Flexible solid state lithium batteries based on graphene inks

Different formulations of solution-processable graphene have been characterised as electrode materials for use in electrochemical energy storage devices. Graphene was fabricated by chemical reduction of exfoliated graphene oxide (GO), and modified with either p-type (e.g. polyaniline) or n-type anionic groups (poly(styrenesulfonate) (PSS−) and poly[2,5-bis(3-sulfonatopropoxy)-1,4-ethynylphenylene-alt-1,4-ethynylphenylene] sodium salt (PPE-SO3−) anion). Solutions of these graphene compounds were deposited on charge collecting electrodes and used as battery cathodes. Electrodes using the anionically-modified graphene inks containing anatase titanate (TiO2) nanoparticles show improved performance over pristine graphene ink as well as the p-type conducting polymer modified ones. In addition, the open circuit voltage of batteries based on TiO2 has been boosted over 3 V with good cyclability when mixed with the graphene ink. Combined with a polymer electrolyte, this work suggests a feasible route towards fully printable rechargeable lithium batteries based on graphene inks. This approach is both versatile and scalable and is adaptable to a wide variety of applications.

[1]  E. Yoo,et al.  Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. , 2008, Nano letters.

[2]  C. Casiraghi Doping dependence of the Raman peaks intensity of graphene close to the Dirac point , 2009, 0908.4480.

[3]  P. J. Ollivier,et al.  Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations , 1999 .

[4]  Yoshiharu Uchimoto,et al.  Polymer electrolyte plasticized with PEG-borate ester having high ionic conductivity and thermal stability , 2002 .

[5]  U Zeitler,et al.  Room-Temperature Quantum Hall Effect in Graphene , 2007, Science.

[6]  Kwang S. Kim,et al.  Large-scale pattern growth of graphene films for stretchable transparent electrodes , 2009, Nature.

[7]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .

[8]  Michael M. Thackeray,et al.  Spinel Anodes for Lithium‐Ion Batteries , 1994 .

[9]  A. Geim,et al.  Two-dimensional gas of massless Dirac fermions in graphene , 2005, Nature.

[10]  Peter G. Bruce,et al.  Energy storage beyond the horizon: Rechargeable lithium batteries , 2008 .

[11]  Craig A. Poland,et al.  Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study. , 2008, Nature nanotechnology.

[12]  C. Berger,et al.  Electronic Confinement and Coherence in Patterned Epitaxial Graphene , 2006, Science.

[13]  C. Natarajan,et al.  Preparation of a nanocrystalline titanium dioxide negative electrode for the rechargeable lithium ion battery , 1998 .

[14]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[15]  K. Novoselov,et al.  Raman spectroscopy of graphene edges. , 2008, Nano letters.

[16]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[17]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[18]  E. Yoo,et al.  Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. , 2009, Nano letters.

[19]  R. Ruoff,et al.  Chemical methods for the production of graphenes. , 2009, Nature nanotechnology.

[20]  Huafeng Yang,et al.  Covalent functionalization of polydisperse chemically-converted graphene sheets with amine-terminated ionic liquid. , 2009, Chemical communications.

[21]  P. Ajayan,et al.  Flexible energy storage devices based on nanocomposite paper , 2007, Proceedings of the National Academy of Sciences.

[22]  A. Ramachandra Reddy,et al.  Preparation and study of conductivity in lithium salt complexes of mixed MEEP : PEO polymer electrolytes , 2004 .

[23]  M. Wakihara,et al.  Influence of Lewis acidic borate ester groups on lithium ionic conduction in polymer electrolytes , 2003 .

[24]  M. Wagemaker,et al.  Equilibrium lithium transport between nanocrystalline phases in intercalated TiO2 anatase , 2002, Nature.

[25]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[26]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[27]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[28]  Ji‐Guang Zhang,et al.  Self-assembled TiO2-graphene hybrid nanostructures for enhanced Li-ion insertion. , 2009, ACS nano.

[29]  A. Reina,et al.  Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. , 2009, Nano letters.

[30]  Tao Zheng,et al.  Mechanisms for Lithium Insertion in Carbonaceous Materials , 1995, Science.