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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.
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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

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Published In

Science Robotics
Volume 5 | Issue 45
August 2020

Submission history

Received: 12 November 2019
Accepted: 23 July 2020

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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

Affiliations

School of Chemistry and Chemical Engineering, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, P. R. China.
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Biomedical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Biointerfaces Institute, University of Michigan, Ann Arbor, MI 48109, USA.
Drew Vecchio
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Biointerfaces Institute, University of Michigan, Ann Arbor, MI 48109, USA.
Chunyan Wang
School of Chemistry and Chemical Engineering, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, P. R. China.
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Biomedical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Biointerfaces Institute, University of Michigan, Ann Arbor, MI 48109, USA.
Xiongye Xiao
Ming Hsieh Department of Electrical and Computer Engineering, University of Southern California, Los Angeles, CA 90089, USA.
Zaixing Jiang
School of Chemistry and Chemical Engineering, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, P. R. China.
Paul Bogdan
Ming Hsieh Department of Electrical and Computer Engineering, University of Southern California, Los Angeles, CA 90089, USA.
Yudong Huang* [email protected]
School of Chemistry and Chemical Engineering, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, P. R. China.
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Biomedical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
Biointerfaces Institute, University of Michigan, Ann Arbor, MI 48109, USA.
Michigan Institute of Transnational Nanotechnology (MITRAN), Ypsilanti, MI, USA.

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Notes

*Corresponding author. Email: [email protected] (Y.H.); [email protected] (N.A.K.)

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