Flat Monolayer Graphene Cathodes for Li-oxygen Micro-batteries

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Flat Monolayer Graphene Cathodes for Li-oxygen Micro-batteries Dahyun Oh, Erik Lara, Noel Arellano, Yong Cheol Shin, Phillip Medina, Jangwoo Kim, Toan Ta, Esin Akca, Cagla Ozgit-Akgun, Gökhan Demirci, Ho-Cheol Kim, Shu-jen Han, Hareem Maune, and Mahesh G. Samant ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b12718 • Publication Date (Web): 07 Dec 2018 Downloaded from http://pubs.acs.org on December 8, 2018

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ACS Applied Materials & Interfaces

Flat Monolayer Graphene Cathodes for Li-oxygen Micro-batteries Dahyun Oh1,2,*, Erik Lara1, Noel Arellano2, Yong Cheol Shin3, Phillip Medina2, Jangwoo Kim2, Toan Ta1, Esin Akca4, Cagla Ozgit-Akgun4, Gökhan Demirci4, Ho-cheol Kim2, Shu-jen Han2, Hareem Maune2, Mahesh G. Samant2 1Chemical

and Materials Engineering Department, San José State University, CA 95112,

USA 2IBM

Almaden Research Center, San Jose, CA 95120, USA

3Korea

Institute of Science and Technology Evaluation and Planning (KISTEP), Seoul,

06775, South Korea 4ASELSAN

Inc. – Microelectronics, Guidance and Electro-Optics Business Sector, Ankara

06750, Turkey * Corresponding author: [email protected] KEYWORDS Micro-batteries, Li-oxygen batteries, Graphene, Microfabrication, Thin film batteries ABSTRACT Miniature batteries can accelerate the development of mobile electronics by providing sufficient energy to power small devices. Typical micro-batteries commonly use thin film inorganic electrodes based on Li-ion insertion reaction. However, they rely on the complicated thin film synthesis method of inorganics containing many elements. Graphene, one atomic 1 ACS Paragon Plus Environment

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layer thick carbon sheet, has diverse physical and chemical properties and is compatible with conventional micron-scale device fabrication. Here we study the use of chemical vapor deposition (CVD) grown monolayer graphene in a two-dimensional configuration, as a future Li-oxygen micro-battery cathode. By maximizing the dissolution of discharge intermediates, we obtain 2,610 Ah/ggraphene of capacity corresponding to 20 % higher areal cathode energy density and 2.7 times higher cathode specific energy than that can be derived from the same volume or mass of conventional Li-ion battery cathode material. Furthermore, a clear observation on the discharge reaction on composite electrodes and their role in the charging reaction was made thanks to the two-dimensional monolayer graphene Li-oxygen battery cathode. We demonstrate an easy integration of two-dimensional CVD graphene cathode into microscale devices by simply transferring or coating the target device substrate with flexible graphene layers. The ability to integrate and use mono-layer graphene on arbitrary device substrates as well as precise control over a chemical derivation of the carbon interface can have a radical impact on future energy storage devices. INTRODUCTION Li-oxygen batteries have been intensely investigated as rechargeable batteries to utilize their high theoretical energy density (3,505 Wh/kgLi2O2)1 starting from 1996 by using polymeric electrolytes2. They are expected to revolutionize the field and make a dramatic impact on mobile electronics and electric vehicles as their expected specific energy is almost three to four times higher (~600 Wh/kgcell)3 than current Li-ion batteries (~150 Wh/kgcell)4. However, Lioxygen batteries’ development has been impeded by their short cycle life compared to Li-ion batteries due to the inherent challenge to reversibly dissociate the products formed during battery operations.5-6 Reactive intermediate products formed during discharge and charge steps degrade the cell components, decreasing the battery life cycle.7-8 Few hundreds of cycles were 2 ACS Paragon Plus Environment

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obtained, however, the cycling test was done with a limited capacity,9-10 not fully utilizing the benefit of high energy density Li-oxygen battery. Although the effort to recharge Li-oxygen battery is rigorously continuing, less attention has been given to fully take advantage of its battery chemistry for the right applications. Other than high specific energy, another main advantage of Li-oxygen battery chemistry is that it does not necessarily require cathode materials that contain limited elements (e.g. cobalt)11 as is the case in conventional Li-ion batteries. Noble metals12-13 or transition metal oxides14-15 in cathodes have been reported to have a catalytic effect in oxygen reduction reaction (ORR, 2Li+ + O2 + 2e- → Li2O2) or oxygen evolution reaction (OER, Li2O2 → 2Li+ + O2 + 2e-) but these elements are not a mandate to operate Li-oxygen batteries. Electrodes made solely with carbon have shown the full operation of Li-oxygen batteries.16-17 Therefore, a cathode with a very thin layer of carbon, such as graphene, is theoretically sufficient to build energy storage devices, especially primary batteries. In particular, less than one nanometer thick graphene cathode can dramatically decrease the size of battery when the graphene layer is used in two-dimensional configurations without sacrificing the storage capability. Here we investigate the application of flat graphene to build 2D Li-oxygen battery cathode while fully utilizing the benefits of easy microfabrication techniques with graphene. Graphene, a single atomic layer of sp2 carbon sheet, is being currently investigated for use in many applications such as medicine,18-20 electronics,21-23 and energy storage24-25 because of its unique electronic structure and ease of modifying the chemical as well as physical properties. Numerous studies have shown that chemical and physical properties of graphene can be modulated by incorporating functional groups26-27 or changing the stacking configuration of sheets28-29. Furthermore, many versatile CMOS fabrication techniques have been developed for creating graphene nano-electronics.30-31 To date, graphene’s usage for Li-oxygen batteries has 3 ACS Paragon Plus Environment


been limited to the construction of porous three-dimensional cathode structures32-33 but twodimensional configurations for a flat cathode have been less explored although many transformative impacts can be made with flat cathodes. We use chemical vapor deposition (CVD) grown graphene to produce large 2D sheets that are structurally comparable to the best mechanically exfoliated graphene available.34-35 The CMOS friendly, CVD grown graphene Li-oxygen battery cathode not only enables simple fabrication of a microscale device for energy storage but also makes the depositions or growths of inorganic layers unnecessary, unlike Li-ion insertion-based cathodes (e.g. LiCoO2, LiFePO4), in building energy storage device components. These CVD grown graphene sheets can be wet-transferred easily to many different substrates (e.g. silicon, glass, polymer)36-37 for device integration and can be patterned using conventional photolithography for ease of device fabrication38-39. In this work, we demonstrate the application of 2D graphene cathodes in Li-oxygen micro batteries that could supply power to future micron-scale devices. We develop a simple microfabrication method, compatible with CMOS device processing, to validate a primary cell with an improved energy density. Furthermore, we exploit the 2D graphene electrode structure to investigate the formation and oxidation of Li2O2 process at the cathode using diverse composite structures and various substrates to clearly identify the Li2O2 distribution during battery cycling. We hypothesized that the Li-oxygen battery discharge capacity can be substantially improved on a planar 2D graphene electrode by using the electrolyte formulations that enhance the solvation of intermediate discharge products.40 By promoting the reaction at the electrolyte-2D graphene interface, Li2O2 could preferably grow in particle shape rather than a film thus increasing the discharge capacity. Furthermore, the planar electrode configuration makes it easier and simpler to monitor the battery reaction compared to a 3D electrode structure. We fabricated a model composite planar electrode with the most common catalyst, RuO2,14, 41 4 ACS Paragon Plus Environment

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to investigate the Li2O2 distribution after ORR on composite electrodes. The easy monitoring of the reaction allows observation of the growth of Li2O2 solely originating from the interaction with a substrate without any interference coming from porous 3D electrodes. We employed the thinnest possible 2D carbon layer, graphene, grown by CVD method, for Li-oxygen battery cathodes. To maximize the discharge capacity of the 2D graphene electrodes, we specifically used electrolytes that enhance the solvation of reaction intermediates during Li2O2 formation. The graphene layer, grown on copper (Cu) foil, was transferred to SiO2/Si substrate using a solution transfer technique to preclude any involvement of Cu in electrochemical reactions. The electrical connection to graphene layer was made by contacting it with a current collector (a stainless steel mesh) as shown in Figure 1A. We tested the flat graphene cathode with the electrolyte containing lithium nitrate (LiNO3) that has shown a

higher

solubility

of

intermediate

discharge

products

than

lithium

bis(trifluoromethanesulfonyl)imide (LiTFSI).40 The Li-oxygen battery was assembled with electrolytes of 0.5 M LiNO3 in tetraethylene glycol dimethyl ether (TEGDME) and equilibrated with the oxygen environment (1,140 Torr). The graphene cathode on SiO2/Si substrate maintained a flat discharge potential around 2.47 V (vs. Li/Li+) after a slight fluctuation of voltage, possibly due to the initial transport issue, at the first 0.03 mAh/cm2 of discharge period (Figure 1B). At this given current density (0.006 mA/cm2) and electrolyte formulation, we expect that the discharge process on the flat graphene electrode will be dominated by the solution mechanism that allows the diffusion of O2- in electrolyte to form toroidal Li2O2 particles. With the voltage cutoff at 2.1 V, 0.088 mAh/cm2 of areal capacity (corresponding to 2,610 Ah/ggraphene of capacity and 0.22 mWh/cm2 of energy density) was obtained at 0.006 mA/cm2 of current density. The current density applied during the electrochemical measurement in this work (0.006 mA/cm2) was 5 ACS Paragon Plus Environment


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about six times higher and resulted more than three times higher areal capacity than previously reported Li-oxygen battery employing flat graphene cathodes.42 Furthermore, these areal and specific energy densities obtained from graphene Li-oxygen batteries are higher than the energy density achievable from a conventional Li-ion cell. Compared to one of the most common cathode materials, LiCoO2, the areal cathode energy density obtained with graphene (0.22 mWh/cm2) in this work was 20 % higher than that can be obtained from the same volume of LiCoO2 as Li2O2 in cathodes. In addition, the cathode specific energy (including the mass of electrode and discharge product, Li2O2) with graphene electrode is 2.7 times higher (2,917 Wh/kggraphene+Li2O2) than that of LiCoO2 (1,068 Wh/kgLiCoO2). Detailed calculations and cycling performance of graphene cathode (Figure S1) are provided in the supporting information. We observed that the discharge products grew preferably on the graphene surface rather than on the bare SiO2/Si wafer surface without any ORR promotors. Raman spectroscopy (Figure 1C) analysis and Scanning Electron Microscopy (SEM) micrographs (Figures 1D and 1E) were used to confirm that these discharge products were in fact Li2O2. The graphene electrode was mostly covered with discharge products as it is observed by SEM in Figures 1D and 1E. But the bare SiO2/Si region, which was exposed due to scratched graphene layer (Figure 1E inset), did not present any significant Li2O2 growth after the battery discharge. This supports the fact that SiO2/Si wafer resulted in an almost zero capacity during the Li-oxygen battery discharge as shown by the discharge test in Figure 1B (grey). Furthermore, on Raman spectrum in Figure 1C, a new peak positioned at 787 cm-1 appeared for discharged electrodes (orange, tested at the current density of 0.006 mA/cm2) compared to pristine graphene electrodes (dark green). This peak at 787 cm-1 corresponds to O-O bond from Li2O2.43 Graphene electrodes were also investigated using SEM after discharge (Figure 1D).

SEM

images showed toroidal or oval shaped particles. In the higher magnification image (inset of 6 ACS Paragon Plus Environment

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Figure 1D), we could observe that these toroidal particles had a substructure made of stacked sheets. Combined together, the data strongly supports the conclusion that flat graphene electrodes successfully formed Li2O2 similar to 3D porous carbon electrodes, and that Li2O2 particles were selectively grown on the carbon surface. After observing the fact that Li2O2 particles favorably grow on the graphene surface compared to the SiO2/Si surface, we fabricated a model cathode that had a composite structure made of (1) graphene and (2) SiO2/Si surface to simulate the composite structure made of regions (1) promoting ORR and (2) less effectively growing Li2O2, representing (1) graphene and (2) SiO2/Si surface, respectively. Holes with a square shape were patterned on graphene by electron-beam lithography so that SiO2/Si surface was exposed in a regular pattern. Conventional electron-beam lithography was used to create a resist mask (poly(methyl methacrylate), PMMA) by writing an array of 25 μm2 sized squares that were 50 μm apart (Figure 2A). After developing the resist, the graphene inside the square shaped holes was removed by oxygen based reactive ion etching (RIE) process to expose the native SiO2/Si surface as shown in the inset of optical image, Figure 2A. The detailed experimental conditions are included in the supporting information. Two different points (A and B in Figure 2A inset) were analyzed by Raman spectroscopy to examine the presence of graphene layers inside the square pattern after the oxygen plasma treatment. As shown in Figure 2B, characteristic peaks for graphene were not observed inside the square pattern (position A) while they were detected at position B (G and 2D bands at 1,595 and 2,682 cm-1, respectively. The intensity ratio of G and 2D peaks (I2D/IG=1.93) corresponds to the value reported for monolayer graphene in literature44). Our model cathode thus had a total surface area ratio of 10 to 1 for carbon to SiO2/Si surface.

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The square patterned model cathode also demonstrated the preferential growth of Li2O2 particles on the graphene surface rather than the exposed SiO2/Si surface inside the graphene pattern, verified by SEM. To compare the discharge process of square patterned against the plain un-patterned graphene electrodes, electrodes were discharged with 0.03 mAh/cm2 of capacity and the distribution of Li2O2 particles after discharge was observed (Figure 3A-C). From the SEM images shown in Figure 3A (discharged plain un-patterned graphene electrode) and 3B (discharged square patterned graphene electrode), we deduced that the patterned electrode (Figure 3B) presented a bright square pattern while the plain graphene electrode was fully covered with Li2O2 (Figure 3A). For square patterned graphene electrodes, the bright square pattern was shown after the discharge (0.03 mAh/cm2 of capacity), and this was found to be because of the different Li2O2 thickness on SiO2/Si surface inside the pattern compared to the graphene region by thickness measurement with SEM. We tilted the sample stage by 52 ° (Figure 3C) and measured the thickness of discharge products at different regions of square patterned graphene electrodes. On this patterned graphene electrode, around 290-520 nm thick Li2O2 layers were observed on the graphene region while the SiO2/Si surface inside the patterned region (square shape) was covered with only ~110 nm thick Li2O2 layers. The accumulation of Li2O2 inside the pattern (SiO2/Si surface) was unexpected as we had not observed a clear discharge profile that had a plateau around 2.9 V with SiO2/Si electrodes in Figure 1B. This might be due to the presence of graphene around the SiO2/Si pattern that provides discharge products or some small residual carbon left after the RIE process inside the pattern. The current density that we applied (0.006 mA/cm2)45 and the electrolyte formulation (0.5 M LiNO3 in TEGDME) were known to promote ORR via disproportionation of LiO2 (2LiO2 → Li2O2+O2) than the charge transfer (2Li++O2+2e- → Li2O2).46 Therefore, the nonconductive surface like SiO2/Si could serve as the discharge product deposition site when 8 ACS Paragon Plus Environment

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the ORR promotor is present around because a direct contact to the conductive surface like graphene might not be necessary for Li2O2 formed by the disproportionation process. The deposition of Li2O2 on SiO2/Si surface around the graphene was observed not only inside the pattern but also along the graphene edge as can be seen in Figure S2. This result indicates that the discharge product could be deposited on SiO2/Si surface once it is surrounded by ORR promotor (carbon). While the ORR of the bare SiO2/Si wafer without ORR promotor was insignificant as it was seen by the small discharge capacity in Figure 1B (grey), SiO2/Si surface surrounded by ORR promotor such as carbon can serve as Li2O2 deposition sites. We investigated the effect of composite square patterned graphene electrode (with graphene and SiO2/Si) on cycling at two different depths of discharge (0.006 and 0.011 mAh/cm2). The voltage profiles of the first cycle of Li-oxygen battery with the composite graphene cathode and the plain graphene cathode were compared. Although there could be OER voltage variations between different battery cells with the same configurations, the composite graphene cathode with the SiO2/Si surface generally showed ~120-170 mV lower charging potential at half the full charge capacity. Patterned composite graphene cathodes showed ~3.65 V of charging potential while plain structure cathodes showed 3.77-3.83 V when they were cycled with 0.006 mAh/cm2 of capacity (a representative potential profile is included in Figure 3D). However, the charging potential became similar for both the composite and plain graphene cathodes when we almost doubled the fixed cycling capacity, to 0.011 mAh/cm2 (Figure 3E). This clearly shows that the charge transfer becomes sluggish as discharge products get thicker so that the overpotential increases due to thick insulating Li2O2 particles regardless of cathode surface structures. This voltage hysteresis might originate from the byproducts7 or the poor conductivity47 of toroidal Li2O2 particles as reported previously.



The cathode surface effect on the oxidation of Li2O2 was seen to be more pronounced from the distribution of residual Li2O2 on graphene electrodes after the charging. We cycled the Li-oxygen batteries with 0.011 mAh/cm2 of capacity for both patterned and plain graphene electrodes and observed the electrodes with SEM after cycling. Although batteries were cycled with 100 % of coulombic efficiency (discharged capacity = charged capacity = 0.011 mAh/cm2), we observed residual discharge products in both patterned and plain graphene electrodes. This incomplete oxidation of Li2O2 has been observed in many literatures48-49 and the mismatch between the consumed charge and left-over discharge products is because the charge is used up for the side reaction not for the oxidation of Li2O2. While the plain graphene electrode had a uniformly distributed residual Li2O2 coverage (Figure 3F), patterned electrodes had a more populated residual Li2O2 on the SiO2/Si region (5 × 5 μm2 of the square, Figures 3G and H area 2) than the graphene region (Figure 3H area 1). This proves that the carbon surface definitely helps the charging although it does not completely oxidize Li2O2 during the charging step. This could be due to the better electron transfer to Li2O2 from carbon layer than from a SiO2/Si surface (square region). The Li2O2 displaced in the square shaped holes seems to be no longer electrically connected in batteries. One interesting feature is that plain graphene electrodes in Figure 3F showed more residual Li2O2 than patterned electrodes as shown in Figure 3G. It is possible that Li2O2 particles in a square region (SiO2/Si surface) lowered down the amount of Li2O2 that needed to be oxidized on graphene surface compared to the plain graphene electrode. Thus, patterned electrodes showed lower charging overpotential when the batteries were discharged with the shallow depth of discharge as the discharge product was moved out to the SiO2/Si surface. This imbalance between the amount of Li2O2 formed during discharge and the amount of Li2O2 deposited on graphene surface to be oxidized may lower down the overpotential or improve the charging efficiency of Li-oxygen battery at the first few 10 ACS Paragon Plus Environment

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cycles. However, the residual Li2O2 will continuously pile up inside the battery cell, resulting in a poor life cycle of Li-oxygen batteries. Another possible route to lower the kinetic overpotential during the charging step with patterned electrodes might be due to the presence of pits or holes created because of Li2O2 thickness difference or heterogeneous deposition of discharge products on the patterned region compared to the plain region. The recent finding from Byon et al.50 indicates that the initial oxidation of thin Li2O2 layer was observed first at the lower OER potential (100 °C hot plate inside the Ar glove box and the electrolyte was freshly made right before every battery measurement) was then added. Assembled cells were purged with O2 (~1,140 Torr, Research Purity, Matheson Tri-Gas®) through the capillary connected to SwagelokTM type cells and rested at least 1 h before electrochemical measurements.

Supporting Information Energy density comparison calculation, experimental details on graphene cathode preparation, photolithography, RuO2 film deposition, materials analysis, and electrochemical measurement. A digital image of RuO2/Graphene composite electrode.

AUTHOR INFORMATION Corresponding Author *Dahyun Oh [email protected] Author Contributions



D.O. designed the experiments and supervised the project. E.L. contributed to SEM analysis. N. A. performed the photolithography. Y.C.S analyzed the Raman data and commented on the graphene transfer process. D.O., P.M., J.K., T.T., E.A., C.O.A., G.D., and H.M. performed experiments and analyzed the data. S.J.H. commented on the graphene analysis. M.G.S. fabricated RuO2 film and analyzed the thin film data. All authors discussed the results and commented on the manuscript.

NOTES The authors declare no competing financial interests.

ACKNOWLEDGMENT We appreciate Dr. Damon B. Famer for the experimental discussion regarding the graphene transfer. D.O. is grateful for the professional development start-up fund support from San José State University. We acknowledge all the support from IBM Almaden Research Center Battery group members for fruitful discussions. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

REFERENCES

(1) Gao, X.; Chen, Y.; Johnson, L. R.; Jovanov, Z. P.; Bruce, P. G. A Rechargeable Lithium–Oxygen Battery with Dual Mediators Stabilizing the Carbon Cathode. Nat. Energy 2017, 2, 17118.


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(2) Abraham, K. M.; Jiang, Z. A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery. J. Electrochem. Soc. 1996, 143 (1), 1-5. (3) Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J.-M. Li–O2 and Li–S Batteries with High Energy Storage. Nat. Mater. 2011, 11, 19. (4) Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and Challenges in Enabling the Lithium Metal Electrode for High-Energy and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3 (1), 16-21. (5) Luntz, A. C.; McCloskey, B. D. Nonaqueous Li–Air Batteries: A Status Report. Chem. Rev. 2014, 114 (23), 11721-11750. (6) Radin, M. D.; Siegel, D. J. Charge Transport in Lithium Peroxide: Relevance for Rechargeable MetalAir Batteries. Energy Environ. Sci. 2013, 6 (8), 2370-2379. (7) McCloskey, B. D.; Speidel, A.; Scheffler, R.; Miller, D. C.; Viswanathan, V.; Hummelshøj, J. S.; Nørskov, J. K.; Luntz, A. C. Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O2 Batteries. J. Phys. Chem. Lett. 2012, 3 (8), 997-1001. (8) Mahne, N.; Schafzahl, B.; Leypold, C.; Leypold, M.; Grumm, S.; Leitgeb, A.; Strohmeier, Gernot A.; Wilkening, M.; Fontaine, O.; Kramer, D.; Slugovc, C.; Borisov, Sergey M.; Freunberger, Stefan A. Singlet Oxygen Generation as a Major Cause for Parasitic Reactions During Cycling of Aprotic Lithium–Oxygen Batteries. Nat. Energy 2017, 2, 17036. (9) Asadi, M.; Sayahpour, B.; Abbasi, P.; Ngo, A. T.; Karis, K.; Jokisaari, J. R.; Liu, C.; Narayanan, B.; Gerard, M.; Yasaei, P.; Hu, X.; Mukherjee, A.; Lau, K. C.; Assary, R. S.; Khalili-Araghi, F.; Klie, R. F.; Curtiss, L. A.; Salehi-Khojin, A. A Lithium–Oxygen Battery with a Long Cycle Life in an Air-Like Atmosphere. Nature 2018, 555, 502. (10) Shang, C.; Dong, S.; Hu, P.; Guan, J.; Xiao, D.; Chen, X.; Zhang, L.; Gu, L.; Cui, G.; Chen, L. Compatible Interface Design of Coo-Based Li-O2 Battery Cathodes with Long-Cycling Stability. Sci. Rep. 2015, 5, 8335. (11) Zubi, G.; Dufo-López, R.; Carvalho, M.; Pasaoglu, G. The Lithium-Ion Battery: State of the Art and Future Perspectives. Renewable and Sustainable Energy Rev. 2018, 89, 292-308. (12) Gittleson, F. S.; Sekol, R. C.; Doubek, G.; Linardi, M.; Taylor, A. D. Catalyst and Electrolyte Synergy in Li-O2 Batteries. Phys. Chem. Chem. Phys. 2014, 16 (7), 3230-3237. (13) Shao, Y.; Park, S.; Xiao, J.; Zhang, J.-G.; Wang, Y.; Liu, J. Electrocatalysts for Nonaqueous Lithium– Air Batteries: Status, Challenges, and Perspective. ACS Catal. 2012, 2 (5), 844-857.



(14) Oh, D.; Virwani, K.; Tadesse, L.; Jurich, M.; Aetukuri, N.; Thompson, L. E.; Kim, H.-C.; Bethune, D. S. Effect of Transition Metal Oxide Cathodes on the Oxygen Evolution Reaction in Li–O2 Batteries. J. Phys. Chem. C 2017, 121 (3), 1404-1411. (15) Wang, Z.-L.; Xu, D.; Xu, J.-J.; Zhang, X.-B. Oxygen Electrocatalysts in Metal-Air Batteries: From Aqueous to Nonaqueous Electrolytes. Chem. Soc. Rev. 2014, 43 (22), 7746-7786. (16) Mitchell, R. R.; Gallant, B. M.; Thompson, C. V.; Shao-Horn, Y. All-Carbon-Nanofiber Electrodes for High-Energy Rechargeable Li-O2 Batteries. Energy Environ. Sci. 2011, 4 (8), 2952-2958. (17) Jin, X.; Xiahui, Y.; Qingmei, C.; P., M. I.; Paul, D.; Chun-Chih, C.; Wei, F.; Dunwei, W. Three Dimensionally Ordered Mesoporous Carbon as a Stable, High-Performance Li–O2 Battery Cathode. Angew. Chem. 2015, 127 (14), 4373-4377. (18) Xili, D.; Haifeng, L.; Yubo, F. Graphene-Based Materials in Regenerative Medicine. Adv. Healthcare Mater. 2015, 4 (10), 1451-1468. (19) Priyadarsini, S.; Mohanty, S.; Mukherjee, S.; Basu, S.; Mishra, M. Graphene and Graphene Oxide as Nanomaterials for Medicine and Biology Application. J. Nanostruct. Chem. 2018, 8 (2), 123-137. (20) Feng, L.; Liu, Z. Graphene in Biomedicine: Opportunities and Challenges. Nanomedicine 2011, 6 (2), 317-324. (21) Soldano, C.; Stefani, A.; Biondo, V.; Basiricò, L.; Turatti, G.; Generali, G.; Ortolani, L.; Morandi, V.; Veronese, G. P.; Rizzoli, R.; Capelli, R.; Muccini, M. ITO-Free Organic Light-Emitting Transistors with Graphene Gate Electrode. ACS Photonics 2014, 1 (10), 1082-1088. (22) Song, D.; Mahajan, A.; Secor, E. B.; Hersam, M. C.; Francis, L. F.; Frisbie, C. D. High-Resolution Transfer Printing of Graphene Lines for Fully Printed, Flexible Electronics. ACS Nano 2017, 11 (7), 74317439. (23) Dongdong, L.; Wen-Yong, L.; Yi-Zhou, Z.; Wei, H. Printable Transparent Conductive Films for Flexible Electronics. Adv. Mater. 2018, 30 (10), 1704738. (24) Xie, Y.; Liu, Y.; Zhao, Y.; Tsang, Y. H.; Lau, S. P.; Huang, H.; Chai, Y. Stretchable All-Solid-State Supercapacitor with Wavy Shaped Polyaniline/Graphene Electrode. J. Mater. Chem. A 2014, 2 (24), 9142-9149. (25) David, L.; Bhandavat, R.; Singh, G. MoS2/Graphene Composite Paper for Sodium-Ion Battery Electrodes. ACS Nano 2014, 8 (2), 1759-1770.


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(26) Soumen, D.; Sanjay, S.; Virendra, S.; Daeha, J.; M., D. J.; David, R.; Jordan, A.; Lei, Z.; I., K. S.; T., S. W.; Sudipta, S. Oxygenated Functional Group Density on Graphene Oxide: Its Effect on Cell Toxicity. Part. Part. Syst. Charact. 2013, 30 (2), 148-157. (27) Toda, K.; Furue, R.; Hayami, S. Recent Progress in Applications of Graphene Oxide for Gas Sensing: A Review. Anal. Chim. Acta 2015, 878, 43-53. (28) Hajlaoui, M.; Sediri, H.; Pierucci, D.; Henck, H.; Phuphachong, T.; Silly, M. G.; de Vaulchier, L.-A.; Sirotti, F.; Guldner, Y.; Belkhou, R.; Ouerghi, A. High Electron Mobility in Epitaxial Trilayer Graphene on Off-Axis SiC(0001). Sci. Rep. 2016, 6, 18791. (29) Bao, C.; Yao, W.; Wang, E.; Chen, C.; Avila, J.; Asensio, M. C.; Zhou, S. Stacking-Dependent Electronic Structure of Trilayer Graphene Resolved by Nanospot Angle-Resolved Photoemission Spectroscopy. Nano Lett. 2017, 17 (3), 1564-1568. (30) Goossens, S.; Navickaite, G.; Monasterio, C.; Gupta, S.; Piqueras, J. J.; Pérez, R.; Burwell, G.; Nikitskiy, I.; Lasanta, T.; Galán, T.; Puma, E.; Centeno, A.; Pesquera, A.; Zurutuza, A.; Konstantatos, G.; Koppens, F. Broadband Image Sensor Array Based on Graphene–CMOS Integration. Nat. Photonics 2017, 11, 366. (31) Koczorowski, W.; Kuświk, P.; Przychodnia, M.; Wiesner, K.; El-Ahmar, S.; Szybowicz, M.; Nowicki, M.; Strupiński, W.; Czajka, R. CMOS- Compatible Fabrication Method of Graphene-Based Micro Devices. Mater. Sci. Semicond. Process. 2017, 67, 92-97. (32) Zhou, W.; Zhang, H.; Nie, H.; Ma, Y.; Zhang, Y.; Zhang, H. Hierarchical Micron-Sized Mesoporous/Macroporous Graphene with Well-Tuned Surface Oxygen Chemistry for High Capacity and Cycling Stability Li–O2 Battery. ACS Appl. Mater. Interfaces 2015, 7 (5), 3389-3397. (33) Peng, Z.; Rutao, W.; Mu, H.; Junwei, L.; Shan, X.; Xingbin, Y. 3D Hierarchical Co/CoO-GrapheneCarbonized Melamine Foam as a Superior Cathode toward Long-Life Lithium Oxygen Batteries. Adv. Funct. Mater. 2016, 26 (9), 1354-1364. (34) Lin, Y.-M.; Dimitrakopoulos, C.; Jenkins, K. A.; Farmer, D. B.; Chiu, H.-Y.; Grill, A.; Avouris, P. 100GHz Transistors from Wafer-Scale Epitaxial Graphene. Science 2010, 327 (5966), 662-662. (35) Banszerus, L.; Schmitz, M.; Engels, S.; Dauber, J.; Oellers, M.; Haupt, F.; Watanabe, K.; Taniguchi, T.; Beschoten, B.; Stampfer, C. Ultrahigh-Mobility Graphene Devices from Chemical Vapor Deposition on Reusable Copper. Sci. Adv. 2015, 1 (6). (36) Lin, W.-H.; Chen, T.-H.; Chang, J.-K.; Taur, J.-I.; Lo, Y.-Y.; Lee, W.-L.; Chang, C.-S.; Su, W.-B.; Wu, C.-I. A Direct and Polymer-Free Method for Transferring Graphene Grown by Chemical Vapor Deposition to Any Substrate. ACS Nano 2014, 8 (2), 1784-1791.



(37) Martins, L. G. P.; Song, Y.; Zeng, T.; Dresselhaus, M. S.; Kong, J.; Araujo, P. T. Direct Transfer of Graphene onto Flexible Substrates. Proc. Natl. Acad. Sci. 2013, 110 (44), 17762-17767. (38) Wu, Z.-S.; Parvez, K.; Feng, X.; Mullen, K. Photolithographic Fabrication of High-Performance AllSolid-State Graphene-Based Planar Micro-Supercapacitors with Different Interdigital Fingers. J. Mater. Chem. A 2014, 2 (22), 8288-8293. (39) Shi, R.; Xu, H.; Chen, B.; Zhang, Z.; Peng, L.-M. Scalable Fabrication of Graphene Devices through Photolithography. Appl. Phys. Lett. 2013, 102 (11), 113102. (40) Burke, C. M.; Pande, V.; Khetan, A.; Viswanathan, V.; McCloskey, B. D. Enhancing Electrochemical Intermediate Solvation through Electrolyte Anion Selection to Increase Nonaqueous Li–O2Battery Capacity. Proc. Natl. Acad. Sci. 2015, 112 (30), 9293-9298. (41) Zelang, J.; Pan, L.; Fujun, L.; Ping, H.; Xianwei, G.; Mingwei, C.; Haoshen, Z. Core–Shell-Structured CNT@RuO2 Composite as a High-Performance Cathode Catalyst for Rechargeable Li–O2 Batteries. Angew. Chem., Int. Ed. 2014, 53 (2), 442-446. (42) Yang, Y.; Zhang, T.; Wang, X.; Chen, L.; Wu, N.; Liu, W.; Lu, H.; Xiao, L.; Fu, L.; Zhuang, L. Tuning the Morphology and Crystal Structure of Li2O2: A Graphene Model Electrode Study for Li–O2 Battery. ACS Appl. Mater. Interfaces 2016, 8 (33), 21350-21357. (43) S., G. F.; C., Y. K. P.; G., K. D.; Youssef, S. S.; Won-Hee, R.; Yang, S.-H.; D., T. A. Raman Spectroscopy in Lithium–Oxygen Battery Systems. ChemElectroChem 2015, 2 (10), 1446-1457. (44) Qi, Z.; Zhu, X.; Jin, H.; Zhang, T.; Kong, X.; Ruoff, R. S.; Qiao, Z.; Ji, H. Rapid Identification of the Layer Number of Large-Area Graphene on Copper. Chem. Mater. 2018, 30 (6), 2067-2073. (45) Adams, B. D.; Radtke, C.; Black, R.; Trudeau, M. L.; Zaghib, K.; Nazar, L. F. Current Density Dependence of Peroxide Formation in the Li–O2 Battery and Its Effect on Charge. Energy Environ. Sci. 2013, 6 (6), 1772-1778. (46) Aurbach, D.; McCloskey, B. D.; Nazar, L. F.; Bruce, P. G. Advances in Understanding Mechanisms Underpinning Lithium–Air Batteries. Nat. Energy 2016, 1, 16128. (47) Radin, M. D.; Siegel, D. J. Charge Transport in Lithium Peroxide: Relevance for Rechargeable Metal–Air Batteries. Energy Environ. Sci. 2013, 6 (8), 2370-2379. (48) McCloskey, B. D.; Valery, A.; Luntz, A. C.; Gowda, S. R.; Wallraff, G. M.; Garcia, J. M.; Mori, T.; Krupp, L. E. Combining Accurate O2 and Li2O2 Assays to Separate Discharge and Charge Stability Limitations in Nonaqueous Li–O2 Batteries. J. Phys. Chem. Lett. 2013, 4 (17), 2989-2993.


Page 28 of 30

Page 29 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(49) Wu, M. C.; Zhao, T. S.; Tan, P.; Jiang, H. R.; Zhu, X. B. Cost-Effective Carbon Supported Fe2O3 Nanoparticles as an Efficient Catalyst for Non-Aqueous Lithium-Oxygen Batteries. Electrochim. Acta 2016, 211, 545-551. (50) Hong, M.; Yang, C.; Wong, R. A.; Nakao, A.; Choi, H. C.; Byon, H. R. Determining the Facile Routes for Oxygen Evolution Reaction by in Situ Probing of Li–O2 Cells with Conformal Li2O2 Films. J. Am. Chem. Soc. 2018, 140 (20), 6190-6193. (51) Wang, H.; Yang, Y.; Liang, Y.; Zheng, G.; Li, Y.; Cui, Y.; Dai, H. Rechargeable Li-O2 Batteries with a Covalently Coupled MnCo2O4-Graphene Hybrid as an Oxygen Cathode Catalyst. Energy Environ. Sci. 2012, 5 (7), 7931-7935. (52) Shui, J.-L.; Karan, N. K.; Balasubramanian, M.; Li, S.-Y.; Liu, D.-J. Fe/N/C Composite in Li–O2 Battery: Studies of Catalytic Structure and Activity toward Oxygen Evolution Reaction. J. Am. Chem. Soc. 2012, 134 (40), 16654-16661. (53) Mar, S. Y.; Chen, C. S.; Huang, Y. S.; Tiong, K. K. Characterization of RuO2 Thin Films by Raman Spectroscopy. Appl. Surf. Sci. 1995, 90 (4), 497-504. (54) Gittleson, F. S.; Yao, K. P. C.; Kwabi, D. G.; Sayed, S. Y.; Ryu, W.-H.; Shao-Horn, Y.; Taylor, A. D. Raman Spectroscopy in Lithium–Oxygen Battery Systems. ChemElectroChem 2015, 2 (10), 1446-1457. (55) Nanda, J.; Bilheux, H.; Voisin, S.; Veith, G. M.; Archibald, R.; Walker, L.; Allu, S.; Dudney, N. J.; Pannala, S. Anomalous Discharge Product Distribution in Lithium-Air Cathodes. J. Phys. Chem. C 2012, 116 (15), 8401-8408. (56) P., B.; H., L.; L., K.; J., M. Fully Reversible Homogeneous and Heterogeneous Li Storage in RuO2 with High Capacity. Adv. Funct. Mater. 2003, 13 (8), 621-625. (57) Murphy, D. W.; Di Salvo, F. J.; Carides, J. N.; Waszczak, J. V. Topochemical Reactions of Rutile Related Structures with Lithium. Mater. Res. Bull. 1978, 13 (12), 1395-1402. (58) Bergner, B. J.; Schürmann, A.; Peppler, K.; Garsuch, A.; Janek, J. Tempo: A Mobile Catalyst for Rechargeable Li-O2 Batteries. J. Am. Chem. Soc. 2014, 136 (42), 15054-15064. (59) Xia, C.; Kwok, C. Y.; Nazar, L. F. A High-Energy-Density Lithium-Oxygen Battery Based on a Reversible Four-Electron Conversion to Lithium Oxide. Science 2018, 361 (6404), 777-781.

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Flat Monolayer Graphene Cathodes for Li-oxygen Micro-batteries

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