Direct synthesis of tin spheres/nitrogen-doped porous carbon composite by self-formed template method for enhanced lithium storage

doi:10.1016/j.jmst.2021.06.054

Abstract

Abstract:

To inhibit the agglomeration of tin-based nanomaterials and simplify the complicated synthesis process, a facile and eco-friendly self-formed template method is reported to synthesize tin submicron spheres dispersed in nitrogen-doped porous carbon (Sn/NPC) by pyrolysis of a mixture of disodium stannous citrate and urea. The vital point of this strategy is the formation of Na₂CO₃ templates during pyrolysis. This self-formed Na₂CO₃ acts as porous templates to support the formation of NPC. The obtained NPC provides good electronic conductivity, ample defects, and more active sites. Serving as anode for Li-ion batteries, the Sn/NPC electrode obtains a stable discharge capacity of 674.1 mAh/g after 150 cycles at 0.1 A/g. Especially, a high discharge capacity of 331.2 mAh/g can be achieved after 1100 cycles at 3 A/g. Additionally, a full cell coupled with LiCoO₂ as cathode yields a discharge capacity of 524.8 mAh/g after 150 cycles at 0.1 A/g. In-situ XRD is implemented to investigate the alloying/dealloying reaction mechanisms. Density functional theory calculation ulteriorly explicates that NPC heightens intrinsic electronic conductivity, and NPC especially pyrrolic-N and pyridinic-N doping facilitates the Li-adsorption ability. Climbing image nudged elastic band method reveals low Li⁺ diffusion energy barrier in presence of N atoms, which accounts for the terrific electrochemical properties of Sn/NPC electrode.

Key words: Tin submicron spheres, Nitrogen-doped porous carbon, Self-formed template, In-situ XRD, Li-ion batteries

Kun Liu, Jia-ao Wang, Hongfei Zheng, Xiaodong Sun, Zhimo Yang, Jianzong Man, Xinyu Wang, Juncai Sun. Direct synthesis of tin spheres/nitrogen-doped porous carbon composite by self-formed template method for enhanced lithium storage[J]. J. Mater. Sci. Technol., 2022, 104: 88-97.

Figures/Tables 7

Fig. 1. Morphological characterization: (a) Schematic diagram of the preparation procedure for Sn/NPC, (b-c) SEM images of Sn/PC, (d-e) SEM images and (f) EDS mappings of Sn/NPC, (g-h) TEM and (i) HRTEM images of Sn/NPC.

Fig. 2. Structural and surface elemental characterizations of Sn/PC and Sn/NPC: (a) XRD patterns, (b) Raman spectra, (c) TGA curve, (d) N2 adsorption/desorption isotherms, (e) Pore-size distribution. (f) XPS survey spectrum for Sn/PC and Sn/NPC. High-resolution XPS spectrum of (g) Sn 3d, (h) C 1s and (i) N 1s for Sn/NPC.

Fig. 3. Electrochemical properties: (a) CV profiles of Sn/NPC electrode. (b) Cycling performance of both electrodes and CE of Sn/NPC electrode at 0.1 A/g. (c) GCD curves of Sn/NPC electrode. (d) Rate capability of both electrodes. (e) Charge/discharge profiles of Sn/NPC electrode ranging from 0.1 to 3 A/g. (f) EIS spectrum and (g) LSV of both electrodes. (h) Long cycling performance and CE of Sn/NPC electrode at 3 A/g.

Fig. 4. Kinetics analyses of Sn/NPC: (a) GITT curves and (b) the Li+ diffusion coefficients. (c) CV curves measured from 0.1 to 1 mV/s. (d) Relationship between log (i) versus log (v). (e) Capacitive-controlled contribution at 0.2 mV/s. (f) The percentage of capacitive and diffusion-controlled contributions.

Fig. 5. First-principles calculations: Calculated partial density of states (PDOS) for (a) Sn/NPC and (b) Sn/PC. The Li+ diffusion energy barrier for (c) Sn/NPC and (d) Sn/PC. Theoretical simulations of Li atom adsorption. Top view of Li atom adsorbed in (e) N doping, (f) graphitic-N doped, (g) pyrrolic-N, (h) pyridinic-N doped C structures and the corresponding adsorption energies.

Fig. 6. Phase evolution during the initial lithiation/delithiation process. (a) In-situ XRD analysis of Sn/NPC electrode at 200 mA/g: contour plot (the left), XRD patterns of Sn, Li2Sn5, LiSn, and Li7Sn3 (the top), and corresponding charge/discharge profiles (the right). In-situ XRD patterns of the first (b) discharge and (c) charge process.

Fig. 7. Electrochemical features of Sn/NPC||LiCoO2 full cell: (a) Schematic diagram of the full cell. (b) GCD curves and (c) cycling performance at 0.1 A/g. (d) Rate capability and (e) corresponding GCD curves. (f) Cycling performance at 1 A/g.

References 57

[1]	Y.J. Zhu, M. Yang, Q.Y. Huang, D.R. Wang, R.B. Yu, J.Y. Wang, Z.J. Zheng, D. Wang, Adv. Mater. 32 (2020) 1906205-1906211. DOI URL
[2]	C. Yu, X. Tian, Z. Xiong, Z. Zhang, Z. Sun, X. Piao, J. Alloy. Compd. 869 (2021) 159124-159132. DOI URL
[3]	M. Liang, Y. Huang, Y. Lin, G. Liang, C. Huang, L. Chen, J. Li, Q. Feng, C. Lin, Z. Huang, J. Mater. Sci. Technol. 83 (2021) 66-74. DOI URL
[4]	C. Zhua, Y. Zhang, Z. Wu, Z. Ma, X. Guo, F. Guo, J. Zhang, Y. Li, J. Mater. Sci. Technol. 87 (2021) 18-28. DOI URL
[5]	Z. Zhao, Z. Wang, D.K. Denis, X. Sun, J. Zhang, L. Hou, X. Zhang, C. Yuan, Elec-trochim. Acta 307 (2019) 20-29.
[6]	R. Mo, X. Tan, F. Li, R. Tao, J. Xu, D. Kong, Z. Wang, B. Xu, X. Wang, C. Wang, J. Li, Y. Peng, Y. Lu, Nat. Commun. 11 (2020) 1374. DOI URL
[7]	Y. Tang, C. Bi, D. Zhang, G. Hou, H. Cao, L. Wu, G. Zheng, Q. Wu, Micropor. Mesopor. Mat. 274 (2019) 76-82. DOI URL
[8]	X. Dong, W. Liu, X. Chen, J. Yan, N. Li, S. Shi, S. Zhang, X. Yang, Chem. Eng. J. 350 (2018) 791-798. DOI URL
[9]	Y. Xu, Q. Liu, Y. Zhu, Y. Liu, A. Langrock, M.R. Zachariah, C. Wang, Nano Lett. 13 (2013) 470-474. DOI URL
[10]	A. Nurpeissova, A. Adi, A. Aishova, A. Mukanova, S.-S. Kim, Z. Bakenov, Mater. Today Energy 16 (2020) 100397-1003104.
[11]	R. Miyazaki, T. Hihara, J. Power Sources 427 (2019) 15-20. DOI
[12]	X. Huang, S. Cui, J. Chang, P.B. Hallac, C.R. Fell, Y. Luo, B. Metz, J. Jiang, P.T. Hur-ley, J. Chen, Angew. Chem. Int. Ed. 54 (2015) 1490-1493. DOI URL
[13]	Y. Cheng, Z. Yi, C. Wang, Y. Wu, L. Wang, Chem. Eng. J. 330 (2017) 1035-1043. DOI URL
[14]	S. Niu, Z. Wang, M. Yu, M. Yu, L. Xiu, S. Wang, X. Wu, J. Qiu, ACS Nano 12 (2018) 3928-3937. DOI URL
[15]	Y. Li, C. Ou, J. Zhu, Z. Liu, J. Yu, W. Li, H. Zhang, Q. Zhang, Z. Guo, Nano Lett. 20 (2020) 2034-2046. DOI URL
[16]	X. Tao, R. Wu, Y. Xia, H. Huang, W. Chai, T. Feng, Y. Gan, W. Zhang, ACS Appl. Mater. Interfaces 6 (2014) 3696-3702. DOI URL
[17]	Y. Zhang, L. Jiang, C. Wang, Nanoscale 7 (2015) 11940-11944. DOI URL
[18]	Y. Zhang, G. Wu, Y. Shi, Y. Hu, Y. Sun, Z. Ju, Q. Zhuang, Chemistry Select 4 (2019) 1285-1291.
[19]	Z. Zhu, S. Wang, J. Du, Q. Jin, T. Zhang, F. Cheng, J. Chen, Nano Lett 14 (2014) 153-157. DOI URL
[20]	D. Li, X. Ren, Q. Ai, Q. Sun, L. Zhu, Y. Liu, Z. Liang, R. Peng, P. Si, J. Lou, J. Feng, L. Ci, Adv. Energy Mater. 8 (2018) 1802386. DOI URL
[21]	C. Guo, Q. Yang, J. Liang, L. Wang, Y. Zhu, Y. Qian, Mater. Lett. 184 (2016) 332-335. DOI URL
[22]	X. Hu, X. Sun, S.J. Yoo, B. Evanko, Fengru Fan, S. Cai, C. Zheng, W. Hu, G.D. Stuck, Nano Energy 56 (2019) 828-839. DOI URL
[23]	J. Cui, H. Zhang, Y. Liu, S. Li, W. He, J. Hu, J. Sun, Electrochim. Acta 334 (2020) 135619-135628. DOI URL
[24]	W. Wang, Z. Du, J. Qian, F. Chen, Mater. Lett. 259 (2020) 126827-126830. DOI URL
[25]	R. Dai, W. Sun, Y. Wang, Electrochim. Acta 217 (2016) 123-131. DOI URL
[26]	Y. Pan, L. Yin, M. Li, Ceram. Int. 45 (2019) 12072-12079. DOI URL
[27]	Y. Guo, X. Zeng, Y. Zhang, Z. Dai, H. Fan, Y. Huang, W. Zhang, H. Zhang, J. Lu, F. Huo, Q. Yan, ACS Appl. Mater. Interfaces 9 (2017) 17172-17177. DOI URL
[28]	G. Liu, M. Huang, Z. Zhang, B. Xi, H. Li, S. Xiong, J. Energy Chem. 53 (2021) 175-184. DOI URL
[29]	T. Wang, D. Legut, Y. Fan, J. Qin, X. Li, Q. Zhang, Nano Lett. 20 (2020) 6199-6205. DOI URL
[30]	C. Guo, W.C. Zhang, Y. Liu, J.P. He, S. Yang, M.K. Liu, Q.H. Wang, Z.P. Guo, Adv. Funct. Mater. 29 (2019) 1901925-1901932. DOI URL
[31]	H. Ying, S. Zhang, Z. Meng, Z. Sun, W. Han, J. Mater. Chem. A 5 (2017) 8334-8342. DOI URL
[32]	R. Hu, Y. Ouyang, T. Liang, H. Wang, J. Liu, J. Chen, C. Yang, L. Yang, M. Zhu, Adv. Mater. 29 (2017) 1605006-1605015. DOI URL
[33]	B. Ma, J. Luo, X. Deng, Z. Wu, Z. Luo, X. Wang, Y. Wang, ACS Appl. Nano Mater. 12 (2018) 6989-6999.
[34]	L. Ma, X. Shen, G. Zhu, Z. Ji, H. Zhou, Carbon 77 (2014) 255-265. DOI URL
[35]	W. Ni, J.L. Cheng, L.Y. Shi, X.D. Li, B. Wang, Q. Guan, L. Huang, G.F. Gu, H. Li, J. Mater. Chem. A 2 (2014) 19122-19130. DOI URL
[36]	D.H. Youn, A. Heller, C.B. Mullins, Chem. Mater. 28 (2016) 1343-1347. DOI URL
[37]	L. Sun, T. Ma, J. Zhang, X. Guo, C. Yan, X. Liu, Electrochim. Acta 321 (2019) 134672-134679. DOI URL
[38]	F. Zhang, Y. Wang, W. Guo, S. Rao, P. Mao, Chem. Eng. J. 360 (2019) 1509-1516. DOI URL
[39]	F. Zhang, Y. Wang, W. Guo, P. Mao, S. Rao, P. Xiao, J. Alloy Compd. 829 (2020) 154579-154587. DOI URL
[40]	H. Zhang, X. Huang, O. Noonan, L. Zhou, C. Yu, Adv. Funct. Mater. 27 (2017) 1606023-1606028. DOI URL
[41]	L. Ao, C. Wu, Y. Xu, X. Wang, K. Jiang, L. Shang, Y. Li, J. Zhang, Z. Hu, J. Chu, J. Alloy Compd. 819 (2020) 153036-153048. DOI URL
[42]	W.Q. Yao, S.B. Wu, L. Zhan, Y.L. Wang, Chem. Eng. J. 361 (2019) 329-341. DOI URL
[43]	Y. Liu, N. Zhang, L. Jiao, J. Chen, Adv. Mater. 27 (2015) 6702-6707. DOI URL
[44]	L.G. Bulusheva, A.V. Okotrub, A.G. Kurenya, H.K. Zhang, H.J. Zhang, X.H. Chen, Carbon 49 (2011) 4013-4023. DOI URL
[45]	X. Ye, Z. Lin, S. Liang, X. Huang, X. Qiu, Y. Qiu, X. Liu, D. Xie, H. Deng, X. Xiong, Z. Lin, Nano Lett. 19 (2019) 1860-1866. DOI URL
[46]	Z. Wang, J. Bai, H. Xu, G. Chen, S. Kang, X. Li, J. Colloid Interf. Sci. 577 (2020) 329-336. DOI URL
[47]	Y.H. Xu, J.C. Guo, C.S. Wang, J. Mater. Chem. 22 (2012) 9562-9567. DOI URL
[48]	S. Liang, X. Zhu, P. Lian, W. Yang, H. Wang, J. Solid State Chem. 184 (2011) 1400-1404. DOI URL
[49]	X. Li, Y. Zhong, M. Cai, M.P. Balogh, D. Wang, Y. Zhang, R. Li, X. Sun, Elec-trochim. Acta 89 (2013) 387-393.
[50]	J.H. Lee, S.H. Oh, S.Y. Jeong, Y.C. Kang, J.S. Cho, Nanoscale 10 (2018) 21483-21491. DOI PMID
[51]	C. Gu, Y. Mai, J. Zhou, Y. You, J. Tu, J. Power Sources 214 (2012) 200-207. DOI URL
[52]	D. Song, J. Park, K. Kim, L.S. Lee, J.Y. Seo, Y.-K. Oh, Y.-J. Kim, M.-H. Ryou, Y.M. Lee, K. Lee, Electrochim. Acta 250 (2017) 59-67. DOI URL
[53]	N. Zhang, Q. Zhao, X. Han, J. Yang, J. Chen, Nanoscale 6 (2014) 2827-2832. DOI PMID
[54]	S. Gao, N. Wang, S. Li, D. Li, Z. Cui, G. Yue, J. Liu, X. Zhao, L. Jiang, Y. Zhao, Angew. Chem. Int. Ed. 59 (2020) 2465-2472. DOI URL
[55]	J. Gao, X. Cheng, S. Lou, Y. Ma, P. Zuo, C. Du, Y. Gao, G. Yin, J. Alloy. Compd. 728 (2017) 534-540. DOI URL
[56]	S.-B. Xia, L.-F. Yao, H. Guo, X. Shen, J.-M. Liu, F.-X. Cheng, J.-J. Liu, J. Power Sources 440 (2019) 227162-227170. DOI URL
[57]	M. de Jong, W. Chen, T. Angsten, A. Jain, R. Notestine, A. Gamst, M. Sluiter, C.K. Ande, S. van der Zwaag, J.J. Plata, C. Toher, S. Curtarolo, G. Ceder, K.A. Pers-son, M. Asta, Sci. Data 2 (2015) 150009-150021. DOI URL