3D-Printed, Superelastic Polypyrrole–Graphene Electrodes with Ultrahigh Areal Capacitance for Electrochemical Energy Storage

Qi, Zhen; Ye, Jianchao; Chen, Wen; Biener, Juergen; Duoss, Eric B.; Spadaccini, Christopher M.; Worsley, Marcus A.; Zhu, Cheng

doi:10.1002/admt.201800053

Title: 3D-Printed, Superelastic Polypyrrole–Graphene Electrodes with Ultrahigh Areal Capacitance for Electrochemical Energy Storage

Journal Article · Thu Jun 07 00:00:00 EDT 2018 · Advanced Materials Technologies

DOI:https://doi.org/10.1002/admt.201800053· OSTI ID:1839866

Qi, Zhen ^[1]; Ye, Jianchao ^[1]; Chen, Wen ^[1]; Biener, Juergen ^[1]; Duoss, Eric B. ^[1]; Spadaccini, Christopher M. ^[1]; Worsley, Marcus A. ^[1]; Zhu, Cheng ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Abstract Disruptive custom electronics require a transformation in energy storage systems from traditional thin‐film units to shape conformable 3D components. However, current thick electrodes suffer from uncontrollable geometries and architectures, which lead to ion diffusion limitations, and poor mechanical properties. Here, designed, superelastic polypyrrole (PPy)‐coated graphene aerogel (GA) electrodes are fabricated via 3D printing and polymer self‐assembly methods. This resilient GA template (up to 90% compression) can be printed into any desired shape including engineered 3D architectures with periodic macropores, which promote the uniform deposition and adhesion of PPy onto the support. The coated PPy thin film increases the specific gravimetric capacitance of the GA electrode from 14 to 395 F g ⁻¹ with 90% retention after 5000 charging–discharging cycles. The capacitance remains the same value after 100 times compression cycles. It also improves the compressive strength by one order of magnitude from 0.14 to 2.4 MPa. Areal capacitance and energy density of the PPy–GA electrode are 2 F cm ⁻² and 0.78 mWh cm ⁻² , respectively, which to the best of the knowledge break the record for compressible electrodes, respectively. This approach enables the fabrication of complex architectured energy storage modules with enhanced compressibility, ultrahigh areal electrochemical performance, and excellent cyclability.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344; DE‐AC52‐07NA27344

OSTI ID:: 1839866

Alternate ID(s):: OSTI ID: 1441053

Report Number(s):: LLNL-JRNL-744282; 898944

Journal Information:: Advanced Materials Technologies, Vol. 3, Issue 7; ISSN 2365-709X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 57 works

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References (53)

Shape-morphing composites with designed micro-architectures Rodriguez, Jennifer N.; Zhu, Cheng; Duoss, Eric B. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep27933	journal	June 2016
Self-assembled three-dimensional and compressible interdigitated thin-film supercapacitors and batteries Nyström, Gustav; Marais, Andrew; Karabulut, Erdem Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8259	journal	May 2015
A comprehensive understanding of electrode thickness effects on the electrochemical performances of Li-ion battery cathodes Zheng, Honghe; Li, Jing; Song, Xiangyun Electrochimica Acta, Vol. 71, p. 258-265 https://doi.org/10.1016/j.electacta.2012.03.161	journal	June 2012
Preparation of Novel 3D Graphene Networks for Supercapacitor Applications Cao, Xiehong; Shi, Yumeng; Shi, Wenhui Small, Vol. 7, Issue 22 https://doi.org/10.1002/smll.201100990	journal	September 2011
Noble-Metal-Promoted Three-Dimensional Macroassembly of Single-Layered Graphene Oxide Tang, Zhihong; Shen, Shuling; Zhuang, Jing Angewandte Chemie, Vol. 122, Issue 27 https://doi.org/10.1002/ange.201000270	journal	May 2010
TiO ₂ @C core–shell nanowires for high-performance and flexible solid-state supercapacitors Zheng, Huimin; Zhai, Teng; Yu, Minghao J. Mater. Chem. C, Vol. 1, Issue 2 https://doi.org/10.1039/C2TC00047D	journal	January 2013
Engineering three-dimensional hybrid supercapacitors and microsupercapacitors for high-performance integrated energy storage El-Kady, Maher F.; Ihns, Melanie; Li, Mengping Proceedings of the National Academy of Sciences, Vol. 112, Issue 14 https://doi.org/10.1073/pnas.1420398112	journal	March 2015
Energy Scavenging for Mobile and Wireless Electronics Paradiso, J. A.; Starner, T. IEEE Pervasive Computing, Vol. 4, Issue 1 https://doi.org/10.1109/MPRV.2005.9	journal	January 2005
Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon Pech, David; Brunet, Magali; Durou, Hugo Nature Nanotechnology, Vol. 5, Issue 9, p. 651-654 https://doi.org/10.1038/nnano.2010.162	journal	August 2010
Highly Compression-Tolerant Supercapacitor Based on Polypyrrole-mediated Graphene Foam Electrodes Zhao, Yang; Liu, Jia; Hu, Yue Advanced Materials, Vol. 25, Issue 4 https://doi.org/10.1002/adma.201203578	journal	October 2012
A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres Liu, Jian; Yang, Tianyu; Wang, Da-Wei Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3798	journal	December 2013
High-performance stacked in-plane supercapacitors and supercapacitor array fabricated by femtosecond laser 3D direct writing on polyimide sheets Wang, Shutong; Yu, Yongchao; Li, Ruozhou Electrochimica Acta, Vol. 241 https://doi.org/10.1016/j.electacta.2017.04.138	journal	July 2017
Processable aqueous dispersions of graphene nanosheets Li, Dan; Müller, Marc B.; Gilje, Scott Nature Nanotechnology, Vol. 3, Issue 2 https://doi.org/10.1038/nnano.2007.451	journal	January 2008
Reversibly Compressible, Highly Elastic, and Durable Graphene Aerogels for Energy Storage Devices under Limiting Conditions Hong, Jin-Yong; Bak, Bo Mee; Wie, Jeong Jae Advanced Functional Materials, Vol. 25, Issue 7 https://doi.org/10.1002/adfm.201403273	journal	December 2014
Ion Intercalation Induced Capacitance Improvement for Graphene-Based Supercapacitor Electrodes Liu, Tianyu; Zhu, Cheng; Kou, Tianyi ChemNanoMat, Vol. 2, Issue 7 https://doi.org/10.1002/cnma.201600107	journal	May 2016
Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores Zhu, Cheng; Liu, Tianyu; Qian, Fang Nano Letters, Vol. 16, Issue 6, p. 3448-3456 https://doi.org/10.1021/acs.nanolett.5b04965	journal	January 2016
Solid-State Supercapacitor Based on Activated Carbon Cloths Exhibits Excellent Rate Capability Wang, Gongming; Wang, Hanyu; Lu, Xihong Advanced Materials, Vol. 26, Issue 17 https://doi.org/10.1002/adma.201304756	journal	February 2014
Highly Compressible and All-Solid-State Supercapacitors Based on Nanostructured Composite Sponge Niu, Zhiqiang; Zhou, Weiya; Chen, Xiaodong Advanced Materials, Vol. 27, Issue 39 https://doi.org/10.1002/adma.201502263	journal	August 2015
Controlling Material Reactivity Using Architecture Sullivan, Kyle T.; Zhu, Cheng; Duoss, Eric B. Advanced Materials, Vol. 28, Issue 10 https://doi.org/10.1002/adma.201504286	journal	December 2015
Noble-Metal-Promoted Three-Dimensional Macroassembly of Single-Layered Graphene Oxide Tang, Zhihong; Shen, Shuling; Zhuang, Jing Angewandte Chemie International Edition, Vol. 49, Issue 27, p. 4603-4607 https://doi.org/10.1002/anie.201000270	journal	May 2010
Fabrication of an arbitrary-shaped and nitrogen-doped graphene aerogel for highly compressible all solid-state supercapacitors Jiang, Degang; Li, Chenwei; Yang, Wenrong Journal of Materials Chemistry A, Vol. 5, Issue 35 https://doi.org/10.1039/C7TA04917J	journal	January 2017
Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions Yu, Zenan; Tetard, Laurene; Zhai, Lei Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03229B	journal	January 2015
Three dimensional (3D) flexible graphene foam/polypyrrole composite: towards highly efficient supercapacitors Chabi, Sakineh; Peng, Chuang; Yang, Zhuxian RSC Advances, Vol. 5, Issue 6 https://doi.org/10.1039/C4RA13743D	journal	January 2015
3D carbon based nanostructures for advanced supercapacitors Jiang, Hao; Lee, Pooi See; Li, Chunzhong Energy Environ. Sci., Vol. 6, Issue 1 https://doi.org/10.1039/C2EE23284G	journal	January 2013
Three-Dimensional Printing of Elastomeric, Cellular Architectures with Negative Stiffness Duoss, Eric B.; Weisgraber, Todd H.; Hearon, Keith Advanced Functional Materials, Vol. 24, Issue 31 https://doi.org/10.1002/adfm.201400451	journal	May 2014
Graphene-Based Supercapacitor with an Ultrahigh Energy Density Liu, Chenguang; Yu, Zhenning; Neff, David Nano Letters, Vol. 10, Issue 12 https://doi.org/10.1021/nl102661q	journal	December 2010
Freestanding, Hydrophilic Nitrogen-Doped Carbon Foams for Highly Compressible All Solid-State Supercapacitors Xiao, Kang; Ding, Liang-Xin; Liu, Guoxue Advanced Materials, Vol. 28, Issue 28 https://doi.org/10.1002/adma.201601125	journal	May 2016
Ultrasmall Integrated 3D Micro-Supercapacitors Solve Energy Storage for Miniature Devices Meng, Chuizhou; Maeng, Jimin; John, Simon W. M. Advanced Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1002/aenm.201301269	journal	December 2013
Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors Beidaghi, Majid; Gogotsi, Yury Energy & Environmental Science, Vol. 7, Issue 3 https://doi.org/10.1039/c3ee43526a	journal	January 2014
Micro-Supercapacitors Based on Interdigital Electrodes of Reduced Graphene Oxide and Carbon Nanotube Composites with Ultrahigh Power Handling Performance Beidaghi, Majid; Wang, Chunlei Advanced Functional Materials, Vol. 22, Issue 21 https://doi.org/10.1002/adfm.201201292	journal	June 2012
3D printed functional nanomaterials for electrochemical energy storage Zhu, Cheng; Liu, Tianyu; Qian, Fang Nano Today, Vol. 15 https://doi.org/10.1016/j.nantod.2017.06.007	journal	August 2017
Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage El-Kady, Maher F.; Kaner, Richard B. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2446	journal	February 2013
Flexible and stretchable power sources for wearable electronics Zamarayeva, Alla M.; Ostfeld, Aminy E.; Wang, Michael Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1602051	journal	June 2017
Thixotropic rheology of concentrated alumina colloidal gels for solid freeform fabrication Zhu, Cheng; Smay, James E. Journal of Rheology, Vol. 55, Issue 3 https://doi.org/10.1122/1.3573828	journal	May 2011
3-Dimensional Graphene Carbon Nanotube Carpet-Based Microsupercapacitors with High Electrochemical Performance Lin, Jian; Zhang, Chenguang; Yan, Zheng Nano Letters, Vol. 13, Issue 1 https://doi.org/10.1021/nl3034976	journal	December 2012
Electrophoretic Deposition of Thermites onto Micro-Engineered Electrodes Prepared by Direct-Ink Writing Sullivan, K. T.; Zhu, C.; Tanaka, D. J. The Journal of Physical Chemistry B, Vol. 117, Issue 6, p. 1686-1693 https://doi.org/10.1021/jp306440t	journal	September 2012
Optimizing supercapacitor electrode density: achieving the energy of organic electrolytes with the power of aqueous electrolytes Merrill, M. D.; Montalvo, E.; Campbell, P. G. RSC Advances, Vol. 4, Issue 81 https://doi.org/10.1039/C4RA08114E	journal	January 2014
Carbon nanotube-polypyrrole core-shell sponge and its application as highly compressible supercapacitor electrode Li, Peixu; Shi, Enzheng; Yang, Yanbing Nano Research, Vol. 7, Issue 2 https://doi.org/10.1007/s12274-013-0388-5	journal	December 2013
Flexible and Stretchable Energy Storage: Recent Advances and Future Perspectives Liu, Wei; Song, Min-Sang; Kong, Biao Advanced Materials, Vol. 29, Issue 1 https://doi.org/10.1002/adma.201603436	journal	November 2016
3D-Printed Transparent Glass Nguyen, Du T.; Meyers, Cameron; Yee, Timothy D. Advanced Materials, Vol. 29, Issue 26 https://doi.org/10.1002/adma.201701181	journal	April 2017
Three-dimensional graphene oxide/polypyrrole composite electrodes fabricated by one-step electrodeposition for high performance supercapacitors Cao, Jianyun; Wang, Yaming; Chen, Junchen Journal of Materials Chemistry A, Vol. 3, Issue 27 https://doi.org/10.1039/C5TA02920A	journal	January 2015
High-rate in-plane micro-supercapacitors scribed onto photo paper using in situ femtolaser-reduced graphene oxide/Au nanoparticle microelectrodes Li, R. -Z.; Peng, Rui; Kihm, K. D. Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE03637B	journal	January 2016
Redox-Active Polypyrrole: Toward Polymer-Based Batteries Song, H.-K.; Palmore, G. T. R. Advanced Materials, Vol. 18, Issue 13, p. 1764-1768 https://doi.org/10.1002/adma.200600375	journal	July 2006
On-chip and freestanding elastic carbon films for micro-supercapacitors Huang, P.; Lethien, C.; Pinaud, S. Science, Vol. 351, Issue 6274 https://doi.org/10.1126/science.aad3345	journal	February 2016
Catenary shape evolution of spanning structures in direct-write assembly of colloidal gels Zhu, Cheng; Smay, James E. Journal of Materials Processing Technology, Vol. 212, Issue 3 https://doi.org/10.1016/j.jmatprotec.2011.04.005	journal	March 2012
Origin of Reduced Graphene Oxide Enhancements in Electrochemical Energy Storage Radich, James G.; Kamat, Prashant V. ACS Catalysis, Vol. 2, Issue 5 https://doi.org/10.1021/cs3001286	journal	April 2012
Laser-induced porous graphene films from commercial polymers Lin, Jian; Peng, Zhiwei; Liu, Yuanyue Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6714	journal	December 2014
Alternating Stacked Graphene-Conducting Polymer Compact Films with Ultrahigh Areal and Volumetric Capacitances for High-Energy Micro-Supercapacitors Wu, Zhong-Shuai; Parvez, Khaled; Li, Shuang Advanced Materials, Vol. 27, Issue 27 https://doi.org/10.1002/adma.201501643	journal	June 2015
Structural Optimization of 3D Porous Electrodes for High-Rate Performance Lithium Ion Batteries Ye, Jianchao; Baumgaertel, Andreas C.; Wang, Y. Morris ACS Nano, Vol. 9, Issue 2 https://doi.org/10.1021/nn505490u	journal	December 2014
Graphene-based in-plane micro-supercapacitors with high power and energy densities Wu, Zhong–Shuai; Parvez, Khaled; Feng, Xinliang Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3487	journal	September 2013
Highly compressible 3D periodic graphene aerogel microlattices Zhu, Cheng; Han, T. Yong-Jin; Duoss, Eric B. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7962	journal	April 2015
Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations Liu, Lili; Niu, Zhiqiang; Chen, Jun Chemical Society Reviews, Vol. 45, Issue 15 https://doi.org/10.1039/C6CS00041J	journal	January 2016
Three-dimensional carbon architectures for electrochemical capacitors Song, Yu; Liu, Tianyu; Qian, Fang Journal of Colloid and Interface Science, Vol. 509 https://doi.org/10.1016/j.jcis.2017.07.081	journal	January 2018

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Title: 3D-Printed, Superelastic Polypyrrole–Graphene Electrodes with Ultrahigh Areal Capacitance for Electrochemical Energy Storage

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