Issue

Vol. 13 (2021)

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

https://doi.org/10.1007/s40820-020-00587-y
Jinlin Yang
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, People’s Republic of China
Xiaowei Wang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Wenrui Dai
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Xu Lian
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Xinhang Cui
National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Suzhou 215123, Jiangsu, China
Weichao Zhang
Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, People’s Republic of China
Kexin Zhang
Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, People’s Republic of China
Ming Lin
Institute of Materials Research and Engineering (IMRE), Agency of Science, Technology, and Research (A*STAR), 3 Research Link, Singapore 117602, Singapore
Ruqiang Zou
Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, People’s Republic of China
Kian Ping Loh
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Quan‑Hong Yang
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, People’s Republic of China
Wei Chen
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, People’s Republic of China

Corresponding Author: Wei Chen

phycw@nus.edu.sg

Nano-Micro Letters, Vol. 13 (2021), Article Number: 98

Abstract

Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries (SIBs). Ultra-micropores (< 0.5 nm) of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na+ but allow the entrance of naked Na+ into the pores, which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics. Herein, a molten diffusion–carbonization method is proposed to transform the micropores (> 1 nm) inside carbon into ultra-micropores (< 0.5 nm). Consequently, the designed carbon anode displays an enhanced capacity of 346 mAh g−1 at 30 mA g−1 with a high ICE value of ~ 80.6% and most of the capacity (~ 90%) is below 1 V. Moreover, the high-loading electrode (~ 19 mg cm−2) exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm−2 at 25 °C and 5.32 mAh cm−2 at − 20 °C. Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results, the designed ultra-micropores provide the extra Na+ storage sites, which mainly contributes to the enhanced capacity. This proposed strategy shows a good potential for the development of high-performance SIBs.


Highlights:


1 Hard-carbon anode dominated with ultra-micropores (< 0.5 nm) was synthesized for sodium-ion batteries via a molten diffusion–carbonization method.
2 The ultra-micropores dominated carbon anode displays an enhanced capacity, which originates from the extra sodium-ion storage sites of the designed ultra-micropores.
3 The thick electrode (~ 19 mg cm−2) with a high areal capacity of 6.14 mAh cm−2 displays an ultrahigh cycling stability and an outstanding low-temperature performance.

Keywords

Carbon anode Ultra-micropores Extra sodium-ion storage sites Low-voltage capacity High areal capacity
Yang, Jinlin, Xiaowei Wang, Wenrui Dai, Xu Lian, Xinhang Cui, Weichao Zhang, Kexin Zhang, Ming Lin, Ruqiang Zou, Kian Ping Loh, Quan‑Hong Yang, and Wei Chen. 2021. “From Micropores to Ultra-Micropores Inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage”. Nano-Micro Letters 13 (March):98. https://doi.org/10.1007/s40820-020-00587-y.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. H. Hou, X. Qiu, W. Wei, Y. Zhang, X. Ji, Carbon anode materials for advanced sodium-ion batteries. Adv. Energy Mater. 7(24), 1602898 (2017). https://doi.org/10.1002/aenm.201602898
  2. X. Wu, Y. Chen, Z. Xing, C.W.K. Lam, S.-S. Pang et al., Advanced carbon-based anodes for potassium-ion batteries. Adv. Energy Mater. 9(21), 1900343 (2019). https://doi.org/10.1002/aenm.201900343
  3. Y. Shao, G. Zhong, Y. Lu, L. Liu, C. Zhao et al., A novel nasicon-based glass-ceramic composite electrolyte with enhanced Na-ion conductivity. Energy Storage Mater. 23, 514–521 (2019). https://doi.org/10.1016/j.ensm.2019.04.009
  4. C. Zhao, F. Ding, Y. Lu, L. Chen, Y.S. Hu, High-entropy layered oxide cathodes for sodium-ion batteries. Angew. Chem. Int. Ed. 59(1), 264–269 (2020). https://doi.org/10.1002/anie.201912171
  5. J. Zhang, D.-W. Wang, W. Lv, L. Qin, S. Niu et al., Ethers illume sodium-based battery chemistry: Uniqueness, surprise, and challenges. Adv. Energy Mater. 8(26), 1801361 (2018). https://doi.org/10.1002/aenm.201801361
  6. J. Zhang, D.-W. Wang, W. Lv, S. Zhang, Q. Liang et al., Achieving superb sodium storage performance on carbon anodes through an ether-derived solid electrolyte interphase. Energy Environ. Sci. 10(1), 370–376 (2017). https://doi.org/10.1039/C6EE03367A
  7. Y. Lu, X. Rong, Y.-S. Hu, L. Chen, H. Li, Research and development of advanced battery materials in china. Energy Storage Mater. 23, 144–153 (2019). https://doi.org/10.1016/j.ensm.2019.05.019
  8. C. Zeng, F. Xie, X. Yang, M. Jaroniec, L. Zhang et al., Ultrathin titanate nanosheets/graphene films derived from confined transformation for excellent Na/K ion storage. Angew. Chem. Int. Ed. 57(28), 8540–8544 (2018). https://doi.org/10.1002/anie.201803511
  9. Y. Liu, B.V. Merinov, W.A. Goddard, Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals. Proc. Natl. Acad. Sci. USA 113(14), 3735–3739 (2016). https://doi.org/10.1073/pnas.1602473113
  10. H. Zhang, I. Hasa, S. Passerini, Beyond insertion for na-ion batteries: Nanostructured alloying and conversion anode materials. Adv. Energy Mater. 8(17), 1702582 (2018). https://doi.org/10.1002/aenm.201702582
  11. F. Xie, L. Zhang, Q. Gu, D. Chao, M. Jaroniec et al., Multi-shell hollow structured Sb2S3 for sodium-ion batteries with enhanced energy density. Nano Energy 60, 591–599 (2019). https://doi.org/10.1016/j.nanoen.2019.04.008
  12. F. Xie, L. Zhang, C. Ye, M. Jaroniec, S.Z. Qiao, The application of hollow structured anodes for sodium-ion batteries: from simple to complex systems. Adv. Mater. 31(38), e1800492 (2019). https://doi.org/10.1002/adma.201800492
  13. B. Chen, Y. Meng, F. Xie, F. He, C. He et al., 1D sub-nanotubes with anatase/bronze TiO2 nanocrystal wall for high-rate and long-life sodium-ion batteries. Adv. Mater. 30(46), e1804116 (2018). https://doi.org/10.1002/adma.201804116
  14. Y. Xiao, X. Zhao, X. Wang, D. Su, S. Bai et al., A nanosheet array of Cu2Se intercalation compound with expanded interlayer space for sodium ion storage. Adv. Energy Mater. 10(25), 2000666 (2020). https://doi.org/10.1002/aenm.202000666
  15. Y. Xiao, D. Su, X. Wang, S. Wu, L. Zhou et al., CuS microspheres with tunable interlayer space and micropore as a high-rate and long-life anode for sodium-ion batteries. Adv. Energy Mater. 8(22), 1800930 (2018). https://doi.org/10.1002/aenm.201800930
  16. D. Saurel, B. Orayech, B. Xiao, D. Carriazo, X. Li et al., From charge storage mechanism to performance: a roadmap toward high specific energy sodium-ion batteries through carbon anode optimization. Adv. Energy Mater. 8(17), 1703268 (2018). https://doi.org/10.1002/aenm.201703268
  17. D.A. Stevens, J.R. Dahn, High capacity anode materials for rechargeable sodium-ion batteries. J. Electrochem. Soc. 147(4), 1271–1273 (2000). https://doi.org/10.1149/1.1393348
  18. D.A. Stevens, J.R. Dahn, The mechanisms of lithium and sodium insertion in carbon materials. J. Electrochem. Soc. 148(8), A803–A811 (2001). https://doi.org/10.1149/1.1379565
  19. D.A. Stevens, J.R. Dahn, An in situ small-angle X-ray scattering study of sodium insertion into a nanoporous carbon anode material within an operating electrochemical cell. J. Electrochem. Soc. 147(12), 4428–4431 (2000). https://doi.org/10.1149/1.1394081
  20. S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki et al., Electrochemical Na insertion and solid electrolyte interphase for hard-carbon electrodes and application to Na-ion batteries. Adv. Funct. Mater. 21(20), 3859–3867 (2011). https://doi.org/10.1002/adfm.201100854
  21. K. Gotoh, T. Ishikawa, S. Shimadzu, N. Yabuuchi, S. Komaba et al., NMR study for electrochemically inserted Na in hard carbon electrode of sodium ion battery. J. Power Sources 225, 137–140 (2013). https://doi.org/10.1016/j.jpowsour.2012.10.025
  22. J.M. Stratford, P.K. Allan, O. Pecher, P.A. Chater, C.P. Grey, Mechanistic insights into sodium storage in hard carbon anodes using local structure probes. Chem. Commun. 52(84), 12430–12433 (2016). https://doi.org/10.1039/C6CC06990H
  23. Y. Cao, L. Xiao, M.L. Sushko, W. Wang, B. Schwenzer et al., Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Lett. 12(7), 3783–3787 (2012). https://doi.org/10.1021/nl3016957
  24. S. Qiu, L. Xiao, M.L. Sushko, K.S. Han, Y. Shao et al., Manipulating adsorption-insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage. Adv. Energy Mater. 7(17), 1700403 (2017). https://doi.org/10.1002/aenm.201700403
  25. J. Ding, H. Wang, Z. Li, A. Kohandehghan, K. Cui et al., Carbon nanosheet frameworks derived from peat moss as high performance sodium ion battery anodes. ACS Nano 7(12), 11004–11015 (2013). https://doi.org/10.1021/nn404640c
  26. E.M. Lotfabad, J. Ding, K. Cui, A. Kohandehghan, W.P. Kalisvaart et al., High-density sodium and lithium ion battery anodes from banana peels. ACS Nano 8(7), 7115–7129 (2014). https://doi.org/10.1021/nn502045y
  27. S. Alvin, H.S. Cahyadi, J. Hwang, W. Chang, S.K. Kwak et al., Revealing the intercalation mechanisms of lithium, sodium, and potassium in hard carbon. Adv. Energy Mater. 10(20), 2000283 (2020). https://doi.org/10.1002/aenm.202000283
  28. C. Bommier, T.W. Surta, M. Dolgos, X. Ji, New mechanistic insights on Na-ion storage in nongraphitizable carbon. Nano Lett. 15(9), 5888–5892 (2015). https://doi.org/10.1021/acs.nanolett.5b01969
  29. Z. Li, L. Ma, T.W. Surta, C. Bommier, Z. Jian et al., High capacity of hard carbon anode in Na-ion batteries unlocked by pox doping. ACS Energy Lett. 1(2), 395–401 (2016). https://doi.org/10.1021/acsenergylett.6b00172
  30. Z. Li, C. Bommier, Z.S. Chong, Z. Jian, T.W. Surta et al., Mechanism of Na-ion storage in hard carbon anodes revealed by heteroatom doping. Adv. Energy Mater. 7(18), 1602894 (2017). https://doi.org/10.1002/aenm.201602894
  31. B. Zhang, C.M. Ghimbeu, C. Laberty, C. Vix-Guterl, J.-M. Tarascon, Correlation between microstructure and Na storage behavior in hard carbon. Adv. Energy Mater. 6(1), 1501588 (2016). https://doi.org/10.1002/aenm.201501588
  32. Q. Meng, Y. Lu, F. Ding, Q. Zhang, L. Chen et al., Tuning the closed pore structure of hard carbons with the highest Na storage capacity. ACS Energy Lett. 4(11), 2608–2612 (2019). https://doi.org/10.1021/acsenergylett.9b01900
  33. Y. Li, Y. Lu, Q. Meng, A.C.S. Jensen, Q. Zhang et al., Regulating pore structure of hierarchical porous waste cork-derived hard carbon anode for enhanced Na storage performance. Adv. Energy Mater. 9(48), 1902852 (2019). https://doi.org/10.1002/aenm.201902852
  34. Y. Lu, C. Zhao, X. Qi, Y. Qi, H. Li et al., Pre-oxidation-tuned microstructures of carbon anodes derived from pitch for enhancing Na storage performance. Adv. Energy Mater. 8(27), 1800108 (2018). https://doi.org/10.1002/aenm.201800108
  35. C. Zhao, Q. Wang, Y. Lu, B. Li, L. Chen et al., High-temperature treatment induced carbon anode with ultrahigh Na storage capacity at low-voltage plateau. Sci. Bulletin 63(17), 1125–1129 (2018). https://doi.org/10.1016/j.scib.2018.07.018
  36. Y. Li, Y.-S. Hu, H. Li, L. Chen, X. Huang, A superior low-cost amorphous carbon anode made from pitch and lignin for sodium-ion batteries. J. Mater. Chem. A 4(1), 96–104 (2016). https://doi.org/10.1039/C5TA08601A
  37. Y. Li, L. Mu, Y.-S. Hu, H. Li, L. Chen et al., Pitch-derived amorphous carbon as high performance anode for sodium-ion batteries. Energy Storage Mater. 2, 139–145 (2016). https://doi.org/10.1016/j.ensm.2015.10.003
  38. J. Choi, M.E. Lee, S. Lee, H.-J. Jin, Y.S. Yun, Pyroprotein-derived hard carbon fibers exhibiting exceptionally high plateau capacities for sodium ion batteries. ACS Appl. Energy Mater. 2(2), 1185–1191 (2019). https://doi.org/10.1021/acsaem.8b01734
  39. Z. Bi, Q. Kong, Y. Cao, G. Sun, F. Su et al., Biomass-derived porous carbon materials with different dimensions for supercapacitor electrodes: a review. J. Mater. Chem. A 7(27), 16028–16045 (2019). https://doi.org/10.1039/C9TA04436A
  40. J. Yang, S. Xiao, X. Cui, W. Dai, X. Lian et al., Inorganic-anion-modulated synthesis of 2D nonlayered aluminum-based metal-organic frameworks as carbon precursor for capacitive sodium ion storage. Energy Storage Mater. 26, 391–399 (2020). https://doi.org/10.1016/j.ensm.2019.11.010
  41. B. Yang, J. Chen, S. Lei, R. Guo, H. Li et al., Spontaneous growth of 3D framework carbon from sodium citrate for high energy- and power-density and long-life sodium-ion hybrid capacitors. Adv. Energy Mater. 8(10), 1702409 (2018). https://doi.org/10.1002/aenm.201702409
  42. Z. Ju, P. Li, G. Ma, Z. Xing, Q. Zhuang et al., Few layer nitrogen-doped graphene with highly reversible potassium storage. Energy Storage Mater. 11, 38–46 (2018). https://doi.org/10.1016/j.ensm.2017.09.009
  43. Z. Ju, S. Zhang, Z. Xing, Q. Zhuang, Y. Qiang et al., Direct synthesis of few-layer F-doped graphene foam and its lithium/potassium storage properties. ACS Appl. Mater. Interfaces 8(32), 20682–20690 (2016). https://doi.org/10.1021/acsami.6b04763
  44. Z. Hong, Y. Zhen, Y. Ruan, M. Kang, K. Zhou et al., Rational design and general synthesis of S-doped hard carbon with tunable doping sites toward excellent Na-ion storage performance. Adv. Mater. 30(29), e1802035 (2018). https://doi.org/10.1002/adma.201802035
  45. Y. Lu, J. Liang, Y. Hu, Y. Liu, K. Chen et al., Accurate control multiple active sites of carbonaceous anode for high performance sodium storage: insights into capacitive contribution mechanism. Adv. Energy Mater. 10(7), 1903312 (2020). https://doi.org/10.1002/aenm.201903312
  46. C. Bommier, X. Ji, P.A. Greaney, Electrochemical properties and theoretical capacity for sodium storage in hard carbon: insights from first principles calculations. Chem. Mater. 31(3), 658–677 (2018). https://doi.org/10.1021/acs.chemmater.8b01390
  47. M.D. Levi, N. Levy, S. Sigalov, G. Salitra, D. Aurbach et al., Electrochemical quartz crystal microbalance (eqcm) studies of ions and solvents insertion into highly porous activated carbons. J. Am. Chem. Soc. 132(38), 13220–13222 (2010). https://doi.org/10.1021/ja104391g
  48. J.M. Griffin, A.C. Forse, W.Y. Tsai, P.L. Taberna, P. Simon et al., In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors. Nat. Mater. 14(8), 812–819 (2015). https://doi.org/10.1038/nmat4318
  49. S.-W. Zhang, W. Lv, C. Luo, C.-H. You, J. Zhang et al., Commercial carbon molecular sieves as a high performance anode for sodium-ion batteries. Energy Storage Mater. 3, 18–23 (2016). https://doi.org/10.1016/j.ensm.2015.12.004
  50. A. Karatrantos, Q. Cai, Effects of pore size and surface charge on Na ion storage in carbon nanopores. Phys. Chem. Chem. Phys. 18(44), 30761–30769 (2016). https://doi.org/10.1039/C6CP04611H
  51. X. Zhang, S. Yang, X. Shan, S. Li, S. Tang, Insights into the effect of the interlayer spacings of bilayer graphene on the desolvation of H(+), Li(+), Na(+), and K(+) ions with water as a solvent: a first-principles study. Phys. Chem. Chem. Phys. 21(42), 23697–23704 (2019). https://doi.org/10.1039/C9CP02922B
  52. J. Chmiola, C. Largeot, P.-L. Taberna, P. Simon, Y. Gogotsi, Desolvation of ions in sub-nanometer pores and its effect on capacitance and double-layer theory. Angew. Chem. Int. Ed. 120(18), 3440–3443 (2008). https://doi.org/10.1002/anie.200704894
  53. H. Zhang, G. Cao, Y. Yang, Z. Gu, Capacitive performance of an ultralong aligned carbon nanotube electrode in an ionic liquid at 60°C. Carbon 46(1), 30–34 (2008). https://doi.org/10.1016/j.carbon.2007.10.023
  54. H. Huang, S. Chen, X. Gao, W. Chen, A.T.S. Wee, Structural and electronic properties of PTCDA thin films on epitaxial graphene. ACS Nano 3(11), 3431–3436 (2009). https://doi.org/10.1021/nn9008615
  55. K.J. Chen, D.G. Madden, T. Pham, K.A. Forrest, A. Kumar et al., Tuning pore size in square-lattice coordination networks for size-selective sieving of CO2. Angew. Chem. Int. Ed. 55(35), 10268–10272 (2016). https://doi.org/10.1002/anie.201603934
  56. N. Sun, Z. Guan, Y. Liu, Y. Cao, Q. Zhu et al., Extended “adsorption–insertion” model: a new insight into the sodium storage mechanism of hard carbons. Adv. Energy Mater. 9(32), 1901351 (2019). https://doi.org/10.1002/aenm.201901351
  57. Y. Liu, J.S. Xue, T. Zheng, J.R. Dahn, Mechanism of lithium insertion in hard carbons prepared by pyrolysis of epoxy resins. Carbon 34(2), 193–200 (1996). https://doi.org/10.1016/0008-6223(96)00177-7
  58. Z. Jian, C. Bommier, L. Luo, Z. Li, W. Wang et al., Insights on the mechanism of Na-ion storage in soft carbon anode. Chem. Mater. 29(5), 2314–2320 (2017). https://doi.org/10.1021/acs.chemmater.6b05474
  59. J. Yang, Z. Ju, Y. Jiang, Z. Xing, B. Xi et al., Enhanced capacity and rate capability of nitrogen/oxygen dual-doped hard carbon in capacitive potassium-ion storage. Adv. Mater. 30(4), 1700104 (2018). https://doi.org/10.1002/adma.201700104
  60. K. Fang, D. Liu, X. Xiang, X. Zhu, H. Tang et al., Air-stable red phosphorus anode for potassium/sodium-ion batteries enabled through dual-protection design. Nano Energy 69, 104451 (2020). https://doi.org/10.1016/j.nanoen.2020.104451
  61. C. Matei Ghimbeu, J. Górka, V. Simone, L. Simonin, S. Martinet et al., Insights on the Na+ ion storage mechanism in hard carbon: discrimination between the porosity, surface functional groups and defects. Nano Energy 44, 327–335 (2018). https://doi.org/10.1016/j.nanoen.2017.12.013
  62. W. Luo, C. Bommier, Z. Jian, X. Li, R. Carter et al., Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent. ACS Appl. Mater. Interfaces 7(4), 2626–2631 (2015). https://doi.org/10.1021/am507679x
  63. B. Cao, Q. Zhang, H. Liu, B. Xu, S. Zhang et al., Graphitic carbon nanocage as a stable and high power anode for potassium-ion batteries. Adv. Energy Mater. 8(25), 1801149 (2018). https://doi.org/10.1002/aenm.201801149
  64. C. Yang, F. Lv, K. Dong, F. Lai, K. Zhao et al., Metallic graphene-like VSe2 ultrathin nanosheets: superior potassium-ion storage and their working mechanism. Adv. Mater. 30(27), 1800036 (2018). https://doi.org/10.1002/adma.201800036
  65. C. Yang, J. Feng, F. Lv, J. Zhou, C. Lin et al., Carbon-coated ultrathin metallic V5Se8 nanosheet for high-energy-density and robust potassium storage. Energy Storage Mater. 35, 1–11 (2021). https://doi.org/10.1016/j.ensm.2020.11.005
  66. X. Yao, Y. Ke, W. Ren, X. Wang, F. Xiong et al., Defect-rich soft carbon porous nanosheets for fast and high-capacity sodium-ion storage. Adv. Energy Mater. 9(6), 1803260 (2018). https://doi.org/10.1002/aenm.201803260
  67. R. Alcántara, P. Lavela, G.F. Ortiz, J.L. Tirado, Carbon microspheres obtained from resorcinol-formaldehyde as high-capacity electrodes for sodium-ion batteries. Electrochem. Solid-State Lett. 8(4), A222–A225 (2005). https://doi.org/10.1149/1.1870612
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 16534 Download : 12518

Most read articles by the same author(s)