Biomorphic structural batteries for robotics
Abstract
Batteries with conformal shape and multiple functionalities could provide new degrees of freedom in the design of robotic devices. For example, the ability to provide both load bearing and energy storage can increase the payload and extend the operational range for robots. However, realizing these kinds of structural power devices requires the development of materials with suitable mechanical and ion transport properties. Here, we report biomimetic aramid nanofibers–based composites with cartilage-like nanoscale morphology that display an unusual combination of mechanical and ion transport properties. Ion-conducting membranes from these aramid nanofiber composites enable pliable zinc-air batteries with cyclic performance exceeding 100 hours that can also serve as protective covers in various robots including soft and flexible miniaturized robots. The unique properties of the aramid ion conductors are attributed to the percolating network architecture of nanofibers with high connectivity and strong nanoscale filaments designed using a graph theory of composite architecture when the continuous aramid filaments are denoted as edges and intersections are denoted as nodes. The total capacity of these body-integrated structural batteries is 72 times greater compared with a stand-alone Li-ion battery with the same volume. These materials and their graph theory description enable a new generation of robotic devices, body prosthetics, and flexible and soft robotics with nature-inspired distributed energy storage.
Get full access to this article
View all available purchase options and get full access to this article.
Already a Subscriber?Sign In
Supplementary Material
Summary
Materials and Methods
Fig. S1. Schematic diagram of overall preparation of the QUPA/ANF membranes.
Fig. S2. Proposed reaction mechanism for PVA chains functionalization with DMOAP.
Fig. S3. PVA and functionalized QUPA composite comparison by XPS spectrum.
Fig. S4. Top-view SEM images of the PVA and QUPA membranes at different magnifications.
Fig. S5. SEM and corresponding EDS mapping images of PVA and QUPA membranes.
Fig. S6. Preparation of ANFs.
Fig. S7. Thermogravimetry curve comparison for the QUPA/ANF composite membrane with different ANF dispersion concentrations.
Fig. S8. SEM images of cross-section morphology of ANF and QUPA/ANF membranes.
Fig. S9. The morphology and color comparisons of the ANF-2.0 membrane after immersing into QUPA polymer solution.
Fig. S10. The pore surface area comparison of porous ANF-2.0 membrane and QUPA/ANF-2.0 composite membrane according to the BET analysis.
Fig. S11. The toughness values of QUPA/ANF with different ANF dispersion concentrations from 0.5 to 2.0 wt %.
Fig. S12. The initial impedance spectra comparison of QUPA/ANF composite membrane with different ANF dispersion concentrations.
Fig. S13. Digital photos of the folding and releasing process of QUPA/ANF-2.0 membrane.
Fig. S14. SEM images of QUPA/ANF-2.0 membrane under different states.
Fig. S15. Fracture energy of QUPA/ANF-2.0 membrane.
Fig. S16. The initial impedance spectra comparison of PVA, QUPA, and QUPA/ANF-2.0.
Fig. S17. The temperature-dependent ionic conductivity comparison of PVA, QUPA, and QUPA/ANF-2.0 membranes.
Fig. S18. The Arrhenius plot comparison of PVA, QUPA, and QUPA/ANF-2.0 membranes.
Fig. S19. The ion concentration and IEC comparison of PVA, QUPA, and QUPA/ANF-2.0 membranes.
Fig. S20. Comparison of the shape changes of QUPA and QUPA/ANF-2.0 membranes after drying at room temperature until a constant weight and dimension were obtained.
Fig. S21. Schematic representation of the rechargeable zinc-air battery.
Fig. S22. The XRD pattern of the cycled zinc electrode with QUPA electrolyte.
Fig. S23. The performance of zinc-air battery with different bending angles.
Fig. S24. Robot measures used in the calculations of its surface area.
Fig. S25. The size of original Li-ion battery.
Fig. S26. Comparison of working time of the robot with original Li-ion battery and six structural zinc-air batteries.
Table S1. Graph theoretical enumerators for description of ANF percolating network materials characterizing network connectivity.
Table S2. Comparison of tensile strength, tensile modulus, and elongation at break of QUPA, ANF, and QUPA/ANF composite membranes.
Table S3. Comparison of tensile strength, Young’s modulus, and elongation at break data for different fiber enhanced polymer hydrogels.
Table S4. Comparison of ionic conductivities of previously developed solid or gel electrolytes.
Table S5. Comparison of ionic conductivity, IEC, ion concentration, water uptake, and swelling ratio of QUPA and QUPA/ANF composite membranes.
Table S6. Summary of solid or gel state flexible rechargeable zinc-air batteries with various electrocatalysts and electrolytes.
Table S7. Summary of the surface area of the robot with different parts of robot.
Table S8. Comparison of battery properties from this work and in drones in (6).
Movie S1. The demonstration of biomorphic structural battery in battery-less humanoid robotic device.
Movie S2. The demonstration of biomorphic structural battery in battery-less scorpion minibot.
Movie S3. Overview of design and implementation of biomimetic composites and biomorphic structural batteries for robotics.
Resources
REFERENCES AND NOTES
1
M. Coelho, T. Oliveira, R. Fernandes, Biochemistry of adipose tissue: An endocrine organ. Arch. Med. Sci. 9, 191–200 (2013).
2
L. M. Schneider, N. Ihrner, D. Zenkert, M. Johansson, Bicontinuous electrolytes via thermally initiated polymerization for structural lithium ion batteries. ACS Appl. Energy Mater. 2, 4362–4369 (2019).
3
C. González, J. J. Vilatela, J. M. Molina-Aldareguía, C. S. Lopes, J. LLorca, Structural composites for multifunctional applications: Current challenges and future trends. Prog. Mater. Sci. 89, 194–251 (2017).
4
W. Johannisson, N. Ihrner, D. Zenkert, M. Johansson, D. Carlstedt, L. E. Asp, F. Sieland, Multifunctional performance of a carbon fiber UD lamina electrode for structural batteries. Compos. Sci. Technol. 168, 81–87 (2018).
5
Y. Zhang, J. Ma, A. K. Singh, L. Cao, J. Seo, C. D. Rahn, C. E. Bakis, M. A. Hickner, Multifunctional structural lithium-ion battery for electric vehicles. J. Intell. Mater. Syst. Struct. 28, 1603–1613 (2017).
6
M. Wang, A. Emre, S. O. Tung, A. Gerber, D. Wang, Y. Huang, V. Cecen, N. A. Kotov, Biomimetic solid-state Zn2+ electrolyte for corrugated structural batteries. ACS Nano 13, 1107–1115 (2019).
7
J. Fu, Z. P. Cano, M. G. Park, A. Yu, M. Fowler, Z. Chen, Electrically rechargeable zinc–air batteries: Progress, challenges, and perspectives. Adv. Mater. 29, 1604685 (2017).
8
Y. Li, H. Dai, Recent advances in zinc–air batteries. Chem. Soc. Rev. 43, 5257–5275 (2014).
9
X. Han, X. Wu, C. Zhong, Y. Deng, N. Zhao, W. Hu, NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes as a highly efficient bifunctional electrocatalyst for rechargeable zinc–air batteries. Nano Energy 31, 541–550 (2017).
10
A. R. Mainar, O. Leonet, M. Bengoechea, I. Boyano, I. de Meatza, A. Kvasha, A. Guerfi, J. A. Blázquez, Alkaline aqueous electrolytes for secondary zinc–air batteries: An overview. Int. J. Energy Res. 40, 1032–1049 (2016).
11
D. U. Lee, J. Scott, H. W. Park, S. Abureden, J.-Y. Choi, Z. Chen, Morphologically controlled Co3O4 nanodisks as practical bi-functional catalyst for rechargeable zinc–air battery applications. Electrochem. Commun. 43, 109–112 (2014).
12
J. F. Parker, C. N. Chervin, E. S. Nelson, D. R. Rolison, J. W. Long, Wiring zinc in three dimensions re-writes battery performance–dendrite-free cycling. Energ. Environ. Sci. 7, 1117–1124 (2014).
13
M. Yang, K. Cao, L. Sui, Y. Qi, J. Zhu, A. Waas, E. M. Arruda, J. Kieffer, M. D. Thouless, N. A. Kotov, Dispersions of aramid nanofibers: A new nanoscale building block. ACS Nano 5, 6945–6954 (2011).
14
S.-O. Tung, S. Ho, M. Yang, R. Zhang, N. A. Kotov, A dendrite-suppressing composite ion conductor from aramid nanofibres. Nat. Commun. 6, 6152 (2015).
15
X. Yao, Y. Hu, B. Cao, R. Peng, J. Ding, Effects of surface molecular chirality on adhesion and differentiation of stem cells. Biomaterials 34, 9001–9009 (2013).
16
L. Wang, Y. Yu, P. C. Chen, D. W. Zhang, C. H. Chen, Electrospinning synthesis of C/Fe3O4 composite nanofibers and their application for high performance lithium-ion batteries. J. Power Sources 183, 717–723 (2008).
17
L. Xu, X. Zhao, C. Xu, N. A. Kotov, Water-rich biomimetic composites with abiotic self-organizing nanofiber network. Adv. Mater. 30, 1703343 (2018).
18
Y. Xue, P. Bogdan, Reliable multi-fractal characterization of weighted complex networks: Algorithms and implications. Sci. Rep. 7, 7487 (2017).
19
C.-C. Yang, Chemical composition and XRD analyses for alkaline composite PVA polymer electrolyte. Mater. Lett. 58, 33–38 (2004).
20
B. Wu, L. Ge, D. Yu, L. Hou, Q. Li, Z. Yang, T. Xu, Cationic metal–organic framework porous membranes with high hydroxide conductivity and alkaline resistance for fuel cells. J. Mater. Chem. A 4, 14545–14549 (2016).
21
Z. Gadjourova, Y. G. Andreev, D. P. Tunstall, P. G. Bruce, Ionic conductivity in crystalline polymer electrolytes. Nat. Commun. 412, 520–523 (2001).
22
K. H. Gopi, S. D. Bhat, Anion exchange membrane from polyvinyl alcohol functionalized with quaternary ammonium groups via alkyl spacers. Ionics 24, 1097–1109 (2018).
23
M. Yang, K. Cao, B. Yeom, M. D. Thouless, A. Waas, E. M. Arruda, N. A. Kotov, Aramid nanofiber-reinforced transparent nanocomposites. J. Compos. Mater. 49, 1873–1879 (2015).
24
Y. Guan, W. Li, Y. Zhang, Z. Shi, J. Tan, F. Wang, Y. Wang, Aramid nanofibers and poly (vinyl alcohol) nanocomposites for ideal combination of strength and toughness via hydrogen bonding interactions. Compos. Sci. Technol. 144, 193–201 (2017).
25
H. Zarrin, S. Sy, J. Fu, G. Jiang, K. Kang, Y.-S. Jun, A. Yu, M. Fowler, Z. Chen, Molecular functionalization of graphene oxide for next-generation wearable electronics. ACS Appl. Mater. Interface 8, 25428–25437 (2016).
26
M. Wang, N. Xu, J. Fu, Y. Liu, J. Qiao, High-performance binary cross-linked alkaline anion polymer electrolyte membranes for all-solid-state supercapacitors and flexible rechargeable zinc–air batteries. J. Mater. Chem. A , 11257–11264 (2019).
27
I. Villaluenga, K. H. Wujcik, W. Tong, D. Devaux, D. H. C. Wong, J. M. DeSimone, N. P. Balsara, Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries. Proc. Natl. Acad. Sci. U.S.A. 113, 52–57 (2016).
28
N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto, A. Mitsui, A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).
29
B. Yeom, T. Sain, T. Lacevic, D. Bukharina, S.-H. Cha, A. M. Waas, E. M. Arruda, N. A. Kotov, Abiotic tooth enamel. Nature 543, 95–98 (2017).
30
N. A. Kotov, I. Dékány, J. H. Fendler, Ultrathin graphite oxide–polyelectrolyte composites prepared by self-assembly: Transition between conductive and non-conductive states. Adv. Mater. 8, 637–641 (1996).
31
C. Lin, S. S. Shinde, X. Li, D.-H. Kim, N. Li, Y. Sun, X. Song, H. Zhang, C. H. Lee, S. U. Lee, J.-H. Lee, Solid-state rechargeable zinc–air battery with long shelf life based on nanoengineered polymer electrolyte. ChemSusChem 11, 3215–3224 (2018).
32
Y. Wei, M. Wang, N. Xu, L. Peng, J. Mao, Q. Gong, J. Qiao, Alkaline exchange polymer membrane electrolyte for high performance of all-solid-state electrochemical devices. ACS Appl. Mater. Interfaces 10, 29593–29598 (2018).
33
J. Fu, J. Zhang, X. Song, H. Zarrin, X. Tian, J. Qiao, L. Rasen, K. Li, Z. Chen, A flexible solid-state electrolyte for wide-scale integration of rechargeable zinc–air batteries. Energ. Environ. Sci. 9, 663–670 (2016).
34
J. Zhang, J. Fu, X. Song, G. Jiang, H. Zarrin, P. Xu, K. Li, A. Yu, Z. Chen, Laminated cross-linked nanocellulose/graphene oxide electrolyte for flexible rechargeable zinc–air batteries. Adv. Energy Mater. 6, 1600476 (2016).
35
X. Wu, W. Chen, X. Yan, G. He, J. Wang, Y. Zhang, X. Zhu, Enhancement of hydroxide conductivity by the di-quaternization strategy for poly(ether ether ketone) based anion exchange membranes. J. Mater. Chem. A 2, 12222–12231 (2014).
36
N. J. Robertson, H. A. Kostalik IV, T. J. Clark, P. F. Mutolo, H. D. Abruña, G. W. Coates, Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications. J. Am. Chem. Soc. 132, 3400–3404 (2010).
37
M. Tanaka, K. Fukasawa, E. Nishino, S. Yamaguchi, K. Yamada, H. Tanaka, B. Bae, K. Miyatake, M. Watanabe, Anion conductive block poly(arylene ether)s: Synthesis, properties, and application in alkaline fuel cells. J. Am. Chem. Soc. 133, 10646–10654 (2011).
38
K. J. Harry, D. T. Hallinan, D. Y. Parkinson, A. A. MacDowell, N. P. Balsara, Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nat. Mater. 13, 69–73 (2014).
39
M. J. Zachman, Z. Tu, S. Choudhury, L. A. Archer, L. F. Kourkoutis, Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).
40
K. Wang, P. Pei, Z. Ma, H. Chen, H. Xu, D. Chen, X. Wang, Dendrite growth in the recharging process of zinc–air batteries. J. Mater. Chem. A 3, 22648–22655 (2015).
41
K. E. K. Sun, T. K. A. Hoang, T. N. L. Doan, Y. Yu, X. Zhu, Y. Tian, P. Chen, Suppression of dendrite formation and corrosion on zinc anode of secondary aqueous batteries. ACS Appl. Mater. Interfaces 9, 9681–9687 (2017).
42
G. Garcia, E. Ventosa, W. Schuhmann, Complete prevention of dendrite formation in Zn metal anodes by means of pulsed charging protocols. ACS Appl. Mater. Interfaces 9, 18691–18698 (2017).
43
C. Lu, V. Raghunathan, K. Roy, Micro-scale energy harvesting: A system design perspective, in 15th Proceedings of the Asia and South Pacific Design Automation Conference, ASP-DAC (IEEE, 2010), pp. 89–94.
44
A. Malti, J. Edberg, H. Granberg, Z. U. Khan, J. W. Andreasen, X. Liu, D. Zhao, H. Zhang, Y. Yao, J. W. Brill, I. Engquist, M. Fahlman, L. Wågberg, X. Crispin, M. Berggren, An organic mixed ion–electron conductor for power electronics. Adv. Sci. 3, 1500305 (2016).
45
L. Hu, N. Liu, M. Eskilsson, G. Zheng, J. McDonough, L. Wågberg, Y. Cui, Silicon-conductive nanopaper for Li-ion batteries. Nano Energy 2, 138–145 (2013).
46
R. Ludwig, New insight into the transport mechanism of hydrated hydroxide ions in water. Angew. Chemie Int. Ed. 42, 258–260 (2003).
47
X. Chen, B. Liu, C. Zhong, Z. Liu, J. Liu, L. Ma, Y. Deng, X. Han, T. Wu, W. Hu, J. Lu, Ultrathin Co3O4 layers with large contact area on carbon fibers as high-performance electrode for flexible zinc–air battery integrated with flexible display. Adv. Energy Mater. 7, 1700779 (2017).
48
B. B. Mandelbrot, Multifractals and 1/f Noise: Wild Self-Affinity in Physics (1963–1976) (Springer Mathematics, 2013).
Information & Authors
Information
Published In

Science Robotics
Volume 5 | Issue 45
August 2020
August 2020
Copyright
Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.
This is an article distributed under the terms of the Science Journals Default License.
Submission history
Received: 12 November 2019
Accepted: 23 July 2020
Acknowledgments
N.A.K. acknowledges the support from Vannewar Bush DoD Fellowship titled “Engineered chiral ceramics” (ONR N000141812876) “Energy- and cost-efficient manufacturing employing nanoparticles” (NSF 1463474), and “Layered composites from branched nanofibers for lithium ion batteries” (NSF 1538180), and “Nanocomposite ion conductors for thin film batteries” (AFOSR FA9550-16-1-0265). M.W. acknowledges the support from the China Scholarship Council, Postdoctoral fellow of Harbin Institute of Technology. P.B. acknowledges the support from the National Science Foundation (NSF) Career Award CPS/CNS-1453860 and the DARPA Young Faculty Award and DARPA Director Award, under grant number N66001-17-1-4044. Author contributions: M.W. prepared QUPA-ANF composites, performed characterization experiments, and cowrote the paper. A.E., C.W., and Z.J. prepared and characterized ANF composites and analyzed batteries performance. D.V. wrote the Python script for StructuralGT and carried out GT calculations of major indexes. X.X. and P.B. calculated the multifractal description of nanofiber composites. Y.H. analyzed the results and participated in writing the paper. N.A.K. conceptualized the study, GT design of composites, calculated GT indexes, and cowrote the paper. Competing interests: N.A.K. is a founder of Elegus Technologies that produces ANF-based separators. N.A.K., A.E., and M.W. are inventors on patent application (insert number) held/submitted by The University of Michigan that covers structural zinc batteries. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper or the Supplementary Materials.
Authors
Funding Information
Air Force Office of Scientific Research: FA9550-16-1-0265
National Science Foundation: 1538180
Metrics & Citations
Metrics
Article Usage
Altmetrics
Citations
Export citation
Select the format you want to export the citation of this publication.
Cited by
- Natural Wood Structure Inspires Practical Lithium–Metal Batteries, ACS Energy Letters, 6, 6, (2103-2110), (2021).https://doi.org/10.1021/acsenergylett.1c00629
- 3D Porous Sponge-Inspired Electrode for High-Energy and High-Power Zinc-Ion Batteries, ACS Applied Energy Materials, 4, 2, (1833-1839), (2021).https://doi.org/10.1021/acsaem.0c02945
- Advanced separators based on aramid nanofiber (ANF) membranes for lithium-ion batteries: a review of recent progress, Journal of Materials Chemistry A, 9, 22, (12923-12946), (2021).https://doi.org/10.1039/D1TA03125B
- Macroscopic-Scale Preparation of Aramid Nanofiber Aerogel by Modified Freezing–Drying Method, ACS Nano, 15, 6, (10000-10009), (2021).https://doi.org/10.1021/acsnano.1c01551
- Recycling of High-Value-Added Aramid Nanofibers from Waste Aramid Resources via a Feasible and Cost-Effective Approach, ACS Nano, 15, 4, (7195-7207), (2021).https://doi.org/10.1021/acsnano.1c00463
- Multifunctional Batteries: Flexible, Transient, and Transparent, ACS Central Science, 7, 2, (231-244), (2021).https://doi.org/10.1021/acscentsci.0c01318
- Underwater maneuvering of robotic sheets through buoyancy-mediated active flutter, Science Robotics, 6, 53, (2021)./doi/10.1126/scirobotics.abe0637
- Aramid nanofiber-based porous membrane for suppressing dendrite growth of metal-ion batteries with enhanced electrochemistry performance, Chemical Engineering Journal, 426, (131924), (2021).https://doi.org/10.1016/j.cej.2021.131924
- Review of Robot Skin: A Potential Enabler for Safe Collaboration, Immersive Teleoperation, and Affective Interaction of Future Collaborative Robots, IEEE Transactions on Medical Robotics and Bionics, 3, 3, (681-700), (2021).https://doi.org/10.1109/TMRB.2021.3097252
- Structural batteries take a load off, Science Robotics, 5, 45, (2021)./doi/10.1126/scirobotics.abd7026
- See more
Loading...
View Options
Get Access
Log in to view the full text
AAAS login provides access to Science for AAAS Members, and access to other journals in the Science family to users who have purchased individual subscriptions.
- Become a AAAS Member
- Activate your AAAS ID
- Purchase Access to Other Journals in the Science Family
- Account Help
Log in via OpenAthens.
Log in via Shibboleth.
More options
Register for free to read this article
As a service to the community, this article is available for free. Login or register for free to read this article.
View options
PDF format
Download this article as a PDF file
Download PDF





