聚丙烯酰胺改性LiFePO4/C正极材料的研究

doi:10.15541/jim20150546

无机材料学报 ›› 2016, Vol. 31 ›› Issue (5): 517-522.DOI: 10.15541/jim20150546 CSTR: 32189.14.10.15541/jim20150546

聚丙烯酰胺改性LiFePO₄/C正极材料的研究

秦显忠¹, 杨改¹, 高剑², 蔡飞鹏¹, 谭春晖¹

(1. 山东省科学院能源研究所, 山东省生物质气化技术重点实验室, 济南 250014; 2. 清华大学核能与新能源技术研究院, 北京 102201)

收稿日期:2015-11-05 修回日期:2015-12-23 出版日期:2016-05-20 网络出版日期:2016-04-25
作者简介:秦显忠(1988–), 女, 硕士研究生. E-mail: qinxianzhong8@126.com
基金资助:
山东省自然科学基金(ZR2013BM023).山东省自主创新重大专项(2014ZZCX05501).济南市高校院所自主创新计划(201402023).山东省科学院青年基金项目(2014QN015)

LiFePO₄/C Cathode Material Modified by Polyacrylamide

QIN Xian-Zhong¹, YANG Gai¹, GAO Jian², CAI Fei-Peng¹, TAN Chu-Hui¹

(1. Key Laboratory of Biomass Gasification Technology, Energy Research Institute of Shandong Academy of Science, Jinan 250014, China; 2. China Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 102201, China)

Received:2015-11-05 Revised:2015-12-23 Published:2016-05-20 Online:2016-04-25
About author:QIN Xian-Zhong. E-mail: qinxianzhong8@126.com
Supported by:
Natural Science Foundation of Shandong Province (ZR2013BM023).Independent Innovation and Achievement Transfomation Project of Shandong Province (2014ZZCX05501).University Institutes Innovation Program of Jinan (201402023) and Youth Science Fouds of Shandong Academy of Sciences (2014QN015)

摘要/Abstract

摘要：

以聚丙烯酰胺(PAM)作为分散剂, 采用液相控制结晶-碳热还原法制备LiFePO₄/C正极材料, 考察了PAM对LiFePO₄/C正极材料性能的影响, 采用热化学分析、X射线衍射、扫描电镜、碳含量分析和充放电测试等分析测试手段对材料进行表征。结果表明, 将PAM溶于酸液中且添加量为1.5wt%时制备的LiFePO₄平均粒径约为100 nm, 颗粒分散较为均匀; 该材料在0.1C、1C、2C、5C和10C倍率下首次放电比容量分别为153.8、142.5、138.4、128.7和124.3 mAh/g, 1C倍率下循环100次后容量保持率仍在99%以上; 交流阻抗分析表明: 1.5wt%PAM改性后的材料的各种阻抗值均降低, 锂离子的导电速率提高了28倍。PAM改性后的LiFePO₄/C正极材料的离子及电子导电性提高了, 具有优良的倍率性能与循环性能, 有利于大规模推广应用。

关键词: 聚丙烯酰胺, LiFePO4/C, 正极材料

Abstract:

LiFePO₄/C composite cathode materials containing different amounts of PAM as dispersing agent were synthesized by controlled crystallization-carbon thermal reduction process, to investigate the effect of polyacrylamide (PAM) on the performance of LiFePO₄/C. Crystal structure, surface morphology and electrochemical properties of the obtained composites dispersed by PAM were studied by the techniques including thermal chemical analysis, X-ray diffraction, scanning electron microscopy, carbon content test, constant current charge and discharge testing. The results showed that LiFePO₄material fabricated with 1.5wt%PAM dissolved in acid dispersed more evenly with good flow ability with average particle size of about 100 nm. The first discharge capacities of 1.5wt%PAM-LFP composites were 153.8, 142.5, 138.4, 128.7 and 124.3 mAh/g at 0.1C, 1C, 2C, 5C and 10C ratios, respectively, which capacity retention can keep above 99% at 1C rate after 100 charge/discharge cycles. According to AC impedance spectra measurements, the impedances of 1.5wt%PAM-LiFePO₄ decreased evidently and the diffusion coefficient of Li ions increased by 28 times, indicating that Li ion and electric conductivity, discharge capacity and cycling performance were greatly improved. The above results show that LiFePO₄/C composite cathode materials dispersed by PAM is suitable for industrial applications.

Key words: polyacrylamide, lithium iron phosphate, cathode material

中图分类号:

TQ174

秦显忠, 杨改, 高剑, 蔡飞鹏, 谭春晖. 聚丙烯酰胺改性LiFePO₄/C正极材料的研究[J]. 无机材料学报, 2016, 31(5): 517-522.

QIN Xian-Zhong, YANG Gai, GAO Jian, CAI Fei-Peng, TAN Chu-Hui. LiFePO₄/C Cathode Material Modified by Polyacrylamide[J]. Journal of Inorganic Materials, 2016, 31(5): 517-522.

图/表 11

图1 前驱体的热重-差热曲线

Fig. 1 TG-DTA curves of the precursor

图2 不同PAM含量的FePO4材料的XRD图谱

Fig. 2 XRD patterns of FePO4 modified with different contents of PAM

图3 不同PAM含量的LiFePO4材料的XRD图谱

Fig. 3 XRD patterns of LiFePO4 modified with different contents of PAM

表1 PAM改性的LiFePO4材料的碳含量

Table 1 Carbon contents of PAM-modified LiFePO4 materials

Sample	LFP	0.5wt% PAM-LFP	1.5wt% PAM-LFP	2.5wt% PAM-LFP	5.0wt% PAM-LFP
C/%	4.4029	4.5497	4.5584	4.5668	4.6721

图4 LiFePO4材料的扫描电镜图片

Fig. 4 SEM images for LiFePO4 coated with different PAM contents a-LFP; b-0.5wt%PAM-LFP; c-1.5wtwt%PAM-LFP; d-2.5wt%PAM-LFP; e-5.0wt%PAM-LFP

图5 合成的LiFePO4材料在0.1C倍率下的首次充放电曲线

Fig. 5 Initial charge and discharge curves of LiFePO4 at 0.1C rate

图6 合成的 LiFePO4在不同倍率下的循环性能

Fig. 6 Cycling performance of LiFePO4 at different rates

图7 合成的LiFePO4材料在1C倍率下循环曲线

Fig. 7 Cycling performance of LiFePO4 at 1C rate

图8 LFP和1.5wt%PAM-LFP样品的循环伏安曲线

Fig. 8 CV curves of LFP and 1.5wt%PAM-LFP samples

图9 样品LFP和1.5wt%PAM-LFP的交流阻抗曲线及等效电路

Fig. 9 AC Impedance spectra and equivalent circuit of ACI modeling for samples LFP and 1.5wt%PAM-LFP

表2 EIS等效电路拟合结果

Table 2 Fitting results of impedance parameters

	R_s/ (×10, Ω)	R_ct/ (×10², Ω)	σ/ (×10^-4, S•cm^-1)	D_Li+/ (×10^-13, cm²•s^-1)
LFP	7.2	3.7	0.0049	0.35
1.5wt%PAM-LFP	5.8	1.6	1.1000	9.80

参考文献 17

[1]	ANSEAN D, GONZALEZ M, VICTOR M, et al.Evaluation of LiFePO4 batteries for electric vehicle applications.IEEE Transactions on Industry Applications, 2015, 51(2): 1855-1863.
[2]	LIN C J, XU S C, LI Z, et al.Thermal analysis of large-capacity LiFePO4 power batteries for electric vehicles. Journal of Power Sources, 2015, 294(5): 633-642.
[3]	PATIMAA N, ABLIZ A, KIMINORIB I.Sythesis and optical-
	electrochemical gas sensing applications of Ni-doped liFePO4 nano-particles.New Journal of Chemisty, 2016, 40(1): 295-301.
[4]	WANG Y G, LIU G D, ZHUO J L, et al.Recent development and performance of LiFePO4 material.Materials Science Forum, 2014, 809(5): 842-845.
[5]	HEUBNER C, SCHNEIDER M, MICHAELIS A.Investigation of charge transfer kinetics of Li-intercalation in LiFePO4.Journal of Power Sources, 2015, 288(3): 115-120.
[6]	WANG J M, CAI F P, YANG G, et al.synthesis of porous LiFePO4/C composite materials by CCVD method.Rare Metal Materials and Engineering, 2015, 44(2): 307-311.
[7]	FREDRICK O, WEN B H, FANG J, et al.Mg substitution clarifies the reaction mechanism of olivine LiFePO4.Advanced Energy Materials, 2015, 5(7): 124-127.
[8]	ZHENG Z M, PANG K W, TANG X C, et al.Solvothermal synthesis and electrochemical performance of hollow LiFePO4 nanoparticles.Journal of Alloys and Compounds, 2015, 640(2): 95-100.
[9]	KIM J M, YIG R, LEE S C, et al.Surfactant-assisted synthesis of hybrid lithium iron phosphate nanoparticles for enhancing electrochemical performance.Journal of Solid State Chemistry, 2013, 197(2): 53-59.
[10]	LUPO F D, MELIGRANA G, GERBALDI C, et al.Surfactant- assisted mild solvothermal synthesis of nanostructured LiFePO4/C cathodes evidencing ultrafast rate capability.Electrochimica Acta, 2015, 156(6): 188-198.
[11]	ZHOU XIN, ZHAO XIN-BING, YU HONG-MING, et al.Electrochemical properties of F-doped LiFePO4/C prepared by solid-state synthesis.Journal of Inorganic Materials, 2008, 23(3): 588-590.
[12]	ZHANG DONG-YUN, ZHANG PEI-XIN, LIN MU-CHONG, et al.Property and structure of carbon-coated LiFePO4.Journal of Inorganic Materials, 2011, 26(3): 265-270.
[13]	YANG G, JIANG C Y, HE X M, et al.Synthesis of size-controllable LiFePO4/C cathode material by controlled crystallization.Journal of New Materials for Electrochemical Systems, 2012, 15(2): 75-78
[14]	AMANDA B M, DANIELLE J M, CHARLES M S.Template-
	directed synthesis of structurally defined branched polymersMacromolecules, 2015, 48(5): 1296-1303.
[15]	宋延华, 张胜利, 李维, 等. PAM在锂离子电池正极材料LiFePO4中的应用. 电池, 2011, 41(1): 9-10.
[16]	SILVEIR K C, SHENG Q, TIAN W D, et al.Libraries of modified polyacrylamides using post-synthetic modification.Journal of Applied Polymer Science, 2015, 132(47): 30-31.
[17]	LU C G, LI W B, TAN Y, et al.Synthesis and aqueous solution properties of hydrophobically modified polyacrylamide.Journal of Applied Polymer Science, 2014, 131(18): 9162-9169.

聚丙烯酰胺改性LiFePO₄/C正极材料的研究

LiFePO₄/C Cathode Material Modified by Polyacrylamide

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