High-Performance Quasi-Solid-State Flexible Aqueous Rechargeable

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High Performance Quasi-Solid-State Flexible Aqueous Rechargeable AgZn Battery Based on Metal-Organic-Framework Derived Ag Nanowires Chaowei Li, Qichong Zhang, Juan Sun, Taotao Li, Songfeng E, Zezhou Zhu, Bing He, Zhenyu Zhou, Qiulong Li, and Yagang Yao ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.8b01675 • Publication Date (Web): 17 Oct 2018 Downloaded from http://pubs.acs.org on October 19, 2018

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ACS Energy Letters

High Performance Quasi-Solid-State Flexible Aqueous Rechargeable Ag-Zn Battery Based on Metal-Organic-Framework Derived Ag Nanowires Chaowei Li+ a,c,d, Qichong Zhang+ a, Juan Suna, Taotao Li a,b,c, Songfeng E a,b, Zezhou Zhua, Bing Hea, Zhenyu Zhou a, Qiulong Li a, Yagang Yao a,b,c* a

Division of Advanced Nanomaterials, Key Laboratory of Nanodevices and Applications, Joint Key

Laboratory of Functional Nanomaterials and Devices, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123, China

b

National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, and

Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China

c

Division of Nanomaterials, Suzhou Institute of Nano-Tech and Nano-Bionics, Nanchang, Chinese

Academy of Sciences, Nanchang 330200, China

d School

of Nano Technology and Nano Bionics, University of Science and Technology of China, Hefei,

230026, China

*Corresponding Author’s Email: [email protected].

[+] These authors contribute equally to this work.

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Abstract: Silver-Zinc (Ag-Zn) batteries are one of the promising aqueous batteries to collect and store solar energy with high energy density, stable output voltage and environmentally benign but the most Ag-Zn batteries have large contact resistance caused by polymer binders and conductive additives, thus leading to their low specific capacity and rate performance. As a proof-of-concept demonstration, we constructed a solar charged planar flexible quasi-solid-state aqueous rechargeable Ag-Zn battery using metal organic framework (MOF) derived Ag nanowires on carbon cloth as a binder-free cathode. Our electrochemical results show that the as-fabricated Ag-Zn battery has a remarkable energy density of 1.87 mWh/cm2 since MOF derived Ag nanowires can provide abundant reaction sites and short electron and ion diffusion paths. Moreover, the as-fabricated Ag-Zn battery integrated with a solar cell can be charged by sunlight. Thus, our findings pave an avenue to develop solar energy powered portable and wearable electronic devices.

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Global warming and energy crisis caused by utilization of fossil fuels are the greatest challenge of this century.1-4 The solar charged storage configurations have already attracted extensive attention because solar power is most clean, sustainable and abundant energy source.5-7 Particularly, the rapid development of flexible and wearable electronics prompt researchers to be interested in harvesting clean energy and develop flexible power configurations for converting and simultaneous storing solar energy.8-10 Numerous efforts have been devoted to the solar-charged-supercapacitor over the past few years.1117

However, short discharge duration and low energy density of supercapacitors limited their wide

application.18,19 Therefore, it is highly urgent to develop high-energy-density energy storage devices with stable output voltage and outstanding safety.20-24 Constructing high-performance aqueous batteries is very effective way to fulfill above-mentioned goal.25-31 To date, a high-performance aqueous battery integrated with solar cell which can not only realize the conversion and storage of free and abundant solar energy but also provide a feasible method to achieve self-charge energy supply remains a formidable challenge. Silver-zinc (Ag-Zn) batteries are one of the most promising aqueous batteries with high energy density, stable output voltage and environmentally benign.32,33 They not only possess comparable specific energy density to commercial lithium-ion batteries but also can deliver high safety and easily large-scale production.34,35 Therefore, flexible Ag-Zn batteries can act as effective energy supply devices for various portable and wearable electronic devices.36,37 However, the most Ag-Zn batteries have large contact resistance caused by polymer binders and conductive additives, thus leading to their low specific 3



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capacity.38 Undoubtedly, directly growth of Ag active materials on current collection as binder-free electrodes are an effective strategy to address this issue.39-41 Metal organic framework (MOF) represents a new class of hybrid materials with crystalline architectures, highly tunable porosities and different functionalities for a wide variety of applications.42-46 MOF-derived Ag nanowires on flexible carbon cloth (CC) are expected to effectively avoid contact resistance as well as maximize the utilization of Ag active materials. As far as we know, there are no available reports on the utilization of MOF derived Ag nanostructures in energy storage applications. This study presents rational design for the first prototype of a solar-charged planar flexible quasisolid-state Ag-Zn battery based on a novel MOF derived Ag nanowire binder-free cathode. The fabricated 1.54 V Ag-Zn battery delivers a remarkable capacity of 1.605 mAh/cm2 at a current density of 0.2 mA/cm2 in aqueous electrolyte. Moreover, we successfully assembled quasi-solid-state Ag-Zn batteries using CC-MOF derived Ag nanowires without any binder as the cathode, KOH polyvinyl alcohol as the solid electrolyte, and CC-Zn nanosheet arrays as the anode. The as-prepared quasi-solidstate Ag-Zn batteries exhibit a high capacity of 1.245 mAh/cm2, a remarkable energy density of 1.87 mWh/cm2, and maximum power density of 2.8 mW/cm2. Based on the Ag-MOF derived Ag nanowire cathode, our solar-charged Ag-Zn battery provides a novel clean solar energy storage solution for nextgeneration portable/wearable electronic applications. The schematic formation of the flexible quasi-solid-state Ag-Zn battery is illustrated in Figure 1. Briefly, Ag-MOF derived Ag nanowires were directly grown on CC to serve as a novel cathode. The AgMOF was first synthesized using a facile solution method and subsequently annealed in ammonia at 500 4


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oC

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for 1 h to obtain the Ag nanowires. Zn nanoflakes were then electrochemically deposited on the CC

to act as an anode. Eventually, the Ag nanowires/CC cathode, Zn anode, separator, and PVA/KOH gel electrolyte are successfully assembled into a flexible device with a classical sandwich structure.

Figure 1. Schematic illustration of the synthesis of the flexible quasi-solid-state Ag-Zn battery. From the microstructure of the as-prepared Ag-MOF/CC (Figure 2a, b), the morphology of AgMOF presents quasi cubic and the sizes are about 1~2 μm. To further investigate the structure of AgMOF, the TEM and high resolution TEM of Ag-MOF are also in agreement with the SEM results (Figure S1). Furthermore, the neighboring lattice fringe of the nanoparticles is 0.38 nm, which matches well with the d111 space of the metal Ag cluster (JCPDS No. 04-0783).47 The TGA curve of Ag-MOF shows two weight loss regions. A rapid loss in weight is observed about 240 oC, owing to the removal of physically absorbed water, organic ligands and the linker decomposition starting and a gradual weight loss stage are attributed to organic ligands turn into N deoped nanocarbon.48 Owing to the etching property of NH3, the NH3 would accelerate the organic ligands decompose into N deoped nanocarbon (Figure S2a). Above this temperature, there are no more thermal responses, thus demonstrating that the Ag-MOF is completely decomposed. The corresponding energy-dispersive spectrometry (EDS) images of Ag-MOF shown in Figure S2b verify the elementary content of Ag, C, and N. The Raman spectrums of Ag-MOF and Ag-MOF after treated in NH3 are shown in Figure S3. The peak at 137 cm-1 is attributed to symmetrical mode of Ag-N. 5



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The peak at 928 cm-1 is related to out-of-plane bending vibration (γ(NH)). those at 1002 and 1149 cm-1 are from the bending vibration (δCH) and out-of-plane methylene groups (ρCH3). The pyrrole ring stretching vibration (ν(R)) are corresponded to those peaks at 1355 and 1484 cm-1 and the out-of-plane bending vibration (γ(R)) is corresponded to the peak at 650 cm-1. What’ more, after treated NH3 at 500 oC

for 1 h, the Raman spectrum only shows the signal of carbon (D peak at 1349cm-1 and G peak 1569

cm-1) which suggests the organic formwork turns into graphitized carbon.49-52 The morphology of AgMOF treated in Ar (500 oC, 1h) still maintains the microstructure of the as-prepared Ag-MOF (Figure 2c). However, after the Ag-MOF treated in NH3/Ar (500 oC, for 1 h), the morphology of the Ag-MOF derived cathode shows the presence of freestanding ~50 nm Ag nanowires grown on the CC without binder, thus guaranteeing the low resistance of electron transfer (Figure 2f). The mechanism of the formation of nanowires is etching amorphous carbon by NH353,54 and the sintering of the silver nanoparticles,55 which can be speculated from the morphological change of the Ag-MOF during the treatment process, as shown in Figure 2d-f. The phase composition and crystalline structure of the Ag nanowires are investigated by XRD (Figure 2g). Excluding the peaks of the CC, all the remaining peaks can be attributed to the face-centered cubic Ag (JCPDS No. 04-0783). The TEM element mapping images (C, N and Ag) of Ag nanowire are shown in Figure S4. Furthermore, the XPS individual level spectrum of Ag 3d is shown in Figure 2h. The Ag 3d5/2 and Ag 3d3/2 spin-orbital photoelectrons are located at 374.6 eV and 368.6 eV, respectively, and these two peaks with a spin energy separation of 6.0 eV which are belonged to metallic silver suggesting that the Ag0 existed in treated sample and match well with the XRD result for the Ag nanowires/CC.50 The survey scan and high-resolution XPS spectra of C and N verify that the elements Ag, C, and N are present in the Ag nanowires/CC (Figure S5a, b, and c). The microstructure of the anode shows that the CC is tightly covered by freestanding Zn nanoflakes with about 60 nm in thickness, thus ensuring a feasible pathway for electron transfer (Figure S6a). The XRD patterns of the Zn nanoflakes in Figure S6b show that all the diffraction peaks, except for some peaks of CC and Zinc oxide are corresponded well with the hexagonal Zn (JCPDS No. 04-0831).56

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Figure 2. (a) SEM of Ag-MOF/CC. (b) The corresponding magnified SEM image. (c) SEM of AgMOF/CC treated in Ar and the SEM of Ag-MOF/CC treated in NH3 at different time (d) 0 min, (e) 30 min, and (f) 60 min. (g) XRD patterns of the Ag-MOF/CC, Ag nanowire/CC. (h) XPS spectrum of Ag 3d in the MOF derived Ag nanowire. Figure 3a comparatively shows the typical redox behaviors of the positive (Ag) and negative (Zn) electrodes by CV characterization demonstrating that an aqueous full cell with high potential can be envisioned. The CV curves of the fabricated batteries in aqueous electrolyte shown in Figure 3b represent two typical well defined redox couples (peak I represents the reaction of ZnO + 2Ag 7


Charge

Zn + Ag2O


(1) and peak II reflects the reaction of Zn + Ag2O

Disharge

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ZnO + 2Ag (2)).57 The capacities of batteries

composed of the Ag-MOF derived Ag nanowires cathodes in different atmospheres are shown in Figure 3c. The battery with annealed in Ar/NH3 displays the higher specific capacity of 1.605 mAh/cm2. In this situation the Ag-MOF can transform into Ag nanowires, which promote the electron transfer between the electroactive layer and the CC current collector and eventually enhance the electrochemical activity (Figure S7). However, the battery with cathode annealed in Ar only shows a capacity of 0.79 mAh/cm2, which was caused by the active materials (Ag) covered a layer of amorphous carbon from the organic framework and thus leading to increase the resistance between the active materials and decrease the utilization of silver. The Nyquist plots of the aqueous Ag-Zn batteries with different cathodes are shown in Figure S8a,b. The relationship between the treatment temperature and the electrochemical performance of the batteries assembled by different cathodes are shown in Figure S9. The capacity (Figure S10) and SEM (Figure S11) of the electrode treated at different temperature in NH3 atmosphere demonstrate that the sample annealed at 500 oC owns the optimal performance. Therefore, our subsequent researches focus on the cathode annealed at 500 oC in Ar/NH3. Figure 3d displays the GCD voltage profiles of the optimized Ag-Zn battery at various current densities ranging from 0.2 to 2 mA/cm2. Apparently, all of the profiles demonstrate typical charging and discharging plateaus between ~1.54 V and ~1.47 V, implying that the battery can be feasibly applied in energy storage. At a small current density of 0.2 mA/cm2, corresponding to about 8 h discharged period, the Ag-Zn battery delivered a capacity of ~1.605 mAh/cm2. What’s more, as shown in Figure 3e, when the current density increased to 2 mA/cm2, the discharge capacity still remains 1.32 mAh/cm2 and the coulombic effectivity is above 8


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98.9%, suggesting that the aqueous batteries have very good rate capability.58 The results for the long term cycle property at a current density of 0.2 mA/cm2 are studied and shown in Figure S12 which exhibit good stability with 90% retention of the initial capacity after 70 cycles.

Figure 3. (a) Comparison of the CV curves of the Zn anode and the Ag cathode at different scan rates. (b) CV curves of the aqueous Ag-Zn battery. (c) GCD curves at 0.2 mA/cm2 of aqueous devices assembled from MOF derived cathodes in different atmospheres. (d) GCD curves of the aqueous Ag-Zn battery. (e) Discharge characteristics and coulombic efficiency of the aqueous AgZn battery. Based on the above results and to further investigate the performance of as-prepared electrodes in solid-state energy storage applications, an quasi-solid-state Ag-Zn battery is fabricated with a polymer electrolyte (PVA-KOH gel), separator, Ag cathode, Zn anode and sealed by PDMS, as shown in Figure 4a. The CV profiles of the fabricated device in Figure 4b clearly display that the redox peaks at various scan rates are similar to those of the aqueous battery (Figure 3b), the reversible oxidation reaction I is 9



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related to formula (1) and reversible reduction reaction II also be corresponded to formula (2). The GCD curves for the battery at current densities vary from 0.2 to 2 mA/cm2 are shown in Figure 4c. Analogous to the CV splines, the two sets of voltage plateaus for the battery obviously corresponding to the oxidation-reduction reactions in equations (1, 2) (restricted between 1.1 to 1.8 V) are shown in Figure 4b. The sharp rise at the beginning of charging process corresponds with the formation of relatively highresistance Ag2O. During the discharging process, there is an initial sharp decline in the potential from 1.8 to 1.5 V. Then the voltage remains a relatively constant about 1.5 V, followed by a rapid decrease at the end. Furthermore, the voltage plateaus in Figure 4c are similar to those at the same current density in Figure 3c, Except for slightly lower, which may be caused by that the ion diffusion and charge transfer in polymer gel electrolyte (PVA/KOH) is more difficult than that in the aqueous electrolyte (Figure S13). In the Nyquist plot shown in Figure S13, the diameter of the semicircle in the high frequency range is tightly correlated with the charge-transfer resistance of the battery. The aqueous battery (4.3 Ω) shows a substantially lower charge-transfer resistance than that of the quasi-solid-state battery (25.6 Ω). Figure S14 shows the cycling performance of the Ag-Zn battery charged to 1.8 V (forming Ag2O). The SEM and XRD pattern of Zn nanoflakes/CC after the cycling test are shown in Figure S15. The decrease in capacity after 60 cycles may be caused by a number of factors along with the battery aging, such as the migration of Ag ions, formation of Zn dendrites, deterioration of the separator or migration of Ag ions or loss of free moisture due to its migration through the interspace of PDMS seal.59,60 Figure S16 shows the self-discharge performance of the battery, which indicates that the battery voltage barely drops after 30 days. The rate performance of the battery is shown in Figure 4d. The capacity of the device at different 10


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current densities, calculated from the related GCD curves, reaches the highest level (1.245 mAh/cm2) at a current density of 0.2 mA/cm2. Even when the current density is increased to 2 mA/cm2, the battery can be seen to deliver a capacity of 1.02 mAh/cm2. Moreover, the coulombic efficiency of the Ag-Zn battery remains 96% during the rate cycling process, which suggests the battery has admirable reversible stability and rate performance. Figure 4e shows the areal power (P) and energy density (E) of the flexible quasi-solid-state Ag-Zn battery. It is obvious that our fabricated Ag-Zn battery demonstrates both competitive power and energy densities. The Ag-Zn battery can deliver a maximum energy density of 1.87 mWh/cm2 and maximum power density of 2.8 mW/cm2. Thus, the overall performance is deemed to higher than the results reported for such as Ag//Zn battery (0.44 mWh/cm2, 1.02 mW/cm2)61, Ni-Zn battery (0.0092 mWh/cm2, 1.01 mW/cm2)62, MnO2 based supercapacitors (0.0054 mWh/cm2, 0.28 mW/cm2)63, VN based supercapacitors (0.1 mWh/cm2, 0.02 mW/cm2)64, Graphene based supercapacitors (0.0016 mWh/cm2, 0.002 mW/cm2)65, Ni-Zn battery (0.015 mWh/cm2, 0.018 mW/cm2)66 We also make a list of flexible battery to compare the electrochemical performance of the recent works with this work as shown in Table S1. (The gravimetric power (P) and energy density (E) of the flexible quasi-solid-state Ag-Zn battery are shown in Figure S17.). In order to demonstrate that our fabricated battery can satisfy the requirements for portable and wearable energy supply devices, we conducted a series of bending tests, the results are shown in Figure 4f. No obvious changes can be observed in the GCD curves at 0.2 mA/cm2 when the as-fabricated device is bent at various angles from 0o to 135o, which suggests that our Ag-Zn battery can withstand the bending and possesses significant flexibility. Furthermore, in Figure S18, the capacity remains more than 93% after bending 135o for 100 cycles, which further demonstrates 11



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the superb mechanical properties of the prepared devices (the photographotos shown in Figure S19). Overall, those remarkable properties demonstrate that the as-prepared flexible quasi-solid-state Ag-Zn battery is a promising candidate for use in the construction of wearable energy supply devices.

Figure 4. Schematic diagram and performances of the fabricated flexible quasi-solid-state Ag-Zn battery. (a) Schematic diagram. (b) CV curves at different scan rates. (c) GCD curves at various current densities. (d) Discharge characteristics and coulombic efficiency. (e) Ragone plots based on the area of the devices. (f) GCD curves of a device bent at various angles at a current density of 1 mA/cm2. Figure 5a presents a schematic illustration of the charge process of the Ag-Zn battery via a flexible commercial solar cell. Figure 5b shows the representative J-V curves of the flexible commercial solar cell. It is clearly seen that our Ag-Zn batteries demonstrate same charge curves charged by solar cell and electrochemical workstation (CHI), respectively (Figure 5c). The variation in the voltage of the battery charged by sunlight is depicted in Figure 5d. To demonstrate the viability of the battery for practical 12


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applications in wearable and portable electronic devices, we connect two fabricated flexible full quasisolid-state Ag-Zn batteries in series to power a set of LEDs. The GCD curves of the as-prepared single battery and two batteries in series are shown in Figure S20. The series assembled Ag-Zn battery can power eight red LEDs.

Figure 5. (a) Schematic illustration of the solar cell charged flexible quasi-solid-state Ag-Zn battery. (b) J-V curves of the solar cell. (c) Comparison of the battery charged by the solar cell with the CHI at same current density. (d) Charging by sunlight and discharging curves of the integrated devices with different currents (the sun represents charging process and the moon represents discharging process). 13



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In summary, we designed and fabricated MOF derived Ag nanowires on flexible CC without any binder as a novel cathode for use in quasi-solid-state aqueous rechargeable Ag-Zn batteries with a stable voltage of 1.54 V. This electrode structure can provide abundant reaction sites and short electron and ion diffusion paths, which endows the fabricated quasi-solid-state Ag-Zn battery with a high areal capacity of 1.245 mAh/cm2 and a remarkable energy density of 1.87 mWh/cm2. Furthermore, our Ag-Zn battery can be fully charged by an integrated flexible commercial solar cell. Thus, the successful attempt of the solar-charged Ag-Zn battery paves the way for the design of next-generation solar energy powered portable and wearable electronics.

Acknowledgements C. Li and Q. Zhang contributed equally to this work. This work was supported by the National Natural Science Foundation of China (Nos. 51522211, 51602339, 51703241 and U1710122), the Key Research Program of Frontier Science of Chinese Academy of Sciences (No. QYZDB-SSW-SLH031), the Thousand Youth Talents Plan, the Postdoctoral Foundation of China (Nos. 2016M601905 and 2017M621855), the Natural Science Foundation of Jiangsu Province, China (Nos. BK20160399), the Postdoctoral Foundation of Jiangsu Province (No. 1601065B), and the Science and Technology Project of Nanchang (2017-SJSYS-008).

Notes The authors declare no competing financial interest. Supporting Information. 14


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The Supporting Information is available free of charge on the ACS Publications website. Materials; Experimental Section; Characterizations; TEM image, TGA and EDS of the Ag-MOF; TEM and element mapping images, XPS spectra of Ag nanowire/CC; SEM image and XRD of Zn nanoflakes/CC and Zn nanoflakes/CC after cyclic test. SEM image of MOF derived Ag nanowires/CC at Ar/NH3; Nyquist plots of the aqueous Ag-Zn batteries with different cathodes and quasi-solid-state Ag-Zn battery; GCD curves of aqueous Ag-Zn batteries assembled by cathodes treated in different temperature; Capacity of cathodes treated in different temperature; Cycling, Self-discharge, Bending performance and Ragone plot of the quasi-solid-state Ag-Zn battery; GCD curves of single device and two devices in series; Photographs of bent quasi-solid-state Ag-Zn battery; Photogarphs of a heart-shaped consisting of 8 LEDs powered by two quasi-solid-state devices in series. References (1) Lewis, N. S. Toward Cost-Effective Solar Energy Use. Science 2007, 315, 798-801. (2) Graetzel, M.; Janssen, R. A.; Mitzi, D. B.; Sargent, E. H. Materials Interface Engineering for SolutionProcessed Photovoltaics. Nature 2012, 488, 304-312. (3) Chen, J.; Huang, Y.; Zhang, N. N.; Zou, H. Y.; Liu, R. Y.; Tao, C. Y.; Fan, X.; Wang, Z. L. MicroCable Structured Textile for Simultaneously Harvesting Solar and Mechanical Energy. Nat. Energy 2016, 1, 16138. (4) Larcher, D.; Tarascon, J. M. Towards Greener and More Sustainable Batteries for Electrical Energy Storage. Nat. Chem. 2014, 7, 19-29. (5) Schmidt, D.; Hager, M. D.; Schubert, U. S. Photo-Rechargeable Electric Energy Storage Systems. 15



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