Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm−2) delivers a charge capacity of ∼588 mAh g−1electrode (∼393 mAh cm−3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

[1]  Guangmin Zhou,et al.  Graphene-Wrapped Fe(3)O(4) Anode Material with Improved Reversible Capacity and Cyclic Stability for Lithium Ion Batteries , 2010 .

[2]  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.

[3]  B. Scrosati,et al.  The role of graphene for electrochemical energy storage. , 2015, Nature materials.

[4]  R. Li,et al.  Superior cycle stability of nitrogen-doped graphene nanosheets as anodes for lithium ion batteries , 2011 .

[5]  G. Singh,et al.  Improved electrochemical capacity of precursor-derived Si(B)CN-carbon nanotube composite as Li-ion battery anode. , 2012, ACS applied materials & interfaces.

[6]  SonBinh T. Nguyen,et al.  Aqueous Suspension and Characterization of Chemically Modified Graphene Sheets , 2008 .

[7]  Biao Zhang,et al.  SnO2–graphene–carbon nanotube mixture for anode material with improved rate capacities , 2011 .

[8]  S. Nguyen,et al.  Graphene oxide, highly reduced graphene oxide, and graphene: versatile building blocks for carbon-based materials. , 2010, Small.

[9]  Jiayan Luo,et al.  Crumpled Graphene-Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes. , 2012, The journal of physical chemistry letters.

[10]  Lidong Li,et al.  Flexible free-standing graphene/SnO₂ nanocomposites paper for Li-ion battery. , 2012, ACS applied materials & interfaces.

[11]  Fei Wei,et al.  Building robust architectures of carbon and metal oxide nanocrystals toward high-performance anodes for lithium-ion batteries. , 2012, ACS nano.

[12]  Yong Min Lee,et al.  Electrospun core-shell fibers for robust silicon nanoparticle-based lithium ion battery anodes. , 2012, Nano letters.

[13]  R. Raj,et al.  Lithium Insertion in Polymer‐Derived Silicon Oxycarbide Ceramics , 2010 .

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

[15]  Yuzhen Wei,et al.  Preparation and improved electrochemical performance of SiCN–graphene composite derived from poly(silylcarbondiimide) as Li-ion battery anode , 2014 .

[16]  Chao Zhong,et al.  Flexible free-standing graphene-silicon composite film for lithium-ion batteries , 2010 .

[17]  Harold H. Kung,et al.  Silicon nanoparticles-graphene paper composites for Li ion battery anodes. , 2010, Chemical communications.

[18]  J. Kašpar,et al.  Determination of the chemical diffusion coefficient of Li-ions in carbon-rich silicon oxycarbide anodes by electro-analytical methods , 2014 .

[19]  David Wexler,et al.  Free-standing single-walled carbon nanotube/SnO2 anode paper for flexible lithium-ion batteries , 2012 .

[20]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[21]  Guangmin Zhou,et al.  Graphene anchored with co(3)o(4) nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance. , 2010, ACS nano.

[22]  H. Dai,et al.  Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries. , 2010, Journal of the American Chemical Society.

[23]  Inhwa Jung,et al.  Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents. , 2009, Nano letters.

[24]  R. Raj,et al.  Cyclic stability and C-rate performance of amorphous silicon and carbon based anodes for electrochemical storage of lithium , 2011 .

[25]  Jeff Dahn,et al.  Hysteresis during Lithium Insertion in Hydrogen‐Containing Carbons , 1996 .

[26]  Arumugam Manthiram,et al.  Materials Challenges and Opportunities of Lithium-ion Batteries for Electrical Energy Storage , 2011 .

[27]  Gurpreet Singh,et al.  Stable and Efficient Li-Ion Battery Anodes Prepared from Polymer- Derived Silicon Oxycarbide−Carbon Nanotube Shell/Core Composites , 2013 .

[28]  K. Müllen,et al.  Fabrication of graphene-encapsulated oxide nanoparticles: towards high-performance anode materials for lithium storage. , 2010, Angewandte Chemie.

[29]  V. Battaglia,et al.  Fe3O4 nanoparticle-integrated graphene sheets for high-performance half and full lithium ion cells. , 2011, Physical chemistry chemical physics : PCCP.

[30]  Meihua Jin,et al.  Adaptable silicon-carbon nanocables sandwiched between reduced graphene oxide sheets as lithium ion battery anodes. , 2013, ACS nano.

[31]  R. Raj,et al.  A Model for the Nanodomains in Polymer‐Derived SiCO , 2006 .

[32]  Phillip K. Koech,et al.  Electrochemically Induced High Capacity Displacement Reaction of PEO/MoS2/Graphene Nanocomposites with Lithium , 2011 .

[33]  Xingcheng Xiao,et al.  Free-Standing Layer-By-Layer Hybrid Thin Film of Graphene-MnO2 Nanotube as Anode for Lithium Ion Batteries , 2011 .

[34]  Yi Cui,et al.  Carbon-silicon core-shell nanowires as high capacity electrode for lithium ion batteries. , 2009, Nano letters.

[35]  G. Yushin,et al.  Deformations in Si-Li anodes upon electrochemical alloying in nano-confined space. , 2010, Journal of the American Chemical Society.

[36]  Lele Peng,et al.  Chemically integrated two-dimensional hybrid zinc manganate/graphene nanosheets with enhanced lithium storage capability. , 2014, ACS nano.

[37]  G. Graff,et al.  Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage. , 2010, ACS nano.

[38]  L. Brinson,et al.  Electrically Conductive “Alkylated” Graphene Paper via Chemical Reduction of Amine‐Functionalized Graphene Oxide Paper , 2010, Advanced materials.

[39]  Kinga Haubner,et al.  The route to functional graphene oxide. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[40]  Yi Cui,et al.  Light-weight free-standing carbon nanotube-silicon films for anodes of lithium ion batteries. , 2010, ACS nano.

[41]  J. Dahn,et al.  Pyrolyzed Polysiloxanes for Use as Anode Materials in Lithium‐Ion Batteries , 1997 .

[42]  L. David,et al.  Synthesis of Surface-Functionalized WS2 Nanosheets and Performance as Li-Ion Battery Anodes. , 2012, The journal of physical chemistry letters.

[43]  R. Ruoff,et al.  Hydrazine-reduction of graphite- and graphene oxide , 2011 .

[44]  Probing the Thermal Deoxygenation of Graphene Oxide Using High-Resolution In Situ X-ray-Based Spectroscopies , 2011, 1108.5911.

[45]  Justin T. Harris,et al.  Electrochemical lithiation of graphene-supported silicon and germanium for rechargeable batteries , 2012 .

[46]  Madan Dubey,et al.  Direct synthesis of lithium-intercalated graphene for electrochemical energy storage application. , 2011, ACS nano.

[47]  Reinhard Niessner,et al.  Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information , 2005 .

[48]  Jun Liu,et al.  In Situ Generation of Few‐Layer Graphene Coatings on SnO2‐SiC Core‐Shell Nanoparticles for High‐Performance Lithium‐Ion Storage , 2012 .

[49]  Xin Zhao,et al.  Flexible holey graphene paper electrodes with enhanced rate capability for energy storage applications. , 2011, ACS nano.

[50]  Hyun-Wook Lee,et al.  A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. , 2014, Nature nanotechnology.

[51]  Jie Lian,et al.  Flexible free-standing graphene–TiO2 hybrid paper for use as lithium ion battery anode materials , 2013 .

[52]  Lei Pan,et al.  Facile synthesis of yolk-shell structured Si-C nanocomposites as anodes for lithium-ion batteries. , 2014, Chemical communications.

[53]  L. David,et al.  Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode , 2015, Scientific Reports.

[54]  Lu Yue,et al.  Enhanced reversible lithium storage in a nano-Si/MWCNT free-standing paper electrode prepared by a simple filtration and post sintering process , 2012 .

[55]  Hiroki Habazaki,et al.  Si-C-O glass-like compound/exfoliated graphite composites for negative electrode of lithium ion battery , 2007 .

[56]  Venkat Srinivasan,et al.  Graphene/Si multilayer structure anodes for advanced half and full lithium-ion cells , 2012 .

[57]  L. David,et al.  Reduced Graphene Oxide Paper Electrode: Opposing Effect of Thermal Annealing on Li and Na Cyclability , 2014 .

[58]  Jaephil Cho,et al.  Elastic a-silicon nanoparticle backboned graphene hybrid as a self-compacting anode for high-rate lithium ion batteries. , 2014, ACS nano.

[59]  R. Riedel,et al.  Polymer-derived-SiCN ceramic/graphite composite as anode material with enhanced rate capability for , 2011 .