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A Flexible Hybrid Zn-Ag /Air Battery with Long Cycle Life Chia-Che Chang, Yi-Cheng Lee, Hsiang-Ju Liao, Yu-Ting Kao, Ji-Yao An, and Di-Yan Wang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06328 • Publication Date (Web): 18 Dec 2018 Downloaded from http://pubs.acs.org on December 22, 2018

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ACS Sustainable Chemistry & Engineering

A Flexible Hybrid Zn-Ag /Air Battery with Long Cycle Life Chia-Che Chang, Yi-Cheng Lee, Hsiang-Ju Liao, Yu-Ting Kao, Ji-Yao An, Di-Yan Wang* Department of Chemistry, Tunghai University, No.1727, Sec.4, Taiwan Boulevard, Xitun District, Taichung 40704, Taiwan E-mail: [email protected]

Abstract A battery with high energy density, large capacity, long cyclability, safety and flexibility is desired to not only power small electronic devices but also provide solutions to large scale energy storage managements. In this work, a hybrid battery of Zn-Ag and Zn-Air (Zn-Ag/Air) has been successfully fabricated, in which Ag acted as an active material at the charging state and as an oxygen reduction reaction catalyst at the discharging state. In traditional zinc air batteries, Ag was used as a catalytic material only. In this work, the sufficient amounts of Ag nanoparticles were covered onto stainless steel wire screen via a facile electrodeposition procedure as not only catalytic materials but also active redox materials. The rigid hybrid battery delivered two discharging plateaus at 1.5 V and 1.1 V, in which the higher one was attributed to reduction of Ag2O to Ag and the lower one resulted from Ag-assisted oxygen reduction reaction. The cyclability test showed that the Coulombic efficiency retained higher than 85% after 1700 cycles. Furthermore, the Zn-Ag/Air hybrid battery was also able to be packed in a pouch cell and demonstrated high flexibility and rechargeable capability. Overall results indicate that the hybrid battery possesses both advantages of Zn-Ag and Zn-Air batteries with improved discharging potential and enhanced storage capacity.

Keyword: Zn-Air battery, Zn-Ag battery, Hybrid battery, Ag nanoparticles, Ex-situ X-ray diffraction

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Introduction With high demands of large-scale energy storage solutions as well as small device battery requirements, such as that used in the Internet of Things (IoT) energy provider, multifunctional batteries are attracting enormous attentions.1,

2

Among few available

technologies, lithium-base batteries have been widely used in portable electronic devices and some large-scale applications for renewable energy storage and frequency balancing,3,

4

however, which safety is still the major concern with posing a fire risk.5, 6 In addition, IoT and big data related devices energy demand is key to future Artificial Intelligence (AI) development so that reliable metal ion batteries will play an important role eventually. There have been several developing rechargeable energy storage technologies almost without safety concern, including metal air batteries,7-11 redox flow batteries,12, 13 aluminum ion batteries,14, 15 etc., for sharing the needs not only in stationary but also portable energy storage devices. In those three mentioned batteries, the zinc air battery is the one shown in the market both as a small device energy source, such as a primary hearing-aid battery, and as a large mobile battery, like mechanically refuelable battery system to power electric bus.11, 16 Therefore, the zinc air battery system was selected to be further improved as an electrically rechargeable battery without the necessity of zinc active materials replacement. There have been some issues remained to be solved, such as oxygen reduction/evolution electrode development for voltage efficiency enhancement and cycle life increase as well. Many oxygen reduction reaction (ORR) catalysts17,

18

coated at the air breathing

electrode for better zinc air batteries’ efficiency have been reported, such as MnO2 based,19 mixed valence CoOx-MnOx,20 NiCo2O4,21 metal tetra-methoxylphenyl porphyrine based (CoTMPP, FeTMPP-Cl/C),22 metal nitride-based,23 spinel-type based,24, 25 perovskite-type,26, 27

and pyrochlore-type based28 (A2B2O6O’) ORR catalysts. There were also oxygen

reduction/evolution

reaction

bifunctional

catalysts

studied

in

literature,

like

La1-xAxFe1-yMnyO3 (A=Sr or Ca), and La0.6Ca0.4Co0.8B0.2O3 (B=Mn, Fe, Co, Ni, or Cu).29 The


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performance of cathodes consisting of MnOx-based catalysts depended mainly on the fabrication method. For example, a stable MnO2-based cathode developed by Rayovac Corp. showed a voltage of 1.15V at 150 mA/cm2 with a 15hr discharging durability test in 30% KOH.30 Ag has high ORR activity and stability in alkaline aqueous solution. The basic catalyst Ag/C with BET characterized 333 m2/g, 15-30 nm particle sizes expressed 0.99V at 200 mA/cm2.31 A nickel–zinc battery is other alkaline aqueous type of rechargeable battery with a higher voltage of 1.7 V and a specific capacity of 58 mAh/g. Although a Zn-air battery can serve as a stationary energy storage device, its discharge voltage is low (1.2V) in comparison with other alkaline aqueous electrolyte batteries due to sluggish rate of oxygen reduction reaction at the cathode. To overcome that issue, Zn-Ag battery was selected and its higher discharge voltage could be potentially applied in the electronic wearable system for human health monitoring, which requires a high energy density and flexible battery that maintains stable and safe operation.32-36 However, traditional Zn-Ag battery preparation did not provide long cycle life owing to poor substrate re-attachment of Ag and Zn through multiple dissolution/deposition. In this work, a Zn-Ag/Air hybrid battery was fabricated mainly through one-step electrodeposition method to form Ag nanoparticles highly covered on the stainless steel wire screen substrate, which was applied as ORR catalysts and active materials as well. The hybrid battery offered high capacity, competitive energy efficiency, long cycle life and mechanical flexibility.

Results and discussion The hybrid battery’s cathode consisted of Ag nanoparticles on the stainless steel screen was constructed by electro-reduction of Ag in the AgNO3 aqueous solution. Figure 1 shows that the morphology of Ag/stain steel screen with varied deposition time. The pristine stainless steel substrate exhibits a clean surface (Figure 1 (a). With 0.5 hr of electrodeposition,



the surface of substrate is covered with Ag nanoparticles. As deposition time increases, the layer of nanoparticles becomes thicker. When the deposition time comes to 1.5 hr, the net structure of the stainless steel becomes obscure due to the aggregation of Ag nanoparticles. The photograph in the middle part of Figure 1 indicates that the white region in the lower part of the stainless steel substrate is the Ag deposited region while the gray region is the original substrate without coatings.

The electrochemical performances of battery with Ag covered stainless steel screen as cathode are presented in Figure 2. The battery uses a tin metal plate as anode and the Ag/stainless steel substrate as cathode measured via galvanostatic charge/discharge and cyclic voltammetry (CV) technique. A tin anode holds two main advantages over a zinc anode, used in most zinc-air batteries reports, including stability over time by proper cut-off discharge voltage setting, and better conductivity even when tin oxides exist. The charging and discharging curves of the battery with different deposition time (Figure 2a) indicates that the battery with the silver cathode through 1hr deposition process expresses the highest specific discharging capacity of 37.3 mAh/g. There are two charging voltage plateaus at 1.70 V and 2.00 V which could be ascribed to the oxidation of Ag to Ag+ (0→I) and Ag+ to Ag2+ (I→II) along with effect of oxygen evolution reaction. The potential jump between these two plateau results from the formation of high resistive AgO layers forming at the second voltage plateau. Moreover, the sharp peaks found between the first and second plateau is attributed to the high resistive Ag2O surrounding the cathode electrode. In the discharging process, two discharging plateaus at 1.80V and 1.50 V represent the reduction of Ag2+ to Ag+ (II→I) and Ag+ to Ag (I → 0), respectively. All these voltage plateaus fit well with the silver redox reaction in the typical Zn-Ag battery. The corresponding cyclic voltammetry test of Zn-Ag battery with silver cathode deposited for 1 hr is presented in Figure 2b. The reversible anodic peaks and cathodic peaks fit well with the voltage plateaus in galvanostatic curves in Figure 2a. These


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two redox couples are the reversible reactions shown as follows: Ag2O + H2O + 2e- ⇌ 2Ag + 2OH- E0 = 0.34 V vs. SHE

(1)

2AgO + H2O + 2e- ⇌ Ag2O + 2OH- E0 = 0.6 V vs. SHE

(2)

To further understand the reaction of silver cathode during charging/discharging process, the ex-situ XRD analysis of our Zn-Ag battery was examined. Figure 3a shows the galvanostatic curve of the examined battery. The silver cathode at different potential state, including pristine silver, charged at 1.80 V and 1.98 V, discharged at 1.81 V, 1.54 V and 0.9 V was chosen for ex-situ XRD analysis. The pristine silver on stainless steel shows sharp signals at 38° and 44°, corresponding to the signals of silver (111) and (200) lattice plane, respectively, revealing a high crystallinity of our electrodeposited silver cathode. Upon charging and discharging, the silver cathode still remains a high crystallinity. By further examining the magnified XRD patterns (Figure 3c), the pattern differences between each potential stay only at the 2 theta region between 30 ° and 35 ° . The pristine silver electrode shows no diffraction peak in this region; however, upon charging to 1.8 V, the signal of 32.9° appears. This peak represents the (111) signal of Ag2O, meaning that the oxidation reaction from Ag(0) to Ag(I) occurs after the first charging plateau. When further charging the battery to 1.98 V, the intensity of Ag2O (111) signal decays with the signals of 32.1°, 32.4° and 34.2° emerging, which represent the lattice plane (200), (-111) and (002) of AgO. The results can be indexed with the literature value of typical crystalline AgO (JCPDS no. 84-1547). Accordingly, the oxidation from Ag2O to AgO occurs at the second voltage plateau of 1.98 V during charging process. In the discharging process, the appearance of Ag2O signal and the decline of AgO signals implies that the reduction from AgO to Ag2O takes place at the first discharging plateau 1.81 V. With discharging to the second discharging plateau, the signals of AgO totally disappear and the signal of Ag2O remains, indicating the fully recovering to Ag2O at the second discharging plateau 1.54 V. When the battery completely discharges, the



signal of Ag2O disappears and reduces to Ag (JCPDS no. 04-0783) completely. With this ex-situ XRD analysis, it’s confirmed that the capacity of the Zn-Ag air battery is truly contributed by the reversible redox reaction of silver cathode during discharging voltage of 1.81V and 1.54V.

The schematic Zn-Ag/Air hybrid battery is illustrated in Figure 4a. The acrylic box contains the electrolyte of 0.2M zinc acetate and 6.0M KOH electrolyte with tin anode and Ag cathode. A tin anode has two major advantages over a conventional anode using zinc plate, including easy observation of real coulombic efficiency for each recharge cycle, and better conductivity even with tin oxide formation on it during life test, while zinc oxide might cause higher overpotential and shorten a battery’s cycle life. The air permeable membrane is hot pressed with Ag coated substrate as a gas diffusion layer and prevents electrolyte leakage as well. To evaluate the cyclability of Zn-Ag/air hybrid battery, the recharge cycling was examined under a current density of 20 mA/cm2. It took ~0.3hr for each cycle. After 551 h, each cycling capacity almost remains the same and the galvanostatic curve keeps unchanged, indicating that the Zn-Ag/Air hybrid battery shows an excellent stability over 1700 cycles. The detailed discharging profile of Zn-Ag air hybrid battery (the inset of figure 4b) exhibits obvious two discharging plateaus at 1.5 V and 1.1 V, which was attributed to reduction of Ag2O to Ag and oxygen to hydroxide ions, respectively. Figure 4c shows that the corresponding Coulombic efficiency remains higher than 85 % over 1700 cycles, revealing a remarkable cyclic performance of Zn-Ag/Air hybrid battery. The charge/discharge polarization curves are demonstrated in Figure 4d. At current density of 20 mA/cm2, the voltage gap between charge and discharge is only 0.06 V. Even though the current density increases to 80 mA/cm2, the voltage gap is only 0.77 V, which is much smaller than previous reported results. To highlight the importance of this work, a rechargeable zinc-air batteries performance


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comparison table was made. In table 1, several state-of-the-art cathode catalysts are listed with excellent discharge voltages and cycle life. The reported catalysts include metal,37-39 metal oxides,8, 40-42 and complex metal/metal oxides.43 In this table, the Ag NWs/3D graphene aerogel catalyst shows the best discharge voltage of 1.36 V under a current density of 5 mA/cm2. Our hybrid battery delivers high discharge voltages at higher current density with two plateaus of 1.5 V and 1.1 V@ 20 mA/cm2, which is superior to other reports. The cycle life of our hybrid battery can be achieved to 1700 cycles under a current density of 20 mA/cm2 with 551 hr operation time, which is also better than reported Co3O4 with 200 cycles and 400 hr duration time. Overall result indicated that the hybrid battery is capable of offering superb discharge voltage and lifespan. The hybrid battery also exhibits flexible and stable characteristics in different assembly containers. Figure 5 shows the charging and discharging curves of Zn-Ag/air hybrid battery packed in a pouch cell. The obvious three discharging plateaus at 1.8 V, 1.54 V and 1.1 V are seen in Figure 5a with capacity of 70 mAh/g. After 40 cycles, its performance remains stable. Figure 5b shows that the hybrid pouch cell can power a red LED. The pouch cell (lower part in the photograph) under a bending strain exhibits a good power to drive LED with high illumination. When the pouch cell is bended to 60% in the x-direction, it’s still able to power a red LED. Overall results demonstrate that the Zn-Ag/air hybrid pouch cell indeed combines both advantages of Zn-Ag and Zn-air batteries with not only discharging voltage enhancement but storage capacity increase.

Conclusions A successful fabrication and operation of a rechargeable/bendable Zn-Ag/air hybrid battery has been demonstrated. The Zn-Ag/air hybrid battery delivered excellent reversible discharging voltage of 1.5 V and 1.1 V at current density of 20 mA cm−2 even after 1800 recharge cycles. The hybrid battery assembled in the pouch cell exhibited a discharging



capacity of 8 mAh with high discharging voltage of 1.8 V, 1.5V and 1.1 V under the current density of 10 mA cm−2. The hybrid battery has been proved to enhance the electrochemical performance and improve the shortcomings of original Zn-Ag and Zn-air batteries with less capacity and lower discharging voltage, respectively. Our finding is expected to pave a path to provide other types of energy storage technologies by combination of aqueous metal ion battery and metal air battery.

Experimental Section. Chemicals and Reagents: Silver nitrate, tartaric acid, nitric acid, zinc metal, zinc acetate, potassium hydroxide, polyvinyl alcohol (PVA), acetone, glutaraldehyde and hydrochloric acid were purchased from Sigma Aldrich. The stainless steel mesh and carbon cloth was purchased from Fu-Sen Wire Mesh Store (ESZ Company) and Cetech Co. Ltd., respectively.

Acid treatment of stainless steel wire screen. The 325 mesh stainless steel type 316L wire screen with an area of 5 cm × 1 cm was used as the substrate for electrochemical deposition of Ag nanoparticles. The stainless steel screen was immersed in the acid solution consisting of 1 mL of pure H2SO4 and 20 mL ethanol to remove additional organic or carbon residue for 15 minutes. Then, the resulting stainless steel substrate was dried in the ambient condition for cathode assembly and further characterizations.

Electrochemical deposition of Ag nanoparticles on the stainless steel wire screen. Place the stainless steel wire screen as working electrode and graphite rod as counter/reference electrode in a 250 mL glass bottle with the electrolyte consisting of 0.2 M AgNO3, 0.05M HNO3, and 0.015M tartaric acid. With charging a constant current density of 5 mA/cm2 for 0.5hr, 1hr, 1.5hr and 2hr, the different morphology and thickness of Ag nanoparticle film was successfully deposited on the substrate (Ag/stainless steel wire screen).


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The deposition area was 1 cm×2 cm. The electrochemical measurement of Zinc/Ag and air hybrid battery. Zinc Ag/air hybrid battery was prepared and tested using a potentiostat (SP-50, Bio-Logic Science Instruments). A polished Tin plate as an anode, Ag/stainless steel wire screen hot pressed with carbon cloth, a gas diffusion layer (GDL), as a cathode, and microporous membrane as a separator were assembled in an acrylic box, which was filled with appropriate amount of 0.2M Zn(CH3COO)2 and 6.0 M KOH aqueous electrolyte. The cathode hot pressed procedure was made under a pressure of 1500 psi at 200 ℃ for one minute.

Polymer solid electrolyte preparation A PVA-gelled electrolyte membrane was prepared by a phase inversion technique. First, a 5 wt% aqueous solution (100 mL) of PVA (99% hydrolyzed, average M w 146000–186000 g mol

−1)

was prepared at 90 °C. When the resulting solution was cooled down to room

temperature, the pH value of the solution was adjusted to 2 with adding HCl solution (5M) and then 1mL of glutaraldehyde (10 wt%) was added for crosslinking process. The resulting solution was casted onto a glass plate and dried for 24 hr. The solid and soft membrane will be formed on the glass plate. After washing with distilled de-ionized water, the resulting membrane was soaked in the electrolyte and equilibrated for 24 h.

The assembly of Zinc Ag/air hybrid pouch battery One side of the pouch was drilled with a hole ~0.8×1.8 cm2 for air contact. Ag/stainless steel wire screen hot pressed with carbon cloth as a cathode was attached with above hole open sheet and sealed by a silicone gel around the hole avoiding electrolyte leakage. Then, PVA-gelled membrane as a separator and a polished zinc plate as an anode was arranged on the Ag/stainless steel substrate step by step. Finally, the resulting pouch cell was sealed by heat sealing machine for later measurements.



Physical Characterization The electrochemical measurement was performed by a potentiostat (SP-50, Bio-Logic Science Instruments). The structure morphology of Ag nanoparticle film on stainless steel wire screen was performed by a scanning electron microscopy (JEOL JSM-7800F Thermal Field Emission Scanning Electron Microscope). Ex-situ of X-ray diffractometer was performed at the beamline of BL23A small/wide angle X-ray scattering (SWAXS) at Taiwan Light Source (TLS) and the beamline of 09A at the Taiwan Photon Source (TPS) in National Synchrotron Radiation Research Center.

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] ORCID Di-Yan Wang: 0000-0003-3084-6050 Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work has been financially supported by the Ministry of Science and Technology of Taiwan (MOST 106-2113-M-029 -006 -MY2 and MOST 106-2632-M-029-001) and Tunghai University. We thank Dr. U-Ser Jeng for assistance at beamline BL23A at Taiwan Light Source (TLS) and Dr. Hwo-Shuenn Sheu, Dr. Yu-Chun Chuang for assistance at beamline 09A at the Taiwan Photon Source (TPS).

Supporting Information


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The Supporting Information is available free of charge on the ACS Publications website. The SI includes SEM images and active surface estimation of Ag NPs deposited on stainless steel screen with different mass loading. Linear sweep voltammetry curves of Ag NPs deposited on stainless steel wire screen for ORR test.

Reference: 1.

Dunn, B.; Kamath, H.; Tarascon, J.-M., Electrical energy storage for the grid: a

battery of choices. Science 2011, 334, (6058), 928-935, DOI: 10.1126/science.1212741. 2.

Hadjipaschalis, I.; Poullikkas, A.; Efthimiou, V., Overview of current and future

energy storage technologies for electric power applications. Renew. Sust. Energ. Rev. 2009, 13, (6-7), 1513-1522, , DOI: 10.1016/j.rser.2008.09.028. 3.

Armand, M.; Tarascon, J.-M., Building better batteries. Nature 2008, 451, (7179),

652, DOI: 10.1038/451652a. 4.

Bruce, P. G.; Scrosati, B.; Tarascon, J. M., Nanomaterials for rechargeable lithium

batteries. Angew. Chem. Int. Ed. 2008, 47, (16), 2930-2946, DOI: 10.1002/anie.200702505. 5.

Wang, Q.; Ping, P.; Zhao, X.; Chu, G.; Sun, J.; Chen, C., Thermal runaway caused

fire and explosion of lithium ion battery. J. Power Sources 2012, 208, 210-224, DOI: 10.1016/j.jpowsour.2012.02.038. 6.

Balakrishnan, P.; Ramesh, R.; Kumar, T. P., Safety mechanisms in lithium-ion

batteries. J. Power Sources 2006, 155, (2), 401-414, DOI: 10.1016/j.jpowsour.2005.12.002. 7.

Lee, J. S.; Tai Kim, S.; Cao, R.; Choi, N. S.; Liu, M.; Lee, K. T.; Cho, J., Metal–air

batteries with high energy density: Li–air versus Zn–air. Adv. Energy Mater. 2011, 1, (1), 34-50,

DOI: 10.1002/aenm.201000010.



8.

Page 12 of 22

Li, Y.; Gong, M.; Liang, Y.; Feng, J.; Kim, J.-E.; Wang, H.; Hong, G.; Zhang, B.;

Dai, H., Advanced zinc-air batteries based on high-performance hybrid electrocatalysts. Nat. Commun. 2013, 4, 1805, DOI: 10.1038/ncomms2812. 9.

Fu, J.; Cano, Z. P.; Park, M. G.; Yu, A.; Fowler, M.; Chen, Z., Electrically

rechargeable zinc–air batteries: progress, challenges, and perspectives. Adv. Mater. 2017, 29, (7), 1604685, DOI: 10.1002/adma.201604685. 10.

Li, Y.; Lu, J., Metal–air batteries: will they be the future electrochemical energy

storage device of choice? ACS Energy Lett. 2017, 2, (6), 1370-1377, DOI: 10.1021/acsenergylett.7b00119. 11.

Li, Y.; Dai, H., Recent advances in zinc–air batteries. Chem. Soc. Rev. 2014, 43,

(15), 5257-5275, DOI: 10.1039/C4CS00015C. 12.

Wang, W.; Luo, Q.; Li, B.; Wei, X.; Li, L.; Yang, Z., Recent progress in redox flow

battery research and development. Adv. Func. Mater. 2013, 23, (8), 970-986, DOI: 10.1002/adfm.201200694. 13.

Li, L.; Kim, S.; Wang, W.; Vijayakumar, M.; Nie, Z.; Chen, B.; Zhang, J.; Xia, G.;

Hu, J.; Graff, G., A stable vanadium redox‐flow battery with high energy density for large‐scale

energy

storage.

Adv.

Energy

Mater.

2011,

1,

(3),

394-400,

DOI:

10.1002/aenm.201100008. 14.

Lin, M.-C.; Gong, M.; Lu, B.; Wu, Y.; Wang, D.-Y.; Guan, M.; Angell, M.; Chen,

C.; Yang, J.; Hwang, B.-J., An ultrafast rechargeable aluminium-ion battery. Nature 2015, 520, (7547), 324, DOI: 10.1038/nature14340. 15.

Wang, D.-Y.; Wei, C.-Y.; Lin, M.-C.; Pan, C.-J.; Chou, H.-L.; Chen, H.-A.; Gong,

M.; Wu, Y.; Yuan, C.; Angell, M., Advanced rechargeable aluminium ion battery with a high-quality

natural

graphite

cathode.

Nat.

Commun.

10.1038/ncomms14283.


2017,

8,

14283,

DOI:

Page 13 of 22 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


16.

Lee, J. S.; Tai Kim, S.; Cao, R.; Choi, N. S.; Liu, M.; Lee, K. T.; Cho, J., Metal–air

batteries with high energy density: Li–air versus Zn–air. Adv. Energy Mater. 2011, 1, (1), 34-50, DOI: 10.1002/aenm.201000010. 17.

Cheng, F.; Chen, J., Metal–air batteries: from oxygen reduction electrochemistry to

cathode catalysts. Chem. Soc. Rev. 2012, 41, (6), 2172-2192, DOI: 10.1039/C1CS15228A. 18.

Pan, J.; Xu, Y. Y.; Yang, H.; Dong, Z.; Liu, H.; Xia, B. Y., Advanced Architectures

and Relatives of Air Electrodes in Zn–Air Batteries. Adv. Sci. 2018, 5, (4), 1700691, DOI: 10.1002/advs.201700691. 19. MnO2

Wei, Z.; Huang, W.; Zhang, S.; Tan, J., Carbon-based air electrodes carrying in

zinc–air

batteries.

J.

Power

Sources

2000,

91,

(2),

83-85,

DOI:

10.1016/S0378-7753(00)00417-1. 20.

Ovshinsky, S. R.; Fierro, C.; Reichman, B.; Mays, W.; Strebe, J.; Fetcenko, M. A.;

Zallen, A.; Hicks, T., Catalyst for fuel cell oxygen electrodes. In US Patents: 2003; Vol. 7097933. 21.

Li, B.; Quan, J.; Loh, A.; Chai, J.; Chen, Y.; Tan, C.; Ge, X.; Hor, T. A.; Liu, Z.;

Zhang, H., A Robust Hybrid Zn-Battery with Ultralong Cycle Life. Nano Lett. 2016, 17, (1), 156-163, DOI: 10.1021/acs.nanolett.6b03691. 22.

Iliev, I.; Gamburzev, S.; Kaisheva, A., Optimization of the pyrolysis temperature of

active carbon-CoTMPP catalysts for air electrodes in alkaline media. J. Power Sources 1986, 17, 345-352, DOI: 10.1016/0378-7753(86)80055-6. 23.

Wang, M.; Qian, T.; Zhou, J.; Yan, C., An efficient bifunctional electrocatalyst for

a zinc–air battery derived from Fe/N/C and bimetallic metal–organic framework composites. ACS Appl. Mater. Interfaces 2017, 9, (6), 5213-5221, DOI: 10.1021/acsami.6b12197. 24.

Prabu, M.; Ketpang, K.; Shanmugam, S., Hierarchical nanostructured NiCo2O4 as

an efficient bifunctional non-precious metal catalyst for rechargeable zinc–air batteries. Nanoscale 2014, 6, (6), 3173-3181, DOI: 10.1039/C3NR05835B.



25.

Prabu, M.; Ramakrishnan, P.; Nara, H.; Momma, T.; Osaka, T.; Shanmugam, S.,

Zinc–air battery: understanding the structure and morphology changes of graphene-supported CoMn2O4 bifunctional catalysts under practical rechargeable conditions. ACS Appl. Mater. Interfaces 2014, 6, (19), 16545-16555, DOI: 10.1021/am5047476. 26.

Hu, J.; Wang, L.; Shi, L.; Huang, H., Oxygen reduction reaction activity of

LaMn1-xCoxO3-graphene nanocomposite for zinc-air battery. Electrochim. Acta 2015, 161, 115-123. 27.

Lee, D. U.; Park, M. G.; Park, H. W.; Seo, M. H.; Ismayilov, V.; Ahmed, R.; Chen,

Z., Highly active Co-doped LaMnO3 perovskite oxide and N-doped carbon nanotube hybrid bi-functional catalyst for rechargeable zinc–air batteries. Electrochem. Commun. 2015, 60, 38-41, DOI: 10.1016/j.elecom.2015.08.001. 28.

Goodenough, J. B.; Manoharan, R.; Paranthaman, M., Surface protonation and

electrochemical activity of oxides in aqueous solution. J. Am. Chem. Soc. 1990, 112, (6), 2076-2082, DOI: 10.1021/ja00162a006. 29.

Lippert, T.; Montenegro, M.; Döbeli, M.; Weidenkaff, A.; Müller, S.; Willmott, P.;

Wokaun, A., Perovskite thin films deposited by pulsed laser ablation as model systems for electrochemical applications. Prog. Solid State Chem. 2007, 35, (2-4), 221-231, DOI: 10.1016/j.progsolidstchem.2007.01.029. 30.

Passaniti, J. L.; Dopp, R. B., Method of making air cathode material having

catalytically active manganese compounds of valance state+ 2. In US Patents: 1995; Vol. 5,378,562. 31.

Wu, C.-Y.; Wu, P.-W.; Lin, P.; Li, Y.-Y.; Lin, Y.-M., Silver-carbon nanocapsule

electrocatalyst for oxygen reduction reaction. J. Electrochem. Soc. 2007, 154, (10), B1059-B1062, DOI: 10.1149/1.2767421. 32.

Kumar, R.; Shin, J.; Yin, L.; You, J. M.; Meng, Y. S.; Wang, J., All‐Printed,

Stretchable Zn‐Ag2O Rechargeable Battery via Hyperelastic Binder for Self‐Powering


Page 14 of 22

Page 15 of 22 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


Wearable

Electronics.

Adv.

Energy

Mater.

2017,

7,

(8),

1602096,

DOI:

10.1002/aenm.201602096 33.

Berchmans, S.; Bandodkar, A. J.; Jia, W.; Ramírez, J.; Meng, Y. S.; Wang, J., An

epidermal alkaline rechargeable Ag–Zn printable tattoo battery for wearable electronics. J Mater. Chem. A 2014, 2, (38), 15788-15795, DOI: 10.1039/C4TA03256J. 34.

Gaikwad, A. M.; Zamarayeva, A. M.; Rousseau, J.; Chu, H.; Derin, I.; Steingart, D.

A., Highly stretchable alkaline batteries based on an embedded conductive fabric. Adv. Mater. 2012, 24, (37), 5071-5076, DOI: 10.1002/adma.201201329 35.

Yan, C.; Wang, X.; Cui, M.; Wang, J.; Kang, W.; Foo, C. Y.; Lee, P. S.,

Stretchable Silver‐Zinc Batteries Based on Embedded Nanowire Elastic Conductors. Adv. Energy Mater. 2014, 4, (5), 1301396, DOI: 10.1002/aenm.201301396. 36.

Kettlgruber, G.; Kaltenbrunner, M.; Siket, C. M.; Moser, R.; Graz, I. M.;

Schwödiauer, R.; Bauer, S., Intrinsically stretchable and rechargeable batteries for self-powered stretchable electronics. J Mater. Chem. A 2013, 1, (18), 5505-5508, DOI: 10.1039/C3TA00019B. 37.

Sumboja, A.; Chen, J.; Zong, Y.; Lee, P. S.; Liu, Z., NiMn layered double

hydroxides as efficient electrocatalysts for the oxygen evolution reaction and their application in

rechargeable

Zn–air

batteries.

Nanoscale

2017,

9,

(2),

774-780,

DOI:

10.1039/C6NR08870H. 38.

Wang, T.; Kaempgen, M.; Nopphawan, P.; Wee, G.; Mhaisalkar, S.; Srinivasan, M.,

Silver nanoparticle-decorated carbon nanotubes as bifunctional gas-diffusion electrodes for zinc–air

batteries.

J.

Power

Sources

2010,

195,

(13),

4350-4355,

DOI:

10.1016/j.jpowsour.2009.12.137. 39.

Hu, S.; Han, T.; Lin, C.; Xiang, W.; Zhao, Y.; Gao, P.; Du, F.; Li, X.; Sun, Y.,

Enhanced Electrocatalysis via 3D Graphene Aerogel Engineered with a Silver Nanowire



Page 16 of 22

Network for Ultrahigh‐Rate Zinc–Air Batteries. Adv. Funct. Mater. 2017, 27, (18), 1700041, DOI: 10.1002/adfm.201700041 40.

Park, M. G.; Lee, D. U.; Seo, M. H.; Cano, Z. P.; Chen, Z., 3D Ordered

Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc–Air Batteries. Small 2016, 12, (20), 2707-2714, DOI: 10.1002/smll.201600051 41.

Du, G.; Liu, X.; Zong, Y.; Hor, T. A.; Yu, A.; Liu, Z., Co3O4

nanoparticle-modified rechargeable

zinc–air

MnO2

nanotube

batteries.

bifunctional

Nanoscale

2013,

oxygen 5,

cathode

(11),

catalysts

4657-4661,

for DOI:

10.1039/C3NR00300K. 42.

Guo, Z.; Li, C.; Li, W.; Guo, H.; Su, X.; He, P.; Wang, Y.; Xia, Y., Ruthenium

oxide coated ordered mesoporous carbon nanofiber arrays: a highly bifunctional oxygen electrocatalyst for rechargeable Zn–air batteries. J. Mater. Chem. A 2016, 4, (17), 6282-6289, DOI: 10.1039/C6TA02030E. 43.

Meng, C.; Ling, T.; Ma, T. Y.; Wang, H.; Hu, Z.; Zhou, Y.; Mao, J.; Du, X. W.;

Jaroniec, M.; Qiao, S. Z., Atomically and electronically coupled Pt and CoO hybrid nanocatalysts for enhanced electrocatalytic performance. Adv. Mater. 2017, 29, (9), 1604607, DOI: 10.1002/adma.201604607


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Figure Captions

Figure 1. SEM images of (a) pristine stainless steel screen and that was covered by Ag nanoparticle film under deposition time of (b) 0.5 hr, (c) 1hr and (d) 1.5 hr electrochemically. The photograph placed in the middle part is the real image of Ag nanoparticle deposited on stainless steel screen.



Figure 2. (a) The charging and discharging curves of the Zn-Ag battery using the Ag/stain steel mesh as cathode electrode with different deposition time were operated in the alkaline electrolyte consisting of 0.2M zinc acetate and 6.0 M KOH. The constant current density was 80 mA/g. (b) CV scan of Ag/stain steel screen with deposition time of 1hr in the same electrolyte under a scan rate of 10 mV. The reacted area of the Ag/stain steel screen is 1cm2


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Figure 3. (a) Two charging voltage states (C 1.8V and C 1.98V) and three discharging voltage states (D 1.81V, D 1.54V and D 0.9V) were point out from charging and discharging curve of Zn-Ag battery for further ex-situ XRD measurement. (b) Ex-situ XRD patterns of Ag electrode in various charging and discharging states (denoted C and D in the figure, respectively). (c) The magnified XRD pattern of the 2 angle ranged from 30° to 35.5° in figure (b).



Figure 4. (a) The schematic illustration of the setup of Zn-Ag/Air hybrid battery. (b) The cyclic stability test of Zn-Ag/Air hybrid battery under a current density of 20 mA/cm2 monitoring continuously for 551 hr. The cyclability test are around 1700 cycles. The inset showed that the detailed discharging profile of Zn-Ag/Air hybrid battery (c) The corresponding Coulumbic efficiency of cyclic test for 1700 cycles. (d) The charge/discharge polarization curves of Zn-Ag/Air hybrid battery.


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Figure 5. (a) The charging and discharging curves of Zn-Ag/Air hybrid battery assembled in the pouch cell. (b) The photograph of the pouch cell driving red LED light with high illumination w/o a strain.



Page 22 of 22

Table 1. State-of-the-art cathode catalysts utilized in rechargeable Zn–air batteries: their impacts on discharge voltage and cyclability. Cathode Catalysts

Battery discharge voltage

Atomically Pt-CoO43

1.1 V

Co3O440 MnO2/Co3O441 RuO2-coated mesoporous carbon42 NiMn LDHs37 Ag/single-walled NCNTs38 Ag NWs/3D Graphene Aerogel39

@ 5 mA/cm2

Battery cyclability (total cycle time)

Anode

30 cycles @ 5mA/cm2

Zn foil

1.21V @ 10 mA/cm2

200 cycles @ 10mA/cm2 (400hr)

Zn plate

1.25 V @ 15 mA/cm2


Zn plate

1.25V @ 4 mA/cm2

100 cycles @ 4 mA/cm2 (33hr)

Zn plate

1.2 V @ 10 mA/cm2

200 cycles @ 10 mA/cm2 (90hr)

Zn plate

1.0 V

-- @ --

@ --

Zn powder

1.36 V @ 5 mA/cm2

1 cycle @ 10 mA/cm2 (48hr)

Zn foil

1.34 V @ 5 mA/cm2


Zn foil

1.5 V, 1.1V @ 20mA/cm2


Sn foil

CoO/NCNT (ORR); NiFe-LDH/CNT (OER)8 Ag

NPs/CFP

work)

(This

TOC figure.

Synopsis A flexible Zn-Ag /Air hybrid battery delivered discharging plateaus at 1.8V, 1.5V and 1.2V with high capacity and good cyclability.


Air Battery with Long Cycle Life - ACS

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