Freeze-drying assisted synthesis of mno/reduced graphene composite and the improved rate cyclic performance for lithium ion batteries

doi:10.19799/j.cnki.2095-4239.2020.0099

Abstract

Abstract:

Taking advantage of manganese oxide (MnO) with high specific capacity and graphene with high conductivity, the composite of MnO/rGO has been synthesized by using freeze-drying assisted hydrothermal method. The structure, morphology and electrochemical performance of MnO/rGO composite are characterized by X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical tests. MnO nanoparticles in MnO/rGO composite are homogeneously dispersed on and wrapped by rGO nanosheets which is helpful in improving the stability and conductivity of MnO during charging/discharging cycles. MnO/rGO delivers specific capacity of 870.4 mA·h/g after 100 cycles at a current density of 0.1 A/g, and it delivers 178.2 mA·h/g after 100 cycles at a current density of 15 A/g. rGO not only improves the conductivity of the composite and suppresses the volume effect of MnO during cycles. The comparison sample prepared by traditional drying assisted hydrothermal synthesis shows obvious agglomeration, lower discharge capacity and worse rate performance. Freeze drying-assisted hydrothermal synthesis method will be potential in synthesizing homogeneous composites of transitional metal oxides/rGO as high performance anode materials for lithium ion batteries.

Key words: lithium ion batteries, anode materials, manganese oxide/reduced graphene, freeze-drying, electrochemical performance

CLC Number:

TM 911

MA Tengfei, MA Chao, SUN Rui, JI Hongmei, YANG Gang. Freeze-drying assisted synthesis of mno/reduced graphene composite and the improved rate cyclic performance for lithium ion batteries[J]. Energy Storage Science and Technology, 2020, 9(4): 1044-1051.

Figures/Tables 7

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Table 1

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References 25

1	WANG J R, FAN H B, SHEN Y M, et al. Large-scale template-free synthesis of nitrogen-doped 3D carbon frame-works as low-cost ultra-long-life anodes for lithium-ion batteries[J]. Chemical Engineering Journal, 2019, 357: 376-383.
2	XIA Y, ZHEN X, DOU X, et al. Green and facile fabrication of hollow porous MnO/C microalgaes for lithium-ion batteries[J]. ACS Nano, 2013, 7(8): 7083-7092.
3	TIAN X M, ZHAO D L, MENG W J, et al. Highly porous MnO/C@rGO nanocomposite derived from Mn-BDC@rGO as high-performance anode material for lithium ion batteries[J]. Journal of Alloys and Compounds, 2019, 792: 487-495.
4	CHEN L F, MA S X, LU S, et al. Biotemplated synthesis of three-dimensional porous MnO/C-N nanocomposites from renewable rapeseed pollen: An anode material for lithium-ion batteries[J]. Nano Research, 2017, 10(1): 1-11.
5	GUO S M, LU G X, QIU S, et al. Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances[J]. Nano Energy, 2014, 9: 41-49.
6	ZHANG W M, WU X L, HU J S, et al. Carbon coated Fe₃O₄ nanospindles as a superior anode marerial for lithium-ion batteries[J]. Advanced Functional Material, 2008, 18(24): 3941-3946.
7	HONG X, LIANG J F, FAN H, et al. Facile fabrication of 3D SnO₂/nitrogen-doped graphene aerogels for superior lithium storage[J]. RSC Advances, 2015, 5(84): 68822-68828.
8	LI J, ZHANG X, GUO J Q, et al. Facile surfactant- and template-free synthesis and electrochemical properties of SnO₂/graphene composites[J]. Journal of Alloys and Compounds, 2016, 674: 44-50.
9	PEI X Y, MO D C, LYU S S, et al. Facile preparation of N-doped MnO/rGO composites as an anode material for high-performance lithium-ion batteries[J]. Applied Surface Science, 2019, 465: 470-477.
10	WU L L, ZHAO D L, CHENG X W, et al. Nanorod Mn₃O₄ anchored on graphenen nanosheet as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance[J]. Journal of Alloys and Compounds, 2017, 728: 383-390.
11	ZHONG K F, XIN X, BIN Z, et al. MnO powder as anode active materials for lithium ion batteries[J]. Journal of Power Sources, 2010, 195(10): 3300-3308.
12	SUN Y M, HU X L, LUO W, et al. Reconstruction of conformal nanoscale MnO on graphene as a high-capacity and long-life anode material for lithium ion batteries[J]. Advanced Functional Material, 2013, 23(19): 2436-2444.
13	LIU R, CHEN X H, ZHOU C L, et al. Controlled synthesis of porous 3D interconnected MnO/C composite aerogel and their excellent lithium-storage properties[J]. Electrochimica Acta, 2019, 306: 143-150.
14	ZHU C Y, SHENG N, AKIYAMA T. MnO nanoparticles embedded in a carbon matrix for a high performance Li ion battery anode[J]. RSC Advances, 2015, 5(27): 21066-21073.
15	CHEN S J, CAI D P, YANG X H, et al. Metal-organic frameworks derived nanocomposites of mixed-valent MnO_x nanoparticles in-situ grown on ultrathin carbon sheets for high-performance supercapacitors and lithium-ion batteries[J]. Electrochimica Acta, 2017, 256: 63-72.
16	PANDEY J, HUA B, NG W, et al. Devolping hierarchically porous MnO_x/NC hybrid nanorods for oxygen reduction and evolution catalysis[J]. Green Chemistry, 2017, 19(12): 2793-2797.
17	DEBNATH B, SALUNKE H G, SHIVAPRASAD S M, et al. Surfactant-mediated resistance to surface oxidation in MnO nanostructures[J]. ACS Omega, 2017, 2(6): 3028-3035.
18	WANG C C, FU J L, ZHANG Y, et al. High ratio of low valence MnO_x microhydrangeas capable of extrmely fast catalytic degradation of organcics[J]. Chemical Communications, 2018, 54(53): 7330-7333.
19	JIANG H, HU Y J, GUO S J, et al. Rational design of MnO/carbon nanopeapods with internal void space for high-rate and long-life Li-ion batteries[J]. ACS Nano, 2014, 8(6): 6038-6046.
20	WANG Y Z, WANG L X, MA Z P, et al. 3D-structure carbon-coated MnO/graphene nanocomposites with exceptional electrochemical performance for Li-ion battery anodes[J]. Journal of Solid State Electrochemistry, 2018, 22(10): 2977-2987.
21	LIU Y Y, JIANG J C, SUN K, et al. MnO-carbon-reduced graphene oxide composite with superior anode Li-ion storage performance[J]. Journal of Nanoparticle Research, 2019, 21(6): 154-163.
22	LV R T, CUI T X, JUN M S, et al. Open-ended, N-doped carbon nanotube-graphene hybrid nanostructures as high-performance catalyst support[J]. Advanced Functional Material, 2011, 21(5): 999-1006.
23	WANG X Y, ZHOU X F, YAO K, et al. A SnO₂/graphene composite as a high stability electrode for lithium ion batteries[J]. Carbon, 2011, 49(1): 133-139.
24	ZAHNG C F, PENG X, GUO Z P, et al. Carbon-coated SnO₂/graphene nanosheets as highly reversible anode materials for lithium ion batteries[J]. Carbon, 2012, 50(5): 1879-1903.
25	LIU X W, YANG Z Z, PAN F S, et al. Anchoring nitrogen-doped TiO₂ nanocrystals on nitrogen-doped 3D graphene frameworks for enhanced lithium storage[J]. Chemistry-A European Journal, 2017, 23(8): 1757-1762.

样品	R_s/Ω	R_SEI/Ω	R_ct/Ω
MG-F	2.6	47.51	3.45
MG-D	3.68	46.02	6.55

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