Abstract
The sodium storage performance of Ge-based materials suffers from poor cycling stability caused by the volume variation and collapse of the structure during cycling process. In this work, Cu3Ge coated by nitrogen-doped carbon (Cu3Ge-NC) nanorods are prepared by annealing the mixture of CuGeO3 nanowires and polyacrylonitrile which acts as nitrogen and carbon source. As anode materials for sodium ion batteries, the outside carbon shell inhibits the serious volume change caused by Na+ insertion/extraction, and the Cu3Ge alloy enhances the sodiation capacity with rapid electron transfer and fast reaction kinetics. Corresponding kinetic analysis indicates pseudocapacitive behaviors play a dominant role in the total capacity at high rates. Hence, the Cu3Ge-NC exhibits favorable rate capability and cycling stability, which delivers a reversible capacity of 160 mAh g−1 for 500 cycles at a current density of 100 mA g−1.
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References
Hao J, Zhang J, Xia G, Liu Y, Zheng Y, Zhang W, Tang Y, Pang WK, Guo Z (2018) Heterostructure manipulation via in situ localized phase transformation for high-rate and highly durable lithium ion storage. ACS Nano 12(10):10430–10438
Hu Z, Tai Z, Liu Q, Wang S-W, Jin H, Wang S, Lai W, Chen M, Li L, Chen L, Tao Z, Chou S-L (2019) Ultrathin 2D TiS2 nanosheets for high capacity and long-life sodium ion batteries. Adv Energy Mater 9(8):1803210
Gao D, Luo S, Zhang Y, Liu J, Wu H, Wang S, He P (2018) Mn3O4/carbon nanotubes nanocomposites as improved anode materials for lithium-ion batteries. J Solid State Electrochem 22(11):3409–3417
Fu L, Wang X, Ma J, Zhang C, He J, Xu H, Chai J, Li S, Chai F, Cui G (2017) Graphene-encapsulated copper tin sulfide submicron spheres as high-capacity binder-free anode for lithium-ion batteries. ChemElectroChem 4(5):1124–1129
Wang X, Fan L, Gong D, Zhu J, Zhang Q, Lu B (2016) Core-Shell Ge@graphene@TiO2 nanofibers as a high-capacity and cycle-stable anode for lithium and sodium ion battery. Adv Funct Mater 26(7):1104–1111
Komaba S, Ishikawa T, Yabuuchi N, Murata W, Ito A, Ohsawa Y (2011) Fluorinated ethylene carbonate as electrolyte additive for rechargeable Na batteries. ACS Appl Mater Inter 3(11):4165–4168
Zhao Q, Bi R, Cui J, Yang X, Zhang L (2018) TiO2–x Nanocages anchored in N-doped carbon fiber films as a flexible anode for high-energy sodium-ion batteries. ACS Appl Energy Mater 1(9):4459–4466
Yang J, Zhou X, Wu D, Zhao X, Zhou Z (2017) S-doped N-rich carbon nanosheets with expanded interlayer distance as anode materials for sodium-ion batteries. Adv Mater 29(6):1604108
Zhou H, Zhang R, Song S, Xiao C, Gao G, Ding S (2018) Dopamine-assisted synthesis of MoS2 nanosheets on carbon nanotube for improved lithium and sodium storage properties. ACS Appl Energy Mater 1(9):5112–5118
Hou H, Banks CE, Jing M, Zhang Y, Ji X (2015) Carbon quantum dots and their derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong cycle life. Adv Mater 27(47):7861–7866
Deng M, Li S, Hong W, Jiang Y, Xu W, Shuai H, Zou G, Hu Y, Hou H, Wang W, Ji X (2019) Octahedral Sb2O3 as high-performance anode for lithium and sodium storage. Mater Chem Phys 223:46–52
Zhang H, Ming H, Zhang W, Cao G, Yang Y (2017) Coupled carbonization strategy toward advanced hard carbon for high-energy sodium-ion battery. ACS Appl Mater Interfaces 9(28):23766–23774
Yin F, Liu Z, Zhao Y, Feng Y, Zhang Y (2017) Electrochemical properties of an Na4Mn9O18-reduced graphene oxide composite synthesized via spray drying for an aqueous sodium-ion battery. Nanomaterials 7(9):253
Abel PR, Fields MG, Heller A, Mullins CB (2014) Tin-germanium alloys as anode materials for sodium-ion batteries. ACS Appl Mater Interfaces 6(18):15860–15867
Wang Z, Zhang X, Yan Y, Zhang Y, Wang Y, Qin C, Bakenov Z (2019) Nanoporous GeO2/Cu/Cu2O network synthesized by dealloying method for stable Li-ion storage. Electrochim Acta 300:363–372
Kajita T, Itoh T (2016) Electrochemical sodium storage in amorphous GeOx powder. Electrochim Acta 195:192–198
Baggetto L, Keum JK, Browning JF, Veith GM (2013) Germanium as negative electrode material for sodium-ion batteries. Electrochem Commun 34:41–44
Qin W, Chen T, Hu B, Sun Z, Pan L (2015) GeO2 decorated reduced graphene oxide as anode material of sodium ion battery. Electrochim Acta 173:193–199
Han J, Qin J, Guo L, Qin K, Zhao N, Shi C, Liu E, He F, Ma L, He C (2018) Ultrasmall Fe2GeO4 nanodots anchored on interconnected carbon nanosheets as high-performance anode materials for lithium and sodium ion batteries. Appl Surf Sci 427:670–679
Lim YR, Jung CS, Im HS, Park K, Park J, Cho WI, Cha EH (2016) Zn2GeO4 and Zn2SnO4 nanowires for high-capacity lithium- and sodium-ion batteries. J Mater Chem A 4(27):10691–10699
Li W, Ke L, Wei Y, Guo S, Gan L, Li H, Zhai T, Zhou H (2017) Highly reversible sodium storage in a GeP5/C composite anode with large capacity and low voltage. J Mater Chem A 5(9):4413–4420
Liu Z, Lu T, Song T, Yu X-Y, Lou XW, Paik U (2017) Structure-designed synthesis of FeS2@C yolk–shell nanoboxes as a high-performance anode for sodium-ion batteries. Energy Environ Sci 10(7):1576–1580
Wang Y, Wang Y, Wang YX, Feng X, Chen W, Qian J, Ai X, Yang H, Cao Y (2019) In situ formation of Co9S8 nanoclusters in sulfur-doped carbon foam as a sustainable and high-rate sodium-ion anode. ACS Appl Mater Interfaces 11(21):19218–19226
Jiang Y, Zou G, Hong W, Zhang Y, Zhang Y, Shuai H, Xu W, Hou H, Ji X (2018) N-rich carbon-coated Co3S4 ultrafine nanocrystals derived from ZIF-67 as an advanced anode for sodium-ion batteries. Nanoscale 10(39):18786–18794
Zheng Z, Wu HH, Chen H, Cheng Y, Zhang Q, Xie Q, Wang L, Zhang K, Wang MS, Peng DL, Zeng XC (2018) Fabrication and understanding of Cu3Si-Si@carbon@graphene nanocomposites as high-performance anodes for lithium-ion batteries. Nanoscale 10(47):22203–22214
Zhang C, Chai F, Fu L, Hu P, Pang S, Cui G (2015) Lithium storage in a highly conductive Cu3Ge boosted Ge/graphene aerogel. J Mater Chem A 3(45):22552–22556
Dong Y, Pei L, Chu X, Zhang W, Zhang Q (2010) Electrochemical behavior of cysteine at a CuGeO3 nanowires modified glassy carbon electrode. Electrochim Acta 55(18):5135–5141
Oh SM, Hwang JY, Yoon CS, Lu J, Amine K, Belharouak I, Sun YK (2014) High electrochemical performances of microsphere C-TiO2 anode for sodium-ion battery. ACS Appl Mater Interfaces 6(14):11295–11301
Xie F, Zhang L, Su D, Jaroniec M, Qiao SZ (2017) Na2Ti3O7@N-doped carbon hollow spheres for sodium-ion batteries with excellent rate performance. Adv Mater 29(24):1700989
Li W, Feng X, Zhang Z, Jin X, Liu D, Zhang Y (2018) A controllable surface etching strategy for well-defined spiny yolk@Shell CuO@CeO2 cubes and their catalytic performance boost. Adv Funct Mater 28(49):1802559
Fu L, Zhang C, Chen B, Zhang Z, Wang X, Zhao J, He J, Du H, Cui G (2017) Graphene boosted Cu2GeS3 for advanced lithium-ion batteries. Inorg Chem Front 4(3):541–546
Chen Y, Li J, Lai Y, Yin M, Zhang Z (2018) Nanospace confined N,P co-doped carbon foams as anode for highly reversible and high capacity sodium ions batteries. J Electroanal Chem 810:207–215
Liu XY, Lin N, Xu KL, Han Y, Lu Y, Zhao YY, Zhou JB, Yi Z, Cao CH, Qian YT (2018) Cu3Ge/Ge@C nanocomposites crosslinked by the in situ formed carbon nanotubes for high-rate lithium storage. Chem Eng J 352:206–213
Fu L, Bi Z, Wei B, Huang L, Zhang X, Chen Z, Liao H, Li M, Shang C, Wang X (2018) Flower-like Cu2SnS3 nanostructure materials with high crystallinity for sodium storage. Nanomaterials 8(7):475
Liu T, Li Y, Zhao L, Zheng F, Guo Y, Li Y, Pan Q, Liu Y, Hu J, Yang C (2019) In situ fabrication of carbon-encapsulated Fe7X8 (X = S, Se) for enhanced sodium storage. ACS Appl Mater Interfaces 11(21):19040–19047
Song X, Li J, Li Z, Xiao Q, Lei G, Hu Z, Ding Y, Kheimeh Sari HM, Li X (2019) Superior sodium storage of carbon-coated NaV6O15 nanotube cathode: pseudocapacitance versus intercalation. ACS Appl Mater Interfaces 11(11):10631–10641
Fang Y, Yu XY, Lou XWD (2018) Formation of hierarchical Cu-doped CoSe2 microboxes via sequential ion exchange for high-performance sodium-ion batteries. Adv Mater 30(21):1706668
Chen W, Qi S, Yu M, Feng X, Cui S, Zhang J, Mi L (2017) Design of FeS2@rGO composite with enhanced rate and cyclic performances for sodium ion batteries. Electrochim Acta 230:1–9
Hong W, Ge P, Jiang Y, Yang L, Tian Y, Zou G, Cao X, Hou H, Ji X (2019) Yolk-Shell-structured bismuth@N-doped carbon anode for lithium-ion battery with high volumetric capacity. ACS Appl Mater Interfaces 11(11):10829–10840
Funding
The authors acknowledge the financial support from the National Natural Science Foundation of China Program (No. 51602111), the Natural Science Foundation of Guangdong Province (2018A030313739), Cultivation project of National Engineering Technology Center (2017B090903008), Xijiang R&D Team (X.W.), Guangdong Provincial Grant (2017A050506009), Special Fund Project of Science and Technology Application in Guangdong (2017B020240002) and 111 projects.
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Hu, L., Shang, C., Huang, L. et al. Cu3Ge coated by nitrogen-doped carbon nanorods as advanced sodium-ion battery anodes. Ionics 26, 719–726 (2020). https://doi.org/10.1007/s11581-019-03230-y
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DOI: https://doi.org/10.1007/s11581-019-03230-y