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SCIENCE CHINA Chemistry
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SCIENCE CHINA Chemistry, Volume 61 , Issue 5 : 515-525(2018) https://doi.org/10.1007/s11426-018-9244-0

Recent progress on Ge oxide anode materials for lithium-ion batteries

Wei Wei 1,2, Jianlong Xu 1, Maotian Xu 1,*, Shiying Zhang 1, Lin Guo 2,*
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  • ReceivedFeb 8, 2018
  • AcceptedMar 9, 2018
  • PublishedMar 23, 2018
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Abstract


Funded by

the National Science Foundation of China(51502009,51532001)

the National Key Basic Research Program of China(2014CB31802)

and the Science Foundation of Henan province(162300410209)


Acknowledgment

This work was supported by the National Science Foundation of China (51502009, 51532001, 21675109), the National Key Basic Research Program of China (2014CB31802), and the Science Foundation of Henan province (162300410209).


Interest statement

The authors declare that they have no conflict of interest.


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    Figure 1

    Scanning electron microscopy (SEM) images of GeO2 nanocubes (a) and GeO2 nanospindles (b); (c) cycling stabilities of GeO2 anodes at 0.1 C; (d) np-GeO2 electrode cycled at various current densities [25] (color online).

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    Figure 2

    SEM images of GeO2 nanorods at low (a) and high (b) magnifications. (c) Cycling performances of GeO2 nanorod electrodes at a current density of 0.2 A g−1. (d) Rate performance of GeO2 nanorods (inset shows the discharge curves of the GeO2 electrode at different current rates from 0.2 to 5 A g−1) [26] (color online).

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    Figure 3

    SEM (a) and transmission electron microscopy (TEM) (b) images of GeO2 IOs. (c) Rate capability test for a GeO2 IOs over 100 cycles at specific currents from 250 to 1000 mA g−1 [27] (color online).

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    Figure 4

    High-resolution TEM images of ∼2-nm (a), ∼6-nm (b), ∼10-nm (c), and ∼35-nm (d) GeO2 nanoparticles. Cycle performances of the ∼2, ∼6, ∼10, and ∼35-nm GeO2 nanoparticles at rates of 0.2 C (e) and 1 C (f) [29] (color online).

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    Figure 5

    SEM images of the GeO2 samples prepared without (a) and with (b) a surfactant. (c) Reversible capacities and coulombic efficiencies of GeO2 nanoparticle electrodes cycled at a current density of 220 mA g−1(0.2 C) in different electrolytes [28].

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    Figure 6

    SEM images of the GeO2/grapheme nanocomposites at low (a) and high (b) magnifications. (c) Cycling performance of GeO2/grapheme nanocomposites and commercial GeO2 particles at a current density of 200 mA g−1. (d) High rate performance of GeO2/grapheme nanocomposites [11] (color online).

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    Figure 7

    SEM images of the multilayer graphene/GeO2 tubular structures: (a) top view, scale bar=20 μm; (b) magnified SEM image of a single rolled-up graphene/GeO2 microtube, scale bar=2 μm. Cycling performance of graphene/GeO2: (c) for 100 cycles at 0.1 C; (d) for 700 cycles at 1 C [30] (color online).

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    Figure 8

    Schematic for the formation of GeO2/C from a germanium citrate complex [32] (color online).

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    Figure 9

    Low- (a) and high-magnification (b) TEM images of the GeO2/MC composite. (c) Cycling performance of the GeO2/MC composite at a constant rate of 1 C (1500 mA g−1). (d) High rate performance of the GeO2/MC composite [64] (color online).

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    Figure 10

    (a) Low-magnification SEM image of GeOx, (b) enlarged SEM image corresponding to the area enclosed by the square in (a). (c) TEM image corresponding to the area enclosed by the square in (b). (d) Reversible capacities of GeOx in the half cell. (e) Reversible discharge capacity of Li(NiCoMn)1/3O2 in the full cell (anode material: GeOx) [33] (color online).

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    Figure 11

    (a) Synthetic illustration of GeOx/RGO nanocomposites. (b) Typical charge/discharge curves (second cycle at each rate) of GeOx/RGO at various C rates (1 C=1000 mA g−1). (c) Rate capability and cycling performance of GeOx/RGO and GeOx at various C rates [75] (color online).

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    Figure 12

    (a) SEM image of VAG@GeOx; (b1) TEM image of a separate VAG@GeOx nanoflake, and the corresponding (b2) C, (b3) O, and (b4) Ge elemental mappings. (c) Cycling performance of the electrodes with different loads, 70 wt% and 61 wt%, both tested at a rate of C/3. (d) Rate performance of the electrode (70 wt% GeOx) at rates of 0.5, 1, 3, 6, and 15 C [35] (color online).

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    Figure 13

    (a) Synthesis process for the Zn2GeO4/g-C3N4 hybrids. Low- (b) and high-magnification (c) SEM images of Zn2GeO4/g-C3N4. (d) Cycling performance of bare g-C3N4, pure Zn2GeO4 nanoparticles, and Zn2GeO4/g-C3N4 at 200 mA g−1. (e) Rate performance of Zn2GeO4/g-C3N4 and pure Zn2GeO4 (Zn2GeO4/g-C3N4–10 and Zn2GeO4/g-C3N4–10 represent weight ratios of g-C3N4 of 10% and 30%, respectively) [85] (color online).

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    Figure 14

    SEM (a) and TEM images (b) of an amorphous Zn2GeO4 sample. (c) Charge-discharge profiles of an amorphous Zn2GeO4 sample at various cycles with a current density of 400 mA g−1. (d) Rate performance of the Zn2GeO4 sample [40] (color online).

  • Table 1   Reported capacities for Ge oxides

    Ge oxides

    Specific capacity (mA h g−1)

    Ref.

    GeO2 nanospindles

    1340 (50th cycle)

    [25]

    GeO2 nanorods

    917 (1st cycle)

    [26]

    Macroporous GeO2

    632 (500th cycle)

    [27]

    GeO2 nanoparticles

    600 (500th cycle)

    [28]

    GeO2 nanoparticles

    816 (100th cycle)

    [29]

    GeO2/graphene

    1110.6 (1st cycle)

    [11]

    Graphene/GeO2 tubular

    919 (100th cycle)

    [30]

    GeO2/graphene

    1021 (1st cycle)

    [31]

    GeO2/C

    914 (1st cycle)

    [32]

    GeOx nanoparticles

    1250 (600th cycle)

    [33]

    GeOx hollow framework

    1315 (1st cycle)

    [34]

    GeOx/graphene

    1008 (100th cycle)

    [35]

    CuGeO3/graphene

    780 (130th cycle)

    [36]

    Ca2Ge7O16

    601 (100th cycle)

    [37]

    Li2GeO3 clusters

    725 (1st cycle)

    [38]

    Co2GeO4 nanosheets

    1026 (150th cycle)

    [39]

    Zn2GeO4

    1250 (500th cycle)

    [40]