Supplementary Information for

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1 Supplementary Information for Highly Self-healable 3D Microsupercapacitor with MXene-Graphene Composite Aerogel Yang Yue, Nishuang Liu, * Yanan Ma, Siliang Wang, Weijie Liu, Cheng Luo Hang Zhang, Feng Cheng, Jiangyu Rao, Xiaokang Hu, Jun Su, and Yihua Gao * Center for Nanoscale Characterization & Devices (CNCD), Wuhan National Laboratory for Optoelectronics (WNLO) and School of Physics, Huazhong University of Science and Technology (HUST), Luoyu Road 1037, Wuhan , P.R. China 1. Areal capacitance ( C real according to the following formulae: ) was calculated from the cyclic voltammetry curves C A S U S (1) real 2 Where S is the total area of the electrodes, A is the area of CV curve, S is the scan rate, U is the potential window. 2. Areal capacitance ( C real ) was calculated from the charge-discharge curves according to the following equations. real C I t U S (2) Where S is the total area of the electrodes, I is the discharge current, t is the discharge time, and U is the potential window during the discharge process. 3. The energy density ( E ) and power density ( P ) of the device can be calculated from the galvanostatic charge-discharge curves according to the following formulae: 1/7200 C U 2 E (3) real P ( E 3600) t (4)

2 Where U is the potential window during the discharge process C real is the area capacitance, and t is the discharge time. Figure S1. (a-d) The SEM images of MXene-rGO composites fabricated by hydrothermal reaction in the reaction kettle for 6 h at temperature of 180. MXene nanosheets became spherical after this reaction. Figure S2. Photograph of the stable MXene-rGO (left), MXene (middle) and rgo

3 (right) water dispersion after one week a) and after two months b). Figure S3. Flake size distributions of GO. Figure S4. (a) Nitrogen adsorption-deposition isotherms and (b) pore size distributions (BJH) for MXene-graphene composite aerogel.

4 Figure S5. (a) Compressive stress-strain curves of MXene-graphene composite aerogel. (b, c) Strength measurement (compressive and tensile) of MXene-graphene composite aerogel. Figure S6. AFM image of MXene nanosheet (a) and its height profile (b) showing the lateral size: nm, thickness: 1.52 nm.

5 Figure S7. The SEM images of MXene-rGO composites. Figure S8. SEM images (a) and Elemental mapping images (b-d) of MXene-rGO composite aerogel.

6 Figure S9. STEM (a,b) and Elemental mapping images (c,d) of MXene nanoflakes coated on rgo nanoflakes. Figure S10. (a) XPS survey spectrum, high-resolution (b) Ti 2p and (c) C 1s spectra of MXene-graphene composite aerogel.

7 Figure S11. CV curves of pure rgo and MXene-rGO composite aerogel with initial weight ratios of 16:1, 2, 3, 4, 5, 6 of GO: MXene.

8 Figure S12. a-h) GDC curves of pure rgo aerogel and MXene-rGO composite aerogel with initial weight ratios of 16:1, 2, 3, 4, 5, 6 of GO: MXene.

9 Figure S13. Ragone plots of the 3D MSCs with MXene-Graphene Composite Aerogel compared to other energy storage devices. Figure S14. (a) The SEM image of the PU in a completely cut state. (b) The SEM image of the PU after self-healing. (c) The SEM image of the PU in the tensile state. (d) The partial enlargement image of (c). (e-h) The partial enlargement image of (d).

10 Eletrode material Areal capacitance Electrolyte Reference rgo 0.51 mf cm -2 Hydrated GO [1] rgo-au 0.77 mf cm -2 H2SO4-PVA [3] GQDs μf cm 2 Na2SO4 [4] 3D Graphebe 10 mf cm -2 H2SO4-PVA [6] Graphene-MXene aerogel 34.6 mf cm -2 H2SO4-PVA This work Table S1. Summary of the areal capacitance of supercapacitor. Aerogel density BET surface area BJH pore Conductivity Elasitic modulus Strength (compression Strength (tension) volume 75%) 12.3mg/cm m²/g cm³/g ~7.2 S/m kpa 20.6 kpa 6.02 kpa Table S2. Physical properties of MXene-graphene composite aerogel. C 1s O 1s Ti 2p F 1s Atomic Conc (%) Table S3. Elements ratio of MXene-graphene composite aerogel from XPS. Reference: 1. Gao, W.; Singh, N.; Song, L.; Liu, Z.; Reddy, A. L. M.; Ci, L.; Vajtai, R.; Zhang, Q.; Wei, B.; Ajayan, P. M., Direct Laser Writing of Micro-supercapacitors on Hydrated Graphite Oxide Films. Nat. Nanotechnol. 2011, 6, Yoo, J. J.; Balakrishnan, K.; Huang, J.; Meunier, V.; Sumpter, B. G.; Srivastava, A.; Conway, M.; Mohana Reddy, A. L.; Yu, J.; Vajtai, R., Ultrathin Planar Graphene Supercapacitors. Nano Lett. 2011, 11, Li, R.-Z.; Peng, R.; Kihm, K.; Bai, S.; Bridges, D.; Tumuluri, U.; Wu, Z.; Zhang,

11 T.; Compagnini, G.; Feng, Z., High-rate in-plane Micro-supercapacitors Scribed onto Photo Paper Using in Situ Femtolaser-reduced Graphene Oxide/Au Nanoparticle Microelectrodes. Energ. Environ. Sci. 2016, 9, Liu, W. ; Feng, Y. ; Yan, X. ; Chen, J. ; Xue, Q., Superior Micro-Supercapacitors Based on Graphene Quantum Dots. Adv. Funct. Mater. 2013, 23, Li, H.; Hou, Y.; Wang, F.; Lohe, M. R.; Zhuang, X.; Niu, L.; Feng, X., Flexible All-Solid-State Supercapacitors with High Volumetric Capacitances Boosted by Solution Processable MXene and Electrochemically Exfoliated Graphene. Adv. Energy Mater. 2017, 7, Zhang, L.; DeArmond, D.; Alvarez, N. T.; Malik, R.; Oslin, N.; McConnell, C.; Adusei, P. K.; Hsieh, Y. Y.; Shanov, V., Flexible Micro-Supercapacitor Based on Graphene with 3D Structure. Small 2017, 13,