Subscriber access provided by UNIV OF NEWCASTLE
Letter
Ultralow Frequency Electrochemical – Mechanical Strain Energy Harvester using 2D Black Phosphorus Nanosheets Nitin Muralidharan, Mengya Li, Rachel E. Carter, Nicholas Galioto, and Cary L. Pint ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.7b00478 • Publication Date (Web): 12 Jul 2017 Downloaded from http://pubs.acs.org on July 17, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Energy Letters is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 24
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Energy Letters
Ultralow
Frequency
Electrochemical
–
Mechanical Strain Energy Harvester using 2D Black Phosphorus Nanosheets Nitin Muralidharan,1,2,‡ Mengya Li,1‡ Rachel E. Carter,1 Nicholas Galioto,1 and Cary L. Pint1,2* 1
Department of Mechanical Engineering, Vanderbilt University, Nashville TN 37235
2
Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, TN
37235 ‡
These authors contributed equally to this work
*Corresponding author:
[email protected] 1 ACS Paragon Plus Environment
ACS Energy Letters
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ABSTRACT: Advances in piezoelectric or triboelectric materials have enabled high frequency platforms for mechanical energy harvesting (> 10 Hz), however virtually all human motions occur below 5 Hz and therefore limits application of these harvesting platforms to human motions. Here we demonstrate a device configuration based on sodiated black phosphorus nanosheets, or phosphorene, where mechano-electrochemical stress-voltage coupling in this material is capable of efficient energy harvesting at frequencies as low as 0.01 Hz. The harvester is tested using both bending and pressing mechanical impulses with peak power delivery of ~42 nW/cm2 and total harvested energy of 0.203 µJ/cm2 in bending mode and ~9 nW/cm2 and 0.792 µJ/cm2 in pressing mode. Our work broadly demonstrates how 2D materials can be effectively leveraged as building blocks in strategies for efficient electrochemical strain energy harvesting.
2 ACS Paragon Plus Environment
Page 2 of 24
Page 3 of 24
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Energy Letters
An ambient mechanical energy harvester converts input mechanical energy into electrical energy, which can be transferred and utilized in other systems.1-2 Conventional methods of ambient mechanical energy harvesting commonly utilize a variety of piezoelectric and triboelectric materials.3-5 Although these materials are capable of effective energy harvesting at high frequencies (>10 Hz), their performance drastically drops when these devices are operated under low frequency ( 30%, Figure S8, see supporting information), lack of understanding of the mechanical properties in both 2D materials and ion-intercalated 2D materials remains a bottleneck toward robust quantitative assessment. At the systems level, one can infer that control of assembly of the nanostructured building blocks will be a critical factor to enable efficient coupling of mechanical energy to electrical energy. At the nanoscale, one can envision a new class of strain harvesters that can be assembled at the singlenanosheet scale. A simple example is a stacked 2D material with locally intercalated ions10, 22, 32 that can function as a nanoscale strain harvesting device for low-frequency motions at the molecular scale in fabrics, liquids, or other media. Our work emphasizes how 2D building blocks are platforms for the design of future strain energy harvesting schemes tuned to harvest energy from low frequency motions.
11 ACS Paragon Plus Environment
ACS Energy Letters
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 12 of 24
Table 1. Performance of the phosphorene 2D energy harvester described in this work. Testing Method Bending
Operational Bending Frequency Radius (Hz) (mm) 0.1
Applied Peak Energy Response Pressure Power Harvested Time 2 2 (MPa) (nW/cm ) (µJ/cm ) (s)
3
42
0.203
5
0.1
~0.2
9.68
0.076
10
0.01
~0.2
9.12
0.792
100
Pressing
In summary, our work demonstrates a 2D material (phosphorene) strain energy harvester configuration relying on mechano-electrochemical stress-voltage coupling at low frequencies relevant to human motions. The assembled harvester was tested in both bending and pressing modes, with experiments demonstrating a peak power delivery of ~42 nW/cm2 (0.1 Hz, RoC = 3 mm) and ~9 nW/cm2 (0.1/0.01 Hz, Load ~0.2 MPa) respectively. The energy output from these devices during bending and pressing were 0.203 µJ/cm2 (0.1 Hz, RoC = 3mm) and 0.792 µJ/cm2 (0.01 Hz, Load ~0.2 MPa) respectively with response times (FWHM of current output – 10 s and 100 s) several orders of magnitude greater than conventional piezoelectric systems which provide highly inefficient harvesting capability at such low frequencies. This provides a framework to exploit (i) the controlled mechanical properties of 2D materials, (ii) the homogenous strain propagation that occurs in 2D material geometries, and (iii) the capability of accessing 2D material energy harvesting tuned to frequencies relevant to human motions. Our results support future work spanning from harvesting mechanical stresses at the nanometer length scales in designer 2D material stacks to designing system-level architectures, such as integrated MEMS-electrochemical harvesting units
12 ACS Paragon Plus Environment
Page 13 of 24
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Energy Letters
that can be functional for a broad range of low-frequency energy harvesting applications complimentary to the state-of-the-art piezoelectric or triboeletric system operation.
Associated Content Supporting Information Supporting information is available and contains experimental methods, Potential safety concerns of the electrochemical-mechanical energy harvesters and strategies to mitigate them, size distribution of exfoliated BP nanosheets, I-t curve of electrophoretic deposition of exfoliated BP onto graphene on Cu, SEM EDS elemental mapping spectra of BP deposited onto graphene on Cu, Raman spectra of the BP on graphene, VOC responses of the device for different bending radii, ∆VOC variation with bending radii, VOC short circuit current response at 0.01 Hz press test, Idealized efficiency analysis. Author Information Corresponding Author *Corresponding author:
[email protected] Notes The authors declare no competing financial interest. Acknowledgements The authors would like to thank Adam Cohn, Keith Share, Anna Douglas, Kate Moyer and Deanna Schauben for useful insights and discussions. We would also like to acknowledge Rizia Bardhan for use of Raman facilities. This work was supported in part
13 ACS Paragon Plus Environment
ACS Energy Letters
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
by the Vanderbilt University discovery grant program, NSF grant CMMI 1400424, and R.C. was supported by a fellowship through the Vanderbilt Institute for Nanoscale Science and Engineering.
REFERENCES (1) Cannarella, J.; Arnold, C. B. Toward Low‐Frequency Mechanical Energy Harvesting Using Energy‐Dense Piezoelectrochemical Materials. Adv. Mater. 2015, 27, 7440-7444. (2) Orrego, S.; Shoele, K.; Ruas, A.; Doran, K.; Caggiano, B.; Mittal, R.; Kang, S. H. Harvesting Ambient Wind Energy With an Inverted Piezoelectric Flag. Appl. Energ. 2017, 194, 212-222. (3) Qin, Y.; Wang, X.; Wang, Z. L. Microfibre–Nanowire Hybrid Structure for Energy Scavenging. Nature 2008, 451, 809-813. (4) Anton, S. R.; Sodano, H. A. A Review of Power Harvesting Using Piezoelectric Materials (2003–2006). Smart Mater. Struct. 2007, 16, R1-R21. (5) Wu, H.; Huang, Y.; Xu, F.; Duan, Y.; Yin, Z. Energy Harvesters for Wearable and Stretchable Electronics: From Flexibility to Stretchability. Adv. Mater. 2016, 28, 9881– 9919. (6) Li, H.; Tian, C.; Deng, Z. D. Energy Harvesting From Low Frequency Applications Using Piezoelectric Materials. Appl. Phys. Rev. 2014, 1, 041301. (7) Mummolo, C.; Mangialardi, L.; Kim, J. H. Quantifying Dynamic Characteristics of Human Walking for Comprehensive Gait Cycle. J. Biomech. Eng. 2013, 135, 091006.
14 ACS Paragon Plus Environment
Page 14 of 24
Page 15 of 24
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Energy Letters
(8) Danion, F.; Varraine, E.; Bonnard, M.; Pailhous, J. Stride Variability in Human Gait: the Effect of Stride Frequency and Stride Length. Gait Posture 2003, 18, 69-77. (9) Muralidharan, N.; Carter, R.; Oakes, L.; Cohn, A. P.; Pint, C. L. Strain Engineering to Modify the Electrochemistry of Energy Storage Electrodes. Sci. Rep. 2016, 6, 27542 (10) Oakes, L.; Carter, R.; Hanken, T.; Cohn, A. P.; Share, K.; Schmidt, B.; Pint, C. L. Interface Strain in Vertically Stacked Two-Dimensional Heterostructured Carbon-MoS2 Nanosheets Controls Electrochemical Reactivity. Nat. Commun. 2016, 7, 11796. (11) Schiffer, Z.; Arnold, C. Characterization and Model of Piezoelectrochemical Energy Harvesting Using Lithium ion Batteries. Exp. Mech. 2017, DOI: 10.1007/s11340-0170291-1. (12) Liu, X. M.; Arnold, C. B. Effects of Cycling Ranges on Stress and Capacity Fade in Lithium-Ion Pouch Cells. J. Electrochem. Soc. 2016, 163, A2501-A2507. (13) Schiffer, Z. J.; Cannarella, J.; Arnold, C. B. Strain Derivatives for Practical Charge Rate Characterization of Lithium Ion Electrodes. J. Electrochem. Soc. 2016, 163, A427A433. (14) Muralidharan, N.; Brock, C. N.; Cohn, A. P.; Schauben, D.; Carter, R. E.; Oakes, L.; Walker, D. G.; Pint, C. L. Tunable Mechanochemistry of Lithium Battery Electrodes. ACS Nano 2017, 11, 6243-6251. (15) Kim, S.; Choi, S. J.; Zhao, K.; Yang, H.; Gobbi, G.; Zhang, S.; Li, J. Electrochemically Driven Mechanical Energy Harvesting. Nat. Commun. 2016, 7, 10146. (16) Tavassol, H.; Jones, E. M.; Sottos, N. R.; Gewirth, A. A. Electrochemical Stiffness in Lithium-Ion Batteries. Nat. Mater. 2016, 15, 1182-1187.
15 ACS Paragon Plus Environment
ACS Energy Letters
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
(17) Zhang, S. Chemomechanical Modeling of Lithiation-Induced Failure in HighVolume-Change Electrode Materials for Lithium Ion Batteries. NPJ Comput. Mater. 2017, 3, 1-11. (18) Castellanos-Gomez, A.; Roldán, R.; Cappelluti, E.; Buscema, M.; Guinea, F.; van der Zant, H. S.; Steele, G. A. Local Strain Engineering in Atomically Thin MoS2. Nano Lett. 2013, 13, 5361-5366. (19) Çakır, D.; Sahin, H.; Peeters, F. M. Tuning of the Electronic and Optical Properties of Single-Layer Black Phosphorus by Strain. Phys. Rev. B 2014, 90, 205421. (20) Jiang, J.-W.; Park, H. S. Negative Poisson's Ratio in Single-Layer Black Phosphorus. Nat. Commun. 2014, 5, 4727. (21) Fei, R.; Yang, L. Strain-Engineering the Anisotropic Electrical Conductance of Few-Layer Black Phosphorus. Nano Lett. 2014, 14, 2884-2889. (22) Sun, J.; Lee, H.-W.; Pasta, M.; Yuan, H.; Zheng, G.; Sun, Y.; Li, Y.; Cui, Y. A Phosphorene–Graphene Hybrid Material as a High-Capacity Anode for Sodium-Ion Batteries. Nat. Nanotechnol. 2015, 10, 980-985. (23) Dahbi, M.; Yabuuchi, N.; Fukunishi, M.; Kubota, K.; Chihara, K.; Tokiwa, K.; Yu, X.-F.; Ushiyama, H.; Yamashita, K.; Son, J.-Y., et al. Black Phosphorus as a HighCapacity, High-Capability Negative Electrode for Sodium-Ion Batteries: Investigation of the Electrode/Electrolyte Interface. Chem. Mater. 2016, 28, 1625-1635. (24) Chen, T.; Zhao, P.; Guo, X.; Zhang, S. Two-Fold Anisotropy Governs Morphological Evolution and Stress Generation in Sodiated Black Phosphorus for Sodium Ion Batteries. Nano Lett. 2017, 17, 2299–2306.
16 ACS Paragon Plus Environment
Page 16 of 24
Page 17 of 24
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Energy Letters
(25) Oakes, L.; Zulkifli, D.; Azmi, H.; Share, K.; Hanken, T.; Carter, R.; Pint, C. L. One Batch Exfoliation and Assembly of Two-Dimensional Transition Metal Dichalcogenide Nanosheets Using Electrophoretic Deposition. J. Electrochem. Soc. 2015, 162, D3063D3070. (26) Oakes, L.; Hanken, T.; Carter, R.; Yates, W.; Pint, C. L. Roll-to-Roll Nanomanufacturing of Hybrid Nanostructures for Energy Storage Device Design. ACS Appl. Mater. Interfaces 2015, 7, 14201-14210. (27) Qi, Y.; McAlpine, M. C. Nanotechnology-Enabled Flexible and Biocompatible Energy Harvesting. Energy Environ. Sci. 2010, 3, 1275-1285. (28) Koka, A.; Zhou, Z.; Sodano, H. A. Vertically Aligned BaTiO3 Nanowire Arrays for Energy Harvesting. Energy Environ. Sci. 2014, 7, 288-296. (29) Xu, S.; Qin, Y.; Xu, C.; Wei, Y.; Yang, R.; Wang, Z. L. Self-Powered Nanowire Devices. Nat. Nanotechnol. 2010, 5, 366-373. (30) Hou, Y.; Zhou, Y.; Yang, L.; Li, Q.; Zhang, Y.; Zhu, L.; Hickner, M. A.; Zhang, Q.; Wang, Q. Flexible Ionic Diodes for Low‐Frequency Mechanical Energy Harvesting. Adv. Energy Mater. 2016, 7, 1601983. (31) Zi, Y.; Guo, H.; Wen, Z.; Yeh, M. H.; Hu, C.; Wang, Z. L. Harvesting LowFrequency (
