Ultrahigh-Capacity Lithium-Oxygen Batteries Enabled by Dry-Pressed Holey Graphene Air Cathodes.

Lithium-oxygen (Li-O2) batteries have the highest theoretical energy density of all the Li-based energy storage systems, but many challenges prevent them from practical use. A major obstacle is the sluggish performance of the air cathode, where both oxygen reduction (discharge) and oxygen evolution (charge) reactions occur. Recently, there have been significant advances in the development of graphene-based air cathode materials with a large surface area and catalytically active for both oxygen reduction and evolution reactions, especially with additional catalysts or dopants. However, most studies reported so far have examined air cathodes with a limited areal mass loading rarely exceeding 1 mg/cm2. Despite the high gravimetric capacity values achieved, the actual (areal) capacities of those batteries were far from sufficient for practical applications. Here, we present the fabrication, performance, and mechanistic investigations of high-mass-loading (up to 10 mg/cm2) graphene-based air electrodes for high-performance Li-O2 batteries. Such air electrodes could be easily prepared within minutes under solvent-free and binder-free conditions by compression-molding holey graphene materials because of their unique dry compressibility associated with in-plane holes on the graphene sheet. Li-O2 batteries with high air cathode mass loadings thus prepared exhibited excellent gravimetric capacity as well as ultrahigh areal capacity (as high as ∼40 mAh/cm2). The batteries were also cycled at a high curtailing areal capacity (2 mAh/cm2) and showed a better cycling stability for ultrathick cathodes than their thinner counterparts. Detailed post-mortem analyses of the electrodes clearly revealed the battery failure mechanisms under both primary and secondary modes, arising from the oxygen diffusion blockage and the catalytic site deactivation, respectively. These results strongly suggest that the dry-pressed holey graphene electrodes are a highly viable architectural platform for high-capacity, high-performance air cathodes in Li-O2 batteries of practical significance.

[1]  Yang Shao-Horn,et al.  Chemical and Morphological Changes of Li–O2 Battery Electrodes upon Cycling , 2012 .

[2]  M. Antonietti,et al.  Vertically Aligned Two-Dimensional Graphene-Metal Hydroxide Hybrid Arrays for Li-O2 Batteries. , 2016, ACS applied materials & interfaces.

[3]  Zhen Zhou,et al.  Hierarchical Carbon–Nitrogen Architectures with Both Mesopores and Macrochannels as Excellent Cathodes for Rechargeable Li–O2 Batteries , 2014 .

[4]  Dong Wook Kim,et al.  Flexible binder-free graphene paper cathodes for high-performance Li-O2 batteries , 2015 .

[5]  Dan Xu,et al.  Novel DMSO-based electrolyte for high performance rechargeable Li-O2 batteries. , 2012, Chemical communications.

[6]  Hee-Dae Lim,et al.  Enhanced Power and Rechargeability of a Li−O2 Battery Based on a Hierarchical‐Fibril CNT Electrode , 2013, Advanced materials.

[7]  B. L. Mehdi,et al.  Formation of interfacial layer and long-term cyclability of Li-O₂ batteries. , 2014, ACS applied materials & interfaces.

[8]  J. Dai,et al.  Scalable holey graphene synthesis and dense electrode fabrication toward high-performance ultracapacitors. , 2014, ACS nano.

[9]  Taewoo Kim,et al.  Superior rechargeability and efficiency of lithium-oxygen batteries: hierarchical air electrode architecture combined with a soluble catalyst. , 2014, Angewandte Chemie.

[10]  Baoyong Liu,et al.  Hierarchical porous nitrogen doped three-dimensional graphene as a free-standing cathode for rechargeable lithium-oxygen batteries , 2016 .

[11]  Yu Huang,et al.  Holey graphene frameworks for highly efficient capacitive energy storage , 2014, Nature Communications.

[12]  Wei Xia,et al.  Perovskite-Type LaSrMnO Electrocatalyst with Uniform Porous Structure for an Efficient Li-O2 Battery Cathode. , 2016, ACS nano.

[13]  H. Hng,et al.  Binder-free graphene foams for O2 electrodes of Li-O2 batteries. , 2013, Nanoscale.

[14]  S. Cai,et al.  Reduced graphene oxide anchoring CoFe2O4 nanoparticles as an effective catalyst for non-aqueous lithium-oxygen batteries. , 2014, Faraday discussions.

[15]  S. Liao,et al.  Ruthenium nanoparticles mounted on multielement co-doped graphene: an ultra-high-efficiency cathode catalyst for Li–O2 batteries , 2015 .

[16]  Zhigang Zak Fang,et al.  A lithium–oxygen battery based on lithium superoxide , 2016, Nature.

[17]  Huakun Liu,et al.  A Metal-Free, Free-Standing, Macroporous Graphene@g-C₃N₄ Composite Air Electrode for High-Energy Lithium Oxygen Batteries. , 2015, Small.

[18]  Adam P. Cohn,et al.  Solution Assembled Single-Walled Carbon Nanotube Foams: Superior Performance in Supercapacitors, Lithium-Ion, and Lithium–Air Batteries , 2014 .

[19]  Yang Shao-Horn,et al.  The discharge rate capability of rechargeable Li–O2 batteries , 2011 .

[20]  Zhaolin Liu,et al.  Influence of carbon pore size on the discharge capacity of Li–O2 batteries , 2014 .

[21]  Y. Joo,et al.  Thermal restacking of graphene structure to improve lithium-air battery cyclability , 2016 .

[22]  Aravindaraj G. Kannan,et al.  A bi-functional metal-free catalyst composed of dual-doped graphene and mesoporous carbon for rechargeable lithium–oxygen batteries , 2015 .

[23]  Juan-Yu Yang,et al.  Polystyrene sphere-mediated ultrathin graphene sheet-assembled frameworks for high-power density Li-O2 batteries. , 2015, Chemical communications.

[24]  Steven D. Lacey,et al.  Highly compressible, binderless and ultrathick holey graphene-based electrode architectures , 2017 .

[25]  Steven D. Lacey,et al.  Dry-Processed, Binder-Free Holey Graphene Electrodes for Supercapacitors with Ultrahigh Areal Loadings. , 2016, ACS applied materials & interfaces.

[26]  Zhen Zhou,et al.  Recent progress in rechargeable alkali metal–air batteries , 2016 .

[27]  Dan Xu,et al.  Flexible lithium–oxygen battery based on a recoverable cathode , 2015, Nature Communications.

[28]  Guanghua Wang,et al.  Doped reduced graphene oxide mounted with IrO 2 nanoparticles shows significantly enhanced performance as a cathode catalyst for Li-O 2 batteries , 2016 .

[29]  Zhen Zhou,et al.  Co3O4 Hollow Nanoparticles and Co Organic Complexes Highly Dispersed on N‐Doped Graphene: An Efficient Cathode Catalyst for Li‐O2 Batteries , 2015 .

[30]  L. Dai,et al.  Carbon-based electrocatalysts for advanced energy conversion and storage , 2015, Science Advances.

[31]  S. Dou,et al.  Ruthenium nanocrystal decorated vertical graphene nanosheets@Ni foam as highly efficient cathode catalysts for lithium-oxygen batteries , 2016 .

[32]  Pengfei Xiao,et al.  CoS2 nanoparticles–graphene hybrid as a cathode catalyst for aprotic Li–O2 batteries , 2016 .

[33]  Seung M. Oh,et al.  Mechanism of Co3O4/graphene catalytic activity in Li–O2 batteries using carbonate based electrolytes , 2013 .

[34]  Dean J. Miller,et al.  Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li-O2 Batteries. , 2016, ACS applied materials & interfaces.

[35]  Zhian Zhang,et al.  Fe/Fe3C decorated 3-D porous nitrogen-doped graphene as a cathode material for rechargeable Li–O2 batteries , 2016 .

[36]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[37]  Bing Sun,et al.  Porous graphene nanoarchitectures: an efficient catalyst for low charge-overpotential, long life, and high capacity lithium-oxygen batteries. , 2014, Nano letters.

[38]  J. Xie,et al.  High‐Performance Li–O2 Batteries with Controlled Li2O2 Growth in Graphene/Au‐Nanoparticles/Au‐Nanosheets Sandwich , 2016, Advanced science.

[39]  Zhen-tao Zhou,et al.  Computational Insights into Oxygen Reduction Reaction and Initial Li2O2 Nucleation on Pristine and N-Doped Graphene in Li–O2 Batteries , 2015 .

[40]  W. Bennett,et al.  Hierarchically porous graphene as a lithium-air battery electrode. , 2011, Nano letters.

[41]  Li Li,et al.  Aprotic and aqueous Li-O₂ batteries. , 2014, Chemical reviews.

[42]  Drew C. Higgins,et al.  Activated and nitrogen-doped exfoliated graphene as air electrodes for metal–air battery applications , 2013 .

[43]  Jun Lu,et al.  Study on the Catalytic Activity of Noble Metal Nanoparticles on Reduced Graphene Oxide for Oxygen Evolution Reactions in Lithium-Air Batteries. , 2015, Nano letters.

[44]  A. Manthiram,et al.  A High Energy Lithium‐Sulfur Battery with Ultrahigh‐Loading Lithium Polysulfide Cathode and its Failure Mechanism , 2016 .

[45]  Robert W. Black,et al.  Non‐Aqueous and Hybrid Li‐O2 Batteries , 2012 .

[46]  Hun‐Gi Jung,et al.  Ruthenium-based electrocatalysts supported on reduced graphene oxide for lithium-air batteries. , 2013, ACS nano.

[47]  Tao Liu,et al.  Cycling Li-O2 batteries via LiOH formation and decomposition , 2015, Science.

[48]  Caroline J. Campbell,et al.  Holey Graphene Nanomanufacturing: Structure, Composition, and Electrochemical Properties , 2015 .

[49]  Huamin Zhang,et al.  Hierarchical micron-sized mesoporous/macroporous graphene with well-tuned surface oxygen chemistry for high capacity and cycling stability Li-O2 battery. , 2015, ACS applied materials & interfaces.

[50]  Bing Sun,et al.  Soft-template synthesis of 3D porous graphene foams with tunable architectures for lithium-O2 batteries and oil adsorption applications , 2014 .

[51]  Jun Chen,et al.  Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. , 2012, Chemical Society reviews.

[52]  Yuyan Shao,et al.  Electrocatalysts for Nonaqueous Lithium–Air Batteries: Status, Challenges, and Perspective , 2012 .

[53]  Weidong Zhou,et al.  Low‐Cost Higher Loading of a Sulfur Cathode , 2016 .

[54]  Tao Zhang,et al.  From Li-O2 to Li-air batteries: carbon nanotubes/ionic liquid gels with a tricontinuous passage of electrons, ions, and oxygen. , 2012, Angewandte Chemie.

[55]  Linda F. Nazar,et al.  Screening for superoxide reactivity in Li-O2 batteries: effect on Li2O2/LiOH crystallization. , 2012, Journal of the American Chemical Society.

[56]  A. Hirata,et al.  3D Nanoporous Nitrogen‐Doped Graphene with Encapsulated RuO2 Nanoparticles for Li–O2 Batteries , 2015, Advanced materials.

[57]  L. Archer,et al.  Nucleation and Growth of Lithium Peroxide in the Li-O2 Battery. , 2015, Nano letters.

[58]  Tao Huang,et al.  Three-dimensional MoSx (1 < x < 2) nanosheets decorated graphene aerogel for lithium–oxygen batteries , 2016 .

[59]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[60]  Jasim Ahmed,et al.  A Critical Review of Li/Air Batteries , 2011 .

[61]  Xingcheng Xiao,et al.  Graphene‐Based Nanocomposites for Energy Storage , 2016 .

[62]  J. Connell,et al.  Nitrogen-Doped Holey Graphene for High-Performance Rechargeable Li–O2 Batteries , 2016 .

[63]  J. Connell,et al.  Nitrogen-Doped Holey Graphene as an Anode for Lithium-Ion Batteries with High Volumetric Energy Density and Long Cycle Life. , 2015, Small.

[64]  Xueliang Sun,et al.  Nitrogen-doped graphene nanosheets as cathode materials with excellent electrocatalytic activity for high capacity lithium-oxygen batteries , 2012 .

[65]  Haegyeom Kim,et al.  Graphene for advanced Li/S and Li/air batteries , 2014 .

[66]  Haoshen Zhou,et al.  Performance-improved Li–O2 battery with Ru nanoparticles supported on binder-free multi-walled carbon nanotube paper as cathode , 2014 .

[67]  Haoshen Zhou,et al.  Effect of Chemical Doping on Cathodic Performance of Bicontinuous Nanoporous Graphene for Li‐O2 Batteries , 2016 .

[68]  Yuyan Shao,et al.  Making Li‐Air Batteries Rechargeable: Material Challenges , 2013 .

[69]  T. Gustafsson,et al.  3-D binder-free graphene foam as a cathode for high capacity Li–O2 batteries , 2016 .

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

[71]  Ruopian Fang,et al.  3D Interconnected Electrode Materials with Ultrahigh Areal Sulfur Loading for Li–S Batteries , 2016, Advanced materials.

[72]  Zhen Zhou,et al.  Heteroatom-doped graphene as electrocatalysts for air cathodes , 2017 .

[73]  Dong Wook Kim,et al.  Graphene paper with controlled pore structure for high-performance cathodes in Li–O2 batteries , 2016 .

[74]  A. Pearse,et al.  Protocols for Evaluating and Reporting Li-O2 Cell Performance. , 2016, The journal of physical chemistry letters.

[75]  Brian J. German,et al.  Performance Analysis and Design of On-Demand Electric Aircraft Concepts , 2012 .

[76]  Jianming Zheng,et al.  High Energy Density Lithium–Sulfur Batteries: Challenges of Thick Sulfur Cathodes , 2015 .

[77]  Yang Shao-Horn,et al.  Probing the Reaction Kinetics of the Charge Reactions of Nonaqueous Li-O2 Batteries. , 2013, The journal of physical chemistry letters.

[78]  Yang Shao-Horn,et al.  Reactivity of carbon in lithium-oxygen battery positive electrodes. , 2013, Nano letters.

[79]  Zhiyu Wang,et al.  Free-standing, hierarchically porous carbon nanotube film as a binder-free electrode for high-energy Li–O2 batteries , 2013 .

[80]  Jun Chen,et al.  N-doped pierced graphene microparticles as a highly active electrocatalyst for Li-air batteries , 2015 .