Anode Catalysts for Direct Hydrazine Fuel Cells: From Laboratory Test to an Electric Vehicle

Serov, Alexey; Padilla, Mónica; Roy, Aaron; Atanassov, Plamen; Sakamoto, Tsunenori; Asazawa, Koichiro; Tanaka, Hirohisa

doi:10.1002/anie.201404734

Cited by 148 publications

(94 citation statements)

References 28 publications

(60 reference statements)

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“…Voltammetric study of Ni(II) formed from Ni(TFSI) 2 and NiCl 2 , respectively.-ZnCl 2 has been recognized as highly soluble in [BMP][TFSI] in which the voltammetric behavior and electrodeposition of Zn has been studied and discussed. 23 The detailed electrochemistry of Zn thus is not mentioned any more here.…”

Section: Resultsmentioning

confidence: 99%

“…Voltammetric study of Zn(II)/Ni(II) mixtures prepared from different sources.- Figure 2 shows the CVs recorded at GCE and PtE in [BMP][TFSI] containing 50 mM each of ZnCl 2 and Ni(TFSI) 2 . The potential was initially scanned in cathodic direction and reversed at the selected potentials as indicated in the figure.…”

Section: 27mentioning

confidence: 99%

“…Since the bath of ZnCl 2 /Ni(TFSI) 2 2 and Ni(TFSI) 2 . The potential was initially scanned in cathodic direction, and two major reductive waves (more widely separated at GCE) were observed.…”

Section: 27mentioning

confidence: 99%

“…The working electrodes were glassy carbon disk electrode (GCE. Geometric area: 0.071 cm 2 ) and platinum disk electrode (PtE. 0.020 cm 2 ) for voltammetric study.…”

Section: Methodsmentioning

confidence: 99%

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Electrochemical Study and Electrodeposition of Zn-Ni Alloys in an Imide-Type Hydrophobic Room-Temperature Ionic Liquid: Feasibility of Using Metal Chlorides as the Metal Sources

Wang

Chen

2018

J. Electrochem. Soc.

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The low or even negligible solubility of most metal chlorides in the imide-type ionic liquids (ILs), such as 1-n-butyl-1-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ([BMP][TFSI]) used here, sometimes brought inconvenience to the electrodeposition in this type of ILs. In this study, it has been demonstrated that NiCl 2 and ZnCl 2 can be used as the metal sources for the electrodeposition of Zn-Ni alloys in [BMP] Zinc-nickel (Zn-Ni) alloys are important industrial materials because they are excellently corrosion-resistant protection coatings for steel, and more environmentally-friendly, compared with the cadmium (Cd) coatings.1 Recently, a report shows that Ni-Zn alloys are good anode materials that can be applied to the direct hydrazine fuel cells.2 Zn-Ni alloys, therefore, can not only be used for corrosion resistance by tradition but also for electrocatalysis. The latter may significantly extend the purposes of Zn-Ni alloys. However, for different applications, the atomic ratios of Zn to Ni in the Zn-Ni alloys are extremely different. A proper electrolyte in which Zn-Ni alloys with diverse compositions can be formed is thus very important. So far, Zn-Ni alloys are mostly electrodeposited from alkaline baths although they have been electrodeposited from acidic acetate baths in which anomalous electrodeposition was encountered, leading to the Zn-rich Zn-Ni alloys and the narrow distribution of Zn content.3 In alkaline baths, cyanide is usually needed or zincate-type baths must be used. The former is a well-known hazardous species, and the latter usually shows a relatively low current efficiency. 4,5 Cyanide-free and non-zincate electrolytes were thus developed but proper complexing agents must be used. 6,7 In contrast to aqueous electrolytes, ionic liquids (ILs) including deep eutectic solvents (DESs) have been the well-known alternatives for the electrodeposition of metals and alloys. 8,9 Because of their tailoring properties, many problems mentioned above, such as anomalous electrodeposition and bath instability, can be resolved by using ILs. Zn-Ni alloys including their alloy filament arrays have been successfully electrodeposited from the traditional chlorozincate ILs.10,11 Choline chloride-based DESs have also been used for the same purpose. ExperimentalThe IL [BMP][TFSI] was prepared using the procedures reported in a previous publication.24 1-n-Butylchloride instead of 1-n-butylbromide, however, was used in this study. The [BMP][TFSI] was stored in a glove box for the subsequent experiments after being dried under vacuum at 120• C for at least one day using a diffusion oil pump. Anhydrous Ni(TFSI) 2 , Zn(TFSI) 2 , NiCl 2 (99.99%), ZnCl 2 (99.99%), and Ni wire (99.98%, 1 mm in diameter) were purchased from Alfa Aesar and used as received without further purification except that Ni wire was cleaned using acetone, diluted hydrochloric acid, and deionized (DI) water in sequence, and then dried under vacuum.A CHI 660E electrochemical analyzer (CH Instruments, Inc.) was utilized for all electrochemi...

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Section: Resultsmentioning

confidence: 99%

Section: 27mentioning

confidence: 99%

Section: 27mentioning

confidence: 99%

“…The working electrodes were glassy carbon disk electrode (GCE. Geometric area: 0.071 cm 2 ) and platinum disk electrode (PtE. 0.020 cm 2 ) for voltammetric study.…”

Section: Methodsmentioning

confidence: 99%

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Electrochemical Study and Electrodeposition of Zn-Ni Alloys in an Imide-Type Hydrophobic Room-Temperature Ionic Liquid: Feasibility of Using Metal Chlorides as the Metal Sources

Wang

Chen

2018

J. Electrochem. Soc.

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“…This is the case especially for Ni-Zn catalysts, which we have applied to the anode catalyst for anion exchange membrane fuel cell vehicles and accomplished successful test driving using non-platinum group metals for both electrodes. 11 This demonstration leads to the need for a better understanding of the mechanism of the hydrazine electrooxidation reaction on a Ni surface. This is important for increased cell performance resulting in a reduction in size and weight of the fuel cell stack.…”

mentioning

confidence: 99%

Mechanism Study of Hydrazine Electrooxidation Reaction on Nickel Oxide Surface in Alkaline Electrolyte by In Situ XAFS

Sakamoto¹,

Kishi²,

Yamaguchi³

et al. 2016

J. Electrochem. Soc.

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This study introduces a new insight on the mechanism of selective electrooxidation of hydrazine in alkaline media. The catalytic process takes place on nickel oxide surface of a Ni oxide nano-particle decorated carbon support (NiO/C). The catalyst was synthesized by wet impregnation and a liquid reduction procedure followed by thermal annealing. In-situ X-ray absorption fine structure (XAFS) spectroscopy was used to investigate the reaction mechanism for hydrazine electrooxidation on NiO surface. The spectra of X-ray absorption near-edge structure (XANES) of Ni K-edge indicated that adsorption of OH − on Ni site during the hydrazine electrooxidation reaction. Density functional theory (DFT) calculations were used to elucidate and suggest the mechanism of the electrooxidation and specifically propose the localization of electron density from OH − to 3d orbital of Ni in NiO. It is found that the accessibility of Ni atomic sites in NiO structure is critical for hydrazine electrooxidation. Based on this study, we propose a possible reaction mechanism for selective hydrazine electrooxidation to water and nitrogen taking place on NiO surface as it is applicable to direct hydrazine alkaline membrane fuel cells. Diversification of fuel is important to enhance the versatility of fuel cells as viable power devices for the next generation. Liquid fuel such as methanol, ethanol, borohydride, formic acid, 2-propanol, dimethyl ether and hydrazine are liquid chemical substances that include hydrogen and are considered an energy source in which hydrogen is an electron carrier. The advantages of liquid fuels include, but are not limited to high energy density and ease of handling at both the energy supply and demand sides. In the case of liquid fuel, simple/existing infrastructure, such as conventional petrol stations, is sufficient as for fuel supply, and while the geographic and temporal gap between energy supply and receipt are being filled this would allow to concentrate and leveraging off energy contribution to the expansion of and market penetration of fuel cell technology.Direct hydrazine hydrate fuel cells (DHFCs) utilizing an anion exchange membrane have recently attracted attention as a clean power device. Hydrazine contains no carbon and excretes harmless nitrogen and water by theoretical electroreaction and non-platinum group metal (PGM) catalysts such as Fe, Co, and Ni. These catalysts have been demonstrated for both the anode and cathode electrodes as shown Fig. 1a. The fuel cell vehicle equipped with no PGM as catalysts was demonstrated at SPring-8 in 2013. We believe this demonstration of DHFCs as a power device contributes to the reduction of CO 2 emissions and begins to address the fossil fuel resource problem. If zero CO 2 emission fuel cell vehicles (FCVs), are to be deployed using carbon-free liquid fuel, the emissions of CO 2 would be associated only with the liquid fuel manufacturing facility side and the measures of reduction of CO 2 emission by the transportation sector are would be supported by the depl...

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Superaerophobic Electrodes for Direct Hydrazine Fuel Cells

Lu¹,

Sun²,

Xu³

et al. 2015

Advanced Materials

251

178

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Direct liquid-feed fuel cells possess high energy and power densities, but suffer from severe adhesion of gas products. Here, a "superaerophobic" surface that enables a small release size and fast evolution behavior of the gas product is introduced, thereby, maximizing and stabilizing the working area. Consequently, the "superaerophobic" nanostructured Cu electrodes exhibit excellent performance as anodes in a direct hydrazine fuel cell.

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Anode Catalysts for Direct Hydrazine Fuel Cells: From Laboratory Test to an Electric Vehicle

Cited by 148 publications

References 28 publications

Electrochemical Study and Electrodeposition of Zn-Ni Alloys in an Imide-Type Hydrophobic Room-Temperature Ionic Liquid: Feasibility of Using Metal Chlorides as the Metal Sources

Electrochemical Study and Electrodeposition of Zn-Ni Alloys in an Imide-Type Hydrophobic Room-Temperature Ionic Liquid: Feasibility of Using Metal Chlorides as the Metal Sources

Mechanism Study of Hydrazine Electrooxidation Reaction on Nickel Oxide Surface in Alkaline Electrolyte by In Situ XAFS

Superaerophobic Electrodes for Direct Hydrazine Fuel Cells

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