Fully Biodegradable Microsupercapacitor for Power Storage in Transient Electronics

In this work, the authors report materials, fabrication strategies, and applications of biodegradable microsupercapacitors (MSCs) built using water-soluble (i.e., physically transient) metal (W, Fe, and Mo) electrodes, a biopolymer, hydrogel electrolyte (agarose gel), and a biodegradable poly(lactic-co-glycolic acid) substrate, encapsulated with polyanhydride. During repetitive charge/discharge cycles, the electrochemical performance of these unusual MSCs is dramatically enhanced, following from the role of pseudocapacitance that originates from metal-oxide coatings generated by electrochemical corrosion at the interface between the water-soluble metal electrode and the hydrogel electrolyte. Systematic studies reveal the dissolution kinetics/behaviors of each individual component of the MSCs, as well as those of the integrated devices. An encapsulation strategy that involves control over the thickness, chemistry, and molecular weight of the constituent materials provides a versatile means to engineer desired functional lifetimes. Demonstration experiments illustrate potential applications of these biodegradable MSCs as transient sources of power in the operation of light-emitting diodes and as charging capacitors in integrated circuits for wireless power harvesting.

[1]  Friedrich-Wilhelm Bach,et al.  Histological and molecular evaluation of iron as degradable medical implant material in a murine animal model. , 2012, Journal of biomedical materials research. Part A.

[2]  S. K. Jewrajka,et al.  Effect of Polyethylene Glycol on Properties and Drug Encapsulation-Release Performance of Biodegradable/Cytocompatible Agarose-Polyethylene Glycol-Polycaprolactone Amphiphilic Co-Network Gels. , 2016, ACS applied materials & interfaces.

[3]  Xu Xiao,et al.  WO3−x/MoO3−x Core/Shell Nanowires on Carbon Fabric as an Anode for All‐Solid‐State Asymmetric Supercapacitors , 2012 .

[4]  N. Huang,et al.  Biocompatibility of pure iron: In vitro assessment of degradation kinetics and cytotoxicity on endothelial cells , 2009 .

[5]  Jun Yan,et al.  Template-assisted low temperature synthesis of functionalized graphene for ultrahigh volumetric performance supercapacitors. , 2014, ACS nano.

[6]  S. Bernasek,et al.  Characterization of the “native” surface thin film on pure polycrystalline iron: A high resolution XPS and TEM study , 2007 .

[7]  Huanyu Cheng,et al.  A Physically Transient Form of Silicon Electronics , 2012, Science.

[8]  Shunqing Tang,et al.  Synthesis and characterization of a degradable composite agarose/HA hydrogel , 2012 .

[9]  M. Somers,et al.  Simultaneous determination of composition and thickness of thin iron-oxide films from XPS Fe 2p spectra , 1996 .

[10]  Xufeng Zhou,et al.  Synthesis of porous graphene/activated carbon composite with high packing density and large specific surface area for supercapacitor electrode material , 2014 .

[11]  Daeil Kim,et al.  High performance flexible double-sided micro-supercapacitors with an organic gel electrolyte containing a redox-active additive. , 2016, Nanoscale.

[12]  Wei Li,et al.  Single-crystal β-NiS nanorod arrays with a hollow-structured Ni3S2 framework for supercapacitor applications , 2016 .

[13]  P. Taberna,et al.  Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors , 2010, Science.

[14]  Jongheop Yi,et al.  A biodegradable gel electrolyte for use in high-performance flexible supercapacitors. , 2015, ACS applied materials & interfaces.

[15]  Hsisheng Teng,et al.  Influence of oxygen treatment on electric double-layer capacitance of activated carbon fabrics , 2002 .

[16]  G. Mcguire,et al.  Study of the x-ray photoelectron spectrum of tungsten—tungsten oxide as a function of thickness of the surface oxide layer , 1972 .

[17]  Wei Luo,et al.  Transient Rechargeable Batteries Triggered by Cascade Reactions. , 2015, Nano letters.

[18]  Waheed A. Badawy,et al.  Corrosion and passivation behaviors of molybdenum in aqueous solutions of different pH , 1998 .

[19]  P. Taberna,et al.  Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors , 2003 .

[20]  K. Yan,et al.  The nucleation and growth of metastable pitting on pure iron , 2009 .

[21]  Jeong Sook Ha,et al.  Fabrication of a stretchable and patchable array of high performance micro-supercapacitors using a non-aqueous solvent based gel electrolyte , 2015 .

[22]  Xian Huang,et al.  Materials, Designs, and Operational Characteristics for Fully Biodegradable Primary Batteries , 2014, Advanced materials.

[23]  E. Stijns,et al.  Colour properties of barrier anodic oxide films on aluminium and titanium studied with total reflectance and spectroscopic ellipsometry , 2004 .

[24]  Jeong Sook Ha,et al.  all-solid-state fl exible micro-supercapacitor arrays with layer-by-layer assembled MWNT / MnO x nanocomposite electrodes † , 2014 .

[25]  Nuo Wang,et al.  Synthesis, characterization, biodegradation, and drug delivery application of biodegradable lactic/glycolic acid polymers. Part II: Biodegradation , 2001, Journal of biomaterials science. Polymer edition.

[26]  Yonggang Huang,et al.  Dissolution chemistry and biocompatibility of single-crystalline silicon nanomembranes and associated materials for transient electronics. , 2014, ACS nano.

[27]  Hirenkumar K. Makadia,et al.  Poly Lactic-co-Glycolic Acid ( PLGA ) as Biodegradable Controlled Drug Delivery Carrier , 2011 .

[28]  K. Hashimoto,et al.  First observation of phase transformation of all four Fe(2)O(3) phases (gamma --> epsilon --> beta --> alpha-phase). , 2009, Journal of the American Chemical Society.

[29]  Ralph E. White,et al.  Power and life extension of battery-ultracapacitor hybrids , 2002 .

[30]  M. Trari,et al.  Investigation on photoelectrochemical and pseudo-capacitance properties of the non-stoichiometric hematite α-Fe2O3 elaborated by sol–gel , 2013 .

[31]  F. Werfel,et al.  Photoemission study of the electronic structure of Mo and Mo oxides , 1983 .

[32]  Huanyu Cheng,et al.  Bioresorbable silicon electronic sensors for the brain , 2016, Nature.

[33]  Mathieu Toupin,et al.  Crystalline MnO2 as Possible Alternatives to Amorphous Compounds in Electrochemical Supercapacitors , 2006 .

[34]  J. Tarascon,et al.  Towards greener and more sustainable batteries for electrical energy storage. , 2015, Nature chemistry.

[35]  Jeffrey W. Long,et al.  To Be or Not To Be Pseudocapacitive , 2015 .

[36]  S. Raghavan,et al.  Electrochemistry of Chemical Vapor Deposited Tungsten Films with Relevance to Chemical Mechanical Polishing , 1996 .

[37]  H. Alshareef,et al.  Nanostructured cobalt sulfide-on-fiber with tunable morphology as electrodes for asymmetric hybrid supercapacitors , 2014 .

[38]  Bruce Dunn,et al.  High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. , 2013, Nature materials.

[39]  Pooi See Lee,et al.  3D carbon based nanostructures for advanced supercapacitors , 2013 .

[40]  John A. Rogers,et al.  Biodegradable Thin Metal Foils and Spin‐On Glass Materials for Transient Electronics , 2015 .

[41]  Xin Zhao,et al.  The role of nanomaterials in redox-based supercapacitors for next generation energy storage devices. , 2011, Nanoscale.

[42]  D. Pech,et al.  Microsupercapacitors as miniaturized energy-storage components for on-chip electronics. , 2017, Nature nanotechnology.

[43]  Chi-Woo Lee,et al.  Molybdenum, molybdenum oxides, and their electrochemistry. , 2012, ChemSusChem.

[44]  A. Shpak,et al.  XPS studies of active elements surface of gas sensors based on WO3−x nanoparticles , 2007 .

[45]  Xian Huang,et al.  Materials for Bioresorbable Radio Frequency Electronics , 2013, Advanced materials.

[46]  Jim P. Zheng,et al.  Hydrous Ruthenium Oxide as an Electrode Material for Electrochemical Capacitors , 1995 .

[47]  Dingshan Yu,et al.  Scalable synthesis of hierarchically structured carbon nanotube–graphene fibres for capacitive energy storage , 2014, Nature Nanotechnology.

[48]  Robert A. Huggins,et al.  Supercapacitors and electrochemical pulse sources , 2000 .

[49]  T. Yamashita,et al.  Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials , 2008 .

[50]  Catia Arbizzani,et al.  Polymer-based supercapacitors , 2001 .

[51]  R. Amal,et al.  Visible light-induced charge storage, on-demand release and self-photorechargeability of WO3 film. , 2011, Physical chemistry chemical physics : PCCP.

[52]  A. Hollenkamp,et al.  Carbon properties and their role in supercapacitors , 2006 .

[53]  Kyung Jin Seo,et al.  Bioresorbable Silicon Electronics for Transient Spatio-temporal Mapping of Electrical Activity from the Cerebral Cortex , 2016, Nature materials.

[54]  A. Stefánsson.  Iron(III) Hydrolysis and Solubility at 25 °C , 2007 .

[55]  B. Dunn,et al.  Pseudocapacitive oxide materials for high-rate electrochemical energy storage , 2014 .

[56]  Zhenghong Lu,et al.  Metal/Metal‐Oxide Interfaces: How Metal Contacts Affect the Work Function and Band Structure of MoO3 , 2013 .

[57]  Taeyoung Kim,et al.  Activated graphene-based carbons as supercapacitor electrodes with macro- and mesopores. , 2013, ACS nano.

[58]  H. Gong,et al.  The Sol-Gel-Derived Nickel-Cobalt Oxides with High Supercapacitor Performances , 2011 .

[59]  G. Thompson,et al.  Oxidation states of molybdenum in oxide films formed in sulphuric acid and sodium hydroxide , 2012 .

[60]  W. Mai,et al.  Quantitative Analysis of Charge Storage Process of Tungsten Oxide that Combines Pseudocapacitive and Electrochromic Properties , 2015 .

[61]  Y. Shao-horn,et al.  Carbon nanotube/manganese oxide ultrathin film electrodes for electrochemical capacitors. , 2010, ACS nano.

[62]  F. G. Sampedro,et al.  Biocompatibility of Agarose Gel as a Dermal Filler: Histologic Evaluation of Subcutaneous Implants , 2007, Plastic and reconstructive surgery.

[63]  Kwadwo Osseo-Asare,et al.  Effect of pH on the Anodic Behavior of Tungsten , 2002 .

[64]  Shigeru Suzuki,et al.  XPS study of oxides formed on the surface of high‐purity iron exposed to air , 2000 .

[65]  Xian Huang,et al.  High‐Performance Biodegradable/Transient Electronics on Biodegradable Polymers , 2014, Advanced materials.

[66]  Qiang Zhang,et al.  Advanced Asymmetric Supercapacitors Based on Ni(OH)2/Graphene and Porous Graphene Electrodes with High Energy Density , 2012 .

[67]  Pierre-Louis Taberna,et al.  Outstanding performance of activated graphene based supercapacitors in ionic liquid electrolyte from −50 to 80 °C , 2013 .

[68]  S. Xie,et al.  Asymmetric Supercapacitors Based on Graphene/MnO2 Nanospheres and Graphene/MoO3 Nanosheets with High Energy Density , 2013 .

[69]  Maria Forsyth,et al.  Electrochemical performance of polyaniline nanofibres and polyaniline/multi-walled carbon nanotube composite as an electrode material for aqueous redox supercapacitors , 2007 .

[70]  Jae-Do Park,et al.  Practical energy harvesting for microbial fuel cells: a review. , 2015, Environmental science & technology.

[71]  Diego Lisbona,et al.  A review of hazards associated with primary lithium and lithium-ion batteries , 2011 .

[72]  Wenwen Xu,et al.  Food‐Materials‐Based Edible Supercapacitors , 2016 .

[73]  Chi-Woo Lee,et al.  Reversible Redox Transition and Pseudocapacitance of Molybdenum/Surface Molybdenum Oxides , 2013 .

[74]  Y. Gogotsi,et al.  Freestanding functionalized carbon nanotube-based electrode for solid-state asymmetric supercapacitors , 2014 .

[75]  Yonggang Huang,et al.  Dissolvable Metals for Transient Electronics , 2014 .

[76]  D. Peeters,et al.  A plasma-assisted approach for the controlled dispersion of CuO aggregates into β iron(III) oxide matrices , 2014 .

[77]  P. Shen,et al.  Simultaneous Formation of Ultrahigh Surface Area and Three‐Dimensional Hierarchical Porous Graphene‐Like Networks for Fast and Highly Stable Supercapacitors , 2013, Advanced materials.

[78]  A. Bond,et al.  Revelation of multiple underlying RuO2 redox processes associated with pseudocapacitance and electrocatalysis. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[79]  Julie M Schoenung,et al.  Human health and ecological toxicity potentials due to heavy metal content in waste electronic devices with flat panel displays. , 2010, Journal of hazardous materials.

[80]  V. Presser,et al.  Niobium carbide nanofibers as a versatile precursor for high power supercapacitor and high energy battery electrodes , 2016 .

[81]  Christoph Fink,et al.  Biocompatibility of corroding tungsten coils: in vitro assessment of degradation kinetics and cytotoxicity on human cells. , 2003, Biomaterials.