喷雾干燥法制备球形Li_3V_2(PO_4)_3/C正极材料及其电化学性能
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摘要
从控制Li_3V_2(PO_4)/C的形貌入手,旨在提高其作为锂离子电池正极材料的电化学性能。以葡萄糖为碳源,CTAB为表面活性剂,利用喷雾干燥法制备了粒径约为1μm的正球形Li_3V_2(PO_4)/C活性材料,颗粒尺寸均匀,振实密度较高。葡萄糖热解碳所形成的包覆层有效提高了材料的导电性,对材料的形貌控制则改善了锂离子扩散能力,因此本文所合成的Li_3V_2(PO_4)/C具良好的电化学性能,材料的锂离子扩散系数相对纯相提升约2个数量级,低于1C倍率下放电比容量均大于115mA·h/g,10C和15C大倍率下放电比容量为85mA·h/g和75mA·h/g左右,5C下循环50次,其库仑效率为96.2%。充放电平台的电位平稳,电位差较小,电化学反应阻抗值小,说明极化现象得到了有效控制。
To enhance the electrochemical performance of Li_3V_2(PO_4)/C as the cathode material of Li-ion batteries, we studied its morphology control. By using the spray drying process, we synthesized a kind of spherical Li_3V_2(PO_4)/C particles with uniform diameter about 1μm and high tap density. Glucose was chosen as the carbon source and CTAB as the surfactant. This spherical Li_3V_2(PO_4)/C has outstanding electrochemical performance which is due to two the main reasons. First, the pyrolytic carbon of glucose coating on the surface of the cathode particle enhanced its conductivity efficiently. Second, the morphological control improved the diffusion of Li+. It had a capacity of more than 115 mA·h/g when discharge rate was less than 1 C. At rate of 10 C and 15 C, the discharge capacities were 85 mA·h/g and75 mA·h/g, respectively. Furthermore, the columbic efficiency is 96.2% after cycle 50 times at 5 C. It exhibited flat and steady platforms on the charge/discharge curve and small electrochemical resistance,which means that polarization phenomenon was effectively controlled.
To enhance the electrochemical performance of Li_3V_2(PO_4)/C as the cathode material of Li-ion batteries, we studied its morphology control. By using the spray drying process, we synthesized a kind of spherical Li_3V_2(PO_4)/C particles with uniform diameter about 1μm and high tap density. Glucose was chosen as the carbon source and CTAB as the surfactant. This spherical Li_3V_2(PO_4)/C has outstanding electrochemical performance which is due to two the main reasons. First, the pyrolytic carbon of glucose coating on the surface of the cathode particle enhanced its conductivity efficiently. Second, the morphological control improved the diffusion of Li+. It had a capacity of more than 115 mA·h/g when discharge rate was less than 1 C. At rate of 10 C and 15 C, the discharge capacities were 85 mA·h/g and75 mA·h/g, respectively. Furthermore, the columbic efficiency is 96.2% after cycle 50 times at 5 C. It exhibited flat and steady platforms on the charge/discharge curve and small electrochemical resistance,which means that polarization phenomenon was effectively controlled.
引文
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[16]DAHN J R,JIANG J,MOSHURCHAK L M,et al.High-rate overcharge protection of LiFePO4-based Li-ion cells using the redox shuttle additive 2,5-ditertbutyl-1,4-dimethoxybenzene[J].Journal of the Electrochemical Society,2005,152:1283-1289.
[17]韩绍昌,张可贺,范长岭,等.环氧树脂作还原剂制备Li3V2(PO4)3的结构和性能[J].湖南大学学报:自然科学版,2013,9:70-73.HAN S C,ZHANG K H,FAN C L,et al.Structure and performance of Li3V2(PO4)3prepared with epoxy resin as the reluctant[J].Journal of Hunan University(Natural Sciences),2013,9:70-73.
[18]LI L F,FAN C L,HAN S C,et al.The influence of different carbon sources on Li3V2(PO4)3/C synthesized by a hybrid sol-gel method as cathode for lithium-ion batteries[J].Engergy Technology,2015,3:955-960.
[2]SAIDI M Y,BARKER J,HUANG H,et al.Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries[J].Journal of Power Sources,2003,119:266-273.
[3]HUANG H,YIN S C,KERR T,et al.Nanostruciured compositions:a high capacity,fast rate Li3V2(PO4)3/carbon cathode for rechargeable lithium batteries[J].Advanced Materials,2002,14:1525-1528.
[4]沈丁,李犇,杨绍斌,等.锂离子电池聚阴离子型正极材料的第一性原理研究进展[J].化工进展,2013,32(4):837-841.SHEN D,LI B,YANG S B,et al.Research progress of first principle of polyanion type cathode material for lithium-ion battery[J].Chemical Industry and Engineering Progress,2013,32(4):837-841.
[5]WU Y,ZHAO X M,SONG Z H,et al.Effect of process medium on the synthesis of carbon coated lithium vanadium phosphate composite using rheological phase reaction method[J].Journal of Power Sources,2015,274:78-83.
[6]LIM C H,JUNG Y H,YEOM S J,et al.Encapsulation of lithium vanadium phosphate in reduced graphene oxide for a lithium-ion battery cathode with stable elevated temperature performance[J].Electrochimica Acta,2017,253:208-213.
[7]江虹,徐江海,郭瑞松,等.CeO2与碳共包覆Li3V2(PO4)3正极材料低温电化学性能[J].硅酸盐学报,2016,44(1):6-12.JIANG H,XU J H,GUO R S,et al.Low-temperature electrochemical properties of CeO2and carbon co-coated Li3V2(PO4)3cathode materials[J].Journal of the Chinese Ceramic Society,2016,44(1):6-12.
[8]BAI G L,YANG Y F.Synthesis and electrochemical properties of polyhedron-shaped Li3V2-xSnx(PO4)3as cathode material for lithiumion batteries[J].Journal of Electroanalytical Chemistry,2013,1:98-102.
[9]李玲芳,韩绍昌,范长岭,等.以溶液法制备的钠掺杂锂离子电池正极材料Li3-xNax V2(PO4)3/C[J].化工进展,2018,37(1):201-205.LI L F,HAN S C,FAN C L,et al.Sodium doped cathode material of lithium ion batteries Li3-xNax V2(PO4)3/C synthesized by solution method[J].Chemical Industry and Engineering Progress,2018,37(1):201-205.
[10]CUI K,HU S,LI Y.Nitrogen-doped graphene nanosheets decorated Li3V2(PO4)3/C nanocrystals as high-rate and ultralong cycle-life cathode for lithium-ion batteries[J].Electrochimica Acta,2016,210:45-49.
[11]CHENG Y,NI X,FENG K,et al.Phase-change enabled 2DLi3V2(PO4)3/C submicron sheets for advanced lithium-ion batteries[J].Journal of Power Sources,2016,326:203-209.
[12]ZHANG B,ZHENG J C.Synthesis of Li3V2(PO4)3/C with high tapdensity and high-rate performance by spray drying and liquid nitrogen quenching method[J].Electrochimica Acta,2013,467:55-61.
[13]ZHANG B,HAN Y D,ZHENG J C,et al.A novel lithium vanadium fluoro-phosphate nanosheet with uniform carbon coating as a cathode material for lithium-ion batteries[J].Journal of Power Sources,2014,264:123-127.
[14]ZHANG H,CONG L,WANG J X.Impact of CTAB on morphology and electrochemical performance of MoS2nanoflowers with improved lithium storage properties[J].Journal of Materials Science:Materials in Electronics,2018,29:3631-3639.
[15]LI L F,FAN C L,HAN S C,et al.Electrochemical performances of Li3V2-(4/3)xTix(PO4)3/C as cathode material for Li-ion batteries synthesized by an ultrasound-assisted sol-gel method[J].Journal of Alloys and Compounds,2015,650:136-142.
[16]DAHN J R,JIANG J,MOSHURCHAK L M,et al.High-rate overcharge protection of LiFePO4-based Li-ion cells using the redox shuttle additive 2,5-ditertbutyl-1,4-dimethoxybenzene[J].Journal of the Electrochemical Society,2005,152:1283-1289.
[17]韩绍昌,张可贺,范长岭,等.环氧树脂作还原剂制备Li3V2(PO4)3的结构和性能[J].湖南大学学报:自然科学版,2013,9:70-73.HAN S C,ZHANG K H,FAN C L,et al.Structure and performance of Li3V2(PO4)3prepared with epoxy resin as the reluctant[J].Journal of Hunan University(Natural Sciences),2013,9:70-73.
[18]LI L F,FAN C L,HAN S C,et al.The influence of different carbon sources on Li3V2(PO4)3/C synthesized by a hybrid sol-gel method as cathode for lithium-ion batteries[J].Engergy Technology,2015,3:955-960.
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