Letter pubs.acs.org/NanoLett
Rapid Thermal Annealing of Cathode-Garnet Interface toward HighTemperature Solid State Batteries Boyang Liu,†,‡,§ Kun Fu,†,‡,§ Yunhui Gong,†,‡ Chunpeng Yang,†,‡ Yonggang Yao,†,‡ Yanbin Wang,†,‡ Chengwei Wang,†,‡ Yudi Kuang,†,‡ Glenn Pastel,†,‡ Hua Xie,†,‡ Eric D. Wachsman,†,‡ and Liangbing Hu*,†,‡ †
Department of Materials Science and Engineering and ‡University of Maryland Energy Research Center, University of Maryland, College Park, Maryland 20742, United States S Supporting Information *
ABSTRACT: High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V2O5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V2O5 cathode was significantly decreased from 2.5 × 104 to 71 Ω·cm2 at room temperature and from 170 to 31 Ω·cm2 at 100 °C. Additionally, the diffusion resistance in the V2O5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V2O5 cathode and garnet solid electrolyte without compromising battery safety or performance. KEYWORDS: Garnet, solid-state battery, high-temperature battery, cathode interface, rapid thermal annealing, Li metal battery
B
batteries with high stability have focused on electrolytes such as molten salts15−18 and polymer electrolytes with improved thermal stability.12,19−22 However, molten salt electrolytes have similar leakage concerns as conventional liquid organic electrolytes at high temperatures and polymer electrolytes tend to have poor mechanical strength at elevated temperatures, which can cause hazardous short-circuiting issues during operation.23 In comparison, ceramic solid-state electrolyte (SSE) will address the fundamental safety concerns of hightemperature batteries due to its high thermal and electrochemical stability.24 Moreover, ceramic SSEs can have increased ionic conductivity at elevated temperatures, which can lead to enhanced performance relative to room temperature operation.25 Therefore, significant interest is directed toward
atteries that can maintain excellent electrochemical performance at high temperatures are necessary for applications in the oil and gas industries, the aerospace sectors, and the military.1−3 These high-temperature batteries can be divided into two subcategories, those with or without intrinsic thermal stability. Batteries without intrinsic thermal stability need protection by cooling systems against high- temperature environments.4−6 Batteries with intrinsic thermal stability do not rely on cooling systems and are able to operate at elevated temperatures and extreme environments.7−9 High-temperature batteries are generally more energy efficient and safer under specific conditions, which makes them suitable for a myriad of high-temperature applications.10−12 The electrolyte for batteries with intrinsic thermal stability still requires significant improvements. Conventional liquid electrolytes have a low boiling point, leakage concerns, and hazardous properties and are not suited for high-temperature applications.13,14 Recent development of high-temperature © 2017 American Chemical Society
Received: May 9, 2017 Revised: July 2, 2017 Published: July 17, 2017 4917
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Figure 1. Schematic of the all-solid-state battery and properties of garnet SSE. (a) Schematic of the all-solid-state battery that can work at high temperatures. (b) Cross-sectional SEM image of garnet LLCZNO. (c) Temperature dependence of the garnet LLCZNO ionic conductivity.
Figure 2. Rapid thermal annealing process and its effect on garnet SSE and cathode. (a) Schematic of the rapid thermal annealing device. (b) Photo of the rapid thermal annealing device. (c) Light spectrum from the heated carbon in the thermal annealing process, indicating that the temperature of the carbon reached 800 °C. (d) Photos of the peel-off experiment and cross-sectional SEM image of the garnet SSE and cathode before rapid thermal annealing. (e) Photos of the peel-off experiment and cross-sectional SEM image of the garnet SSE and cathode after rapid thermal annealing. (f) Raman spectra of the bare garnet surface before and after rapid thermal annealing. (g) XRD patterns of the mixture of garnet powders, V2O5 powders, and CNT before and after rapid thermal annealing.
which results in high and unstable interfacial.33,34 Our recent works have reported methods to address the high interfacial resistance between garnet SSE and Li metal by applying metal or metal oxide interlayers. The interlayers can improve the contact between garnet SSE and Li, and result in significantly decreased interfacial resistance.35−37 However, the garnet SSE and cathode interface remains unsolved because current techniques require long processing time and/or high-temperature sintering processes,38−41 which can cause side reactions
selecting proper ceramic SSEs to meet the performance requirements and operating temperature ranges for specific applications. Among different ceramic SSEs, garnet Li7La3Zr2O12 is promising because of its advantages including high thermal stability,26,27 high ionic conductivity,28,29 and good electrochemical stability against lithium (Li) metal electrodes.30−32 The main challenge associated with garnet SSE is the solid− solid interfaces between the rigid garnet SSE and electrodes, 4918
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equivalent peel-off tests due to the firm contact with the garnet surface as seen in the left panel of Figure 2e. The crosssectional SEM image (right panel in Figure 2e) of the garnet/ cathode interface after rapid thermal annealing clearly demonstrates that the V2O5 material becomes small particles uniformly distributed and tightly integrated with the garnet surface. The morphology change occurs because V2O5 melts above 690 °C during the rapid thermal annealing up to 800 °C. The melting of V2O5 results in good interfacial wetting with the garnet SSE and effectively improves the interfacial contact and decreases the resistance. This rapid thermal annealing technique is applicable for thin-film battery fabrication,49 as demonstrated in this work. For a thin-film battery, no solidstate electrolyte is mixed in the cathode, and ionic conduction in the cathode is provided by the V2O5 material. Because of the small thickness of the cathode after rapid thermal annealing, the conductivity of V2O5 is enough for operation at high temperatures. Owing to the short annealing time, the garnet SSE and cathode materials remain chemically stable after the rapid thermal annealing process. The phase stability of garnet is proven by observing the Raman spectra of pure garnet before and after the rapid thermal annealing process (Figure 2f). Both spectra show peaks in agreement with previously reported cubic phase garnet.50,51 The X-ray diffusion (XRD) patterns of mixed garnet powders, V2O5 powders, and CNT before and after rapid thermal annealing show the appropriate peaks without any impurities, further confirming the stability of V2O5 and garnet after the rapid thermal annealing (Figure 2g). Note the CNT content (5%) is not high enough to show in the XRD pattern. The stability of garnet and V2O5 is further confirmed by energy-dispersive X-ray (EDX) elemental mappings (Supporting Information Figure S3). The EDX mappings show that vanadium stays within the cathode after the rapid thermal annealing process and does not diffuse into the garnet SSE. A process control experiment has been performed by using conventional furnace annealing. A powder mixture of garnet, V2O5, and CNT was heated up to 800 °C in argon atmosphere at a rate of 30 °C/min. This is slower than our rapid thermal annealing method, which reaches the same temperature in 1 s. With such a slow heating ramp, black smoke was observed billowing out of the powder mixtures at 420 °C, most likely due to the CNT oxidation by V2O5. This establishes that there are undesirable reactions between these materials at slowly elevated temperatures that precludes the use of furnace sintering to improve the garnet/cathode interface. Therefore, in contrast to conventional heating methods, the rapid thermal annealing by radiation heating averts significant side reactions between the cathode materials and solid-state electrolyte while improving the interfacial contact. To quantify the effect of rapid thermal annealing on improving the garnet/cathode interfacial contact and reducing resistance, symmetric V2O5/garnet/V2O5 cells were prepared and tested by electrochemical impedance spectroscopy (EIS). The cells were assembled by coating cathode material and CNT current collectors on both sides of the garnet SSE and then applying the rapid thermal annealing. Symmetric cells with the same structure but not treated by the rapid thermal annealing process were also tested for comparison. The symmetric cell before thermal annealing does not show a clear arc for the interfacial impedance, because of the poor interfacial contact (Figure 3a). Inset of Figure 3a is the equivalent circuit of the
between the cathode and garnet SSE.42 Therefore, few cathode materials have been successfully adapted for all-solid-state batteries with low cathode/garnet interfacial impedance and high stability. In this work, we demonstrate a high-temperature all-solidstate lithium metal battery using thermally stable Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZNO) garnet SSE and V2O5 cathode to operate at 100 °C with reliable safety and stable cycling performance. In order to ensure conformal cathode/garnet contact without the increased risk of parasitical reactions associated with long sintering time, we developed a rapid thermal annealing technique to treat the cathode and garnet interface in only a few seconds. With this interface treatment, the cathode/garnet interfacial resistance can be significantly decreased. Both the rapid thermal annealing method and the recently reported strategy of adding polymer/liquid electrolyte in the cathode43,44 can reduce the cathode/electrolyte interfacial impedance and enable stable battery cycling. Compared to batteries with polymer/liquid electrolyte in the cathode, the battery treated by rapid thermal annealing is totally solid-state and all the battery components have high thermal stability. Therefore, batteries constructed using the rapid thermal annealing method have a high stability and greater safety for operation at temperatures higher than 100 °C. This work provides a strategy to develop all-solid-state batteries using garnet solid-electrolyte with ensured performance and safety at high temperatures. Figure 1a exhibits the structure of the all solid-state battery with Li metal anode and garnet SSE. V2O5 was selected as the cathode material because of its high thermal stability with a melting temperature of 690 °C and decomposition temperature of 1750 °C.45,46 Carbon nanotubes (CNT) were mixed with V2O5 in cathode for electron conduction. Figure 1b is a crosssectional scanning electron microscope (SEM) image of garnet SSE. It exhibits the dense structure of garnet SSE, which enables the garnet SSE to have high ionic conductivity and stability at high temperatures, while preventing Li metal dendrite penetration during cycling. The garnet SSE has a high ionic conductivity of 3.7 × 10−4 S/cm at room temperature and the ionic conductivity increases exponentially with temperature to 2.4 × 10−3 S/cm at 100 °C (Figure 1c). The high conductivity at elevated temperatures provides high energy density and efficiency for the high-temperature battery. Figure 2a,b shows a schematic and a photograph of the rapid thermal annealing device used to improve the contact at the garnet/cathode interface. Joule-heated carbon paper was used as a radiation heating source for the rapid thermal treatment, which can be heated up to high temperature within hundreds of milliseconds.47,48 The temperature of the carbon paper was controlled to be around 800 °C, as calculated from the emission spectrum (Figure 2c and derivation details in Supporting Information Figure S2). V2O5 cathode was coated on garnet and put close to the high-temperature heating source for about 10 s for melting and wetting. After rapid thermal annealing, the contact between the V2O5 cathode and the garnet SSE is greatly improved as evidenced from peel-off experiments and cross-sectional SEM observations (Figure 2d,e). Without thermal annealing, the cathode material can be easily detached from the garnet surface as shown in the left panel of Figure 2d, because of the poor interfacial contact, as shown in the cross-sectional SEM images in the right panel of Figure 2d. In contrast, after rapid thermal annealing, the cathode material remains well-adhered in 4919
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50 and 75 °C with the results included in the Supporting Information Figure S4. All the tests demonstrate a significant decrease in the interfacial Rct and the cathode diffusion impedance after rapid thermal annealing, which indicates that the rapid thermal annealing process can effectively improve the garnet/cathode contact, enhance the diffusivity in V2O5 cathode and reduce the battery resistance. A summary of the improvement of the interfacial Rct before and after the rapid thermal annealing at different temperatures are given in Figure 3e,f. At the anode side, Li metal was melted on garnet SSE with a Si interface, using the same method as in ref 35 for the improved wettability. To identify the interfacial resistance between the Li anode and garnet SSE as a part of the full cell resistance, Li/garnet/Li symmetric cells were tested by EIS at 25, 50, and 100 °C (Figure 4a). From the EIS curves, the interfacial areal specific resistance (IASR) of the Li/garnet interface is calculated to be 150, 100, and 20 Ω·cm2 at 25, 50, and 100 °C, respectively. Figure 4b is the voltage profile for galvanostatic cycling of the same Li/garnet/Li symmetric cell as shown in Figure 4a. During 15 h of galvanostatic cycling at 100 °C, the total resistance is constant at 80 Ω·cm2, which includes 8 Ω·cm2 bulk resistance of garnet (calculated from the 2.4 × 10−3 S/cm conductivity at 100 °C and the 200 μm thickness of garnet). Therefore, the total interfacial resistance is 72 Ω·cm2 that when divided by two is 36 Ω·cm2 for each of the two garnet/Li interfaces. Another cell with the same structure was also cycled at 100 °C, showing a more stable voltage profile over a longer period of time (Supporting Information Figure S5). The constant resistance during galvanostatic cycling indicates that the garnet SSE can cycle well with Li metal anodes at high temperatures with constant interfacial resistance because of the chemical and electrochemical stability of garnet against Li metal. To further test the performance in a full cell configuration, the combination of V2O5 cathode and garnet SSE after rapid thermal annealing was assembled into all-solid-state batteries with a Li metal anode. Figure 4c compares the flammability of a traditional battery with polymer separator to the all-solid-state battery with garnet SSE and a V2O5 cathode. The polymer separator in a traditional battery caught fire after a very short time span, whereas the all-solid-state battery with the garnet SSE and V2O5 cathode was stable under the same conditions. This demonstrates the safety of the all-solid-state battery at high temperatures. Figure 4d shows the EIS plots of the Li/ garnet/V2O5 full cell tested at different temperatures (25, 50, 75, and 100 °C), where the bulk resistance, the interfacial Rct and the diffusion impedance all decrease significantly as the operating temperature increases. The bulk resistance and the total interfacial Rct decrease from 125 and ∼300 Ω·cm2 at 25 °C to only 20 and 45 Ω·cm2 at 100 °C, respectively. The decreased interfacial charge transfer resistance is attributed to the stability and improved ionic conductivity of garnet SSE, the well-formed solid-state interface, and the high diffusivities of V2O5 at higher temperatures. The Li/garnet/V2O5 battery cannot cycle at room temperature (Supporting Information Figure S6) because of the low diffusivity of Li+ in V2O5, which is increased at higher temperatures. The specific discharge capacity of the V2O5 cathode in the all-solid-state battery cycled at 100 °C is 150 mAh/g (Figure 4e). For comparison, the battery without rapid thermal annealing shows a larger overpotential and a lower capacity (42 mAh/g) at 100 °C because of the poor contact
Figure 3. Characterizations of the resistance of the cathode/garnet/ cathode symmetric cells. (a) EIS of the cathode symmetric cell originally and after rapid thermal annealing, tested at 25 °C. The diameters of the dash line arcs in all the EIS plots represent the charge transfer resistance on both V2O5/garnet interfaces. (b) EIS of cathode symmetric cell after rapid thermal annealing, tested at 25 °C. (c) EIS of the cathode symmetric cell originally and after rapid thermal annealing, tested at 100 °C. (d) High-frequency region of the EIS of cathode symmetric cell before rapid thermal annealing, tested at 25 °C. Inset is the EIS of the symmetric cell after thermal annealing. (e) Comparison of interfacial charge transfer resistance originally and after rapid thermal annealing, at 25 and 100 °C. (f) Interfacial charge transfer resistance of the symmetric cells originally and after rapid thermal annealing, at different temperatures.
symmetric cells, where R0 is the bulk resistance including the resistances of garnet SSE and CNT current collectors, Rct and CPE1 (constant phase element) are the charge transfer resistance and double layer capacitance on the garnet/cathode interfaces, and Zw and CPE2 are for the diffusion impedance inside of V2O5 cathode, respectively. From equivalent circuit modeling, the Rct before thermal annealing is 2.5 × 104 Ω·cm2 for the cathode/garnet interface, whereas the Rct after rapid thermal annealing dramatically decreases to 71 Ω·cm2 (Figure 3b), a 350 times decrease. The small resistance for an all-solidstate cathode/garnet interface is due to the good contact after rapid thermal annealing. Additionally, the diffusion impedance in the low-frequency region also decreases significantly after thermal annealing, as shown in Figure 3a,b. The decrease of diffusion impedance is possibly due to the morphology change of V2O5 particles after rapid thermal annealing. Parameters for the equivalent circuits are given in the Supporting Information Tables S1 and S2. To successfully operate at high temperature, we also measured the interfacial Rct of garnet/V2O5 at 100 °C, which decreases 5.5 times from 170 to 31 Ω·cm2 between the symmetric cells processed without and with the rapid thermal treatment, respectively (Figure 3c,d). The same test is done at 4920
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Figure 4. Performances and characterizations of the Li metal symmetric cells and full cells. (a) EIS plots of a Li/garnet/Li symmetric cell tested under different temperatures. Inset is the relationship between the interfacial Rct and temperature. (b) Galvanostatic cycling profile of the Li/garnet/ Li symmetric cell at 100 °C. (c) Flammability test of a traditional battery with polymer separator, and the all-solid-state battery with garnet electrolyte. (d) EIS plots of Li/garnet/V2O5 full cells tested under different temperatures. Inset is the zoom-in figure at high-frequency region. (e) Voltage profiles of the first cycle of the Li/garnet/V2O5 full cell, cycled at 100 °C. (f) Discharge capacity and Coulombic efficiency of the Li/garnet/ V2O5 full cell cycled with elevated current densities at 100 °C. (g) EIS profiles of Li/garnet/V2O5 full cell before and after cycling at 100 °C.
significantly decreased from 2.5 × 104 to 71 Ω·cm2 at room temperature and from 170 to 31 Ω·cm2 at 100 °C, respectively. The diffusion resistance inside of the V2O5 cathode material significantly decreases as well. The demonstrated high-temperature battery has a small and stable interfacial resistance of 45 Ω·cm2, exhibits >97% Coulombic efficiency, and maintains a stable discharge capacity at 100 °C. This work provides a strategy to address the high interfacial resistance between V2O5 cathode and garnet solid electrolyte and demonstrates how garnet SSE is a superb candidate for high-temperature solidstate batteries. Methods. Synthesis of LLCZNO Garnet Solid-State Electrolyte. The Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZNO) garnet powders were synthesized by a conventional solid state reaction. Stoichiometric amounts of LiOH·H2O (Alfa Aesar, 98.0%), La2O3 (Alfa Aesar, 99.0%), CaCO3 (Alfa Aesar, 99.0%), ZrO2 (Alfa Aesar, 99.0%), and Nb2O5 (Alfa Aesar, 99.9%) were thoroughly ball milled in isopropanol for 24 h. Ten weight percent excess lithium salt was added to compensate lithium loss during the following heating processes. The mixed precursor powders were dried and calcined at 900 °C for 10 h in air. The calcined powder was ball-milled in isopropanol for 24 h. The dried powders were pressed into disks with diameter of 12.5 mm at 500 MPa and sintered at the temperature of 1050 °C for 12 h in air. Both precursor
between the garnet and cathode (Supporting Information Figure S7). Compared to V2O5/Li batteries with liquid electrolyte,52,53 our battery has a lower average discharge voltage around 2 V. This is attributed to the limited ion diffusion kinetics in the cathode of the all solid state battery, which results in a large polarization. The battery with rapid thermal annealing was cycled at 100 °C at current densities of 50, 100, 150, and 200 mA/g and recovered to 50 mA/g (Figure 4f). After applying a high current density, the capacity returned to 150 mAh/g at the current density of 50 mA/g, which indicates that the cathode/garnet interface remains stable and reversible at current densities up to 200 mA/g. The >97% Coulombic efficiency during cycling indicates the good electrochemical stability of garnet SSE with the Li anode. The EIS plots of the battery before and after cycling further show that the interfacial Rct is kept constant at about 50 Ω·cm2, demonstrating the stability of the garnet/cathode and garnet/Li interfaces during high-temperature cycling (Figure 4g). In summary, we have demonstrated a high-temperature Li metal battery based on garnet solid-state electrolyte with stable electrochemical performance and high efficiency. A rapid thermal annealing process was developed to effectively address the high interfacial resistance between the V2O5 cathode and garnet electrolyte while keeping both materials chemically stable. The resulting cathode/garnet interfacial resistance was 4921
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Nano Letters calcination and final sintering were carried out using alumina crucibles. Disks were embedded in mother powder to mitigate lithium losses at high sintering temperature. After sintering, the garnet disks were polished with sand paper to control the thickness to be ∼200 μm and produce smooth surface. Preparation of V2O5/CNT Cathode Materials on Garnet. The V2O5 powders (99.6%, Sigma-Aldrich) and single wall carbon nanotubes (CNT) (Carbon Solutions) were dispersed in N-methyl-2-pyrrolidone (NMP) (Sigma-Aldrich) solvent with mass ratio 9:1 and total concentration 5 mg/mL. The particles in the solution were dispersed under ultrasonic for 4 h and then dropped on one side of garnet with pipettes. The amount of dropped solution was controlled to be 40 μL/cm2 to achieve 0.2 mg/cm2 cathode mass loading. After dropping, the solvent was evaporated at 150 °C on a hot plate to achieve the cathode/garnet combined structure. After drying up, 0.1 mg/ cm2 of CNT dispersed in NMP (5 mg/mL) was dropped on the top of cathode and dried to achieve current collectors. The thickness of the V2O5 cathode is around 2 μm. Rapid Thermal Annealing of Cathode on Garnet. The rapid thermal annealing device was made by suspending a rectangular piece of carbon paper (1 cm length, 0.8 cm width, and 250 μm thickness) on a glass substrate. The two ends of the carbon paper were connected to copper electrodes with conductive silver paste (SPI Supplies). Volteq HY6020EX power source was used to give electric current. The garnet SSE coated with cathode was put on the glass substrate, beneath the carbon paper. The rapid thermal annealing process was done in a glovebox filled with argon. The radiation spectrum was tested with an optical fiber detector (400 μm diameter) and analyzed with Ocean Optics software. Characterizations. The X-ray diffusion (XRD) phase test of garnet and cathode materials were done with a D8 Advanced system (Bruker AXS, WI, USA) using a Cu Kα radiation source operated at 40 kV and 40 mA. Cathode/garnet mixture for XRD test was composed of garnet, V2O5, and CNT powders with mass ratio 5:4:1. The Raman spectra of the garnet surface were tested by Horiba Jobin-Yvon Raman spectrometer with laser wavelength 532 nm. The morphologies of the interfaces and elemental mappings were tested with a field emission scanning electron microscope (FE-SEM, JEOL 2100F). Assembly of Solid-State Batteries. The blocking cells with garnet electrolyte for impedance test were made by coating Au paste on both sides of a garnet disk and heated at 800 °C for good contact. The V2O5/garnet/V2O5 symmetric cells were made by coating cathode on both sides of garnet and thermally treating either side in sequence. The garnet/cathode combinations after rapid thermal annealing were made into batteries by melting Li metal on the other side of the garnet disks. To improve contact between garnet and Li metal, one 10 nm thick layer of Si was coated on the lithium side of garnet, by plasmaenhanced chemical vapor deposition (PECVD) technique with Oxford Plasmalab System 100. After Si coating, Li metal was coated on garnet by melting and alloying with the Si, at 200 °C. After this, the Li/SSE/cathode cells were assembled in CR2032 coin cell cases. The Li melting and cell assembly process were performed in a glovebox filled with Argon. Electrochemical Tests. The EIS tests and the cycling tests of the batteries were done with Bio-Logic tester. The test temperatures were controlled between room temperature and 100 °C by placing the batteries in a constant temperature chamber. EIS tests were performed with perturbation
amplitudes 20 mV and over frequency range 1 MHz to 10 Hz. The battery cycling cut voltages were 1.2 to 4.5 V.
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ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.nanolett.7b01934. XRD of LLCZN garnet, measurement of the temperature of rapid thermal annealing process, EDX mapping of garnet/V2O5 interface, impedances of V2O5 symmetric cells at 50 and 75 °C, additional performances of Li/ garnet/Li symmetric cell and Li/garnet/V2O5 full cells (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Chunpeng Yang: 0000-0001-7075-3356 Eric D. Wachsman: 0000-0002-0667-1927 Liangbing Hu: 0000-0002-9456-9315 Author Contributions §
B.L. and K.F. contributed equally to this work.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the U.S. Department of Energy, DOE EERE contract #DEEE0006860. We acknowledge the support of the Maryland Nanocenter, its FabLab, and AIMLab. We would like to thank Dr. Wei Luo for help with PECVD Si and manuscript writing.
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REFERENCES
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DOI: 10.1021/acs.nanolett.7b01934 Nano Lett. 2017, 17, 4917−4923
