Synthesis and Electrochemical Performance of LiMn0.6Fe0.4PO4/C Cathode for Lithium-ion Batteries

doi:10.15541/jim20160408

Abstract

Abstract:

The LiMn_0.6Fe_0.4PO₄/C cathode for lithium-ion batteries (LIBs) was synthesized by solvothermal, ball-milling combined with solid phase calcination method using sucrose as a carbon source and oxalic acid as an antioxidant. The final products with different morphologies were obtained by changing sintering temperatures. The structure and morphology of the target products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Cyclic voltammetry and galvanostatic charge and discharge tests were employed to characterize the electrochemical properties of the samples. The results manifest that well-crystallized olivine structure LiMn_0.6Fe_0.4PO₄/C nano-rods and nano-spindles with no obvious impurity phase are obtained. The spindle-like LiMn_0.6Fe_0.4PO₄/C sample S-650 (which was sintered at 650℃) shows a highly monodisperse and homogeneous morphology. Electrochemical analysis results demonstrate that S-650 exhibits the best electrochemical performance with an initial discharge capacity of 119.1 mAh/g at the current density of 0.2 C (1 C=170 mA/g), and a capacity of 148.8 mAh/g is achieved after 80 charge-discharge cycles, in comparison with S-600 (which was sintered at 600℃) and S-700 (which was sintered at 700℃). Meanwhile, S-650 also demonstrates excellent cycling stability even at a high current density of 2C.

Key words: lithium-ion batteries, LiMn0.6Fe0.4PO4/C, cathode material, electrochemical performance

CLC Number:

TQ174

LI Wei, ZHANG Yuan-Jie, WANG Xuan-Peng, NIU Chao-Jiang, AN Qin-You, MAI Li-Qiang. Synthesis and Electrochemical Performance of LiMn_0.6Fe_0.4PO₄/C Cathode for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2017, 32(5): 476-482.

Figures/Tables 6

Fig. 1 XRD patterns of products sintered at different temperatures

Fig. 2 SEM images of S-600(a), S-650 (c) and S-700 (e) and corresponding elemental mapping images (b,d,f)

Fig. 3 N2 adsorption-desorption isotherms (a) and pore-size distribution curve (b) of S-650

Fig. 4 CV curves of S-650 at scan rate of 0.1 mV/s (a); Cycling performance of S-650,S-600 and S-700 at 0.2 C rate (b); Rate capabilities of S-650,S-600 and S-700 (c); Cycling performance of S-650 at 0.5 C rate (d); Charge-discharge curves of S-650 at different current densities (e)

Table1 ICP elemental analyses of S-600, S-650 and S-700

Sample	Li	Mn	Fe	P
S-600	0.91	0.59	0.41	1.00
S-650	0.88	0.68	0.43	1.00
S-700	0.90	0.60	0.41	1.00

Fig. 5 Cycling performance (a) and charge-discharge curves (b) of S-650 at 1 C rate; EIS plots of S-650, S-600 and S-700 in the frequency range from 0.01 Hz to 100 kHz (c)

References 28

[1]	SARAVANAN K, RAMAR V, BALAYA P, et al.Li(MnxFe1-x)PO4/C (x=0.5, 0.75 and 1) nanoplates for lithium storage application.Journal of Materials Chemistry, 2011, 21(38): 14925-14935.
[2]	YANG W C, BI Y J, QIN Y P, et al.LiMn0.8Fe0.2PO4/C cathode material synthesized via co-precipitation method with superior high-rate and low-temperature performances for lithium-ion batteries.Journal of Power Sources, 2015, 275: 785-791.
[3]	NGUYEN TTD, DIMESSO L, CHERKASHININ G, et al.Synthesis and characterization of LiMn1-xFexPO4/carbon nanotubes composites as cathodes for Li-ion batteries.Ionics, 2013, 19(9): 1229-1240.
[4]	CHEN J, ZhAO N, LI G D, et al. High-rate and long-term cycling capabilities of LiFe0.4Mn0.6PO4/C composite for lithium-ion batteries.Journal of Solid State Electrochemistry, 2015, 19(5): 1535-1540.
[5]	MIAO C, BAI P F, JIANG Q Q, et al.A novel synthesis and characterization of LiFePO4 and LiFePO4/C as a cathode material for lithium-ion battery.Journal of Power Sources, 2014, 246: 232-238.
[6]	YANG S L, HU M J, XI L J, et al.Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.ACS Applied Materials & Interfaces, 2013, 5(18): 8961-8967.
[7]	XU G, LI F, TAO Z H, et al.Monodispersed LiFePO4@C core-shell nanostructures for a high power Li-ion battery cathode.Journal of Power Sources, 2014, 246: 696-702.
[8]	WANG T, YIN Y, LIU H W.Synthesis of FePO4 from Fe2O3 and its application in synthesizing cathode material LiFePO4.Journal of Inorganic Materials, 2013, 28(2): 207-211.
[9]	QIN X Z, YANG G, GAO J, et al.LiFePO4/C cathode material modified by polyacrylamide.Journal of Inorganic Materials, 2016, 31(5): 517-522.
[10]	GUO H, WU C Y, XIE J, et al.Controllable synthesis of high-performance LiMnPO4 nanocrystals by a facile one-spot solvothermal process.Journal of Materials Chemistry A, 2014, 2(27): 10581-10588.
[11]	WANG Y R, YANG Y F, YANG Y B, et al.Enhanced electrochemical performance of unique morphological cathode material prepared by solvothermal method.Solid State Communications, 2010, 150(1/2): 81-85.
[12]	QIN Z H, ZHOU X F, XIA Y G, et al.Morphology controlled synthesis and modification of high-performance LiMnPO4 cathode materials for Li-ion batteries.Journal of Materials Chemistry, 2012, 22(39): 21144-21153.
[13]	LI L E, LIU J, CHEN L, et al.Effect of different carbon sources on the electrochemical properties of rod-like LiMnPO4-C nanocomposites.RSC Advances, 2013, 3(19): 6847-6852.
[14]	WANG Y M, WANG F, WANG G J.Sol-Gel synthesis and electrochemical performance of LiMnPO4/C cathode material.Journal of Inorganic Materials, 2013, 28(4): 415-419.
[15]	ZHONG Y J, LI J T, WU Z G, et al.LiMn0.5Fe0.5PO4 solid solution materials synthesized by rheological phase reaction and their excellent electrochemical performances as cathode of lithium ion battery.Journal of Power Sources, 2013, 234: 217-222.
[16]	ZHANG B, WANG X J, LI H, et al.Electrochemical performances of LiFe1-xMnxPO4 with high Mn content.Journal of Power Sources, 2011, 196(16): 6992-6996.
[17]	RAVNSBAEK DB, XIANG K, XING W, et al.Extended solid solutions and coherent transformations in nanoscale olivine cathodes.Nano Letters, 2014, 14(3): 1484-1491.
[18]	HONG Y, TANG Z L, HONG Z J, et al.LiMn1-xFexPO4 (x = 0, 0.1, 0.2) nanorods synthesized by a facile solvothermal approach as high performance cathode materials for lithium-ion batteries.Journal of Power Sources, 2014, 248: 655-659.
	HUANG Y P, LI X, CHEN Z, et al. Effect of sintering temperature on electrochemical performance of LiFe0.4Mn0.6PO4/C cathode materials. Materials Research Innovations, 2014, 18(4): S4-2-5.
[19]	SU J, WU X L, GUO Y G.Preparation and electrochemical properties of LiMn0.8Fe0.2PO4/C nanocomposite.Journal of Inorganic Materials, 2013, 28(11): 1248-1254.
[20]	CHI Z X, ZHANG W, WANG X S, et al.Accurate surface control of core-shell structured LiMn0.5Fe0.5PO4@C for improved battery performance.Journal of Materials Chemistry A, 2014, 2(41): 17359-17365.
[21]	HUANG Y P, TAO T, CHEN Z, et al.Excellent electrochemical performance of LiFe0.4Mn0.6PO4microspheres produced using a double carbon coating process.Journal of Materials Chemistry A, 2014, 2(44): 18831-18837.
[22]	BEZZA I, KAUS M, HEINZMANN R, et al.Mechanism of the delithiation/lithiation process in LiFe0.4Mn0.6PO4: in situ and ex situ investigations on long-range and local structures.The Journal of Physical Chemistry C, 2015, 119(17): 9016-9024.
[23]	ZHOU X, DENG Y F, WAN L N, et al.A surfactant-assisted synthesis route for scalable preparation of high performance of LiFe0.15Mn0.85PO4/C cathode using bimetallic precursor.Journal of Power Sources, 2014, 265: 223-230.
[24]	YI H H, HU C L, FANG H S, et al.Optimized electrochemical performance of LiMn0.9Fe0.1-xMgxPO4/C for lithium ion batteries.Electrochimica Acta, 2011, 56: 4052-4057.
[25]	DUAN J G, HU G R, CAO Y B, et al.Synthesis of high-performance Fe-Mg-co-doped LiMnPO4/C via a mechano-chemical liquid-phase activation technique.Ionics, 2016, 22: 609-619.
[26]	ZONG J, PENG Q W, YU J P, et al.Novel precursor of Mn(PO3(OH))·3H2O for synthesizing LiMn0.5Fe0.5PO4 cathode material.Journal of Power Sources, 2013, 228: 214-219.
[27]	NIU C J, MENG J S, WANG X P, et al.General synthesis of complex nanotubes by gradient electrospinning and controlled pyrolysis.Nature Communications, 2015, 6: 7402.
[28]	WANG X P, NIU C J, MENG J S, et al.Novel K3V2(PO4)3/C bundled nanowires as superior sodium-ion battery electrode with ultrahigh cycling stability.Advanced Energy Materials, 2015, 5(17): 1500716.

Synthesis and Electrochemical Performance of LiMn_0.6Fe_0.4PO₄/C Cathode for Lithium-ion Batteries

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