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SCIENCE CHINA Materials, Volume 62 , Issue 11 : 1515-1536(2019) https://doi.org/10.1007/s40843-019-9464-0

Structure design and mechanism analysis of silicon anode for lithium-ion batteries

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  • ReceivedMay 13, 2019
  • AcceptedJun 22, 2019
  • PublishedJul 30, 2019

Abstract


Funded by

National Programs for Nano-Key Project(2017YFA0206700)

the National Key R&D Program of China(2018YFB1502100)

the National Natural Science Foundation of China(21835004)

111 Project from the Ministry of Education of China(B12015)

the Fundamental Research Funds for the Central Universities

Nankai University(63191711,63191416)


Acknowledgment

This work was supported by the National Programs for Nano-Key Project (2017YFA0206700), the National Key R&D Program of China (2018YFB1502100), the National Natural Science Foundation of China (21835004), 111 Project from the Ministry of Education of China (B12015) and the Fundamental Research Funds for the Central Universities, Nankai University (63191711 and 63191416).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Yan Z, Cheng F and Chen J proposed the topic and outline of the manuscript. Chen X, Li H, and Yan Z collected the related information and wrote the manuscript. All authors contributed to the general discussion and revision.


Author information

Xiang Chen is a PhD candidate at the College of Chemistry, Nankai University. He received his Bachelor degree (2011) and Master degree (2014) from Haerbin Normal University. He moved to Nankai University in 2016. His research focuses on lithium and zinc based batteries.


Zhenhua Yan is a lecturer at the College of Chemistry, Nankai University. He received his Bachelor degree (2011) and Master degree (2014) from Liaocheng University. He obtained his PhD degree from Nankai University in 2018, under the supervision of Prof. Fangyi Cheng and Prof. Jun Chen. His current research interest is nanomaterials for batteries and electrocatalysis.


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  • Figure 1

    Overview of silicon-based anode for LIBs: fundamental challenges, recent structure design strategies toward commercialization, and failure mechanism analysis technologies.

  • Figure 2

    Statistical analysis of the publications on silicon anode in last three decades. The data was up to May 1, 2019.

  • Figure 3

    The crystal structures of silicon (a), lithium (b) and Li22Si5 (c). Redraw phase diagram of Li–Si system (d). Reprinted with permission from Ref. [24], Copyright 2015, Elsevier. Electrode reactions and theoretical capacity of different alloy products (e).

  • Figure 4

    Timeline of selected important breakthroughs in the silicon-based anode.

  • Figure 5

    Schematic illustration of the synthesis process of different nanostructured silicons for LIBs: (a) 0D nanoparticles. Reproduced with permission from Ref. [70]. Copyright 2015, the Royal Society of Chemistry. (b) 1D nanowires. Reprinted with permission from Ref. [72]. Copyright 2017, Springer-Verlag GmbH Germany. (c) 2D nanosheets. Reprinted with permission from Ref. [75]. Copyright 2018, Wiley-VCH Verlag GmbH & Co. (d) 3D hierarchical structures. Reprinted with permission from Ref. [76]. Copyright 2016, American Chemical Society. (e) Porous structure. Reprinted with permission from Ref. [77]. Copyright 2018, Elsevier Ltd. (f) Hollow structures. Reprinted with permission from Ref. [78]. Copyright 2015, Nature Publishing Group.

  • Figure 6

    Schematic illustration of the synthesis process of Si-C composites and the corresponding morphologies or microstructures for LIBs: (a) Core-shell Si@N-C. Reproduced with permission from Ref. [80]. Copyright 2017, American Chemical Society. (b) Yolk-shell p-SiNPs@HC. Reproduced with permission from Ref. [82]. Copyright 2017, American Chemical Society. (c) SiNPs@double carbon shells. Reproduced with permission from Ref. [83]. Copyright 2017 Wiley-VCH Verlag GmbH & Co. (d) Ant-nest-like porous Si-C. Reprinted with permission from Ref. [84]. Copyright 2019, Nature Publishing Group. (e) 3D graphene-Si network. Reproduced with permission from Ref. [85]. Copyright 2015 WILEY-VCH Verlag GmbH & Co.

  • Figure 7

    Si-metal composites. (a) Schematic illustration of the synthesis process of Cu-Si alloy structures, scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS) mapping of CuO/amorphous-Si core-shell structure and the long term cycling performance at 20 A g−1. Repinted with permission from Ref. [86]. Copyright 2015, WILEY-VCH Verlag GmbH & Co. (b) Schematic illustration and SEM of the 3D-NP SiGe structure evolution via chemical dealloying, Cycle performance of the 3D-NP SiGe anodes and Si20 anode at 100 mA g−1 and rate capability of the Si12Ge8 anode at different current densities from 1 to 8 A g−1. Reprinted with permission from Ref. [87]. Copyright 2018, American Chemical Society. (c) Schematic showing of Cu/Si/Ge array grown on a Ni foam substrate, STEM image of a Cu/Si/Ge nanowire with corresponding EDS spectra and capacity performance at a low rate of 0.2 C. Repinted with permission from Ref. [88]. Copyright 2018, the Royal Society of Chemistry.

  • Figure 8

    Metal oxides coating on silicon. (a) Schematic illustration for the fabrication process of the unique core-shell nanostructure of the Si@TiO2 composite. TEM and high resolution TEM (HRTEM) images of the Si@TiO2 composite. Cycling performance of the Si@TiO2 composite and contrast samples at 0.1 C. Reproduced with permission from Ref. [89]. Copyright 2014, American Chemical Society. (b) Schematic of fabrication process of the amorphous-TiO2-coated Si core-shell nanoparticles, STEM image and the corresponding EDS mapping images, schematic and TEM images of structural evolution of the amorphous-TiO2-coated commercial Si nanoparticle electrode during electrochemical cycling, and cycling performance of the Si, Si@a-TiO2, and Si@crystal-TiO2 (c-TiO2) nanoparticle electrodes. Reprinted with permission from Ref. [90]. Copyright 2017, WILEY-VCH Verlag GmbH & Co. (c) Schematic of the fabrication process for LixSi−Li2O/TiyOz core-shell NPs, TEM images of the resultant LixSi−Li2O/TiyOz NPs and cycling performances of LixSi−Li2O/TiyOz core-shell NPs and bare LixSi NPs. Reprinted with permission from Ref. [91]. Copyright 2018, American Chemical Society.

  • Figure 9

    (a) Schematic illustration of the 3D porous PANi-Si electrodes, TEM of the SiNPs coated with PANi polymer layer and cycling performance of the PANi-Si composite electrode and contrast materials at current of 1.0 A g−1. Reproduced with permission from Ref. [92]. Copyright 2013, Nature Publishing Group. (b) Schematic of the fabrication process of PPy@PHSi nanocomposite, TEM and cycling performance of the PHSi and PPy@PHSi nanocomposite at a variety of current densities. Reprinted with permission from Ref. [93]. Copyright 2014, WILEY-VCH Verlag GmbH & Co. (c) Graphical showing of the operation mechanism of PR-PAA during repeated volume changes of SiMPs, together with chemical structures of polyrotaxane and PAA and the corresponding electrochemical performance. Reproduced with permission from Ref. [95]. Copyright 2017, AAAS.

  • Figure 10

    (a) AFM image of the as-fabricated array with a diameter of 1000, 500, 300, 200 and 100 nm pillars and in situ 3D AFM images during lithiation and delithiation of a-Si nanopillars at several electrochemical potentials in the first cycle. Reproduced with permission from Ref. [117]. Copyright 2013, American Chemical Society. (b) Images of height and modulus of the Si nanowire anode after being scraped. The line profiles of the topography (black) and modulus (blue) along the Si nanowire (marked with a dashed red line) and along the horizontal cross section (marked with a dashed yellow line). Reproduced with permission from Ref. [118]. Copyright 2014, American Chemical Society. (c) Schematic showing the structure evolution of patterned Si island during cycling and the resulting impact of volume changes on SEI formation and failure, in-situ AFM images showing opening and closing of SEI cracks that formed during the initial three cycles. Reproduced with permission from Ref. [119]. Copyright 2016, American Chemical Society.

  • Figure 11

    (a) Schematic of surface reactions and cycle behaviors of silicon nanoparticles with different coating conditions and captured in situ TEM images of the alucone-coated Si nanoparticles during the lithiation/delithiation behavior. Reproduced with permission from Ref. [123]. Copyright 2014, American Chemical Society. (b) Schematic of the construction of the electrochemical testing setup, in-situ captured images of a Si NP-filled CNT structure evolution during lithiation and delithiation. Reproduced with permission from Ref. [124]. Copyright 2015, American Chemical Society. (c) Sequential and zoom-in TEM images of the partially lithiated Si nanowire under axial compression, finite element result showing the simulated elastic-plastic deformation in the nanowire that agrees with the zoom-in TEM image and the indentation loads applied to the lithiated electrodes with different Li contents. Reproduced with permission from Ref. [125]. Copyright 2015, Nature Publishing Group.

  • Figure 12

    (a) Schematics of the Si nanowire-composite based cell for the in situ 7Li NMR measurements. (b) Enlarged in-situ 7Li NMR spectra of the Si nanowire-CFGDL composite obtained during the potentiostatic experiment in the first three cycles. (c) Phase transformation diagram for the amorphous silicon nanowires on lithiation and delithiation showing the dependence of the phase evolutions on the rate of cycling. Reproduced with permission from Ref. [126]. Copyright 2014, Nature Publishing Group.

  • Figure 13

    (a) Schematic figure of a cell for in-situ XRD test. (b) In situ XRD results for a stainless steel-mesh (SS-mesh) cell cycled at 0.2 C. Reproduced with permission from Ref. [127]. Copyright 2012, American Chemical Society. (c) Operando Raman setup and electrochemical cell. (d) Linear sweep cyclic voltammograms. (e) Typical Raman spectra including crystalline and amorphous silicon peaks. (f) Evolution of the c-Si transverse optical-longitudinal optical (TO−LO) peak as a function of the scan number during the open-circuit, discharge (green) and charge (purple) cycles. The shadow on the left panel shows the variation of the Raman peak intensity over cycling time and the intensity map on the lower panel indicates the shift of the peak position (highlighted by the black line). (g) Evolution of the current, Raman peak intensity and spectral position as a function of time and applied voltage. Reproduced with permission from Ref. [128]. Copyright 2017, American Chemical Society.

  • Table 1   Summary of synthesis method and electrochemical characteristics of selected Si-based anode nanostructure

    Active materials

    Synthesis method

    Mass loading

    (mg cm−2)

    First cycle capacity

    (mA h g−1) (A g−1)

    Initial Coulombicefficiency

    No. cycles with

    80% capacity retention

    Mic-Si/graphene cage [81]

    Ultrasonication

    0.8

    3300 (0.05)

    93.2%

    No decrease after 100 cycles

    Hierarchically porous Si [78]

    Dispersed in ethanol and cast

    1

    1850 (0.42)

    87%

    60

    Si NPs [98]

    Stirring for 6 h at 200°C

    2.0–2.5

    2500 (0.05)

    85%

    15

    Si NPs [92]

    Solution processes

    0.3–0.4

    1200 (1.0)

    70%

    180

    SiMP [66]

    Condensation reaction

    0.5–0.7

    3200 (0.5)

    80%

    80

    Si/C [99]

    CVD

    1.8

    2277 (0.42)

    90%

    16

    p-Si/C [77]

    Magnesiothermic reduction

    1.1

    2500 (2.6)

    75%

    10

    Si nanorods [101]

    Self-templating synthesis

    1.1

    2705 (0.25)

    60.5%

    No decrease after 500 cycles

    PG-Si [102]

    Chemical reduction ordecompose

    1

    1464 (0.2)

    58%

    70

    Si/C [103]

    CVD

    1–5

    3207 (0.05)

    79%

    No decrease after 100 cycles

    Mesoporous Si [104]

    Pyrolysis

    0.5

    2660 (0.5)

    72.8%

    175

    SiO/G/C [105]

    Heat treatment

    2

    905 (1.0)

    68.1%

    No decrease after 200 cycles

    SiO2 nanowires [106]

    Pyrolysis

    1.0

    2215 (0.5)

    88%

    10

    Si@C [107]

    Pyrolysis

    0.5

    2936 (0.09)

    85%

    10

    MHSiO2@C [108]

    Pyrolysis

    1.73–1.91

    880 (0.5)

    68%

    5

    Si@TiO2 [109]

    Sonication and pyrolysis

    0.8

    1562 (2.1)

    65.8%

    68

    HSi@C [110]

    Reduce HSiO2

    0.7

    1970 (2.0)

    52.4

    No decrease after 200 cycles

    CNT-Si [111]

    Etching by HF

    1.3

    2213 (0.42)

    83.4%

    50

    Mesoporous Si [112]

    Pyrolysis

    0.7–1.2

    2789 (0.36)

    64.1%

    70

    Ferrosilicon [59]

    High energy ball milling

    0.5

    1250 (0.4)

    88%

    No decrease after 100 cycles

    Si/C [113]

    Thermal decomposition

    0.6–1

    1992 (0.2)

    60%

    110

    Si-SHP [114]

    Ultrasonication

    1.13

    2850 (0.1)

    80%

    25

    Si@GO [115]

    3D tomography

    1.2

    2900 (0.42)

    94%

    70

    Si/graphene [116]

    Mechanical stirring

    2

    879 (0.05)

    58.6%

    6