二氧化硅/木质素多孔碳复合材料的制备及作为锂离子电池负极材料的性能

doi:10.7503/cjcu20180436

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (12): 2725.doi: 10.7503/cjcu20180436

二氧化硅/木质素多孔碳复合材料的制备及作为锂离子电池负极材料的性能

李常青^1,⁴, 杨东杰^1,⁴, 席跃宾^1,⁴, 秦延林³, 邱学青^1,^2,⁴()

1. 华南理工大学化学与化工学院
2. 制浆造纸工程国家重点实验室, 广州 510640
3. 广东工业大学轻工化工学院, 广州 510640
4. 华南理工大学广东省绿色精细化学产品工程技术研究开发中心, 广州 510640

收稿日期:2018-06-13 出版日期:2018-12-03 发布日期:2018-08-31
作者简介:
联系人简介: 邱学青, 男, 博士, 教授, 博士生导师, 主要从事木质素资源化利用的应用基础研究. E-mail: cexqqiu@scut.edu.cn
基金资助:
国家自然科学基金(批准号: 21878114, 21436004)和广东省科技计划项目(批准号: 2017B090903003, 2017A030308012)资助.

Synthesis and Electrochemical Performance of Silica/Porous Lignin Carbon Composites as Anode Materials for Lithium-ion Batteries^†

LI Changqing^1,⁴, YANG Dongjie^1,⁴, XI Yuebin^1,⁴, QIN Yanlin³, QIU Xueqing^1,^2,^4,^*()

1. School of Chemistry and Chemical Engineering
2. State Key Lab of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
3. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510640, China
4. Guangdong Province Key Lab of Green Chemical Product Technology,South China University of Technology, Guangzhou 510640, China

Received:2018-06-13 Online:2018-12-03 Published:2018-08-31
Contact: QIU Xueqing E-mail:cexqqiu@scut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21878114, 21436004) and the Science and Technology Program of Guangdong Province, China(Nos.2017B090903003, 2017A030308012).

摘要/Abstract

摘要：

将来源于造纸黑液中的碱木质素(AL)通过水热反应与纳米二氧化硅(SiO₂)复合, 制备了二氧化硅/季铵化碱木质素复合物(SiO₂/QAL), 再经过碳化和酸洗后得到二氧化硅/木质素多孔碳复合材料(SiO₂/PLC). 形貌与结构表征结果表明, SiO₂/PLC的比表面积达到1069 m²/g, 具有平均孔径约20 nm的介孔结构. 二氧化硅纳米颗粒均匀分散在三维网络结构的木质素多孔碳内部. 电化学性能测试结果表明, SiO₂/PLC作为锂离子电池负极材料具有良好的倍率性能和循环性能, 在100 mA/g电流密度下经过100周循环后放电比容量为820 mA·h/g, 在5 A/g大电流密度下嵌锂容量达到235 mA·h/g.

关键词: 锂离子电池, 负极材料, 二氧化硅, 木质素多孔碳

Abstract:

The alkali lignin(AL) derived from pulping liquor was used as raw materials to prepare the silica/quaternized alkali lignin composite(SiO₂/QAL) by hydrothermal reaction, and then the silica/porous lignin carbon composite(SiO₂/PLC) was obtained after carbonization and etching. SiO₂/PLC exhibited a specific surface area of 1069 m²/g and mesoporous pore size of 20 nm on average. As anode materials for lithium-ion batteries, silica nanoparticles were dispersed uniformly in the porous lignin carbon with a three dimensional network, leading to better cycle performance and rate capability. The electrochemical measurement showed that SiO₂/PLC displayed a high capacity of 820 mA·h/g after 100 cycles at a current density of 100 mA/g and 235 mA·h/g at a large current density of 5 A/g.

Key words: Lithium-ion battery, Anode material, Silica, Porous lignin carbon

中图分类号:

O646.21

TrendMD:

李常青, 杨东杰, 席跃宾, 秦延林, 邱学青. 二氧化硅/木质素多孔碳复合材料的制备及作为锂离子电池负极材料的性能. 高等学校化学学报, 2018, 39(12): 2725.

LI Changqing,YANG Dongjie,XI Yuebin,QIN Yanlin,QIU Xueqing. Synthesis and Electrochemical Performance of Silica/Porous Lignin Carbon Composites as Anode Materials for Lithium-ion Batteries^†. Chem. J. Chinese Universities, 2018, 39(12): 2725.

图/表 11

Scheme 1 Schematic illustration for the formation of SiO2/PLC

Fig.1 TG curves of SiO2/LC(a), SiO2/PLC(b) and PLC(c)

Fig.2 XRD patterns(A) and Raman spectra(B) of the as-prepared samplesa. LC; b. PLC; c. SiO2/PLC; d. SiO2.

Fig.3 N2 Adsorption-desorption isotherms of the as-prepared samples(A) and the corresponding pore-size distribution of SiO2/PLC determined from the adsorption isotherm(B)

Fig.4 SEM images of SiO2(A), SiO2/QAL(B), SiO2/LC(C), SiO2/PLC(D), PLC(E) and LC(F)

Fig.5 TEM images of edge structure(A) and internal structure(B) and EDS elemental mappings of C(C), O(D), Si(E) and N(F)

Fig.6 Cycling performance of the as-prepared samples at a current density of 100 mA/g(A) and rate capability of SiO2/PLC(B)

Table 1 Comparison of the lithium-storage performance between SiO2/PLC and previously reported SiO2/C anode materials

Material	Carbon source	$w Si O 2$ (%)	Carbonization temperature/℃	Specific capacity (mA·h·g^-1)/ Current density(mA·g^-1)	Specific capacity (mA·h·g^-1)/ Current density(A·g^-1)	Ref.
Bimodal porous carbon-silica nanocomposites	Resol	~50	850	611/200	300/3	[29]
H-SiO₂/C composite	PAN	50.4	1000	564/200	190/5	[30]
SiO₂/C/graphene spheres	PVP and GO	43	900	605/50	－	[31]
SiO₂-coated graphite flake	Graphitc flake	19	1000	－	480/2.5	[32]
Silica-carbon nanocomposite	Filter paper	31	600	488/100	96/3	[33]
SiO₂/PLC	Lignin	21	600	820/100	235/5	This work

Table 1 Comparison of the lithium-storage performance between SiO2/PLC and previously reported SiO2/C anode materials

Material	Carbon source	$w Si O 2$ (%)	Carbonization temperature/℃	Specific capacity (mA·h·g^-1)/ Current density(mA·g^-1)	Specific capacity (mA·h·g^-1)/ Current density(A·g^-1)	Ref.
Bimodal porous carbon-silica nanocomposites	Resol	~50	850	611/200	300/3	[29]
H-SiO₂/C composite	PAN	50.4	1000	564/200	190/5	[30]
SiO₂/C/graphene spheres	PVP and GO	43	900	605/50	－	[31]
SiO₂-coated graphite flake	Graphitc flake	19	1000	－	480/2.5	[32]
Silica-carbon nanocomposite	Filter paper	31	600	488/100	96/3	[33]
SiO₂/PLC	Lignin	21	600	820/100	235/5	This work

Fig.7 Cyclic voltammograms of SiO2/PLC(A), LC(B), PLC(C) and SiO2(D)

Fig.8 Galvanostatic discharge/charge profiles of SiO2/PLC(A), LC(B), PLC(C) and SiO2(D)

Fig.9 Nyquist plots of EIS spectra of SiO2, LC, PLC and SiO2/PLCInset is the equivalet circuit model used to fit the impedance spectra.

参考文献 41

[1]	Zhang Y., Li Y., Li H., Zhao Y., Yin F., Bakenov Z., Electrochimica Acta,2016, 216, 475—483
[2]	Li H., Wei Y., Zhang Y., Zhang C., Wang G., Zhao Y., Yin F., Bakenov Z., Ceramics International,2016, 42(10), 12371—12377
[3]	Yan N., Wang F., Zhong H., Li Y., Wang Y., Hu L., Chen Q., Scientific Reports,2013, 3(3), 1568
[4]	Chang W.S., Park C.M., Kim J.H., Kim Y.U., Jeong G., Sohn H.J., Energy & Environmental Science,2012, 5(5), 6895—6899
[5]	Gao B., Sinha S., Fleming L., Zhou O., Advanced Materials,2010, 13(11), 816—819
[6]	Tang C., Liu Y., Xu C., Zhu J., Wei X., Zhou L., He L., Yang W., Mai L., Advanced Functional Materials,2018, 28(3), 1704561
[7]	Guo B., Shu J., Wang Z., Yang H., Shi L., Liu Y., Chen L., Electrochemistry Communications,2008, 10(12), 1876—1878
[8]	Wang C.W., Liu K.W., Chen W.F., Zhou J.D., Lin H.P., Hsu C.H., Kuo P.L., Inorganic Chemistry Frontiers,2016, 3(11), 1398—1405
[9]	Tenhaeff W.E., Rios O., More K., Mcguire M.A., Advanced Functional Materials,2013, 24(1), 86—94
[10]	Xia H., Yin Z., Zheng F., Zhang Y., Materials Letters,2017, 205, 83—86
[11]	Liu X., Chen Y., Liu H., Liu Z.Q., Journal of Materials Science & Technology,2017, 33(3), 239—245
[12]	Hao S., Wang Z., Chen L., Materials & Design,2016, 111, 616—621
[13]	Wang S., Zhao N., Shi C., Liu E., He C., He F., Ma L., Applied Surface Science,2018, 433, 428—436
[14]	Wang H., Wu P., Qu M., Si L., Tang Y., Zhou Y., Lu T., Chemelectrochem,2015, 2(4), 508—511
[15]	Zhang W., Yin J., Lin Z., Lin H., Lu H., Wang Y., Huang W., Electrochimica Acta,2015, 176, 1136—1142
[16]	Etacheri V., Wang C., O’Connell M.J., Chan C.K., Pol V.G., Journal of Materials Chemistry A,2015, 3(18), 9861—9868
[17]	Xiong W., Qiu X., Yang D., Zhong R., Qian Y., Li Y., Wang H., Chemical Engineering Journal,2017, 326, 803—810
[18]	Pan D., Wang S., Zhao B., Wu M., Zhang H., Wang Y., Jiao Z., Chemistry of Materials,2009, 21(14), 3136—3142
[19]	Fey T.K., Lee D.C., Lin Y.Y., Kumar T.P., Synthetic Metals,2003, 139(1), 71—80
[20]	Kim C., Park S., Cho J., Lee D., Park T., Lee W., Yang K., Journal of Raman Spectroscopy,2004, 35(35), 928—933
[21]	Wenelska K., Ottmann A., Moszyński D., Schneider P., Klingeler R., Mijowska E., Journal of Colloid and Interface Science,2018, 511, 203—208
[22]	Ji L., Lin Z., Alcoutlabi M., Zhang X., Energy & Environmental Science,2011, 4(8), 2682—2699
[23]	Wang S.X., Yang L., Stubbs L.P., Li X., He C., ACS Applied Materials & Interfaces,2013, 5(23), 12275—12282
[24]	Dong J., Xue Y., Zhang C., Weng Q., Dai P., Yang Y., Zhou M., Li C., Cui Q., Kang X., Tang C., Bando Y., Golberg D., Wang X., Advanced Materials,2017, 29(6), 1603692
[25]	Wang B., Wang Y., Peng Y., Wang X., Wang N., Wang J., Zhao J., Chemical Engineering Journal,2018, 348, 850—859
[26]	Hou J., Cao C., Idrees F., Ma X., ACS Nano,2015, 9(3), 2556—2564
[27]	Yu Y., Zhang J., Xue L., Huang T., Yu A., Journal of Power Sources,2011, 196(23), 10240—10243
[28]	Qie L., Chen W.M., Wang Z.H., Shao Q.G., Li X., Yuan L.X., Hu X.L., Zhang W.X., Huang Y.H., Advanced Materials,2012, 24(15), 2047—2050
[29]	Qiang Z., Liu X., Zou F., Cavicchi K.A., Zhu Y., Vogt B.D., Journal of Physical Chemistry C,2017, 121(31), 16702—16709
[30]	Jiang Y., Mu D., Chen S., Wu B., Zhao Z., Wu Y., Ding Z., Wu F., Journal of Alloys and Compounds,2018, 744, 7—14
[31]	Xiang Z., Chen Y., Li J., Xia X., He Y., Liu H., Journal of Solid State Electrochemistry,2017, 21(8), 2425—2432
[32]	Yang N.H., Wu Y.S., Chou J., Wu H.C., Wu N.L., Journal of Power Sources,2015, 296, 314—317
[33]	Jia D., Wang K., Huang J., Chemical Engineering Journal,2017, 317, 673—686
[34]	Wu X., Shi Z.Q., Wang C.Y., Jin J., Journal of Electroanalytical Chemistry,2015, 746, 62—67
[35]	Yuan Z., Zhao N., Shi C., Liu E., He C., He F., Chemical Physics Letters,2016, 651, 19—23
[36]	Ren Y.R., Yang B., Wei H.M., Ding J.N., Solid State Ionics,2016, 292, 27—31
[37]	Li J., Huang J., Chemical Communications,2015, 51(78), 14590—14593
[38]	Zhou H., Zhu S., Hibino M., Honma I., Ichihara M., Advanced Materials,2003, 15(24), 2107—2111
[39]	Wang M., Jia D., Li J., Huang J., RSC Advances,2014, 4(64), 33981—33985
[40]	Li M., Li J., Li K., Zhao Y., Zhang Y., Gosselink D., Chen P., Journal of Power Sources,2013, 240(1), 659—666
[41]	Ruffo R., Hong S.S., Chan C.K., Huggins R.A., Cui Y., Journal of Physical Chemistry C,2009, 113(26), 11390—11398

二氧化硅/木质素多孔碳复合材料的制备及作为锂离子电池负极材料的性能

Synthesis and Electrochemical Performance of Silica/Porous Lignin Carbon Composites as Anode Materials for Lithium-ion Batteries^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 41

相关文章 15

编辑推荐

Metrics

本文评价

[1]	贾洋刚, 邵霞, 程婕, 王朋朋, 冒爱琴. 赝电容控制型钙钛矿高熵氧化物La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃负极材料的制备及储锂性能[J]. 高等学校化学学报, 2022, 43(8): 20220157.
[2]	张洁, 银波, 刘玮欣, 刘兴平, 连文贤, 唐韶坤. 勃姆石纤维增强二氧化硅气凝胶的制备及性能[J]. 高等学校化学学报, 2022, 43(11): 20220483.
[3]	鲍俊全, 郑仕兵, 苑旭明, 史金强, 孙田将, 梁静. 有机盐PTO(KPD)₂作为高性能锂离子电池正极材料的研究[J]. 高等学校化学学报, 2021, 42(9): 2911.
[4]	李辉阳, 朱思颖, 李莎, 张桥保, 赵金保, 张力. 锂离子电池硅氧化物负极首次库伦效率的影响因素与提升策略[J]. 高等学校化学学报, 2021, 42(8): 2342.
[5]	卓增庆, 潘锋. 基于软X射线光谱的锂电池材料的电子结构与演变的研究进展[J]. 高等学校化学学报, 2021, 42(8): 2332.
[6]	吴卓彦, 李至, 赵旭东, 王倩, 陈顺鹏, 常兴华, 刘志亮. 一步法高效制备纳米Si/C复合材料及其在高性能锂离子电池中的应用[J]. 高等学校化学学报, 2021, 42(8): 2500.
[7]	田润赛, 卢芊, 张洪滨, 张渤, 冯源源, 魏金香, 冯季军. 氮杂碳原位包覆Cu₂O/Co₃O₄@C异质结构复合材料的设计构筑及高效储锂性能[J]. 高等学校化学学报, 2021, 42(8): 2592.
[8]	易聪华, 苏华坚, 钱勇, 李琼, 杨东杰. 木质素纳米炭的制备及作为锂离子电池负极的性能研究[J]. 高等学校化学学报, 2021, 42(6): 1807.
[9]	毛尔洋, 王莉, 孙永明. 锂离子电池高容量合金基含锂负极材料的研究进展[J]. 高等学校化学学报, 2021, 42(5): 1552.
[10]	刘铁峰, 张奔, 盛欧微, 佴建威, 王垚, 刘育京, 陶新永. 硅负极黏结剂的研究进展[J]. 高等学校化学学报, 2021, 42(5): 1446.
[11]	王弈艨, 刘凯, 王保国. 高镍三元正极材料的表面包覆策略[J]. 高等学校化学学报, 2021, 42(5): 1514.
[12]	石颖, 胡广剑, 吴敏杰, 李峰. 低温等离子体在锂离子电池材料中的应用[J]. 高等学校化学学报, 2021, 42(5): 1315.
[13]	王任衡, 肖哲, 李艳, 孙一翎, 范姝婷, 郑俊超, 钱正芳, 贺振江. 固相烧结法制备锂离子电池正极材料Li₂FeP₂O₇及其电化学性能研究[J]. 高等学校化学学报, 2021, 42(4): 1299.
[14]	韩延东, 韩明勇, 杨文胜. 溶胶-凝胶法构筑介孔二氧化硅纳微结构[J]. 高等学校化学学报, 2021, 42(4): 965.
[15]	童诚, 吴文韬, 王挺. 具有不对称孔道结构的小介孔二氧化硅粒子的合成及其高分子杂化膜的构建[J]. 高等学校化学学报, 2021, 42(3): 946.

二氧化硅/木质素多孔碳复合材料的制备及作为锂离子电池负极材料的性能

Synthesis and Electrochemical Performance of Silica/Porous Lignin Carbon Composites as Anode Materials for Lithium-ion Batteries†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 41

相关文章 15

编辑推荐

Metrics

本文评价

Synthesis and Electrochemical Performance of Silica/Porous Lignin Carbon Composites as Anode Materials for Lithium-ion Batteries^†