Fe Mn2−]O4 for lithium-ion batteries

Ohzuku, Tsutomu; Ariyoshi, Kingo; Takeda, Sachio; Sakai, Yoichi

doi:10.1016/s0013-4686(00)00725-8

Cited by 137 publications

(96 citation statements)

References 29 publications

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“…Iron is likely to be in high-spin state 35 and ruthenium in LiMn 2 O 4 was found to be of tetravalent charge. 21 The ionic radii of the dopants (Fe 3+ HS: 65 pm and Ru 4+ : 62 pm 40 ) are larger compared with the substituted (Mn 4+ : 53 pm 40 ) and thus the larger lattice parameters can be explained.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

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 integrated intensity ratios of the (4 0 0)/(3 1 1) and (2 2 0)/(3 1 1) peaks are indices of substitution ions occupying 8a tetrahedral or 16d octahedral positions. A decreasing value of (4 0 0)/(3 1 1) and an increasing value of (2 2 0)/(3 1 1) indicates a rising occupation of the substitution ions at 8a tetrahedral sites or a reducing occupation at 16d octahedral sites [25,35,36]. Integrated peak intensity ratios are presented in Table 3.…”

Section: Resultsmentioning

confidence: 99%

Preparation and electrochemical properties of nanocrystalline LiBxMn2−xO4 cathode particles for Li-ion batteries by ultrasonic spray pyrolysis method

Ebin

Lindbergh

Gürmen

2015

Journal of Alloys and Compounds

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“…The fact that the intensity ratio of 400 by 311 peaks increases with increasing dopant concentration clearly suggests that the boron substituent occupies only the manganese site [17][18][19].…”

Section: Electrode Preparationmentioning

confidence: 99%

Solution synthesis of boron substituted LiMn2O4 spinel oxide for use in lithium rechargeable battery

Thirunakaran

Kim

Kang

et al. 2004

Ionics

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Abstract. An attempt has been made to synthesize LiMn204 spinel and boron substituted LiMn204 with atomic concentration of boron ranging from 0.01-0.20 and using glutaric acid as a chelating agent. The spinels have been characterized using PXRD, CV and galvanostatic charge-discharge studies.The precursor obtained from the glutaric acid assisted gel was calcined initially at 300 ~ for 4 h to obtain the compound and finally at 800 ~ for 4 h so as to obtain homogeneity, high degree of purity and crystallinity for better electrochemical performance. This paper suggests that glutaric acid assisted B 3+ doped (LiBxMn2_xO4) spinel was found to be as an apt candidate with good electrochemical performance for use in lithium battery.

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Synthesis and characterization of 5 V insertion material of Li[Fe Mn2−]O4 for lithium-ion batteries

Cited by 137 publications

References 29 publications

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

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

Preparation and electrochemical properties of nanocrystalline LiBxMn2−xO4 cathode particles for Li-ion batteries by ultrasonic spray pyrolysis method

Solution synthesis of boron substituted LiMn2O4 spinel oxide for use in lithium rechargeable battery

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Synthesis and characterization of 5 V insertion material of Li[Fe Mn2−]O4 for lithium-ion batteries

Cited by 137 publications

References 29 publications

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

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

Preparation and electrochemical properties of nanocrystalline LiBxMn2−xO4 cathode particles for Li-ion batteries by ultrasonic spray pyrolysis method

Solution synthesis of boron substituted LiMn2O4 spinel oxide for use in lithium rechargeable battery

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

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