Graphene Nanoplatelet Composite Cathode for a Chloroaluminate

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Graphene Nanoplatelet Composite Cathode for a Chloroaluminate Ionic Liquid-Based Aluminum Secondary Battery Yuya Uemura, Chih-Yao Chen, Yu Hashimoto, Tetsuya Tsuda, Hajime Matsumoto, and Susumu Kuwabata ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b00341 • Publication Date (Web): 13 Apr 2018 Downloaded from http://pubs.acs.org on April 16, 2018

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ACS Applied Energy Materials

Graphene Nanoplatelet Composite Cathode for a Chloroaluminate Ionic Liquid-Based Aluminum Secondary Battery

Yuya Uemura,† Chih-Yao Chen,† Yu Hashimoto,† Tetsuya Tsuda,*,† Hajime Matsumoto,†,‡ and Susumu Kuwabata*,†,‡

†

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1

Yamada-oka, Suita, Osaka 565-0871, Japan ‡

Department of Energy and Environment, Research Institute of Electrochemical Energy, National

Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan

Corresponding Authors *[email protected] *[email protected]

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ABSTRACT The development of an aluminum secondary battery based on an Al metal anode, a graphene nanoplatelet composite cathode, and a Lewis acidic AlCl3–1-ethyl-3-methylimidazolium chloride ionic liquid electrolyte is demonstrated. Low-cost composite cathodes comprised of only commercially available components are prepared by a standard slurry-coating method, and the cathodes exhibit a reversible capacity reaching 70 mAh g–1 (per graphene nanoplatelet weight) at a current density of 2000 mA g–1 and a good rate capability (~66 % capacity retention at 6000 mA g–1). A notable cyclability of up to 3000 cycles with a coulombic efficiency approaching 99 % is also obtained at 2000 mA g–1.

KEYWORDS: aluminum secondary battery, cathode, graphene nanoplatelet, polymer binder, composite


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1. INTRODUCTION Affordable and reliable energy storage technologies for supporting a renewable-energy-based society are inseparably linked to sustainable development. Toward this end, considerable efforts have been devoted to the development of metal anode secondary batteries using lightweight and multivalent metals, such as zinc, magnesium, and aluminum (Al).1 In particular, Al has long been considered a promising metal anode for several reasons, including its three-electron electrode reaction, moderately low redox potential, and rich natural abundance. Furthermore, Al metal can theoretically provide a much higher volumetric capacity (8046 mAh cm–3) than other lightweight metals.1 However, Al secondary batteries encounter numerous hurdles concerning the cathode, e.g., disintegration of the host material,2 low operation voltage,3,4 rapid capacity decline,5,6 and large reaction overpotential.5,6 Further investigation of the cathodes is urgently needed.7,8. Owing to the long history of Al electroplating, the electrolytes for Al-based batteries studied to date have mostly been derived from plating baths.9 One of the most widely used options is haloaluminate

ionic

liquids

(ILs),

especially

the

Lewis

acidic

AlCl3‒

1-ethyl-3-methylimidazolium chloride ([C2mim]Cl) (AlCl3 molar fraction > 50 mol%) IL, since they exist in a liquid state at 298 K over a wide composition range and have relatively high ionic conductivities and low viscosities.9,10 Recently, Al secondary batteries using pyrolytic graphite foam as the cathode material were demonstrated by Dai and co-workers11 to have decent electrochemical properties in the aforementioned chloroaluminate IL. In addition, other carbon materials, such as carbon paper12, few-layer graphene film13, 3D graphene nanoarchitecture14, and graphene-coated carbon fiber cloth15, have also been shown to be promising materials for hosting chloroaluminate anions ([AlCl4]– or [Al2Cl7]–). Although several promising carbon-based 3 ACS Paragon Plus Environment


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cathode materials have been proposed, the cost-effective production of these carbon materials remains a challenge. Herein, we report the low-cost preparation of a composite cathode with commercially available and inexpensive graphene nanoplatelets as the active material using the well-developed slurry-coating protocol. The electrode characteristics were investigated in a 60.0-40.0 mol% AlCl3−[C2mim]Cl IL electrolyte to determine the conditions that give the best performance.

2. EXPERIMENTAL SECTION The procedures for preparing the Lewis acidic 60.0-40.0 mol% AlCl3−[C2mim]Cl IL were the same as those described by Hussey and Wilkes et al.9,10 After purification of anhydrous AlCl3 (high purity, Nippon Light Metal Company) and [C2mim]Cl (Merck), AlCl3 was gradually added to [C2mim]Cl to prevent thermal decomposition of the [C2mim]+ cations because this simple IL reaction is highly exothermic. The quality of the resulting Lewis acidic IL was improved by constant-current electrolysis between an Al cathode and the anode at –10 mA for 72 hours under agitation at room temperature. Clear and colorless AlCl3−[C2mim]Cl IL was obtained after this purification process. All the preparation processes and electrochemical experiments were conducted in an argon gas-filled glovebox (Vacuum Atmospheres Co., NEXUS II system) with both O2 and H2O concentrations < 1 ppm. The chemical stability of the selected polymer binders toward the Lewis acidic AlCl3−[C2mim]Cl IL was evaluated by soaking test and infrared (IR) spectroscopy using a PerkinElmer Spectrum 100 FT-IR Spectrometer. Graphene nanoplatelet composite cathodes, which were composed of 90 wt% graphene nanoplatelets (Strem Chemicals, width: 5 µm; 4 ACS Paragon Plus Environment

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thickness: 6-8 nm) and 10 wt% polysulfone (Aldrich) or polyimide (DREAMBOND®, Industrial Summit Technology) as the binder, were fabricated by the following procedure. An adequate amount of N-methyl-2-pyrrolidone (NMP, Wako) was added into the powdered mixture and thoroughly blended by ball milling. The homogenous slurry was then coated onto a molybdenum plate current collector and dried under vacuum at 373 K overnight. For the polyimide binder, an additional heat treatment step was performed at 573 K in vacuum for 5 hours to polymerize the binder. Further information on the graphene nanoplatelets used in this research is given in Supporting Information. Electrochemical experiments were conducted in a three- or two-electrode cell connected to an Ivium Technologies CompactStat potentiostat/galvanostat or a Hokuto Denko HJ-1001SD8 battery cycling system. A three-electrode cell was employed for the voltammetric experiments. The graphene nanoplatelet composite cathodes and a coil of 1.0-mm-diameter Al wire (Nilaco, 99.999 %) were used as the working (W.E.) and counter electrodes (C.E.), respectively. The reference electrode (Al(III)/Al) was constructed by placing a 1.0-mm-diameter Al wire (Nilaco, 99.999 %) into a 12-mm-diameter Pyrex tube terminated with a porous G-4 glass frit (Vidrex). The charge/discharge experiments were carried out using a two-electrode cell. Prior to the experiments, a pretreatment process was conducted at 1000 mA g–1 for 10 cycles to stabilize the electrode. All the experiments were conducted in the argon-filled glovebox described above. The specific capacity and current density were calculated based on the weight of graphene nanoplatelets. The electrochemical impedance spectra (EIS) were measured over the frequency range from 50 kHz to 10 mHz with an AC amplitude of 10 mV. The surface morphology of the electrodes was examined by a Keyence VE-9800 or a Hitachi S-3400N scanning electron 5 ACS Paragon Plus Environment


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microscope (SEM) and a Hitachi H-7650 transmission electron microscope (TEM). The crystal structure was characterized by a Rigaku Ultima IV diffractometer with Cu Kα radiation.

3. RESULTS AND DISCUSSION It is known that few cell component options are available for application in Al secondary battery systems since the Lewis acidic chloroaluminate electrolyte can be corrosive.16–19 The selection of polymer binders that possess an appropriate chemical stability in the electrolyte is highly important for the preparation of the composite cathode. Prior to preparation of the electrode, soaking tests of the selected polymer binders were carried out in the Lewis acidic 60.0-40.0 mol% AlCl3−[C2mim]Cl electrolyte. As indicated in Figure 1a, polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) were seriously damaged soon after adding the IL. The other three binders, polytetrafluoroethylene (PTFE), polysulfone, and polyimide, remained visually unchanged for more than 4 weeks. For these macroscopically stable binders, infrared (IR) spectroscopy was performed to probe the chemical structure. The negligible change in the spectrum after storage in the IL for 24 weeks means that those have a great potential as binders for the Al battery (Figure 1b). Based on both appearance and IR spectra, we attempted to fabricate three types of graphene nanoplatelet composite electrodes. Unfortunately, the PTFE binder was not suitable for the fabrication of the electrode, as the weight ratio of PTFE to the graphene nanoplatelets was more than 50 wt%. The electrode characteristics of the composite cathodes with the polysulfone and polyimide binders were then examined. Cyclic voltammograms recorded at the graphene nanoplatelet composite electrodes with the 6 ACS Paragon Plus Environment

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polysulfone and polyimide binders in the 60.0-40.0 mol% AlCl3−[C2mim]Cl IL are shown in Figure 2. The electrodes showed almost the same electrochemical behavior. Several redox couples appeared in the voltage region between 1.5 and 2.4 V, while the voltammogram for the molybdenum current collector itself contained a single anodic wave caused by the electrolyte decomposition initiated ca. 2.5 V (Figure 2a). These redox waves are therefore attributed to the intercalation/deintercalation reactions of chloroaluminate anions.11,20 Cyclic voltammograms recorded over different sweep ranges revealed that the anodic waves labeled a1, a2, a3, and a4 correspond to the cathodic waves labeled c1, c2, c3 and c4, respectively (Figure 2b (inset)). These results strongly suggest that the graphene nanoplatelet composite electrodes can be used as cathodes in an Al secondary battery with the chloroaluminate IL. The charge-discharge profiles of the electrodes in a three-electrode cell at a current density of 2000 mA g–1 (per graphene nanoplatelet weight) are shown in Figure 2c and 2d. The initial charge curve of each electrode was different from the subsequent curves. This difference results from the change in the volume of the host material.20 After the second cycle, the charge-discharge curves were superimposed on the previous curves due to the high reversibility of the electrode reaction. A clear plateau ca. 2.0~2.2 V and another ill-defined voltage variation ca. 1.6~2.0 V appeared in the discharge process. This electrode behavior is slightly different from that of other graphitized carbon material cathodes, which generally exhibit two clear voltage plateaus in the discharge process.21,22 This difference was likely caused by the low crystallinity of the graphene nanoplatelets.13,15 The polyimide binder composite electrode delivered a discharge capacity of ca. 70 mAh g–1, which was slightly higher than that of the polysulfone binder composite electrode. Furthermore, the polyimide binder more effectively retained the reversible capacity (Figure 2e 7 ACS Paragon Plus Environment


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and 2f). A good cyclability over 1000 cycles with an average coulombic efficiency approaching 99 % was achieved at both electrodes. As shown in Figure 3, after 100 cycles of the charge-discharge test, distinct exfoliation of the composite material was observed for the composite electrode with polysulfone binder but not for the polyimide binder. However, scanning electron microscopy (SEM) images of the surface morphologies of both electrodes remained nearly unchanged before and after the cycling test. These results reveal that an adhesion failure between the polysulfone binder composite material and the molybdenum current collector triggered a decrease in the capacity upon cycling. In fact, in lithium-ion battery applications, the polyimide binder is known to exhibit good surface coverage and provide strong adhesion between the active materials and current collectors.23,24 Taken together, we concluded that polyimide is an ideal binder for the Al secondary battery with a haloaluminate IL electrolyte. Figure 4 illustrates the rate capabilities of the graphene nanoplatelet-polyimide composite electrode in a three-electrode beaker cell. The cell was charged/discharged at various current densities of 1000, 1500, 2000, 4000, 6000, 8000, and 10,000 and then again at 1000 mA g–1. The 10th charge/discharge cycle of the graphene nanoplatelet-polyimide composite cathode is shown for each current density in Figure 4a. The capacities strongly depended on the charge/discharge rates, similar to other battery systems. For example, the discharge capacities were ca. 70 mAh g–1 at 1000 mA g–1 and 46 mAh g–1 at 6000 mA g–1. The latter capacity indicates that the cell could be charged within 30 seconds and provide 66 % of the full capacity. At an even higher rate of 10,000 mA g–1, almost half the capacity was retained. When the charge/discharge rate was returned to 1000 mA g–1, the discharge capacity also returned to the original discharge capacity, suggesting that the electrode was sufficiently robust (Figure 4b). Compared to conventional 8 ACS Paragon Plus Environment

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Li-ion batteries, a large charge transfer resistance was observed for the cell tested (Figure S2). The impedance mainly arises from the anodic reaction (Al deposition/stripping),25 suggesting that modification of the Al anode is a key to further improve the rate capability. The long-term cycling performance of the graphene nanoplatelet-polyimide electrode was evaluated at 2000 mA g–1 using a specialized two-electrode cell, as shown in Figure 5a. Satisfactory cyclability was achieved over 3000 cycles without any decay of the capacity. The discharge capacity was maintained at ca. 70 mAh g–1, and an average coulombic efficiency of 98.4 % was obtained (Figure 5b and c). Interestingly, these cathode characteristics are equal to those of other self-standing carbon-based cathodes.11,12 As stated in recent publications, it is worth emphasizing that anionic species, e.g., [AlCl4]– and [Al2Cl7]–, in the electrolyte acts as redox active materials during the charge-discharge process.8,26,27 This is inherently distinct from the case of a rocking-chair type battery such as a Li-ion battery. In other words, for the Al-based battery using a chloroaluminate IL electrolyte, adjustment of the weight ratio of the electrolyte to the whole cell is crucial so as to achieve an optimal energy density. Therefore, in addition to the investigation of electrode materials, the electrolyte with a higher chloroaluminate anionic species concentration should be also developed to increase the cell-level capacity.

4. CONCLUSIONS In summary, the feasibility of commercially available and inexpensive graphene nanoplatelets as a new cathode material for Al secondary batteries has been demonstrated. Graphene nanoplatelet composite electrodes with polysulfone and polyimide binders performed well in the Lewis acidic 9 ACS Paragon Plus Environment


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60.0-40.0 mol% AlCl3−[C2mim]Cl IL electrolyte. The cathode made from polyimide binder showed favorable battery characteristics in terms of reversible capacity, rate capability, and cyclability, and these characteristics were comparable to those of sophisticated, self-standing carbon-based cathodes. These findings create opportunities for constructing low-cost Al secondary batteries with decent performances.


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Figure 1. (a) Photographs of the various polymer binders before and after the soaking tests in the Lewis acidic 60.0-40.0 mol% AlCl3‒[C2mim]Cl IL electrolyte. The binders were (A) polyimide, (B) polysulfone, (C) polytetrafluoroethylene (PTFE), (D) polyvinylidene fluoride (PVDF), and (E) polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP). (b) Infrared spectra for selected binders before (black line) and after (red line) storage in the IL for 24 weeks.



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Figure 2. Cyclic voltammograms recorded at the graphene nanoplatelet electrodes containing (a) polysulfone binder and (b) polyimide binder in the Lewis acidic 60.0-40.0 mol% AlCl3‒ [C2mim]Cl electrolyte. The sweep rates were 5 mV s−1. The voltammograms at a bare molybdenum current collector and at the polyimide composite electrode over different potential ranges are shown in Figure 2a and the inset of 2b, respectively. (c, d) Charge/discharge curves and (e, f) cyclability of the graphene nanoplatelet composite electrodes containing (c, e) polysulfone binder and (d, f) polyimide binder. The current density was 2000 mA g−1, and the potential range was 0.8–2.4 V (vs. Al(III)/Al).


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Figure 3. Photographs and SEM images of the graphene nanoplatelet composite electrodes containing (a) polysulfone binder and (b) polyimide binder before and after a 100-cycle test at a current density of 2000 mA g−1 in the potential range of 0.8–2.4 V (vs. Al(III)/Al). The electrolyte was 60.0-40.0 mol% AlCl3‒[C2mim]Cl.



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Figure 4. (a) Tenth charge/discharge cycle of the graphene nanoplatelet composite electrode containing polyimide binder obtained for each applied current density. The electrolyte was 60.0-40.0 mol% AlCl3‒[C2mim]Cl, and the applied current densities were 1000, 1500, 2000, 4000, 6000, 8000, and 10,000 mA g−1. (b) Specific capacity and coulombic efficiency as a function of the current density and cycle number.


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Figure 5. Long-term electrode characteristics of the graphene nanoplatelet composite cathode containing polyimide binder. (a) Schematic illustration of the two-electrode cell used in the experiments. (b) Charge/discharge curves at the 1st, 2nd, 1000th, and 3000th cycles. (c) Results of the cyclability test conducted at 2000 mA g−1. The voltage range was 0.8–2.4 V (vs. Al(III)/Al), and the electrolyte was 60.0-40.0 mol% AlCl3‒[C2mim]Cl.



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ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: XXXXXXXXXXX.

SEM, TEM, SAED, and XRD data of graphene nanoplatelets; Additional electrochemical data (PDF)

AUTHOR INFORMATION

Corresponding Author *[email protected]

*[email protected] Notes The authors declare no competing financial interests.

ACKNOWLEDGMENTS This research was partially supported by JSPS KAKENHI Grant Numbers 15H03591, 15K13287, and 15H02202 and by the Advanced Low Carbon Technology Research and Development Program (ALCA) for Specially Promoted Research for Innovative Next Generation Batteries 16 ACS Paragon Plus Environment

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(SPRING), Japan Science and Technology Agency (JST). Anhydrous AlCl3 was provided by Nippon Light Metal Company.



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Graphene Nanoplatelet Composite Cathode for a Chloroaluminate

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