Ultralow Frequency Electrochemical – Mechanical Strain Energy

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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

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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]

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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.

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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.

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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

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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

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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.

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