Synthesis and electrochemical properties of Zn-doped, carbon coated lithium vanadium phosphate cathode materials for lithium-ion batteries

Yang, Yuexia; Xu, Weiwei; Guo, Ruisong; Liu, Lan; Wang, Shanshan; Xie, Dong; Wan, Yizao

doi:10.1016/j.jpowsour.2014.07.005

Cited by 37 publications

(18 citation statements)

References 41 publications

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“…25 Besides, doping Na + , Ca 2+ cations in the Li site also enhances the electrochemistry properties of LVP. The crystal structure, morphology and electrochemical properties of B-doped Li 3 V 2 (PO 4 ) 3 are investigated.…”

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confidence: 99%

Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials

et al. 2015

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B-doped compounds Li 3 V 2 (P 1-x B x O 4 ) 3 /C (x = 0, 0.01, 0.03, 0.07) are prepared by a sol-gel method. The crystal structure, morphology and electrochemical properties of B-doped Li 3 V 2 (PO 4 ) 3 are investigated. X-ray diffraction (XRD) analysis indicates that B atom enters the crystal structure of Li 3 V 2 (PO 4 ) 3 but does not change the monoclinic structure. Cycle stability and rate performances measurements reveal that moderate B doping improves the electrochemical properties of Li 3 V 2 (PO 4 ) 3 . Among all the B-doped samples, Li 3 V 2 (P 0.97 B 0.03 O 4 ) 3 /C shows the largest initial discharge capacity, best cycle stability and rate performances. In the potential range 3.0-4.3 V, Li 3 V 2 (P 0.97 B 0.03 O 4 ) 3 /C delivers the discharge capacity of 127.5 mAh/g at 0.2 C rate, while at 20 C the discharge capacity remains above 100 mAh/g. After 100 cycles, the discharge capacity retention is 98%. Moreover, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) curves indicate that B doping not only decreases the charge transfer resistance but increases the Li-ion diffusion rate.Ce 3+ , Zn 2+ , Mg 2+ , Ni 2+ , Co 2+ , Zr 4+ and Ti 4+ partly replacing the V 3+ ion, the capacity, cycling stability, electronic conductivity or Li + ion diffusion properties can be improved significantly. 8, 16-24 Yang et al synthesized Zn-doped Li 3 V 2-x Zn x (PO 4 ) 3 (x = 0, 0.02, 0.04, 0.06) cathode materials and found that Li 3 V 1.96 Zn 0.04 (PO 4 ) 3 possesses the highest electronic conductivity, initial discharge capacity of 105.5 mAh/g at 5C and better capacity retention property than the primary LVP. 25 Besides, doping Na + , Ca 2+ cations in the Li site also enhances the electrochemistry properties of LVP. 26, 27 Chen et al use the dopant of Na + with larger ionic radius to improve the Li + diffusion with three times by broadening the Li + transportation channels of the crystal structures. 27 In addition, doping at two different sites simultaneously or at the same sites with different cations were studied as well. For example, Li 2.5 Na 0.5 V (2-2x/3) Ni x (PO 4 ) 3 28 and Li 3 V 1.9 Ti 0.05 Mn 0.05 (PO 4 ) 3 29 were both explored and the electrochemical properties were partly enhanced. On the contrast, there are few reports about anion doping, especially at P site. Only Cland Fanions have been researched to substitute the entire (PO 4 ) 3group, which has positive effect on the electrochemical properties. 30, 31The chlorine-doped Li 3 V 2 (PO 4 ) 3 sample possessed higher ionic, electronic conductivity, and better cycling stability. 31Due to the lighter atom weight of B than P, borate could induce higher theory capacity than phosphate. In addition, as proved in LiFePO 4 , 32, 33 B doping can inhibit the crystal growth, which reduces the particle size. In addition, the weaker B-O bond than P-O bond can provide borate larger Li + diffusion. At the same time, B doping makes the PO 4 octahedral distorted, which can decrease the band gap of phosphate Where n is the number of electrons transferre...

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Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials

et al. 2015

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“…Therefore, it is of great importance to develop new cathode materials with a large capacity, high working voltage, excellent safety, good cycling life, and low-cost [8]. Among the vast number of reported cathode materials, NASICON-structured monoclinic Li 3 V 2 (PO 4 ) 3 (LVP) has drawn much attention, because of an average 4.0 V (~0.6 V higher than LiFePO 4 ) extraction/reinsertion voltage obtained between 3.0 and 4.8 V, a higher theoretical capacity of 197 mAh·g −1 for the complete removal of three Li + ions [9,10], and a low cost. However, the main drawback of pure LVP is its very low intrinsic electronic conductivity, which causes high electrode polarization and restricts its application in the field of dynamic batteries [11,12,13].…”

Section: Introductionmentioning

confidence: 99%

“…To overcome this problem, strenuous efforts have been devoted to improving the electronic conductivity of LVP, including lattice doping with metal ions [10,14,15,16,17], surface coating with carbon sources [18,19,20] or high electrical conductivity metal oxides [21,22,23], reducing particle size [24,25], and controlling particle morphologies [26,27,28]. Among these modified techniques, it is common to combine carbon with high electron conductivity and form Li 3 V 2 (PO 4 ) 3 /carbon (LVPC) composites.…”

Section: Introductionmentioning

confidence: 99%

“…On this basis, it is preferable to dope LVP with trace elements to produce lattice defects and further enhance its intrinsic conductivity. Over the years, studies relating to cation doping have been extensively explored, such as V-site substitutions with Zn 2+ [10], Mg 2+ [29], Fe 2+ /Fe 3+ [15,30], Cr 3+ [31], Co 2+ [32], Ce 3+ [16], Al 3+ [17], and La 3+ [33], and Li-site substitutions with Na + [34,35] and K + [14]. However, anion doping has been less often attempted and it is mainly substituted at the polyanion PO 4 3− -site of LVP.…”

Section: Introductionmentioning

confidence: 99%

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Preparation and Electrochemical Properties of Li3V2(PO4)3−xBrx/Carbon Composites as Cathode Materials for Lithium-Ion Batteries

Cao

Zhu

et al. 2017

Nanomaterials

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Li3V2(PO4)3−xBrx/carbon (x = 0.08, 0.14, 0.20, and 0.26) composites as cathode materials for lithium-ion batteries were prepared through partially substituting PO43− with Br−, via a rheological phase reaction method. The crystal structure and morphology of the as-prepared composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and electrochemical properties were evaluated by charge/discharge cycling and electrochemical impedance spectroscopy (EIS). XRD results reveal that the Li3V2(PO4)3−xBrx/carbon composites with solid solution phase are well crystallized and have the same monoclinic structure as the pristine Li3V2(PO4)3/carbon composite. It is indicated by SEM images that the Li3V2(PO4)3−xBrx/carbon composites possess large and irregular particles, with an increasing Br− content. Among the Li3V2(PO4)3−xBrx/carbon composites, the Li3V2(PO4)2.86Br0.14/carbon composite shows the highest initial discharge capacity of 178.33 mAh·g−1 at the current rate of 30 mA·g−1 in the voltage range of 4.8–3.0 V, and the discharge capacity of 139.66 mAh·g−1 remains after 100 charge/discharge cycles. Even if operated at the current rate of 90 mA·g−1, Li3V2(PO4)2.86Br0.14/carbon composite still releases the initial discharge capacity of 156.57 mAh·g−1, and the discharge capacity of 123.3 mAh·g−1 can be maintained after the same number of cycles, which is beyond the discharge capacity and cycleability of the pristine Li3V2(PO4)3/carbon composite. EIS results imply that the Li3V2(PO4)2.86Br0.14/carbon composite demonstrates a decreased charge transfer resistance and preserves a good interfacial compatibility between solid electrode and electrolyte solution, compared with the pristine Li3V2(PO4)3/carbon composite upon cycling.

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“…Extensive research work has been conducted on the development of cation doped Li 3 V 2 (PO 4 ) 3 . A slight amount of cation ions partially substituting V in Li 3 V 2 (PO 4 ) 3 such as Mg [16], Al [17], Co [18], Sn [19,20], Mn [21], Fe [22], Nb [23], Ni [24], W [25], Mo [26], have been widely used as alternatively effective methods. Therefore carbon coating combined with cation doping may be an effective way to improve the overall electrochemical performance of Li 3 V 2 (PO 4 ) 3 .…”

Section: Introductionmentioning

confidence: 99%

Influences of neodymium doping on magnetic and electrochemical properties of Li3V2(PO4)3/C synthesized via a sol–gel method

Liu

Qiu

Mai

et al. 2015

Journal of Power Sources

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Synthesis and electrochemical properties of Zn-doped, carbon coated lithium vanadium phosphate cathode materials for lithium-ion batteries

Cited by 37 publications

References 41 publications

Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials

Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials

Preparation and Electrochemical Properties of Li3V2(PO4)3−xBrx/Carbon Composites as Cathode Materials for Lithium-Ion Batteries

Influences of neodymium doping on magnetic and electrochemical properties of Li3V2(PO4)3/C synthesized via a sol–gel method

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Synthesis and electrochemical properties of Zn-doped, carbon coated lithium vanadium phosphate cathode materials for lithium-ion batteries

Cited by 37 publications

References 41 publications

Synthesis and electrochemical properties of Li3V2(P1−xBxO4)3/C cathode materials

Synthesis and electrochemical properties of Li3V2(P1−xBxO4)3/C cathode materials

Preparation and Electrochemical Properties of Li3V2(PO4)3−xBrx/Carbon Composites as Cathode Materials for Lithium-Ion Batteries

Influences of neodymium doping on magnetic and electrochemical properties of Li3V2(PO4)3/C synthesized via a sol–gel method

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Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials

Synthesis and electrochemical properties of Li₃V₂(P_1−xB_xO₄)₃/C cathode materials