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In-Plane Vacancy-Enabled High-Power SiGraphene Composite Electrode for Lithium-Ion Batteries

Xin Zhao, Cary M. Hayner, Mayfair C. Kung, and Harold H. Kung*
The current insatiable appetite for more efcient electrical energy storage devices with a exible and/or compact conguration, fed by the proliferation of portable electronics with ever increasing functional complexity, will be even more difcult to satisfy when electried vehicles become the preferred mode of transportation, and energy harvesting from intermittent sources evolves into the practiced norm.[14] Incorporation of the attractive features of supercapacitors with high rate performance and rechargeable batteries with high energy densities into a single unit would enable the design of high-capacity energy storage devices for sustainable power delivery.[57] Thus far, however, this goal has proved to be difcult to attain. Strategies used to boost the power capability of electrode materials for Li-ion batteries generally involve reducing the domain size of the active charge-storage material (e.g., Si) in the electrode to shorten the ion diffusion paths, such as by fabricating vertically aligned 1-D nanostructures or ultrathin coatings on nanofoams and metallic mesh.[8,9] Generally, such an approach suffers from limited overall charge storage capacity due to a low mass fraction of the active component in the electrode. Fabricating porous electrode frameworks using sacricial templates is another approach,[1012] but these porous electrodes introduce different problems, such as congurational inexibility imposed by mechanical fragility and a dramatic drop in volumetric energy density consequential of reduced packing densities. Here we demonstrate that graphene sheets possessing a high density of in-plane, -sized carbon vacancies can be transformed into a exible, 3-D conducting graphenic scaffold with excellent crossplane ion diffusivity and tolerance to structural deformation. When employed as a structural platform to incorporate high storage-capacity materials, such as Si, a stable, self-supporting composite electrode with enhanced accessible interior and high rate capacity is obtained, representing an attractive electrode candidate towards high-performance Li-ion batteries. Furthermore, the composite is ductile and offers congurational exibility, and can be produced by cost-effective processes. Our 3-D graphenic scaffold was constructed with aligned graphene sheets, derived from exfoliated graphene oxide sheets into which in-plane, nm-sized carbon vacancies were introduced by a facile wet chemical method. It confers a combination of advantageous features over reported electrodes systems: i) Facile ion transport throughout the structure, enabled by new diffusion channels created with in-plane carbon vacancies. This overcomes the characteristic high resistance of graphene material for Li ion transport due to their extreme width-to-thickness aspect ratio and inter-sheet aggregation.[1317] ii) Superior electrical conductivity and high packing density derived from the compact structure of interconnecting graphitic domains.[18,19] iii) Sustained structural integrity as a result of the high exibility of the graphene sheets to accommodate large volume variations of high-capacity embedded storage materials during charge/discharge cycle.[17,2022] These advantages were demonstrated with a self-supporting, exible electrode consisted of Si nanoparticles embedded in a 3-D graphenic scaffold, as shown schematically in Figure 1. This Sigraphene composite electrode achieved an unprecedented reversible capacity of around 1100 mAh g1 at 8 A g1, a rate equivalent to full discharge in 8 min, or approximately 3200 mAh g1 at 1 A g1, repeatable up to 99.9% between cycles for over 150 cycles. The graphenic scaffold was constructed by rst exfoliating graphite akes into graphene oxide (GO) sheets.[23] After washing, suspensions of GO were sonicated in aqueous HNO3 solutions in a procedure similar to the ones used to generate defects on carbon nanotube sidewalls[24] and scissor GO into polyaromatic hydrocarbons,[25] except that a lower acid concentration and a reduced sonication period rendered our method a milder version. Four different acid concentrations were investigated (see the Supporting Information for details), and the resulting samples with induced structural defects are

Dr. X. Zhao, C. M. Hayner, Prof. M. C Kung, Prof. H. H. Kung Department of Chemical and Biological Engineering Northwestern University Evanston, Illinois, 60208, USA E-mail: hkung@northwestern.edu

DOI: 10.1002/aenm.201100426

Figure 1. A schematic drawing (not to scale) of a section of a composite electrode material constructed with a graphenic scaffold with in-plane carbon vacancy defects. The graphene sheets with these holey defects are displaced from each other for clarity. Electrochemically active components, for example, Si nanoparticles (large spheres), are sandwiched between graphene sheets, and these composites are structurally integrated with a 3-D graphenic network of interconnecting graphitic domains formed by reconstituting these graphene sheets. Li ions (small spheres) can diffuse easily across graphene sheets throughout the structure by passing through the in-plane vacancy defects.

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labeled deGO-I, -II, -III, and -IV, respectively. To obtain a Si-deGO composite paper, an aqueous mixture of deGO and Si nanoparticles (approximately 50 nm diameter) was ltered and dried. The acid-sonication treatment created carbon vacancies with carboxylate groups decorating the defect edge sites.[24] Palladium nanoparticles, formed by reduction of Pd ions that bind to these carboxylates during examination with electron microscopy, were used as a vehicle to examine the dependence of defect generation on the severity of treatment. Figure 2ae show bright-eld TEM images of GO and deGOs, and Figure S1 in the Supporting Information shows the complementary Z-contrast images. As expected, the densities of Pd particles and larger pores on deGO increased with increasing severity of acid treatment. A high magnication image of deGO-III (Figure 2f) shows Pd clusters arranged in ring formations, consistent with their location at the perimeter of the window-like porous defects. Many observable defects were 1020 nm in diameter. These observations are in agreement with X-ray photoelectron spectroscopic (XPS) measurements which showed that the acid-oxidation treatment increased the peak area of oxygencontaining functional groups relative to aromatic carbon (Figure S2). Thermal reduction of deGO to form a 3-D graphenic scaffold (deG) was accomplished in a ow of either Ar or 10% H2 in Ar at 700 C for 1 h with similar results. XPS conrmed removal of most of the O in the sample (Figure S3 and S4).[26,27] The largest porous defects observed on thermally reduced deGO were roughly <10 nm, 20 nm, 100 nm, and >100 nm for samples I, II, III, and IV, respectively (Figure S5). Figure 2. TEM images of Pd-stained graphene oxide samples: a) GO, b) deGO-I, c) deGO-II, Both deG and Si-deG papers were highly d) deGO-III, and, e) deGO-IV. f) A high magnication image of a highlighted region in (d), conducting (Table S1 and S2), exible, and showing approximately 3 nm Pd particles in ring-like arrangements. The crystalline regions of remained integral when bent (Figure 3a and graphene oxide are indicated by arrows. b). In fact, the Si-deG papers were more ductile than the deG papers, possibly because of the presence of upon graphene combustion in thermogravimetric analysis. SEM roughly 30% by volume of loosely assembled Si nanoparticles images revealed homogeneously dispersed Si nanoparticles in Si-deG that can be deformed readily. X-ray diffraction consandwiched between reassembled graphene sheets, along with rmed the presence of both crystalline graphite domains and visible porosity on the basal planes of deG (Figure 3c and d). disordered regions, as indicated by a sharp peak at 2 = 26.5 Synchrotron nonresonant X-ray Raman scattering (XRS) of on top of a broad hump (Figure S6). There was a slight shift SideG lms showed the absence of silicon carbide phase. of the hump towards lower angle as the acid concentration The Raman spectra of the reduced SideG and SiG samples increased, implying reduced van der Waals attraction between showed little change in the intensities of the D bands (approxithe reconstituted graphene sheets with large numbers of mately 1350 cm1) relative to the G bands (approximately carbon vacancies. The XRD pattern of an SiG sample showed 1580 cm1) (Figure S9). The intensity ratios of the D/G bands the crystalline graphite diffraction peak shifted to 2 = 26.3, corresponded to an approximately 4 nm sized ordered graphconsistent with Si nanoparticles embedded between graphene itic domain calculated using the empirical Tuinstra-Koenig relalayers (Figure S7). The Si contents in these SideG papers were tion.[28] This is consistent with the fact that samples containing estimated to be 6570 wt-% (Figure S8), based on weight losses in-plane defects remained intact, mechanically strong, and

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that 83% of its theoretical capacity was maintained after 150 cycles (Figure 4a). The initial irreversible capacity losses were mostly due to the formation of solid electrolyte interphase (SEI)[29] and reactions of Li with residual O and H-containing groups in graphene.[30] When tested at 8 A g1, a reversible capacity of approximately 1100 mAh g1 was obtained, which degraded at approximately 0.34% per cycle for 150 cycles. This specic current corresponded to a rate of approximately 8C based on the accessible storage capacity, or approximately 2.6C based on the theoretical capacity (theoretical C-rate). The characteristic voltage plateaus for phase transformation of amorphous Si at 0.30.17 V and 0.10.05 V (lithiation), and 0.20.4 V and 0.450.58 V (delithiation)[31] remained distinguishable even at such high rates (Figure 4b). This illustrates that our SideG composites can deliver an exceptionally high energy output even at a rate one order of magnitude higher than for other reported Sicarbon composites.[17,32,33] Capacity fade of the composite electrodes could be reduced by cycling through a narrower range of 0.10.55 V to minimize the destructive effect of volume variation and possible dissolution and re-formation of SEI at high voltages. At 4 A g1 (around 1.3C theoretical), the capacity fade was as low as approximately 0.1% per cycle, and a reversible capacity of approximately 600 mAh g1 was maintained after 150 cycles. The high cycling stability and rate capability of SideGII is demonstrated in Figure 4c. Reversibility of storage capacity was observed when the rate was rst stepwise increased from 0.1 to 8 A g1 and then switched back. The ability to maintain a high capacity at high rates for the SideG samples was attributed to the much shortened Li diffusion path Figure 3. Microstructures of Sigraphene composite papers. a) Digital image of a SideGOthroughout the electrode, leading to a fully III paper. b) Digital image a SideG-III paper. c) SEM image of the top surface of a SideG-III paper. d) SEM image of the cross-section of a SideG-III paper, the inset shows Si nanoparticles accessible interior and fast lithiation and delembedded between graphene sheets uniformly. e) SEM image of the top surface of SideG-III ithiation reactions of Si nanoparticles. This paper at higher magnication, with circles highlighting the in-plane defects. f) HRTEM image was conrmed by electrochemical impedof crushed SideG-III showing the distribution of approximately 50 nm Si nanoparticles in the ance spectroscopy. Nyquist plots (Figure S10) graphene sheets, the inset shows the circled region at higher magnication. The Si nanopar- of SideG showed a pronounced reducticles have an amorphous SiOx surface layer with a thickness of 23 nm outside the metallic tion in both the charge-transfer resistance crystalline core. A reconstituted graphitic phase composed of graphene is also identied. and the Warburg coefcient[34] compared with SiG, whereas the constant phase element increased gradually, implying a more capacitive interface electrically conducting, and the TEM images showing defects (Figure S11, Table S3 and S4). dispersed in the graphene planes. The defect size and density strongly inuenced the electroElectrochemical properties were characterized using a halfchemical performance of SideG composites, while reduction cell arrangement with a Li foil as the counter electrode. After 5 of SideGO in different atmospheres showed minor effects charge/discharge cycles at 1 A g1 between 0.021.5 V (vs. Li/ (Figure 4 and S12). Without the intentional defects, the capacity Li+), an approximately 5 m thick Ar-reduced SideG-II paper of SiG diminished by around 90% when the rate was increased exhibited a reversible capacity close to its theoretical value of from C/30 to 2.6C (theoretical). SideG-II was the most tolerant approximately 3200 mAh g1 (see the Experimental Section). to high rates, maintaining 34% of the theoretical capacity at Thereafter, the capacity loss was only 0.14% per cycle, such

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Figure 4. Electrochemical characterization of approximately 5 m thick SideG and deG paper anodes. a) Specic delithiation capacity (solid) and coulombic efciency (open) of Ar-reduced SideG-II between 0.021.5 V at 1 and 8 A g1 (C/3 and 2.6C based on a theoretical capacity of 3052 mAh g1), and between 0.10.55 V at 4 A g1 (1.3C). b) Fifth-cycle charge/discharge curves of Ar-reduced SideG-II at 1, 4, and 8 A g1. c) Specic delithiation capacity (solid) and coulombic efciency (open) of Ar-reduced SideG-II between 0.022.0 V at current densities of 0.1, 0.2, 0.4, 1, 2, 4, and 8 A g1 (C/30, C/15, C/7.6, C/3, C/1.5, 1.3C, and 2.6C) and recovery of the original capacity when switched back to 0.1 A g1. d) Ar-reduced and H2/Ar-reduced SideG between 0.021.5 V at current densities of 0.1, 0.2, 0.4, 1, 2, 4, and 8 A g1. e) Specic delithiation capacity (solid) and coulombic efciency (open) of Ar-reduced and H2/Ar-reduced deG-II between 0.022.0 V at current densities of 0.05, 0.1, 0.2, 0.5, 1, 1.5, and 2 A g1 (C/7.4, C/3.7, C/1.8, 1.3C, 2.7C, 4C, and 5.4C based on a theoretical capacity of 372 mAh g1 of graphenic materials). Capacity is calculated using the total mass of each electrode.

8 A g1. This suggests that there is an optimal pore size and/or density of defects, which might be attributed to a combination of factors including diffusivity of Li ions, ability of the porous graphene sheets to retain Si nanoparticles and accommodate their volume changes, as well as formation and nature of SEI at the defect sites. SEM images showed that at the optimal conditions, the SideG papers remained integral after rate tests (Figure S13). While most of the data were collected using 5 m thick electrodes, similar benecial effects of the defects were observed

with 20 m thick electrodes (Figure S12). That the benecial effects were due to in-plane defects and enhanced ion diffusivity throughout the composite paper was further supported by the surface area and pore size distribution information, shown in Figure S14. A sample with defects showed a higher surface area and, most importantly, much larger mesopore volume, consistent with easier access to more internal volumes of the composite paper. The benecial effect of in-plane defects was apparent even for the graphenic scaffold without Si. With induced defects, a capacity as high as 180 mAh g1 was

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obtained at a current of 2 A g1 for deG-III, compared to only 70 mAh g1 without defects (Figure 4e). The coulombic efciencies were very close to 100% with no obvious capacity fade over the 100 cycles tested. Whereas the effect of atomic defects on the electronic and magnetic properties of graphene has captured much attention,[35,36] we have demonstrated the benecial effects of nanometer-sized in-plane vacancies on ion transport for use in a 3-D graphenic scaffold that can be fabricated into hybrid materials with a hitherto unachievable combination of power capability and storage capacity for battery electrode applications, without sacricing its mechanical properties. Very significantly, the preparation method employed can be easily adapted and scaled up to existing high-throughput processing protocols, such as spray-coating, inkjet printing, and roll-to-roll deposition, for electrode manufacture. These high-performance, freestanding graphenic composite sheets with engineered porosity for cross-plane transport may also nd broad applications as support scaffolds and membranes for water desalination and remediation as well as in curvilinear electronics, catalytic, biofuel and biomimetric systems with new functionalities.[37,38]

Theoretical capacity of SiG composite is calculated as: 4200 mAh g1 (Si theoretical capacity) 70% (Si wt-%) + 372 mAh g1 (graphene theoretical capacity) 30% (graphene wt-%) = 3052 mAh g1.

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Supporting Information
Supporting Information is available from the Wiley Online Library or from the author.

Acknowledgements
This research was supported by the U.S. Department of Energy, Basic Energy Sciences, grant DE-AC02-06CH11357 through the Center for Electrical Energy Storage, an Energy Frontier Research Center. We thank Dr. Shuyou Li (EPIC, NU), Dr. Xinqi Chen (KECK, NU), and Mr. Yuki Kusachi (Nissan) for helpful discussions. Received: July 28, 2011 Revised: August 23, 2011 Published online: October 6, 2011

Experimental Section
Material Synthesis: GO was synthesized from ake graphite by a modied Hummers method.[23] Introduction of in-plane carbon defects was achieved by mixing approximately 0.1% w/w aqueous GO suspension with different amounts of 70% concentrated HNO3 (GO suspension/70% HNO3 volume ratio of 1:5 (sample I), 1:7.5 (II), 1:10 (III) and 1:12.5 (IV)), and sonicating in a bath sonicator for 1 h. The resulting deGO was ltered and washed using an Anodisc membrane lter, followed by air drying. The GO or deGO papers were reduced with either a ow of Ar (approximately 90 mL min1) or 10% hydrogen in Argon (approximately 100 mL min1 total ow) at 700 C for 1 h to form G or deG. To form Sigraphene paper composites, an aqueous, homogeneous suspension of air-exposed Si nanoparticles and GO or deGO of the appropriate weight ratios was vacuum-ltered, dried, and thermally reduced as described above. Structural Characterization: The as-prepared (de)GO and (de)G samples were characterized with eld emission scanning electron microscopy (FE-SEM), eld emission transmission electron microscopy (FE-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), synchrotron nonresonant X-ray Raman scattering (XRS), Raman spectroscopy, and surface area and pore size distribution measurements. The Pd-stained (de)GO was prepared by mixing (de)GO with a dilute aqueous Pd(OAc)2 solution. Thermogravimetric analysis (TGA) was performed on crushed Si(de)G composite papers in air. Sheet resistance was measured with a four-point probe technique with an electrode separation of 1 mm using a Keithley 2400 Sourcemeter. Electrochemical Tests: Half-cell tests were conducted using twoelectrode coin cells with Li metal as the counter electrode, assembled in an argon-lled glove box, at various current densities, typically in the voltage range of 0.021.5 V vs Li/Li+. Electrochemical measurements of Si(de)G composite papers were carried out using three-electrode Swagelok-type cells, with an independent Li metal reference electrode. Electrochemical cycling of Si(de)G composite electrodes was performed using two different procedures, either at various current densities in the voltage range of 0.022 V vs Li/Li+ or a constant currentconstant voltage (CCCV) method. Electrochemical impedance spectroscopy (EIS) measurements were conducted on two-electrode Swagelok-type cells by applying an AC voltage of 10 mV amplitude and DC open circuit voltage (OCV) in the frequency range of 1 MHz0.01 Hz at room temperature.

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