磷化镍/氮磷共掺杂碳负极材料的制备及其电化学性能研究

doi:10.13208/j.electrochem.200713

摘要/Abstract

摘要：

以离子液体为碳源和氮源、次亚磷酸钠为磷源、乙酸镍为镍源,一步法制备了磷化镍/氮磷共掺杂碳(Ni₂P/NPC)复合材料。SEM、TEM等检测结果表明Ni₂P纳米颗粒在N、P共掺杂碳骨架上均匀分布。将所制备Ni₂P/NPC作为锂离子电池负极材料时,Ni₂P/NPC电极在0.1、0.5、1、3和5 A·g^-1电流密度下的放电比容量分别为377.7、 294.1、 265.4、211.7和187.5 mAh·g^-1。当电流密度重新回到0.1 A·g^-1,放电比容量为368.1 mAh·g^-1。电极结构在大倍率下可以保持稳定,表现出优异的倍率性能。在0.5 A·g^-1的电流密度下经200次循环后放电比容量维持在301.8 mAh·g^-1,容量保持率为80.7%,CV曲线证实Ni₂P/NPC在储锂过程中是由扩散过程和电容行为共同控制。

关键词: 磷化镍, 氮磷共掺杂碳, 储锂

Abstract:

In recent years, the nickel-based phosphide has drawn great attention because of its low intercalation/deintercalation platform and lower polarization compared to sulfides and oxides as anodes for next-generation high-energy lithium-ion batteries. The Ni₂P anode can deliver high theoretical specific capacity of 542 mAh·g^-1, but it subject to a conversion reaction mechanism, which make them unsuitable for commercial applications. The agglomeration of Ni₂P nanoparticles during material fabrication and the structural deterioration of electrode associated with large volume change during charge-discharge process lead to poor cycle stability and low utilization of active materials. Meanwhile, the low intrinsic conductivity of Ni₂P is also sluggish electrochemical reaction kinetics. Herein, we design a facile and viable approach to synthesize Ni₂P/NPC composites with a stable structure to address these issues. This new approach entails synthesis of Ni₂P/NPC by a N and P co-doped carbon framework with ionic liquids assistance during synthesis. This stable composite structure can serve as anode material of lithium ion batteries with good electrochemical performance. The Ni₂P/NPC composites were prepared by one-step method using ionic liquids as carbon and nitrogen sources, while sodium hypophosphite and nickel acetate as phosphorus and nickel sources, respectively. The results of SEM and TEM show that Ni₂P nanoparticles were uniformly distributed on the N and P co-doped carbon framework. When the Ni₂P/NPC composite was used as an anode material of lithium ion batteries, the discharge specific capacities were 377.7, 294.1, 265.4, 211.7 and 187.5 mAh·g^-1 at 0.1, 0.5, 1, 3 and 5 A·g^-1, respectively. When the current density returned to 0.1 A·g^-1, the discharge specific capacity reached 368.1 mAh·g^-1. The Ni₂P/NPC structure could be kept stable at high rate, showing excellent rate performance. The fabricated Ni₂P/NPC anode delivered the discharge specific capacity of 301.8 mAh·g^-1 with the capacity retention of 80.7% after 200 cycles at 0.5 A·g^-1. Finally, CV curves confirmed that the lithium storage of Ni₂P/NPC colud be controlled by diffusion process and capacitance behavior.

Key words: nickel phosphide, nitrogen and phosphorous co-doped carbon, lithium storage

胡健, 蒙延双, 胡倩茹. 磷化镍/氮磷共掺杂碳负极材料的制备及其电化学性能研究[J]. 电化学（中英文）, 2021, 27(5): 540-548.

Jian Hu, Yan-Shuang Meng, Qian-Ru Hu. Synthesis of Nickel Phosphide/Nitrogen Phosphorus Co-Doped Carbon and Its Application in Lithium Ion Batteries[J]. Journal of Electrochemistry, 2021, 27(5): 540-548.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200713

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I5/540

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参考文献 30

[1]	Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657. doi: 10.1038/451652a URL
[2]	Chen D J, Zhou Z Q, Feng C, Lü W Q, Wei Z H, Zhang K H L, Lin B, Wu S H, Lei T Y, Guo X Y, Zhu G L, Jian X, Xiong J, Traversa E, Dou S X, He W D. An upgraded lithium ion battery based on a polymeric separator incorporated with anode active materials[J]. Adv. Energy Mater., 2019, 9(15): 1803627. doi: 10.1002/aenm.v9.15 URL
[3]	Qi W, Shapter J G, Wu Q, Yin T, Gao G, Cui D X. Nanostructured anode materials for lithium-ion batteries: principle, recent progress and future perspectives[J]. J. Mater. Chem. A, 2017, 5(37): 19521-19540. doi: 10.1039/C7TA05283A URL
[4]	Scrosati B, Garche J. Lithium batteries: Status, prospects and future[J]. J. Power Sources, 2010, 195(9): 2419-2430. doi: 10.1016/j.jpowsour.2009.11.048 URL
[5]	Jin J Y, Wang Z W, Wang R, Wang J L, Huang Z D, Ma Y W, Li H, Wei S H, Huang X, Yan J X, Li S Z, Huang W. Achieving high volumetric lithium storage capacity in compact carbon materials with controllable nitrogen doping[J]. Adv. Funct. Mater., 2019, 29(12): 1807441. doi: 10.1002/adfm.v29.12 URL
[6]	Pralong V, Souza D C S, Leung K T, Nazar L F. Reversible lithium uptake by CoP₃ at low potential: role of the anion[J]. Electrochem. Commun., 2002, 4(6): 516-520. doi: 10.1016/S1388-2481(02)00363-6 URL
[7]	Lou P L, Cui Z H, Jia Z Q, Sun J Y, Tan Y B, Guo X X. Monodispersed carbon-coated cubic NiP₂ nanoparticles anchored on carbon nanotubes as ultra-long-life anodes for reversible lithium storage[J]. ACS Nano, 2017, 11(4): 3705-3715. doi: 10.1021/acsnano.6b08223 URL
[8]	Carenco S, Surcin C, Morcrette M, Larcher D, Mezailles N, Boissiere C, Sanchez C. Improving the Li-electrochemical properties of monodisperse Ni₂P nanoparticles by self-generated carbon coating[J]. Chem. Mater., 2012, 24(4): 688-697. doi: 10.1021/cm203164a URL
[9]	Feng Y Y, OuYang Y, Peng L, Qiu H J, Wang H L, Wang Y. Quasi-graphene-envelope Fe-doped Ni₂P sandwiched nanocomposites for enhanced water splitting and lithium storage performance[J]. J. Mater. Chem. A, 2015, 3(18): 9587-9594. doi: 10.1039/C5TA01103E URL
[10]	Li M, Du H R, Kuai L, Huang K F, Xia Y Y, Geng B Y. Scalable dry production process of a superior 3D net-like carbon‐based iron oxide anode material for lithium-ion batteries[J]. Angew. Chem. Int. Ed., 2017, 56(41): 12649-12653. doi: 10.1002/anie.v56.41 URL
[11]	Green O, Grubjesic S, Lee S W, Firestone M A. The design of polymeric ionic liquids for the preparation of functional materials[J]. Polym. Rev., 2009, 49(4): 339-360. doi: 10.1080/15583720903291116 URL
[12]	Kang X C, Sun X F, Han B X. Synjournal of functional nanomaterials in ionic liquids[J]. Adv. Mater., 2016, 28(6): 1011-1030. doi: 10.1002/adma.201502924 URL
[13]	Zhang H F(张韩方), Wei F(魏风), Sun J(孙健), Jing M Y(荆梦莹), He X J(何孝军). Ionic liquid assisted synjournal of porous carbons from rice husk for supercapacitors[J]. J. Electrochem.(电化学), 2019, 25(6): 764-772.
[14]	Chen T Q, Pan L K, Lu T, Fu C L, Chua D H C, Sun Z. Fast synjournal of carbon microspheres via a microwave-assisted reaction for sodium ion batteries[J]. J. Mater. Chem. A, 2014, 2(5): 1263-1267. doi: 10.1039/C3TA14037G URL
[15]	Pimenta M A, Dresselhaus G, Dresselhaus M S, Cancado L G, Jorio A, Saito R. Studying disorder in graphite-based systems by Raman spectroscopy[J]. Phys. Chem. Chem. Phys., 2007, 9(11): 1276-1290. pmid: 17347700
[16]	Zheng F C, Yang Y, Chen Q W. High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework[J]. Nat. Commun., 2014, 5(5): 5261. doi: 10.1038/ncomms6261 URL
[17]	Lu Y Y, Li Z W, Bai Z Y, Mi H Y, Ji C C, Pang H, Yu C, Qiu J S. High energy-power Zn-ion hybrid supercapacitors enabled by layered B/N co-doped carbon cathode[J]. Nano Energy, 2019, 66: 104132. doi: 10.1016/j.nanoen.2019.104132 URL
[18]	Xia Q Y, Yang H, Wang M, Yang M, Guo Q B, Wan L M, Xia H, Yu Y. High energy and high power lithium-ion capacitors based on boron and nitrogen dual-doped 3D carbon nanofibers as both cathode and anode[J]. Adv. Energy Mater., 2017, 7(22): 1701336. doi: 10.1002/aenm.201701336 URL
[19]	Wang H G, Yuan C P, Zhou R, Duan Q, Li Y H. Self-sacrifice template formation of nitrogen-doped porous carbon microtubes towards high performance anode materials in lithium ion batteries[J]. Chem. Eng. J., 2017, 316: 1004-1010. doi: 10.1016/j.cej.2017.02.059 URL
[20]	Ma W P, Xie L J, Dai L Q, Sun G H, Chen J Z, Su F Y, Cao Y F, Lei H, Kong Q Q, Chen C M. Influence of phosphorus doping on surface chemistry and capacitive behaviors of porous carbon electrode[J]. Electrochim. Acta, 2018, 266: 420-430. doi: 10.1016/j.electacta.2018.02.031 URL
[21]	Wu Z S, Winter A, Chen L, Sun Y, Turchanin A, Feng X L, Mullen K. Three-dimensional nitrogen and boron Co-doped graphene for high-performance all-solid-state supercapacitors[J]. Adv. Mater., 2012, 24(37): 5130-5135. doi: 10.1002/adma.201201948 URL
[22]	Huang L J, Cao X X, Pan A Q, Chen J, Kong X Z, Yang Y Q, Liang S Q, Cao G Z. Bimetallic phosphides embedded in hierarchical P-doped carbon for sodium ion battery and hydrogen evolution reaction applications[J]. Sci. China. Mater., 2019, 62(12): 1857-1867. doi: 10.1007/s40843-019-9474-0 URL
[23]	Dong C F, Guo L J, He Y Y, Chen C J, Qian Y T, Chen Y N, Xu L Q. Sandwich-like Ni₂P nanoarray/nitrogen-doped graphene nanoarchitecture as a high-performance anode for sodium and lithium ion batteries[J]. Energy Stor. Mater., 2018, 15: 234-241.
[24]	Zheng J L, Huang X M, Pan X, Teng C, Wang N. Yolk-shelled Ni₂P@carbon nanocomposite as high-performance anode material for lithium and sodium ion batteries[J]. Appl. Surf. Sci., 2019, 473: 699-705. doi: 10.1016/j.apsusc.2018.12.225 URL
[25]	Lu Y, Wang X L, Mai Y J, Xiang J Y, Zhang H, Li L, Gu C D, Tu J P, Mao S X. Ni₂P/graphene sheets as anode materials with enhanced electrochemical properties versus lithium[J]. J. Phys. Chem. C, 2012, 116(42): 22217-22225. doi: 10.1021/jp3073987 URL
[26]	Guo H N, Cai H C, Li W Q, Chen C C, Chen K, Zhang Y, Li Y W, Wang M Y, Wang Y J. Tailored Ni₂P nanoparticles supported on N-doped carbon as a superior anode material for Li-ion batteries[J]. Inorg. Chem. Front., 2019, 6(7): 1881-1889. doi: 10.1039/C9QI00480G URL
[27]	Xia Q, Zhao H L, Du Z H, Zhang Z J, Li S M, Gao C H, Swierczek K. Design and synjournal of a 3-D hierarchical molybdenum dioxide/nickel/carbon structured composite with superior cycling performance for lithium ion batteries[J]. J. Mater. Chem. A, 2016, 4(2): 605-611. doi: 10.1039/C5TA07052J URL
[28]	Brousse T, B'elanger D, Long J W. To be or not to be pseudocapacitive?[J]. J. Electrochem. Soc., 2015, 162(5): A5185-A5189. doi: 10.1149/2.0201505jes URL
[29]	Li J B, Li J L, Yan D, Hou S J, Xu X T, Lu T, Yao Y F, Mai W J, Pan L K. Design of pomegranate-like clusters with NiS₂ nanoparticles anchored on nitrogen-doped porous carbon for improved sodium ion storage performance[J]. J. Mater. Chem. A, 2018, 6(15): 6595-6605. doi: 10.1039/C8TA00557E URL
[30]	Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage[J]. Energy Environ. Sci., 2014, 7(5): 1597-1614. doi: 10.1039/c3ee44164d URL