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SCIENCE CHINA Materials, Volume 61, Issue 2: 210-232(2018) https://doi.org/10.1007/s40843-017-9154-2

Recent advances in flexible supercapacitors based on carbon nanotubes and graphene

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  • ReceivedAug 28, 2017
  • AcceptedOct 31, 2017
  • PublishedDec 15, 2017

Abstract

Owing to the rapidly growing market for flexible electronics, there is an urgent demand to develop flexible energy storage devices. Flexible supercapacitors have received much attention due to their good flexibility, fast charge/discharge rate and long lifecycle times. Carbon nanotubes (CNTs) and graphene have good mechanical properties, which make them suitable for flexible supercapacitors. Based on different nanostructures of CNTs and graphene, we summarized the recent progress in CNTs- and graphene-based flexible supercapacitors with a brief description of the basic principles for evaluating their performance. Special emphasis was given to fabrication methods, capacitive performance and electrode configurations of different flexible supercapacitors. Furthermore, the remaining challenges and future research directions for CNTs- and graphene-based flexible supercapacitors have also been discussed.


Funded by

the National Natural Scientific Foundation of China(21503116)

Taishan Scholars Program of Shandong Province(tsqn20161004)

the Youth 1000 Talent Program of China.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21503116), Taishan Scholars Program of Shandong Province (TSQN20161004) and the Youth 1000 Talent Program of China.


Interest statement

The authors declare that they have no conflict of interests.


Contributions statement

Li K and Zhang J conceived and wrote the paper. All authors discussed and commented on the manuscript.


Author information

Kang Li obtained his bachelor degree from Nanjing University, and now is a graduate student in Shandong University under the supervision of Prof. Jintao Zhang. His research interest focuses on the carbon-based nanomaterials for flexible energy storage devices.


Jintao Zhang obtained his PhD degree from the National University of Singapore in 2012. Prior to joining Shandong University as a full professor, he has been a postdoctoral fellow at Nanyang Technological University and Case Western Reserve University. His research interests include the rational design & synthesis of advanced materials for electrochemical energy storage and conversion devices (e.g., metal-air batteries, supercapacitors and fuel cells) and electrocatalysis.


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  • Figure 1

    Schematic illustration of a two-electrode supercapacitor.

  • Figure 2

    (a) Schematic illustration for preparing buckled SWCNT film on PDMS. Reproduced with permission from Ref. [43]. Copyright 2013, Wiley-VCH. (b) Photograph of the fabricated supercapacitors without carbon paste current collectors. Reproduced with permission from Ref. [50]. Copyright 2014, the American Chemical Society. SEM images of buckled structures formed in CNT films at different levels of omnidirectional pre-strain (c) 50%, (d) 100%, (e) 150%, and (f) 200%. (g) Photos of buckled CNT film at various stretching states. Reproduced with permission from Ref. [45]. Copyright 2014, the American Chemical Society.

  • Figure 3

    (a) Schematic illustration for the assembly of CNTs on copper and photographs of the copper foils before and after the deposition of CNTs. (b) SA-CNT films transferred to different substrates: glass (left), PET (middle), paper (right). Reproduced with permission from Ref. [56]. Copyright 2017, Wiley-VCH. (c) Schematic diagram showing the GelMA/DNA-coated MWCNT inks formed though hydrogen bonding, hydrophobic interactions, and π–π stacking interactions between MWCNT and GelMA/DNA. (d) Photograph of black conductive ink and high-resolution TEM image of individual or bundled GelMA/DNA-wrapped MWCNTs. (e) Fluorescence images of cardiac fibroblasts cultured on ink patterns printed on PEG-coated PET film. F-actin and cell nuclei were immunostained and fluorescently labeled green and blue, respectively. Reproduced with permission from Ref. [55]. Copyright 2016, Wiley-VCH.

  • Figure 4

    (a) SEM image of a single layer of SWCNT bundles peeled off from a thick film. (b) The sketch diagrams of a single layer film based on (left) continuous SWCNT/PANI reticulate structure and (right) randomly overlapped SWCNT/PANI bundles. “Blue” and “brown” parts represent SWCNT bundle skeleton and PANI skin. Reproduced with permission from [41]. Copyright 2012, the Royal Society of Chemistry. (c) Scheme of re-expanding process of CNT film. Reproduced with permission from Ref. [44]. Copyright 2015, the Royal Society of Chemistry. (d) Ragone plots of the supercapacity device (inset is 53 blue LEDs powered by a flexible SC pack consisting of 4 series-connected supercapacity devices). Reproduced with permission from Ref. [52] Copyright 2015, Elsevier. (e) Cross-sectional SEM images of Ti3C2Tx/MWCNT papers. Reproduced with permission from Ref. [49]. Copyright 2014, Wiley-VCH. (f) SEM images of aligned CNT/MoS2 composite films with 3.1 wt.% amounts of MoS2. Reproduced with permission from Ref. [46]. Copyright 2016, Wiley-VCH. (g) Cross-sectional SEM image of the freestanding CNT/MnO2 NT hybrid film. Reproduced with permission from Ref. [51]. Copyright 2014, the Royal Society of Chemistry.

  • Figure 5

    (a) Digital photograph of the flexible symmetric supercapacitor with a filtration paper as separator. Reproduced with permission from Ref. [64]. Copyright 2012, Wiley-VCH. SEM images of bare aligned MWCNTs at low (b) and high (c) resolution. The supercapacitor wire woven into other CNT fibers (d) and a textile composed of aramid fibers (e). The red arrows show the wire. Reproduced with permission from Ref. [62]. Copyright 2013, the Royal Society of Chemistry. (f) Photograph of multilayered clothes. (g) Schematic illustration to the integrated energy textile. The enlarged view shows the working mechanism. Reproduced with permission from Ref. [67]. Copyright 2014, Wiley-VCH.

  • Figure 6

    SEM images of CNT arrays before (a) and after (b) PANI deposition. Reproduced with permission from Ref. [68] Copyright 2017, Elsevier. Low (c) and high (d) magnification SEM images of the PCNTAs@CFs. (e) Photographs of PCNTAs@CFs symmetric device at different bending states. (f) Cycle stability tested at different bending states with the inset showing CV curves obtained at different bending states at a scan rate of 500 mV s−1. Reproduced with permission from Ref. [70]. Copyright 2016, Wiley-VCH.

  • Figure 7

    (a) CV curves of the CNT@Fe2O3 sponge under different compressed conditions (0, 10%, 30%, 50% and 70%) at 5 mV s−1. The inset shows the specific capacitance of the samples under different compressive strains at a scan rate of 5 mV s−1. Reproduced with permission from Ref. [74]. Copyright 2015, the Royal Society of Chemistry. (b) Continuous spinning of Pt/CNT core/sheath yarns: photograph of the flyer spinner and schematics of working elements. (c) Schematic showing formation of the core/sheath yarn structure. Reproduced with permission from Ref. [77]. Copyright 2014, the American Chemical Society.

  • Figure 8

    (a) Cross-section view of a GF@3D-G showing the core GF surrounding with standing graphene sheets. Photos of the textile embedded with two GF@3D-G fiber supercapacitors in flat (b) and bending (c) state, respectively. (d) CV curves of two GF@3D-G fiber supercapacitors as the textile in flat (b) and bending (c) states with a scan rate of 50 mV s−1. Reproduced with permission from Ref. [84]. Copyright 2013, Wiley-VCH. (e) The scheme of the RGO-GO-RGO supercapacitor device, where RGO layers were in contact with the Au sheets. The thin plastic layer of polyvinylidene chloride (PVDC) was partially coated on the Au surface to prevent the short circuit of two Au electrodes. Reproduced with permission from Ref. [86]. Copyright 2014, the Royal Society of Chemistry.

  • Figure 9

    SEM images of the cross-section and the surface of RGO fibers prepared by NLC (a) and LC (b) spinning. R represent the jet stretch ratio. (c) Photo of a 3 V yarn supercapacitor assembled from six bundles of RGO fibers. This device was sewed into a textile and could power a red light-emission diode (LED) for 5 min after being charged to 3 V at a scan rate of 10 mV s−1 for (5 min). Reproduced with permission from Ref. [89]. Copyright 2015, Elsevier. (d) Schematic diagrams of the stretchable and self-healable mechanism. Reproduced with permission from Ref. [93]. Copyright 2017, the American Chemical Society.

  • Figure 10

    (a) Cross-sectional SEM image of the original GP without CB. (b) Cross sectional HIM images of the pillared GP with the addition of 20 vol.% CB. Reproduced with permission from Ref. [94]. Copyright 2012, Wiley-VCH. (c) Schematic of the 3D SWCNT-bridged graphene block. KOH activation generates nanoscale pores in the graphene layers. (d) Cross-sectional SEM image containing dangling SWCNTs (magnified in the inset). Reproduced with permission from Ref. [103]. Copyright 2015, the American Chemical Society. (e) Schematic illustration of ultrathin laser-processed graphene based micro-planar supercapacitors. (f) Photographic image of LPG-MPS arrays. (Inset is a single unit). Reproduced with permission from Ref. [106]. Copyright 2016, Elsevier.

  • Figure 11

    (a) SEM images of the RGO films. Reproduced with permission from Ref. [107]. Copyright 2015, Wiley-VCH. (b) Schematic illustration of the formation mechanism of layer-by-layer b-Ni(OH)2/graphene nanohybrids. (c) HR-TEM image and the structural model of the layer-by-layer nanohybrids. Reproduced with permission from Ref. [108]. Copyright 2012, Elsevier.

  • Figure 12

    (a) Schematic diagram and photographs of the fabrication process of flexible solid-state supercapacitors based on graphene hydrogel films. (b) CV curves of the flexible solid-state device at 10 mV s−1 for different bending angles. Reproduced with permission from Ref. [115]. Copyright 2013, the American Chemical Society. (c) Two devices connected in series can power the digital temperature and humidity meter at both a normal (right) and bending (left) state. Reproduced with permission from Ref. [116]. Copyright 2014, the Royal Society of Chemistry. (d) Cross-section SEM image of a 3D porous RGO film after long-term reduction. (e) CV curves of an all solid-state supercapacitor tested at a scan rate of 50 mV s−1 under different bending angles. (f) The device retains about 91% of the initial capacitance after 500 cycles when tested under the bent state. Reproduced with permission from Ref. [117]. Copyright 2016, Wiley-VCH.

  • Table 1   Comparison of the performance of graphene-based flexible supercapacitors

    Electrode

    Conductivity

    (S cm−1)

    Electrolyte

    Specific capacitance

    (F g−1)

    Areal capacitance (mF cm−2)

    Energy density

    Power density

    Capacitance retention in flexibility test

    Ref.

    GF@3D-G

    10–20

    H2SO4-PVA

    25–40

    1.2–1.7

    0.4–1.7×10−7 W h cm−2

    6–100×10−6 W cm−2

    [84]

    RGO on Au wire

    /

    H3PO4-PVA

    /

    6.49

    /

    /

    90% (1000 cycles at 90°)

    [85]

    RGO-GO-RGO fiber

    /

    1-Butyl-3-methylimidazolium tetra-fluoroborate

    /

    1.2

    2–5.4×10−4 W h cm−2

    3.6–9×10−2 W cm−2

    ~100% (160 bending test)

    [86]

    RGO fiber

    41.7

    1 mol L−1 H2SO4

    279

    /

    5.76 W h kg−1

    47.3 W kg−1

    91% (1000 times bending from 0–180°)

    [89]

    CNT/graphene fiber

    12

    1 mol L−1 Na2SO4

    200.4

    0.98

    /

    /

    ~50% (1000 bending cycles)

    [90]

    GO/FWCNT fiber

    210.7

    H3PO4-PVA

    /

    38.8 F cm−3

    3.4 mW h cm−3

    0.7 W cm−3

    /

    [91]

    GF-MnO2

    172

    H3PO4-PVA

    /

    42

    1.46 ×

    10−3 mW h cm−2

    2.94 mW cm−2

    /

    [82]

    MnO2/G/GF

    10

    H2SO4-PVA

    34–36

    9.1–9.6

    /

    /

    ~105% (1000 straight-bend cycles)

    [92]

    RGO/MWCNTs/PPy fiber

    /

    H3PO4-PVA

    /

    25.9 F cm−3

    0.94 mW h cm−3

    7.32 mW cm−3

    82.4% (stretched to 200%)

    [93]

    CB pillared graphene paper

    /

    6 mol L−1 KOH

    138

    /

    26 W h kg−1

    5.1 kW kg−1

    /

    [94]

    GN/MWCNT film

    /

    6 mol L−1 KOH

    265

    /

    /

    /

    /

    [102]

    CNT-bridged graphene

    394

    1-Ethyl-3-methylimidazolium tetrafluoroborate

    199

    /

    117.2 W h L−1

    424 kW L−1

    /

    [103]

    SSG film

    0.87

    H2SO4-PVA

    245

    /

    8.01 W h kg−1

    5.97 kW kg−1

    /

    [104]

    LSG film

    17.38

    H3PO4-PVA

    /

    3.67

    1.36 mW h cm−3

    20 W cm−3

    95% (1000 bending cycles)

    [97]

    LSG-MnO2

    /

    1 mol L−1 Na2SO4

    1145

    400

    22–42 W h L−1

    10 kW L−1

    /

    [105]

    LPG

    /

    LiCl-PVA

    /

    3.9

    0.98 mW h cm−3

    300 mW cm−3

    /

    [106]

    RGO film

    1.12

    1 mol L−1 H2SO4

    /

    71

    4.9 µW h cm −2

    40,000 µW cm−2

    96.7% (5,000 bending cycles)

    [107]

    Graphene-PANI paper

    15 Ω sq−1

    1 mol L−1 H2SO4

    763

    /

    /

    /

    /

    [98]

    β-Ni(OH)2/graphene

    /

    KOH-PVA

    /

    2.57

    /

    /

    ~100% (500 bending cycles)

    [108]

    Sulfur-doped graphene

    95

    H2SO4-PVA

    553 μF cm−2

    3.1 mW h cm−3

    1191 W cm−3

    [109]

    Graphene hydrogel

    /

    H2SO4-PVA

    196

    372

    0.61 W h kg−1

    0.67 kW kg−1

    /

    [115]

    3D H-RGO

    /

    6 mol L−1 KOH

    220

    /

    /

    /

    80% (120° 10,000 cycles)

    [116]

    Cellular graphene films

    19.05

    H3PO4-PVA

    284.2

    34

    1.11 W h L−1

    7.8–14.3 kW kg−1

    91% (500 bending cycles)

    [117]

    RGO-F/PANI foam

    16

    1 mol L−1 H2SO4

    790

    /

    17.6 W h kg−1

    98 kW kg−1

    /

    [119]

    Ag-GF-OMC

    762

    6 mol L−1 KOH

    213

    4.5 W h kg−1

    5040 W kg−1

    92% (200 bending cycles at 90°)

    [123]

    O/N codoped graphene foam

    /

    1 mol L−1 H2SO4

    /

    375 μF cm−2

    16 W h kg−1

    17 kW kg−1

    /

    [124]

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