Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading
Abstract
Retaining sound electrochemical performance of electrodes at high mass loading holds critical importance to energy storage. Pseudocapacitive materials such as manganese oxide (MnO2) deposited on current collectors have achieved outstanding gravimetric capacitances, sometimes even close to their theoretical values. However, this is only achievable with very small mass loading of active material typically less than 1 mg cm-2. Increasing mass loading often leads to drastic decay of capacitive performance due to sluggish ion diffusion in bulk material. In this work, we demonstrate a 3D printed graphene aerogel electrode with MnO2 loading of 182.2 mg cm-2, which achieves a record-high areal capacitance of 44.13 F cm-2. Most importantly, this 3D printed graphene aerogel/MnO2 electrode can simultaneously achieve excellent capacitance normalized to area, gravimetry, and volume, which is the trade-off for most electrodes. This work successfully validates the feasibility of printing practical pseudocapacitive electrodes, which might revolutionize pseudocapacitor fabrication.
- Authors:
-
- Univ. of California, Santa Cruz, CA (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1581898
- Report Number(s):
- LLNL-JRNL-751399
Journal ID: ISSN 2542-4351; 937270
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Joule
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2542-4351
- Publisher:
- Elsevier - Cell Press
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 3D printing; capacitors; ultrahigh mass loading; MnO2; efficient ion diffusion; graphene; pseudocapacitors; aerogels; areal capacitance; energy storage
Citation Formats
Yao, Bin, Chandrasekaran, Swetha, Zhang, Jing, Xiao, Wang, Qian, Fang, Zhu, Cheng, Duoss, Eric B., Spadaccini, Christopher M., Worsley, Marcus A., and Li, Yat. Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading. United States: N. p., 2018.
Web. doi:10.1016/j.joule.2018.09.020.
Yao, Bin, Chandrasekaran, Swetha, Zhang, Jing, Xiao, Wang, Qian, Fang, Zhu, Cheng, Duoss, Eric B., Spadaccini, Christopher M., Worsley, Marcus A., & Li, Yat. Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading. United States. https://doi.org/10.1016/j.joule.2018.09.020
Yao, Bin, Chandrasekaran, Swetha, Zhang, Jing, Xiao, Wang, Qian, Fang, Zhu, Cheng, Duoss, Eric B., Spadaccini, Christopher M., Worsley, Marcus A., and Li, Yat. Thu .
"Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading". United States. https://doi.org/10.1016/j.joule.2018.09.020. https://www.osti.gov/servlets/purl/1581898.
@article{osti_1581898,
title = {Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading},
author = {Yao, Bin and Chandrasekaran, Swetha and Zhang, Jing and Xiao, Wang and Qian, Fang and Zhu, Cheng and Duoss, Eric B. and Spadaccini, Christopher M. and Worsley, Marcus A. and Li, Yat},
abstractNote = {Retaining sound electrochemical performance of electrodes at high mass loading holds critical importance to energy storage. Pseudocapacitive materials such as manganese oxide (MnO2) deposited on current collectors have achieved outstanding gravimetric capacitances, sometimes even close to their theoretical values. However, this is only achievable with very small mass loading of active material typically less than 1 mg cm-2. Increasing mass loading often leads to drastic decay of capacitive performance due to sluggish ion diffusion in bulk material. In this work, we demonstrate a 3D printed graphene aerogel electrode with MnO2 loading of 182.2 mg cm-2, which achieves a record-high areal capacitance of 44.13 F cm-2. Most importantly, this 3D printed graphene aerogel/MnO2 electrode can simultaneously achieve excellent capacitance normalized to area, gravimetry, and volume, which is the trade-off for most electrodes. This work successfully validates the feasibility of printing practical pseudocapacitive electrodes, which might revolutionize pseudocapacitor fabrication.},
doi = {10.1016/j.joule.2018.09.020},
journal = {Joule},
number = 2,
volume = 3,
place = {United States},
year = {Thu Oct 18 00:00:00 EDT 2018},
month = {Thu Oct 18 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Materials for electrochemical capacitors
journal, November 2008
- Simon, Patrice; Gogotsi, Yury
- Nature Materials, Vol. 7, Issue 11
Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014
- Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
- Energy & Environmental Science, Vol. 7, Issue 5
High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance
journal, April 2013
- Augustyn, Veronica; Come, Jérémy; Lowe, Michael A.
- Nature Materials, Vol. 12, Issue 6
Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials
journal, March 2015
- Acerce, Muharrem; Voiry, Damien; Chhowalla, Manish
- Nature Nanotechnology, Vol. 10, Issue 4
Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide
journal, September 2013
- Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E.
- Science, Vol. 341, Issue 6153
Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance
journal, November 2014
- Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang
- Nature, Vol. 516, Issue 7529
Engineering of MnO2-based nanocomposites for high-performance supercapacitors
journal, October 2015
- Wang, Jian-Gan; Kang, Feiyu; Wei, Bingqing
- Progress in Materials Science, Vol. 74
WO3-x@Au@MnO2 Core-Shell Nanowires on Carbon Fabric for High-Performance Flexible Supercapacitors
journal, January 2012
- Lu, Xihong; Zhai, Teng; Zhang, Xianghui
- Advanced Materials, Vol. 24, Issue 7
Supercapacitor Behavior with KCl Electrolyte
journal, April 1999
- Lee, Hee Y.; Goodenough, J. B.
- Journal of Solid State Chemistry, Vol. 144, Issue 1
Ostwald Ripening Improves Rate Capability of High Mass Loading Manganese Oxide for Supercapacitors
journal, July 2017
- Song, Yu; Liu, Tianyu; Yao, Bin
- ACS Energy Letters, Vol. 2, Issue 8
Effect of Crystallographic Structure of MnO 2 on Its Electrochemical Capacitance Properties
journal, February 2008
- Devaraj, S.; Munichandraiah, N.
- The Journal of Physical Chemistry C, Vol. 112, Issue 11
Low-Cost High-Performance Solid-State Asymmetric Supercapacitors Based on MnO 2 Nanowires and Fe 2 O 3 Nanotubes
journal, January 2014
- Yang, Peihua; Ding, Yong; Lin, Ziyin
- Nano Letters, Vol. 14, Issue 2
Oxygen vacancies enhancing capacitive properties of MnO2 nanorods for wearable asymmetric supercapacitors
journal, September 2014
- Zhai, Teng; Xie, Shilei; Yu, Minghao
- Nano Energy, Vol. 8
Enhanced Supercapacitor Performance of MnO 2 by Atomic Doping
journal, January 2013
- Kang, Jianli; Hirata, Akihiko; Kang, Lijing
- Angewandte Chemie International Edition, Vol. 52, Issue 6
Freestanding Three-Dimensional Graphene/MnO 2 Composite Networks As Ultralight and Flexible Supercapacitor Electrodes
journal, December 2012
- He, Yongmin; Chen, Wanjun; Li, Xiaodong
- ACS Nano, Vol. 7, Issue 1
Symmetrical MnO 2 –Carbon Nanotube–Textile Nanostructures for Wearable Pseudocapacitors with High Mass Loading
journal, October 2011
- Hu, Liangbing; Chen, Wei; Xie, Xing
- ACS Nano, Vol. 5, Issue 11
Engineering three-dimensional hybrid supercapacitors and microsupercapacitors for high-performance integrated energy storage
journal, March 2015
- El-Kady, Maher F.; Ihns, Melanie; Li, Mengping
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 14
Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores
journal, January 2016
- Zhu, Cheng; Liu, Tianyu; Qian, Fang
- Nano Letters, Vol. 16, Issue 6, p. 3448-3456
Highly compressible 3D periodic graphene aerogel microlattices
journal, April 2015
- Zhu, Cheng; Han, T. Yong-Jin; Duoss, Eric B.
- Nature Communications, Vol. 6, Issue 1
Multifunctional, Ultra-Flyweight, Synergistically Assembled Carbon Aerogels
journal, February 2013
- Sun, Haiyan; Xu, Zhen; Gao, Chao
- Advanced Materials, Vol. 25, Issue 18
Nanostructured porous MnO2 on Ni foam substrate with a high mass loading via a CV electrodeposition route for supercapacitor application
journal, August 2014
- Yang, Jie; Lian, Lifang; Ruan, Hongcheng
- Electrochimica Acta, Vol. 136
Carbon fabric-aligned carbon nanotube/MnO2/conducting polymers ternary composite electrodes with high utilization and mass loading of MnO2 for super-capacitors
journal, December 2012
- Lv, Peng; Feng, Yi Y.; Li, Yu
- Journal of Power Sources, Vol. 220
An Electrochemical Capacitor with Applicable Energy Density of 7.4 Wh/kg at Average Power Density of 3000 W/kg
journal, April 2015
- Zhai, Teng; Lu, Xihong; Wang, Hanyu
- Nano Letters, Vol. 15, Issue 5
Paper-based solid-state supercapacitors with pencil-drawing graphite/polyaniline networks hybrid electrodes
journal, November 2013
- Yao, Bin; Yuan, Longyan; Xiao, Xu
- Nano Energy, Vol. 2, Issue 6
Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage
journal, December 2015
- Lin, T.; Chen, I. -W.; Liu, F.
- Science, Vol. 350, Issue 6267
Flexible Transparent Molybdenum Trioxide Nanopaper for Energy Storage
journal, May 2016
- Yao, Bin; Huang, Liang; Zhang, Jing
- Advanced Materials, Vol. 28, Issue 30
Polypyrrole-coated paper for flexible solid-state energy storage
journal, January 2013
- Yuan, Longyan; Yao, Bin; Hu, Bin
- Energy & Environmental Science, Vol. 6, Issue 2
Liquid-Mediated Dense Integration of Graphene Materials for Compact Capacitive Energy Storage
journal, August 2013
- Yang, X.; Cheng, C.; Wang, Y.
- Science, Vol. 341, Issue 6145
3D MnO2–graphene composites with large areal capacitance for high-performance asymmetric supercapacitors
journal, January 2013
- Zhai, Teng; Wang, Fuxin; Yu, Minghao
- Nanoscale, Vol. 5, Issue 15
Freestanding Mesoporous VN/CNT Hybrid Electrodes for Flexible All-Solid-State Supercapacitors
journal, July 2013
- Xiao, Xu; Peng, Xiang; Jin, Huanyu
- Advanced Materials, Vol. 25, Issue 36
A Scalable Free-Standing V 2 O 5 /CNT Film Electrode for Supercapacitors with a Wide Operation Voltage (1.6 V) in an Aqueous Electrolyte
journal, June 2016
- Wu, Jiabin; Gao, Xiang; Yu, Huimin
- Advanced Functional Materials, Vol. 26, Issue 33
Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance
journal, January 2018
- Feng, Dawei; Lei, Ting; Lukatskaya, Maria R.
- Nature Energy, Vol. 3, Issue 1
An excellent cycle performance of asymmetric supercapacitor based on bristles like α-MnO2 nanoparticles grown on multiwalled carbon nanotubes
journal, March 2016
- Vinny, R. T.; Chaitra, K.; Venkatesh, Krishna
- Journal of Power Sources, Vol. 309
Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes
journal, May 2018
- Xia, Yu; Mathis, Tyler S.; Zhao, Meng-Qiang
- Nature, Vol. 557, Issue 7705
Robust graphene composite films for multifunctional electrochemical capacitors with an ultrawide range of areal mass loading toward high-rate frequency response and ultrahigh specific capacitance
journal, January 2018
- Zhang, Miao; Yu, Xiaowen; Ma, Hongyun
- Energy & Environmental Science, Vol. 11, Issue 3
Inkjet printing of δ-MnO2 nanosheets for flexible solid-state micro-supercapacitor
journal, July 2018
- Wang, Yang; Zhang, Yi-Zhou; Dubbink, David
- Nano Energy, Vol. 49
3D Interdigital Au/MnO 2 /Au Stacked Hybrid Electrodes for On-Chip Microsupercapacitors
journal, April 2016
- Hu, Haibo; Pei, Zhibin; Fan, Hongjin
- Small, Vol. 12, Issue 22
All-wood, low tortuosity, aqueous, biodegradable supercapacitors with ultra-high capacitance
journal, January 2017
- Chen, Chaoji; Zhang, Ying; Li, Yiju
- Energy & Environmental Science, Vol. 10, Issue 2
Direct Growth of Birnessite-Type MnO 2 on Treated Carbon Cloth for a Flexible Asymmetric Supercapacitor with Excellent Cycling Stability
journal, January 2016
- Nakayama, Masaharu; Osae, Shogo; Kaneshige, Koki
- Journal of The Electrochemical Society, Vol. 163, Issue 10
Laser Scribing of High-Performance and Flexible Graphene-Based Electrochemical Capacitors
journal, March 2012
- El-Kady, M. F.; Strong, V.; Dubin, S.
- Science, Vol. 335, Issue 6074
Stabilized TiN Nanowire Arrays for High-Performance and Flexible Supercapacitors
journal, September 2012
- Lu, Xihong; Wang, Gongming; Zhai, Teng
- Nano Letters, Vol. 12, Issue 10
Flexible and cross-linked N-doped carbon nanofiber network for high performance freestanding supercapacitor electrode
journal, July 2015
- Cheng, Yongliang; Huang, Liang; Xiao, Xu
- Nano Energy, Vol. 15
Amorphous Mixed-Valence Vanadium Oxide/Exfoliated Carbon Cloth Structure Shows a Record High Cycling Stability
journal, February 2017
- Song, Yu; Liu, Tian-Yu; Yao, Bin
- Small, Vol. 13, Issue 16
Works referencing / citing this record:
3D Printed High‐Loading Lithium‐Sulfur Battery Toward Wearable Energy Storage
journal, January 2020
- Chen, Chenglong; Jiang, Jiangmin; He, Wenjie
- Advanced Functional Materials, Vol. 30, Issue 10
Intrapore‐Texturized Vanadia‐Hydrate Supercapacitor with Ultrahigh Area‐Normalized Capacitance
journal, October 2019
- Chen, Ying-Chu; Treptow, Jens; Hsu, Yu-Kuei
- physica status solidi (a), Vol. 216, Issue 22
Versatile N‐Doped MXene Ink for Printed Electrochemical Energy Storage Application
journal, July 2019
- Yu, Lianghao; Fan, Zhaodi; Shao, Yuanlong
- Advanced Energy Materials, Vol. 9, Issue 34
Rheological Issues in Carbon-Based Inks for Additive Manufacturing
journal, January 2019
- O’Mahony, Charlie; Haq, Ehtsham Ul; Sillien, Christophe
- Micromachines, Vol. 10, Issue 2
A review on synthesis of graphene, h-BN and MoS2 for energy storage applications: Recent progress and perspectives
journal, July 2019
- Kumar, Rajesh; Sahoo, Sumanta; Joanni, Ednan
- Nano Research, Vol. 12, Issue 11
A universal in situ strategy for charging supercapacitors
journal, January 2019
- Luo, Zhiling; Liu, Changhong; Fan, Shoushan
- Journal of Materials Chemistry A, Vol. 7, Issue 25
Densely Functionalized Cyanographene Bypasses Aqueous Electrolytes and Synthetic Limitations Toward Seamless Graphene/β‐FeOOH Hybrids for Supercapacitors
journal, October 2019
- Talande, Smita V.; Bakandritsos, Aristides; Jakubec, Petr
- Advanced Functional Materials, Vol. 29, Issue 51
3D Printing of Electrochemical Energy Storage Devices: A Review of Printing Techniques and Electrode/Electrolyte Architectures
journal, November 2019
- Cheng, Meng; Deivanayagam, Ramasubramonian; Shahbazian‐Yassar, Reza
- Batteries & Supercaps, Vol. 3, Issue 2
3D All Printing of Polypyrrole Nanotubes for High Mass Loading Flexible Supercapacitor
journal, September 2019
- Gu, Yifan; Zhang, Yan; Shi, Yunhui
- ChemistrySelect, Vol. 4, Issue 36
Cobalt-Containing Nanoporous Nitrogen-Doped Carbon Nanocuboids from Zeolite Imidazole Frameworks for Supercapacitors
journal, August 2019
- Song, Yu; Zhang, Mingyue; Liu, Tianyu
- Nanomaterials, Vol. 9, Issue 8
3D Exfoliated Carbon Paper toward Highly Loaded Aqueous Energy Storage Applications
journal, September 2019
- Song, Yu; Duan, Sicong; Yang, Duo
- Energy Technology, Vol. 7, Issue 11
A Universal Converse Voltage Process for Triggering Transition Metal Hybrids In Situ Phase Restruction toward Ultrahigh‐Rate Supercapacitors
journal, May 2019
- Guo, Wei; Yu, Chang; Li, Shaofeng
- Advanced Materials, Vol. 31, Issue 28
3D Printing of Ultralight Biomimetic Hierarchical Graphene Materials with Exceptional Stiffness and Resilience
journal, July 2019
- Peng, Meiwen; Wen, Zhen; Xie, Lingjie
- Advanced Materials, Vol. 31, Issue 35
An ultrathin defect-rich Co 3 O 4 nanosheet cathode for high-energy and durable aqueous zinc ion batteries
journal, January 2019
- Lu, Yongzhuang; Wang, Jing; Zeng, Siqi
- Journal of Materials Chemistry A, Vol. 7, Issue 38
Sulfur-Deficient Porous SnS2−x Microflowers as Superior Anode for Alkaline Ion Batteries
journal, January 2020
- Zhang, Lei; Yao, Bin; Sun, Congli
- Materials, Vol. 13, Issue 2
Flexible 3D hierarchical porous NiCo2O4/CC electrode decorated by nitrogen-doped carbon from polyaniline carbonization for high-performance supercapacitors
journal, February 2020
- Zhang, Kai; Wang, Qiguan; Thota, Apparao
- Journal of Materials Science, Vol. 55, Issue 14
Structural engineering to maintain the superior capacitance of molybdenum oxides at ultrahigh mass loadings
journal, January 2019
- Liu, Ji-Chi; Li, Hui; Batmunkh, Munkhbayar
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Free-standing transition metal oxide electrode architectures for electrochemical energy storage
journal, July 2019
- Spencer, Michael A.; Augustyn, Veronica
- Journal of Materials Science, Vol. 54, Issue 20
Chemistry from 3D printed objects
journal, April 2019
- Hartings, Matthew R.; Ahmed, Zeeshan
- Nature Reviews Chemistry, Vol. 3, Issue 5
Electrochemical in situ construction of vanadium oxide heterostructures with boosted pseudocapacitive charge storage
journal, January 2020
- Dong, Ran; Song, Yu; Yang, Duo
- Journal of Materials Chemistry A, Vol. 8, Issue 3
MnO2@NiO nanosheets@nanowires hierarchical structures with enhanced supercapacitive properties
journal, October 2019
- Zhao, Xiaoli; Liu, Xiaoying; Li, Fei
- Journal of Materials Science, Vol. 55, Issue 6
3D‐Printed Structure Boosts the Kinetics and Intrinsic Capacitance of Pseudocapacitive Graphene Aerogels
journal, January 2020
- Yao, Bin; Chandrasekaran, Swetha; Zhang, Haozhe
- Advanced Materials, Vol. 32, Issue 8
Rheological Issues in Carbon-Based Inks for Additive Manufacturing
journal, January 2019
- O’Mahony, Charlie; Haq, Ehtsham Ul; Sillien, Christophe
- Micromachines, Vol. 10, Issue 2