盐酸活化对石墨相氮化碳(g-C_3N_4)结构和g-C_3N_4/S锂硫电池正极复合材料性能的影响
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摘要
以三聚氰胺为原料制备石墨相氮化碳(g-C_3N_4),加入盐酸进行水热处理得到酸活化的g-C_3N_4。研究了盐酸活化对g-C_3N_4结构、形貌及锂硫电池g-C_3N_4/S正极复合材料电化学性能的影响。实验结果表明:盐酸活化处理后,g-C_3N_4的层间距变化不显著。随着盐酸浓度增大,g-C_3N_4比表面积先增大后减小,当盐酸浓度为2.5wt%时,比表面积最大为86.1 m2·g-1,与未处理g-C_3N_4的13 m2·g-1相比提高了5～6倍;盐酸活化g-C_3N_4/S正极复合材料的比容量和循环性能也呈现先增大后减小的趋势,当盐酸浓度为2.5wt%时,比容量和循环性能最好,比容量为1 538mAh·g-1,循环50次后容量保持率为77.8%,电化学性能与比表面积呈强相关性。
Graphite carbonitride(g-C_3N_4)was prepared from melamine and hydrothermally treated with hydrochloric acid to obtain acid-activated g-C_3N_4.The effects of hydrochloric acid activation on the structure and morphology of g-C_3N_4 and the electrochemical performance of g-C_3N_4/S cathode composites were investigated experimentally.The experimental results show that g-C_3N_4 layer spacing does not change significantly after hydrochloric acid activation.With the increase of hydrochloric acid concentration,the specific surface area of the g-C_3N_4 sample first increases and then decreases.When the concentration of hydrochloric acid is 2.5 wt%,the maximum specific surface area is 86.1 m2·g-1,which is 5-6 times higher than untreated g-C_3N_4 of 13 m2·g-1.The specific capacity and cycle performance of hydrochloric acid activated g-C_3N_4/S cathode composites also increase first and then decrease.When the concentration of hydrochloric acid is 2.5 wt%,the specific capacity and cycle performance of the hydrochloric acid activated g-C_3N_4/S cathode composite sample are the best,and the specific capacity is 1 538 mAh·g-1.After50 cycles,its capacity holding rate is 77.8%.The electrochemical performance and specific surface area of hydrochloric acid activated g-C_3N_4/S cathode composites show a strong correlation.
Graphite carbonitride(g-C_3N_4)was prepared from melamine and hydrothermally treated with hydrochloric acid to obtain acid-activated g-C_3N_4.The effects of hydrochloric acid activation on the structure and morphology of g-C_3N_4 and the electrochemical performance of g-C_3N_4/S cathode composites were investigated experimentally.The experimental results show that g-C_3N_4 layer spacing does not change significantly after hydrochloric acid activation.With the increase of hydrochloric acid concentration,the specific surface area of the g-C_3N_4 sample first increases and then decreases.When the concentration of hydrochloric acid is 2.5 wt%,the maximum specific surface area is 86.1 m2·g-1,which is 5-6 times higher than untreated g-C_3N_4 of 13 m2·g-1.The specific capacity and cycle performance of hydrochloric acid activated g-C_3N_4/S cathode composites also increase first and then decrease.When the concentration of hydrochloric acid is 2.5 wt%,the specific capacity and cycle performance of the hydrochloric acid activated g-C_3N_4/S cathode composite sample are the best,and the specific capacity is 1 538 mAh·g-1.After50 cycles,its capacity holding rate is 77.8%.The electrochemical performance and specific surface area of hydrochloric acid activated g-C_3N_4/S cathode composites show a strong correlation.
引文
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[2]熊仕昭,洪晓斌,谢凯,等.改善锂硫电池循环性能的研究进展[J].化工进展,2011,30(5):991-996.XIONG S Z,HONG X B,XIE K,et al.Advance in improvement of cycle life of lithium-sulfur batteries[J].Chemical Industry&Engineering Progress,2011,30(5):991-996(in Chinese).
[3] JI X,LEE K T,NAZAR L F.A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries[J].Nature Materials,2009,2460(17):500-506.
[4] LI Y,FITCH B.Effective enhancement of lithium-ion battery performance using SLMP[J].Electrochemistry Communications,2011,13(7):664-667.
[5]刘珍红,孙晓刚,邱治文,等.多壁碳纳米管纸作正极集流体的锂硫电池性能[J].复合材料学报,2017,34(4):873-880.LIU Z H,SUN X G,QIU Z W,et al.Performance of lithium sulfur batteries using multiwalled carbon nanotube paper as cathode current collector[J].Acta Materiae Compositae Sinica,2017,34(4):873-880(in Chinese).
[6] LIN C,LEON L.Recent advances in lithium-sulfur batteries[J].Journal of Power Sources,2014,267:770-783.
[7] VAUGHEY J T,LIU G,ZHANG J.Stabilizing the surface of lithium metal[J].MRS Bulletin,2014,39:429-435.
[8]闫崇,李向南,曹朝霞,等.高能球磨法制备PTFE/科琴黑-C柔性复合材料及其电化学应用[J].复合材料学报,2016,33(10):2390-2396.YAN C,LI X N,CAO Z X,et al.Preparation of PTFE/Ketjen Black-C flexible composites by high energy ball milling method and its electrochemical application[J].Acta Materiae Compositae Sinica,2016,33(10):2390-2396(in Chinese).
[9]吴锋,吴生先,陈人杰,等.锂硫电池正极用硫碳复合材料的制备和电化学研究[J].北京理工大学学报,2009,29(8):737-740.WU F,WU S X,CHEN R J,et al.Preparation and electrochemical properties of sulfur-carbon composite as cathode materials for the lithium-sulfur batteries[J].Transactions of Beijing Institute of Technology,2009,29(8):737-740(in Chinese).
[10] SHIM J,STRIEBEL K A,CAIRNS E J.The lithium/sulfur rechargeable cell[J].Journal of the Electrochemical Society,2002,149(10):1321-1325.
[11] ZHANG J Y,KONG L B,ZHAN L Z,et al.Sulfur organic polymer:Noval cathode active material for rechargeable lithium batteries[J].Journal of Power Sources,2007,168(1):278-281.
[12] JI X,LEE K T,NAZAR L F.A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries[J].Nature Materials,2009,8(6):500-506.
[13]陈宗宗,张瑞丰.基于Polymer-S-C/SiO2多层结构大孔电极锂硫离子电池的制备与性能[J].复合材料学报,2014,31(2):525-531.CHEN Z Z,ZHANG R F.Preparation and performance of lithium-sulfur batteries based on multilayer structure in polymer-S-C/SiO2 macroporous electrodes[J].Acta Materiae Compositae Sinica,2014,31(2):525-531(in Chinese).
[14] MENG Z,XIE Y,CAI T W,et al.Graphene-like g-C3N4,nanosheets/sulfur as cathode for lithium-sulfur battery[J].Electrochimica Acta,2016,210:829-836.
[15] LIU J H,LI W F,DUAN L M,et al.A graphene-like oxygenated carbon nitride material for improved cycle-life lithium/sulfur batteries[J].Nano Letters,2015,15(8):5137-5140.
[16] PANG Q,NAZAR L F.Long-life and high-areal-capacity LiS batteries enabled by a light-weight polar host with intrinsic polysulfide adsorption[J]. ACS Nano,2016,10(4):4111-4113.
[17] YAN S C,LI Z S,ZOU Z G.Photodegradation performance of g-C3N4fabricated by directly heating melamine[J].Langmuir,2009,25(17):10397-10401.
[18] CAO J,CHEN C,ZHAO Q,et al.A flexible nanostructured paper of a reduced graphene oxide-sulfur composite for high-performance lithium-sulfur batteries with unconventional configurations[J].Advanced Materials,2016,28(43):9629-9631.
[19]吴思展.类石墨氮化碳(g-C3N4)的合成、加工处理、修饰及其光催化性能的研究[D].广州:华南理工大学,2014.WU S Z.Synthesis,processing and modification of graphitic carbon nitride with enhanced photocatalytic activity[D].Guangzhou:South China University of Technology,2014(in Chinese).
[20] ZHANG Y,THOMAS A,ANTONIETTI M,et al.Activation of carbon nitride solids by protonation:Morphology changes,enhanced ionic conductivity,and photoconduction experiments[J].Journal of the American Chemical Society,2009,131(1):50-52.
[21]杨晓晖,王红军,陆希峰,等.石墨型C3N4的固态合成及嵌锂性能研究[J].化学学报,2009,67(11):1166-1170.YANG X H,WANG H J,LU X F,et al.Solid-state synthesis of graphite-like C3N4and its reversible Li+intercalation[J].Acta Chimica Sinica,2009,67(11):1166-1170(in Chinese).