Antisite defects and Mg doping in LiFePO4: a first-principles investigation

Zhang, Hua; Tang, Yuanhao; Shen, Jiabing; Xin, Xiaogui; Cui, Lixia; Chen, Lijiang; Ouyang, Chuying; Shi, Siqi; Chen, Liquan

doi:10.1007/s00339-011-6309-0

Cited by 53 publications

(42 citation statements)

References 45 publications

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“…[33] The electronic exchange correlation energy was modeled using the Perdew-Burke--Ernzerhof (PBE) function within the generalized gradient approximation (GGA). [34] The wave functions were expanded by means of plane waves using a kinetic energy cutoff of 350 eV. All atomic configurations were fully relaxed until the Hellmann-Feynman forces on all the atoms were smaller than 0.01 eV…”

Section: Methodsmentioning

confidence: 99%

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Shi

et al. 2014

ChemSusChem

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Nanorod-like CuS and Cu2 S have been fabricated by a hydrothermal approach without using any surfactant and template. The electrochemical behavior of CuS and Cu2 S nanorod anodes for lithium-ion batteries reveal that they exhibit stable lithium-ion insertion/extraction reversibility and outstanding rate capability. Both of the electrodes exhibit excellent capacity retentions irrespective of the rate used, even at a high current density of 3200 mA g(-1) . More than 370 mAh g(-1) can be retained for the CuS electrode and 260 mAh g(-1) for the Cu2 S electrode at the high current rate. After 100 cycles at 100 mA g(-1) , the obtained CuS and Cu2 S electrodes show discharge capacities of 472 and 313 mAh g(-1) with retentions of 92% and 96%, respectively. Together with the simplicity of fabrication and good electrochemical properties, CuS and Cu2 S nanorods are promising anode materials for practical use the next-generation lithium-ion batteries.

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Section: Methodsmentioning

confidence: 99%

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Shi

et al. 2014

ChemSusChem

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“…From the first-principles density-functional theory, Mg doping prefers to reside at Fe site rather than Li site, leading to high lithium ion diffusion. 137 By using X-ray diffraction for a partially (de)lithiated LiMg 0.2 Fe 0.8 PO 4 sample, a recent study indicates the existence of stable equilibrium intermediate phases (Fig. 7).…”

Section: Element Dopingmentioning

confidence: 97%

Olivine LiFePO₄: the remaining challenges for future energy storage

Wang

Sun

2015

Energy Environ. Sci.

448

260

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Since the first report in 1997, olivine LiFePO 4 has been considered as the most competitive cathode material for electric vehicles due to its high thermal stability and safety, therefore, numerous efforts have been made to understand and improve the performance of LiFePO 4 . In spite of some breakthrough advances, large-scale application of LiFePO 4 batteries in transportation still meets many technical obstacles. In our previous review paper, we mainly discussed carbon coating technology, one most important breakthrough in LiFePO 4 development. In combination with the latest advances in the LiFePO 4 field, here we provide an updated overview of current research activities and highlight some key challenges (fastcharging, lithiation-delithiation mechanism, surface chemistry stability, etc.) for future LiFePO 4 development. These obstacles necessitate the understanding of LiFePO 4 under in situ or in operando condition; as a result, the application of advanced synchrotron X-ray technology (mainly imaging tools) is also briefly summarized. In addition, considering to the new research trend in next-generation battery system, the up-to-date understanding and exploration of olivine phosphate for Na-ion batteries also expect new research hotspots in energy storage field. A couple of practical issues with strong industrial interests are also included. . Broader contextRechargeable batteries can effectively store electrical energy as chemical energy, and release it as needed, providing a good choice for electric vehicle (EV) applications. Naturally, safety concerns are the key issue for the application of battery technology in EVs. Olivine LiFePO4 is considered to be the most promising cathode material for lithium-ion batteries due to its environmental friendliness, high cycling performance and safety characteristics. Some important breakthroughs in recent years have allowed its successful commercialization. In spite of its success, the commercial application of LiFePO4 batteries in EVs has still been hindered by some technological obstacles. Here we provide an update on our previous review, and overview the most significant advances dealing with the remaining challenges for this promising battery material. New research direction and future trends are also discussed.

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“…7,21À30 In addition, our predicted occupancy sites also agree with the calculation results of Density Functional Theory that Mg 2þ and Mo 6þ occupy the Fe site preferentially. 31,32 However, it should be pointed out that our results only indicate which site a dopant prefers to occupy. Some ions can occupy both Li and Fe sites according to the experimental results.…”

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confidence: 66%

SITE SELECTIVITY IN DOPED POLYANION CATHODE MATERIALS FORLi-ION BATTERIES

Shao

Xue

2013

Funct. Mater. Lett.

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We propose a simple and effective method to determine the occupancy preference of cations doped in polyanion cathode materials for Li-ion batteries based on ionic electronegativity and ionic radius. The occupancy site can be predicted by comparing the combined deviation degree of electronegativity and radius between the dopant and the substituted ion, and dopants prefer to occupy the site where the deviation degree is less. Based on this method, we predicted the preferred occupancy sites of 38 frequently used ions doped in LiFePO 4 and Li 3 V 2 (PO 4 ) 3 , which can be in accordance with the available experimental and other calculated results. This simple method established in current work can serve as an effective tool to well predict the preferred occupancy sites of cations doped in cathode materials, which can provide powerful guidance in designing cathode materials for high-performance Li-ion batteries.Since LiFePO 4 was first proposed by Goodenough and coworkers in 1997, 1 polyanion compounds have been highlighted as one kind of the most promising cathode materials for Li-ion batteries because of their intrinsical stability and favorable electrochemical properties. 2 Unfortunately, the large-scale application of these pristine compounds was limited due to their low electronic conductivity and slow lithium ion diffusion. 3 Doping of alien ions can always influence the electronic structure of materials such as the type and concentration of defects, leading to the increase of the electronic conductivity, 4 and also influence the crystal structure, for example, increased lattice parameter can facilitate lithium ion migration in the lattice. 5 However, there are also some arguments that doping on the Li sites can reduce assessable capacity by blocking Li diffusion. 6 It is generally accepted that Li moves preferably along the b crystallographic direction, which can be considered to be one dimension diffusion channel. According to defect chemistry theory, an externally doped metal atom or ion often functions as the primary factor determining access to the materials' internal structure by replacing certain lattice atoms and forming either distortions or defects within the materials. 7 Polyanion materials have two metal sites, M1 (Li) and M2 (transition metal), and the dopants' occupying at different sites will influence the final properties of the materials differently. So identifying the location of doped ions in the host lattice is crucial to better understand the structureÀproperty relationships and the electrochemical behaviors of polyanion cathode materials.Experimental and theoretical efforts have been made to investigate the site selectivity of doped ions in cathode materials, which are very helpful for understanding the structureÀ property relationships of cathode materials. X-ray diffraction Rietveld crystal structure correction method, electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) methods have been utilized to study the micro defect structure and Nb 5þ dopant...

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Antisite defects and Mg doping in LiFePO4: a first-principles investigation

Cited by 53 publications

References 45 publications

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Olivine LiFePO₄: the remaining challenges for future energy storage

SITE SELECTIVITY IN DOPED POLYANION CATHODE MATERIALS FORLi-ION BATTERIES

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Antisite defects and Mg doping in LiFePO4: a first-principles investigation

Cited by 53 publications

References 45 publications

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Synthesis of One‐Dimensional Copper Sulfide Nanorods as High‐Performance Anode in Lithium Ion Batteries

Olivine LiFePO4: the remaining challenges for future energy storage

SITE SELECTIVITY IN DOPED POLYANION CATHODE MATERIALS FORLi-ION BATTERIES

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Product

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Olivine LiFePO₄: the remaining challenges for future energy storage