1. School of Materials Science and Engineering, Shandong University of Technology, Zibo 255000, China 2. Shandong Guiyuan Advanced Ceramic Company Limited, Zibo 255086, China 3. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
Tricobalt tetroxide (Co3O4) is one of the promising anodes for lithium-ion batteries (LIBs) due to its high theoretical capacity. However, the poor electrical conductivity and the rapid capacity decay hamper its practical application. In this work, we design and fabricate a hierarchical Co3O4 nanorods/N-doped graphene (Co3O4/NG) material by a facile hydrothermal method. The nitrogen-doped graphene layers could buffer the volume change of Co3O4 nanorods during the delithium/lithium process, increase the electrical conductivity, and profit the diffusion of ions. As an anode, the Co3O4/NG material reveals high specific capacities of 1873.8 mA·h·g−1 after 120 cycles at 0.1 A·g−1 as well as 1299.5 mA·h·g−1 after 400 cycles at 0.5 A·g−1. Such superior electrochemical performances indicate that this work may provide an effective method for the design and synthesis of other metal oxide/N-doped graphene electrode materials.
Z Wang, L Chen, J Feng, et al.. In-situ grown SnO2 nanospheres on reduced GO nanosheets as advanced anodes for lithium-ion batteries. ChemistryOpen, 2019, 8(6): 712–718 https://doi.org/10.1002/open.201900120
pmid: 31275792
2
M Liu, X Deng, Y Ma, et al.. Well-designed hierarchical Co3O4 architecture as a long-life and ultrahigh rate capacity anode for advanced lithium-ion batteries. Advanced Materials Interfaces, 2017, 4(19): 1700553 https://doi.org/10.1002/admi.201700553
3
F Chen, Z Chen, Z Dai, et al.. Self-templating synthesis of carbon-encapsulated SnO2 hollow spheres: A promising anode material for lithium-ion batteries. Journal of Alloys and Compounds, 2020, 816: 152495 https://doi.org/10.1016/j.jallcom.2019.152495
4
Z Chen, S Wang, Z Zhang, et al.. Facile synthesis of Co3O4/Co@N-doped carbon nanotubes as anode with improved cycling stability for Li-ion batteries. Electrochimica Acta, 2018, 292: 575–585 https://doi.org/10.1016/j.electacta.2018.09.189
5
C Liang, D Cheng, S Ding, et al.. The structure dependent electrochemical performance of porous Co3O4 nanoplates as anode materials for lithium-ion batteries. Journal of Power Sources, 2014, 251: 351–356 https://doi.org/10.1016/j.jpowsour.2013.11.105
6
H Li, Z Li, X Wu, et al.. Shale-like Co3O4 for high performance lithium/sodium ion batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(21): 8242–8248 https://doi.org/10.1039/C6TA02417C
7
Z Zhang, Y Fu, X Yang, et al.. Hierarchical MoSe2 nanosheets/reduced graphene oxide composites as anodes for lithium-ion and sodium-ion batteries with enhanced electrochemical performance. ChemNanoMat, 2015, 1(6): 409–414 https://doi.org/10.1002/cnma.201500097
8
Y Wang, X Zhang, G Wen. Dual carbon protected SnO2 with superior lithium storage performance. Applied Surface Science, 2020, 531: 147331 https://doi.org/10.1016/j.apsusc.2020.147331
9
C Geng, J Yu, F Shi. Few-layers of graphene modified TiO2/graphene composites with excellent electrochemical properties for lithium-ion battery. Ionics, 2019, 25(7): 3059–3068 https://doi.org/10.1007/s11581-019-02894-w
10
Y Zhang, K Zhang, S Ren, et al.. 3D nanoflower-like composite anode of α-Fe2O3/coal-based graphene for lithium-ion batteries. Journal of Alloys and Compounds, 2019, 792: 828–834 https://doi.org/10.1016/j.jallcom.2019.04.011
11
W Qiu, H Xiao, Y Li, et al.. Nitrogen and phosphorus codoped vertical graphene/carbon cloth as a binder-free anode for flexible advanced potassium ion full batteries. Small, 2019, 15(23): 1901285 https://doi.org/10.1002/smll.201901285
pmid: 31034142
12
Y Hong, W Mao, Q Hu, et al.. Nitrogen-doped carbon coated SnO2 nanoparticles embedded in a hierarchical porous carbon framework for high-performance lithium-ion battery anodes. Journal of Power Sources, 2019, 428: 44–52 https://doi.org/10.1016/j.jpowsour.2019.04.093
13
A T E Vilian, B Dinesh, M Rethinasabapathy, et al.. Hexagonal Co3O4 anchored reduced graphene oxide sheets for high-performance supercapacitors and non-enzymatic glucose sensing. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(29): 14367–14379 https://doi.org/10.1039/C8TA04941F
14
H Ying, S Zhang, Z Meng, et al.. Ultrasmall Sn nanodots embedded inside N-doped carbon microcages as high-performance lithium and sodium ion battery anodes. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(18): 8334–8342 https://doi.org/10.1039/C7TA01480E
15
D H Youn, N A Patterson, H Park, et al.. Facile synthesis of Ge/N-doped carbon spheres with varying nitrogen content for lithium ion battery anodes. ACS Applied Materials & Interfaces, 2016, 8(41): 27788–27794 https://doi.org/10.1021/acsami.6b09857
pmid: 27709881
16
W Ni, J Cheng, L Shi, et al.. Integration of Sn/C yolk–shell nanostructures into free-standing conductive networks as hierarchical composite 3D electrodes and the Li-ion insertion/extraction properties in a gel-type lithium-ion battery thereof. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(45): 19122–19130 https://doi.org/10.1039/C4TA04554H
17
S Huang, M Wang, P Jia, et al.. N-graphene motivated SnO2@SnS2 heterostructure quantum dots for high performance lithium/sodium storage. Energy Storage Materials, 2019, 20: 225–233 https://doi.org/10.1016/j.ensm.2018.11.024
18
H Zeng, B Xing, L Chen, et al.. Nitrogen-doped porous Co3O4/graphene nanocomposite for advanced lithium-ion batteries. Nanomaterials, 2019, 9(9): 1253 https://doi.org/10.3390/nano9091253
pmid: 31484387
19
J Zhang, F Li, W Chen, et al.. Facile synthesis of hollow Co3O4-embedded carbon/reduced graphene oxides nanocomposites for use as efficient electrocatalysts in oxygen evolution reaction. Electrochimica Acta, 2019, 300: 123–130 https://doi.org/10.1016/j.electacta.2019.01.100
20
Y Zhao, C Liu, R Yi, et al.. Facile preparation of Co3O4 nanoparticles incorporating with highly conductive MXene nanosheets as high-performance anodes for lithium-ion batteries. Electrochimica Acta, 2020, 345: 136203 https://doi.org/10.1016/j.electacta.2020.136203
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X Zhao, H Xu, Z Hui, et al.. Electrostatically assembling 2D nanosheets of MXene and MOF-derivatives into 3D hollow frameworks for enhanced lithium storage. Small, 2019, 15(47): 1904255 https://doi.org/10.1002/smll.201904255
pmid: 31588685
22
K Feng, H W Park, X Wang, et al.. High performance porous anode based on template-free synthesis of Co3O4 nanowires for lithium-ion batteries. Electrochimica Acta, 2014, 139: 145–151 https://doi.org/10.1016/j.electacta.2014.07.005
23
C Yan, G Chen, X Zhou, et al.. Template-based engineering of carbon-doped Co3O4 hollow nanofibers as anode materials for lithium-ion batteries. Advanced Functional Materials, 2016, 26(9): 1428–1436 https://doi.org/10.1002/adfm.201504695
24
S Wang, R Wang, J Chang, et al.. Self-supporting Co3O4/graphene hybrid films as binder-free anode materials for lithium ion batteries. Scientific Reports, 2018, 8(1): 3182 https://doi.org/10.1038/s41598-018-21436-4
pmid: 29453375
25
M Jing, M Zhou, G Li, et al.. Graphene-embedded Co3O4 rose-spheres for enhanced performance in lithium ion batteries. ACS Applied Materials & Interfaces, 2017, 9(11): 9662–9668 https://doi.org/10.1021/acsami.6b16396
pmid: 28256819
26
M Wu, H Chen, L Lv, et al.. Graphene quantum dots modification of yolk–shell Co3O4@CuO microspheres for boosted lithium storage performance. Chemical Engineering Journal, 2019, 373: 985–994 https://doi.org/10.1016/j.cej.2019.05.100
27
D Wu, C Wang, H Wu, et al.. Synthesis of hollow Co3O4 nanocrystals in situ anchored on holey graphene for high rate lithium-ion batteries. Carbon, 2020, 163: 137–144 https://doi.org/10.1016/j.carbon.2020.03.007
28
Y Liu, H Wan, H Zhang, et al.. Engineering surface structure and defect chemistry of nanoscale cubic Co3O4 crystallites for enhanced lithium and sodium storage. ACS Applied Nano Materials, 2020, 3(4): 3892–3903 https://doi.org/10.1021/acsanm.0c00614
29
C Wang, F Wang, L Zhang, et al.. Multi-dimensionally hierarchical self-supported Cu@Cu2+1O@Co3O4 heterostructure enabling superior lithium-ion storage and electrocatalytic oxygen evolution. Chemical Engineering Journal, 2021, 405: 126699 https://doi.org/10.1016/j.cej.2020.126699
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Y Huang, Y Fang, X F Lu, et al.. Co3O4 hollow nanoparticles embedded in mesoporous walls of carbon nanoboxes for efficient lithium storage. Angewandte Chemie International Edition, 2020, 59(45): 19914–19918 https://doi.org/10.1002/anie.202008987
pmid: 32697016
31
B G Choi, S J Chang, Y B Lee, et al.. 3D heterostructured architectures of Co3O4 nanoparticles deposited on porous graphene surfaces for high performance of lithium ion batteries. Nanoscale, 2012, 4(19): 5924–5930 https://doi.org/10.1039/c2nr31438j
pmid: 22899185
32
H Chen, B E Jia, X Lu, et al.. Two-dimensional SnSe2/CNTs hybrid nanostructures as anode materials for high-performance lithium-ion batteries. Chemistry, 2019, 25(42): 9973–9983 https://doi.org/10.1002/chem.201901487
pmid: 31099094
33
X Chen, L Lv, W Sun, et al.. Ultrasmall MoC nanoparticles embedded in 3D frameworks of nitrogen-doped porous carbon as anode materials for efficient lithium storage with pseudocapacitance. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(28): 13705–13716 https://doi.org/10.1039/C8TA03176B
34
B H Hou, Y Y Wang, Q L Ning, et al.. Self-supporting, flexible, additive-free, and scalable hard carbon paper self-interwoven by 1D microbelts: Superb room/low-temperature sodium storage and working mechanism. Advanced Materials, 2019, 31(40): 1903125 https://doi.org/10.1002/adma.201903125
pmid: 31402540
35
J Xie, X Li, H Lai, et al.. A robust solid electrolyte interphase layer augments the ion storage capacity of bimetallic-sulfide-containing potassium-ion batteries. Angewandte Chemie International Edition, 2019, 58(41): 14740–14747 https://doi.org/10.1002/anie.201908542
pmid: 31496040
36
J B Cook, H-S Kim, T C Lin, et al.. Pseudocapacitive charge storage in thick composite MoS2 nanocrystal-based electrodes. Advanced Energy Materials, 2017, 7(2): 1601283 https://doi.org/10.1002/aenm.201601283
