Cobalt Phthalocyanine Catalyzed Lithium-Air Batteries

Trahan, Matthew; Jia, Qingying; Mukerjee, Sanjeev; Plichta, Edward J.; Hendrickson, Mary; Abraham, K. M.

doi:10.1149/2.118309jes

Cited by 56 publications

(55 citation statements)

References 52 publications

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“…Compared with water, DMSO has a slightly higher viscosity but a lower vapor pressure [85], so as a diluent for RTILs it may be able to increase their conductivity while maintaining low volatility. As a polar solvent, DMSO also facilitates the solvation of Zn ions [86] and is capable of stabilizing oxygen reduction reaction intermediates (superoxide radicals) [87]. All these features make DMSO a potentially good additive to RTILs for Zn-air battery applications.…”

Section: Hybrid Electrolytesmentioning

confidence: 99%

Rechargeable Zn-air batteries: Progress in electrolyte development and cell configuration advancement

Ivey

Xie³

et al. 2015

Journal of Power Sources

265

170

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Section: Hybrid Electrolytesmentioning

confidence: 99%

Rechargeable Zn-air batteries: Progress in electrolyte development and cell configuration advancement

Ivey

Xie³

et al. 2015

Journal of Power Sources

265

170

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“…As a result, the activation energy for electron transfer is lowered to provide a higher voltage for the Li-air cells utilizing DMSO-based electrolytes. 38,39 Thus, high donor number solvents homogeneously catalyze O 2 reduction reaction through an outer Helmholtz plane (OHP) process as shown in Figure 14. 38 The homogeneous ORR catalysis is so dominant that cathode catalysts such as CoPC showed little ORR catalytic 38 activity in DMSO-based electrolytes.…”

Section: Solvent-directed Orr Catalysismentioning

confidence: 99%

Electrolyte-Directed Reactions of the Oxygen Electrode in Lithium-Air Batteries

Abraham

2014

J. Electrochem. Soc.

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131

133

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Non-aqueous electrolytes play a prominent role in the redox reactions of the oxygen electrode in the non-aqueous Li-air battery. In all electrolytes the initial O 2 reduction reaction (ORR) product is superoxide, O 2 − , whose stability is determined by the Lewis acidity of the ion-pairing cations present in the medium as governed by the Hard Soft Acid Base (HSAB) theory. Our results suggest that depending on the basicity of the solvent as measured by its Donor Number (DN), the superoxide will be stabilized to varying lengths of time before transforming to O 2 2− via a chemical or an electrochemical reaction. Organic solvents decrease the Lewis acidity of Li + through the formation of solvates, Li + (solvent) n . As a result, high DN solvents such as dimethyl sulfoxide (DMSO), which decrease Li + acidity more than low DN solvents, provide longer life-time for the soft base O 2 − by forming the ion pair, Li + (DMSO) n -O 2 − . In low DN solvents such as 1, 2-dimethoxy ethane (DME) and tetraethyleneglycol dimethyl ether (TEGDME), the LiO 2 rapidly decomposes to the peroxide, Li 2 O 2 . As the ionic bond strength between the O 2 reduction product and the conducting salt cation becomes stronger, its rechargeability becomes poorer. Solvent electron donor property affects ORR catalysis also. There is intense world-wide research and development of a rechargeable lithium battery based on the Li/O 2 chemical couple, popularly known as the Li-air battery, encouraged by its very high theoretical specific energy (5200 Wh/kg) and low cost of the materials from which it can be fabricated.1,2 The theoretical specific energy of the Li-air battery is surpassed only by a battery based on the Li/F 2 couple.3 However, F 2, because of its high reactivity, is an impractical electrode material to construct batteries for powering consumer products such as cellphones, laptop computers, tablets, digital cameras, and electric vehicles. This leaves Li-air as the candidate of choice for an ultra-high energy density, low cost (air is free) rechargeable lithium battery. The Li-air battery is environmentally friendly as nontoxic electrolytes and other materials, besides Li and O 2, needed for fabricating it can be formulated. It is a safe battery despite having a Li metal anode because the cathode active material is not stored inside the battery cell.The Li-air battery is one of many metal-air batteries that could conceivably be fabricated (Table I).Among the various metal-O 2 couples, the Li-air is the most attractive battery since the cell discharge reaction involving metallic Li and oxygen to yield Li 2 O, according to the reaction 4Li + O 2 → 2Li 2 O, has an open circuit voltage of 2.91 V and a theoretical specific energy of 5200 Wh/kg (Table I). In practice, oxygen does not have to be stored in the battery which makes the theoretical specific energy excluding oxygen to be 11140 Wh/kg when the battery is initially fabricated. The battery weight will increase and its specific energy will decrease as it is discharged due to the accumulation ...

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“…As mentioned above, DBBQ does not operate as an electrocatalyst like, for example, the phthalocyanines described previously 29,46 (Fig. 1) [47][48][49] .…”

Section: The Mechanism Of O 2 Reduction In the Presence Of Dbbqmentioning

confidence: 78%

Erratum: Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions

Gao¹,

Chen²,

Johnson³

et al. 2016

Nature Mater

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On discharge, the Li-O 2 battery can form a Li 2 O 2 film on the cathode surface, leading to low capacities, low rates and early cell death, or it can form Li 2 O 2 particles in solution, leading to high capacities at relatively high rates and avoiding early cell death. Achieving discharge in solution is important and may be encouraged by the use of high donor or acceptor number solvents or salts that dissolve the T he high theoretical specific energy of the rechargeable Li-O 2 battery has generated intense interest in the possibility of a practical device that could deliver energy storage significantly in excess of today's lithium-ion batteries 1-9 . However, major challenges hinder the development of such a technology 1-6,10-14 . Typically a Li-O 2 battery is composed of a lithium metal anode separated by an aprotic electrolyte solution from a porous O 2 cathode. The reaction at the cathode involves, on discharge, the reduction of O 2 to form Li 2 O 2 , with oxidation of the latter on charge. Growth of Li 2 O 2 on the cathode surface leads to low capacities, poor rates and early cell death [15][16][17] . In contrast, if Li 2 O 2 can be induced to grow in the electrolyte solution then high discharge capacities at relatively high rates and avoiding early cell death is possible 15 . It is clearly important to operate a Li-O 2 battery in which Li 2 O 2 grows in solution.A number of groups have elucidated the mechanism of O 2 reduction to Li 2 O 2 on discharge 15,16,[18][19][20][21] . The reduction proceeds through the following general steps: 22,[27][28][29][30] . High donor number salts have been shown to increase the capacity fourfold and reduce the discharge overpotential by ∼30-50 mV over low donor number salts 22 . Viologens 27,28 , phthalocyanines 29 and quinones 30 have been investigated as possible soluble reduction catalysts. Although the studies of such catalysts are important, in most cases there is little or no direct evidence demonstrating that they promote formation of Li 2 O 2 in solution and not on the electrode surface because they rely on electrochemical measurements alone. Yet past work on Li-O 2 batteries has shown how essential it is to provide more than electrochemical evidence in this field 31 . In some cases, soluble catalysts show an increase in discharge voltage (lower overpotential) as small as, for example, 40 mV (refs 28,29), which is very unlikely to be sufficient to shut off the direct reduction of O 2 to Li 2 O 2 , essential to stop detrimental Li 2 O 2 film formation. Also, none of the previous studies in low donor number solvents exhibited a significant increase in capacity on discharge at a relatively high rate, which is important for a successful Li-O 2 battery.Here we demonstrate that addition of DBBQ (2,5-di-tert-butyl-1,4-benzoquinone) to a weakly solvating (low donor number) electrolyte solution, LiTFSI in ether 22 , promotes O 2 reduction to Li 2 O 2 in solution while halving the discharge overpotential (increasing the discharge potential), suppressing the growth of a Li 2...

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Cobalt Phthalocyanine Catalyzed Lithium-Air Batteries

Cited by 56 publications

References 52 publications

Rechargeable Zn-air batteries: Progress in electrolyte development and cell configuration advancement

Rechargeable Zn-air batteries: Progress in electrolyte development and cell configuration advancement

Electrolyte-Directed Reactions of the Oxygen Electrode in Lithium-Air Batteries

Erratum: Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions

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