Diffusional mechanism of deintercalation in LiFe1−yMnyPO4 cathode material

Molenda, Janina; Ojczyk, W.; Świerczek, Konrad; Zając, Wojciech; Krok, F.; Dygas, J.R.; Liu, Ru‐Shi

doi:10.1016/j.ssi.2006.03.047

Cited by 117 publications

(99 citation statements)

References 34 publications

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“…No impurity phases were detected by XRD. The single phase characteristic of the LiFe 1-x Mn x PO 4 samples in the whole substitution range (0≤x≤1) was also reported by Molenda and coworkers [18]. polarization.…”

Section: Resultssupporting

confidence: 77%

Enhanced low-temperature performance of slight Mn-substituted LiFePO4/C cathode for lithium ion batteries

et al. 2011

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Low temperature performance of LiFePO 4 /C cathode was remarkably improved by slight Mn-substitution. Electrochemical measurements showed that about 95% of the discharge capacity of LiFe 0.98 Mn 0.02 PO 4 /C cathode at 20°C was obtained at 0°C, compared to 85% of that of LiFePO 4 /C cathode. The LiFe 0.98 Mn 0.02 PO 4 /C sample also presented enhanced rate performance at -20°C with the discharge capacities of 124.4 mA h/g (0.1C), 99.8 mA h/g (1C), 80.7mAh/g (2C) and 70 mA h/g (5C), respectively, while pristine LiFePO 4 /C only delivered capacities of 120.5 mA h/g (0.1C), 90.7 mA h/g (1C), 70.4 mA h/g (2C) and 52.2 mA h/g (5C). Cyclic voltammetry measurements demonstrated an obvious improvement of the lithium insertion-extraction process of the LiFePO 4 /C cathode by slight Mn-substitution. The results of FSEM observation and electrical conductivity measurement indicated that slight Mn-substitution minimized the particle size of LiFe 0.98 Mn 0.02 PO 4 /C and also obviously improved the electrical conductivity of the compound, thus obviously enhances the interface reaction process on the cathode. Lithium ion phosphate has been intensively investigated in recent years as the most promising cathode material for large-scale lithium ion batteries (such as EV and HEV ) due to its low cost, low toxicity, reasonable capacity and good thermal stability [1][2][3][4]. Commercial application of this material has made great progress. It has been successfully used in batteries for laptops, power tools and electric bicycles, etc. However, there are still a number of issues to work out before the batteries are suitable for EV and HEV application, such as high rate capability and low temperature performance. Several effective approaches such as carbon coating on the particle surface [5][6][7][8], minimizing the particle size [9][10][11], and cation substitution [12] have been applied to overcome the high rate problems at room temperature. However, efforts still need to be focused on enhancing low temperature performance of LiFePO 4 cathode. Although many efforts have been made on improving the low *Corresponding author (email: liaoxz@sjtu.edu.cn) temperature performance of lithium ion batteries by developing new low temperature electrolytes [13][14][15], improving the low temperature properties of the electrode materials is also imperative. In our previous work [16], we reported the low temperature performance of LiFePO 4 /C cathode in a quaternary carbonate-based electrolyte. It was found that charge-discharge behavior of LiFePO 4 /C cathode was obviously impeded at low temperature. The increase of chargetransfer resistance and the decrease of lithium ion diffusion capability were the main performance limiting aspects at low temperature. In our present work, we managed to improve the rate capability of LiFePO 4 /C cathode at low temperatures by slight Mn-substitution of Fe-site in LiFePO 4 structure.

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Section: Resultssupporting

confidence: 77%

Enhanced low-temperature performance of slight Mn-substituted LiFePO4/C cathode for lithium ion batteries

et al. 2011

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“…These shoulders correspond to the voltage regions, where one electrochemical reaction is replaced by another one (left from Co-peak for LiCo 0. 6 It can indicate the solid-solution domains in the extractioninsertion mechanism, which will be discussed later in details.…”

Section: Resultsmentioning

confidence: 99%

Mixed LiCo0.6M0.4PO4 (M = Mn, Fe, Ni) phosphates: cycling mechanism and thermal stability

Bramnik

Trots²,

Hofmann

et al. 2009

Phys. Chem. Chem. Phys.

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Editorial 8 (y = 1, 2, 3, 4, 4.5) The electrochemical delithiation of LiCo 0.6 M 0.4 PO 4 phosphates (M = Mn, Fe, Ni) was studied by in situ synchrotron diffraction. In all three metallophosphates the oxidation-reduction of 3d-elements proceed via two-phase mechanisms leading to two-phase regions, corresponding to the Co 2+ /Co 3+ and M 2+ /M 3+ reactions. The Ni 2+ /Ni 3+ reaction was not revealed, neither by the potentiostatic intermittent titration technique (PITT) nor by diffraction. In the two-phase reaction, the olivine-like structure of the cathode remains preserved, which is characteristic of this type of materials. Pronounced solid-solution domains were observed during both lithium extraction and insertion. The thermal stability of the charged cathodes is limited by the presence of Co 3+ and its intrinsic instability in these compounds.

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“…Molenda, 1997), Li x FePO 4 (J. Molenda et al, 2006) prove the key role of electronic structure on the intercalation process. Variations of the EMF of the Li/Li + /Li x M a X b cell corresponds to those of electrochemical potential of electrons (Fermi level) of the cathode material brought about by lithium intercalation (J.…”

Section: Fig 1 Different Type Structures Capable To Lithium Intercamentioning

confidence: 93%

Composite Cathode Material for Li-Ion Batteries Based on LiFePO4 System.

Molenda¹,

Molenda²

2011

Metal, Ceramic and Polymeric Composites for Various Uses

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Diffusional mechanism of deintercalation in LiFe1−yMnyPO4 cathode material

Cited by 117 publications

References 34 publications

Enhanced low-temperature performance of slight Mn-substituted LiFePO4/C cathode for lithium ion batteries

Enhanced low-temperature performance of slight Mn-substituted LiFePO4/C cathode for lithium ion batteries

Mixed LiCo0.6M0.4PO4 (M = Mn, Fe, Ni) phosphates: cycling mechanism and thermal stability

Composite Cathode Material for Li-Ion Batteries Based on LiFePO4 System.

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