锂离子电池正极材料LiMn_(0.6)Fe_(0.4)PO_4/C的制备及电化学性能
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摘要
以蔗糖为碳源,以草酸为抗氧化剂,采用溶剂热、球磨和固相烧结相结合的方法制备了LiMn_(0.6)Fe_(0.4)PO_4/C正极材料,并通过改变烧结温度得到了不同形貌结构的目标产物。以金属锂片为对电极,组装成锂离子半电池,探究其电化学性能。研究结果表明,当烧结温度为650℃时,该材料表现出优异的电化学性能,在0.2C(1C=170 mA/g)的电流密度下,起始容量为119.1 mAh/g,循环80次之后,容量上升到148.8 mAh/g,并且该材料在大电流密度下也表现出优异的循环稳定性。
The LiMn_(0.6)Fe_(0.4)PO_4/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_(0.6)Fe_(0.4)PO_4/C nano-rods and nano-spindles with no obvious impurity phase are obtained. The spindle-like LiMn_(0.6)Fe_(0.4)PO_4/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.
The LiMn_(0.6)Fe_(0.4)PO_4/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_(0.6)Fe_(0.4)PO_4/C nano-rods and nano-spindles with no obvious impurity phase are obtained. The spindle-like LiMn_(0.6)Fe_(0.4)PO_4/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.
引文
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[28]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.
[29]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.
[2]YANG W C,BI Y J,QIN Y P,et al.Li Mn0.8Fe0.2PO4/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 Li Mn1-xFexPO4/carbon nanotubes composites as cathodes for Li-ion batteries.Ionics,2013,19(9):1229–1240.
[4]CHEN J,Zh AO N,LI G D,et al.High-rate and long-term cycling capabilities of Li Fe0.4Mn0.6PO4/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 Li Fe PO4 and Li Fe PO4/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 Li Fe PO4 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 Li Fe PO4@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 Fe PO4 from Fe2O3 and its application in synthesizing cathode material Li Fe PO4.Journal of Inorganic Materials,2013,28(2):207–211.
[9]QIN X Z,YANG G,GAO J,et al.Li Fe PO4/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 Li Mn PO4 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 Li Mn PO4 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 Li Mn PO4-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 Li Mn PO4/C cathode material.Journal of Inorganic Materials,2013,28(4):415–419.
[15]ZHONG Y J,LI J T,WU Z G,et al.Li Mn0.5Fe0.5PO4 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 Li Fe1-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.Li Mn1-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.
[19]HUANG Y P,LI X,CHEN Z,et al.Effect of sintering temperature on electrochemical performance of Li Fe0.4Mn0.6PO4/C cathode materials.Materials Research Innovations,2014,18(4):S4-2-5.
[20]SU J,WU X L,GUO Y G.Preparation and electrochemical properties of Li Mn0.8Fe0.2PO4/C nanocomposite.Journal of Inorganic Materials,2013,28(11):1248–1254.
[21]CHI Z X,ZHANG W,WANG X S,et al.Accurate surface control of core–shell structured Li Mn0.5Fe0.5PO4@C for improved battery performance.Journal of Materials Chemistry A,2014,2(41):17359–17365.
[22]HUANG Y P,TAO T,CHEN Z,et al.Excellent electrochemical performance of Li Fe0.4Mn0.6PO4microspheres produced using a double carbon coating process.Journal of Materials Chemistry A,2014,2(44):18831–18837.
[23]BEZZA I,KAUS M,HEINZMANN R,et al.Mechanism of the delithiation/lithiation process in Li Fe0.4Mn0.6PO4:in situ and ex situ investigations on long-range and local structures.The Journal of Physical Chemistry C,2015,119(17):9016–9024.
[24]ZHOU X,DENG Y F,WAN L N,et al.A surfactant-assisted synthesis route for scalable preparation of high performance of Li Fe0.15Mn0.85PO4/C cathode using bimetallic precursor.Journal of Power Sources,2014,265:223–230.
[25]YI H H,HU C L,FANG H S,et al.Optimized electrochemical performance of Li Mn0.9Fe0.1-xMgxPO4/C for lithium ion batteries.Electrochimica Acta,2011,56:4052–4057.
[26]DUAN J G,HU G R,CAO Y B,et al.Synthesis of high-performance Fe–Mg-co-doped Li Mn PO4/C via a mechano-chemical liquid-phase activation technique.Ionics,2016,22:609–619.
[27]ZONG J,PENG Q W,YU J P,et al.Novel precursor of Mn(PO3(OH))·3H2O for synthesizing Li Mn0.5Fe0.5PO4 cathode material.Journal of Power Sources,2013,228:214–219.
[28]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.
[29]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.