Dense Graphene Monolith for High Volumetric Energy Density Li-S Batteries

Li, Huan; Tao, Ying; Zhang, Chen; Liu, Donghai; Luo, Jiayan; Fan, Weichao; Xu, Yue; Li, Youzhi; You, Conghui; Pan, Zheng -Ze; Ye, Mingchun; Chen, Zhengyu; Dong, Zhang; Wang, Da -Wei; Kang, Feiyu; Lu, Jun; Yang, Quan -Hong

doi:10.1002/aenm.201703438

Title: Dense Graphene Monolith for High Volumetric Energy Density Li-S Batteries

Journal Article · Mon Mar 12 00:00:00 EDT 2018 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201703438· OSTI ID:1466311

Li, Huan ^[1]; Tao, Ying ^[1]; Zhang, Chen ^[1]; Liu, Donghai ^[1]; Luo, Jiayan ^[1]; Fan, Weichao ^[1]; Xu, Yue ^[1]; Li, Youzhi ^[1]; You, Conghui ^[2]; Pan, Zheng -Ze ^[2]; Ye, Mingchun ^[1]; Chen, Zhengyu ^[1]; Dong, Zhang ^[1]; Wang, Da -Wei ^[3]; Kang, Feiyu ^[2];

^[4]; Yang, Quan -Hong ^[5]

Tianjin Univ., Tianjin (China)
Tsinghua Univ., Shenzhen (China)
UNSW Australia (The Univ. of New South Wales), Sydney, NSW (Australia)
Argonne National Lab. (ANL), Argonne, IL (United States)
Tianjin Univ., Tianjin (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin (China)

Abstract Despite the outstanding gravimetric performance of lithium–sulfur (Li–S) batteries, their practical volumetric energy density is normally lower than that of lithium‐ion batteries, mainly due to the low density of nanostructured sulfur as well as the porous carbon hosts. Here, a novel approach is developed to fabricate high‐density graphene bulk materials with “ink‐bottle‐like” mesopores by phosphoric acid (H ₃ PO ₄ ) activation. These pores can effectively confine the polysulfides due to their unique structure with a wide body and narrow neck, which shows only a 0.05% capacity fade per cycle for 500 cycles (75% capacity retention) for accommodating polysulfides. With a density of 1.16 g cm ⁻³ , a hybrid cathode containing 54 wt% sulfur delivers a high volumetric capacity of 653 mA h cm ⁻³ . As a result, a device‐level volumetric energy density as high as 408 W h L ⁻¹ is achieved with a cathode thickness of 100 µm. This is a periodic yet practical advance to improve the volumetric performance of Li–S batteries from a device perspective. This work suggests a design principle for the real use Li–S batteries although there is a long way ahead to bridge the gap between Li–S batteries and Li–ion batteries in volumetric performance.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Natural Science Foundation of China (NSFC); USDOE

Grant/Contract Number:: AC02-06CH11357; DE–AC02–06CH11357

OSTI ID:: 1466311

Alternate ID(s):: OSTI ID: 1425506

Journal Information:: Advanced Energy Materials, Vol. 8, Issue 18; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 102 works

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References (49)

Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V. Pure and Applied Chemistry, Vol. 87, Issue 9-10 https://doi.org/10.1515/pac-2014-1117	journal	October 2015
Porosity in granular carbons activated with phosphoric acid Molina-Sabio, M.; RodRíguez-Reinoso, F.; Caturla, F. Carbon, Vol. 33, Issue 8 https://doi.org/10.1016/0008-6223(95)00059-M	journal	January 1995
High Sulfur Loading in Hierarchical Porous Carbon Rods Constructed by Vertically Oriented Porous Graphene-Like Nanosheets for Li-S Batteries Zheng, Zongmin; Guo, Hongchen; Pei, Fei Advanced Functional Materials, Vol. 26, Issue 48 https://doi.org/10.1002/adfm.201601897	journal	July 2016
Compressed porous graphene particles for use as supercapacitor electrodes with excellent volumetric performance Li, Huan; Tao, Ying; Zheng, Xiaoyu Nanoscale, Vol. 7, Issue 44 https://doi.org/10.1039/C5NR06113J	journal	January 2015
Activated carbons from yellow poplar and white oak by H3PO4 activation Jagtoyen, Marit; Derbyshire, Frank Carbon, Vol. 36, Issue 7-8 https://doi.org/10.1016/S0008-6223(98)00082-7	journal	January 1998
Towards superior volumetric performance: design and preparation of novel carbon materials for energy storage Zhang, Chen; Lv, Wei; Tao, Ying Energy & Environmental Science, Vol. 8, Issue 5 https://doi.org/10.1039/C5EE00389J	journal	January 2015
A high-density graphene–sulfur assembly: a promising cathode for compact Li–S batteries Zhang, Chen; Liu, Dong-Hai; Lv, Wei Nanoscale, Vol. 7, Issue 13 https://doi.org/10.1039/C4NR06863G	journal	January 2015
Recent advances in the textural characterization of hierarchically structured nanoporous materials Cychosz, Katie A.; Guillet-Nicolas, Rémy; García-Martínez, Javier Chemical Society Reviews, Vol. 46, Issue 2 https://doi.org/10.1039/C6CS00391E	journal	January 2017
Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage Xu, Fei; Tang, Zhiwei; Huang, Siqi Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8221	journal	June 2015
Nitrogen-Doped Aligned Carbon Nanotube/Graphene Sandwiches: Facile Catalytic Growth on Bifunctional Natural Catalysts and Their Applications as Scaffolds for High-Rate Lithium-Sulfur Batteries Tang, Cheng; Zhang, Qiang; Zhao, Meng-Qiang Advanced Materials, Vol. 26, Issue 35 https://doi.org/10.1002/adma.201401243	journal	May 2014
Monodispersed Sulfur Nanoparticles for Lithium–Sulfur Batteries with Theoretical Performance Chen, Hongwei; Wang, Changhong; Dong, Weiling Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl504963e	journal	December 2014
Smaller Sulfur Molecules Promise Better Lithium–Sulfur Batteries Xin, Sen; Gu, Lin; Zhao, Na-Hong Journal of the American Chemical Society, Vol. 134, Issue 45 https://doi.org/10.1021/ja308170k	journal	October 2012
Designing high-energy lithium–sulfur batteries Seh, Zhi Wei; Sun, Yongming; Zhang, Qianfan Chemical Society Reviews, Vol. 45, Issue 20 https://doi.org/10.1039/C5CS00410A	journal	January 2016
Reactivation of dissolved polysulfides in Li–S batteries based on atomic layer deposition of Al2O3 in nanoporous carbon cloth Han, Xiaogang; Xu, Yunhua; Chen, Xinyi Nano Energy, Vol. 2, Issue 6 https://doi.org/10.1016/j.nanoen.2013.05.003	journal	November 2013
Synthetic carbons activated with phosphoric acid Puziy, A. M.; Poddubnaya, O. I.; Martı́nez-Alonso, A. Carbon, Vol. 40, Issue 9 https://doi.org/10.1016/S0008-6223(01)00317-7	journal	August 2002
Graphene-based materials for electrochemical energy storage devices: Opportunities and challenges Lv, Wei; Li, Zhengjie; Deng, Yaqian Energy Storage Materials, Vol. 2 https://doi.org/10.1016/j.ensm.2015.10.002	journal	January 2016
Partially unzipped carbon nanotubes for high-rate and stable lithium–sulfur batteries Jeong, Y. C.; Lee, K.; Kim, T. Journal of Materials Chemistry A, Vol. 4, Issue 3 https://doi.org/10.1039/C5TA07818K	journal	January 2016
N/P-Codoped Thermally Reduced Graphene for High-Performance Supercapacitor Applications Wang, Chunlei; Zhou, Ying; Sun, Li The Journal of Physical Chemistry C, Vol. 117, Issue 29 https://doi.org/10.1021/jp4015959	journal	July 2013
Stabilization of Insoluble Discharge Products by Facile Aniline Modification for High Performance Li-S Batteries Kim, Jae Ho; Kim, Taehoon; Jeong, Yo Chan Advanced Energy Materials, Vol. 5, Issue 14 https://doi.org/10.1002/aenm.201500268	journal	May 2015
HEMP-derived activated carbon fibers by chemical activation with phosphoric acid Rosas, J. M.; Bedia, J.; Rodríguez-Mirasol, J. Fuel, Vol. 88, Issue 1 https://doi.org/10.1016/j.fuel.2008.08.004	journal	January 2009
Highly Reversible Lithium/Dissolved Polysulfide Batteries with Carbon Nanotube Electrodes Fu, Yongzhu; Su, Yu-Sheng; Manthiram, Arumugam Angewandte Chemie International Edition, Vol. 52, Issue 27 https://doi.org/10.1002/anie.201301250	journal	May 2013
Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors Tao, Ying; Xie, Xiaoying; Lv, Wei Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02975	journal	October 2013
Polysulfide Shuttle Study in the Li/S Battery System Mikhaylik, Yuriy V.; Akridge, James R. Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976 https://doi.org/10.1149/1.1806394	journal	January 2004
True Performance Metrics in Electrochemical Energy Storage Gogotsi, Y.; Simon, P. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1213003	journal	November 2011
Liquid-Type Cathode Enabled by 3D Sponge-Like Carbon Nanotubes for High Energy Density and Long Cycling Life of Li-S Batteries Pu, Xiong; Yang, Gang; Yu, Choongho Advanced Materials, Vol. 26, Issue 44 https://doi.org/10.1002/adma.201403337	journal	October 2014
Self-Assembly of Graphene Oxide at Interfaces Shao, Jiao-Jing; Lv, Wei; Yang, Quan-Hong Advanced Materials, Vol. 26, Issue 32 https://doi.org/10.1002/adma.201400267	journal	May 2014
One-pot self-assembly of graphene/carbon nanotube/sulfur hybrid with three dimensionally interconnected structure for lithium–sulfur batteries Niu, Shuzhang; Lv, Wei; Zhang, Chen Journal of Power Sources, Vol. 295 https://doi.org/10.1016/j.jpowsour.2015.06.122	journal	November 2015
Adsorption hysteresis in ink-bottle pore Morishige, Kunimitsu; Tateishi, Noriko The Journal of Chemical Physics, Vol. 119, Issue 4 https://doi.org/10.1063/1.1585014	journal	July 2003
Aligned carbon nanotube/sulfur composite cathodes with high sulfur content for lithium–sulfur batteries Cheng, Xin-Bing; Huang, Jia-Qi; Zhang, Qiang Nano Energy, Vol. 4 https://doi.org/10.1016/j.nanoen.2013.12.013	journal	March 2014
Porosity development in activated carbons obtained from date pits under chemical activation with phosphoric acid Girgis, Badie S.; El-Hendawy, Abdel-Nasser A. Microporous and Mesoporous Materials, Vol. 52, Issue 2 https://doi.org/10.1016/S1387-1811(01)00481-4	journal	April 2002
Aligned sulfur-coated carbon nanotubes with a polyethylene glycol barrier at one end for use as a high efficiency sulfur cathode Huang, Jia-Qi; Zhang, Qiang; Zhang, Shu-Mao Carbon, Vol. 58 https://doi.org/10.1016/j.carbon.2013.02.037	journal	July 2013
Graphene materials for lithium–sulfur batteries Yu, Mingpeng; Li, Rui; Wu, Mingmao Energy Storage Materials, Vol. 1 https://doi.org/10.1016/j.ensm.2015.08.004	journal	November 2015
Long-life Li/polysulphide batteries with high sulphur loading enabled by lightweight three-dimensional nitrogen/sulphur-codoped graphene sponge Zhou, Guangmin; Paek, Eunsu; Hwang, Gyeong S. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8760	journal	July 2015
Nanostructured sulfur cathodes Yang, Yuan; Zheng, Guangyuan; Cui, Yi Chemical Society Reviews, Vol. 42, Issue 7, p. 3018-3032 https://doi.org/10.1039/c2cs35256g	journal	January 2013
Pie-like electrode design for high-energy density lithium–sulfur batteries Li, Zhen; Zhang, Jin Tao; Chen, Yu Ming Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9850	journal	November 2015
High sulfur loading composite wrapped by 3D nitrogen-doped graphene as a cathode material for lithium–sulfur batteries Wang, Chao; Su, Kai; Wan, Wang J. Mater. Chem. A, Vol. 2, Issue 14 https://doi.org/10.1039/C3TA14921H	journal	January 2014
Evolution of the effect of sulfur confinement in graphene-based porous carbons for use in Li–S batteries Jia, Xiangling; Zhang, Chen; Liu, Juanjuan Nanoscale, Vol. 8, Issue 8 https://doi.org/10.1039/C5NR08839A	journal	January 2016
Dense integration of graphene and sulfur through the soft approach for compact lithium/sulfur battery cathode Li, Hongfei; Yang, Xiaowei; Wang, Xiaomin Nano Energy, Vol. 12 https://doi.org/10.1016/j.nanoen.2015.01.007	journal	March 2015
Preparation of activated carbon from lignin by chemical activation Hayashi, Jun’ichi; Kazehaya, Atsuo; Muroyama, Katsuhiko Carbon, Vol. 38, Issue 13 https://doi.org/10.1016/S0008-6223(00)00027-0	journal	January 2000
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage Lin, T.; Chen, I. -W.; Liu, F. Science, Vol. 350, Issue 6267 https://doi.org/10.1126/science.aab3798	journal	December 2015
A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage Yang, Yuan; Zheng, Guangyuan; Cui, Yi Energy & Environmental Science, Vol. 6, Issue 5 https://doi.org/10.1039/c3ee00072a	journal	January 2013
A Metal-Free Supercapacitor Electrode Material with a Record High Volumetric Capacitance over 800 F cm ⁻³ Xu, Yue; Tao, Ying; Zheng, Xiaoyu Advanced Materials, Vol. 27, Issue 48 https://doi.org/10.1002/adma.201504151	journal	November 2015
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F. Nature Materials, Vol. 8, Issue 6, p. 500-506 https://doi.org/10.1038/nmat2460	journal	May 2009
3D Interconnected Electrode Materials with Ultrahigh Areal Sulfur Loading for Li-S Batteries Fang, Ruopian; Zhao, Shiyong; Hou, Pengxiang Advanced Materials, Vol. 28, Issue 17 https://doi.org/10.1002/adma.201506014	journal	March 2016
Preparation of activated carbon from bituminous coal with phosphoric acid activation Teng, Hsisheng; Yeh, Tien-Sheng; Hsu, Li-Yeh Carbon, Vol. 36, Issue 9 https://doi.org/10.1016/S0008-6223(98)00127-4	journal	September 1998
Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang Nature, Vol. 516, Issue 7529 https://doi.org/10.1038/nature13970	journal	November 2014
Highly Reversible Lithium/Dissolved Polysulfide Batteries with Carbon Nanotube Electrodes Fu, Yongzhu; Su, Yu-Sheng; Manthiram, Arumugam Angewandte Chemie, Vol. 125, Issue 27, p. 7068-7073 https://doi.org/10.1002/ange.201301250	journal	May 2013
Synthetic carbons activated with phosphoric acid Puziy, A. M.; Poddubnaya, O. I.; Martı́nez-Alonso, A. Carbon, Vol. 40, Issue 9 https://doi.org/10.1016/s0008-6223(01)00318-9	journal	August 2002

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25 ENERGY STORAGE
graphene monolith
ink-bottle-like pores
lithium-polysulfide batteries
polysulfides
volumetric performance