Understanding and controlling the chemical evolution and polysulfide-blocking ability of lithium–sulfur battery membranes cast from polymers of intrinsic microporosity

Doris, Sean E.; Ward, Ashleigh L.; Frischmann, Peter D.; Li, Longjun; Helms, Brett A.

doi:10.1039/c6ta06401a

Cited by 46 publications

(31 citation statements)

References 41 publications

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“…The solid Li-ion conducting membranes can be inorganic or polymeric, or a hybrid of both. However, many traditional solid-polymer electrolytes (SPE) are still permeable to polysulfides, 21 whereas solid-state inorganic electrolytes (SSIE) 23,24 can fully retain polysulfides in the positive electrode compartment. The approach using carbon or hybrid interlayers, 1,4 similar to polymeric membranes, does not completely block but significantly reduces polysulfide access to the negative electrode.…”

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confidence: 99%

“…These approaches include encapsulation by or addition of adsorbing inorganic materials, polymers and their composites, electrode coating and adsorptive additives to the electrode, physical barriers in the form of membranes and interlayers. [13][14][15][16][17][18][19][20][21][22] Physical barriers are the simplest and most versatile, as they can be tailored separately from the positive electrode or other parts of the cell. The solid Li-ion conducting membranes can be inorganic or polymeric, or a hybrid of both.…”

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confidence: 99%

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Viability of Polysulfide-Retaining Barriers in Li–S Battery

Berg

Trabesinger

2017

J. Electrochem. Soc.

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Lithium-sulfur (Li-S) batteries are among the most promising candidates for future high-energy, low-cost energy-storage systems. However, still many challenges have to be solved on the way to their commercialization. One of the most prominent of those is related to the polysulfide shuttle. In recent years, various approaches have been developed to contain, control or eliminate its effects, and thus to achieve higher specific charge, higher coulombic efficiencies and longer cycling life. One of recurring approaches is best described as introducing 'polysulfide barriers', either inorganic or polymeric membranes with lithium-ion conduction or interlayers with adsorptive properties, preventing polysulfides from reaching the lithium metallic anode. All of these approaches result in improved performance and longer cycling life of the Li-S battery. However, little attention has been given to the commercial viability of such solutions. Here we present a simple model to evaluate the practicability of polysulfide barriers in terms of gravimetric and volumetric energy densities as well as cost. We take into account the effects of barrier thickness, the physical properties and cost of the materials they are made of, as well as account for sulfur loading when assessing the viability of polysulfide barrier implementation into a practical Li-S cell. The Li-S battery combines several attractive properties, most importantly a high theoretical energy density, high theoretical specific charge and low cost.1-5 Moreover, the abundance of elemental sulfur -the active material in the Li-S battery -makes commercialization of this system even more desirable. The main drawback of sulfur as the active material is its insulating nature, which also applies to the Li 2 S, an end product of the lithiation reaction upon discharge. 5,6 However, the most detrimental process within Li-S cells is the polysulfide shuttle, which is triggered when highly soluble long-chain polysulfides are formed upon sulfur lithiation. Due to their high mobility in electrolyte, they can leach out from the positive electrode and reside in the electrolyte. There, polysulfides disproportionate in contact with other polysulfides or sulfur, and are partially oxidized or reduced when interacting with the positive or negative electrode, respectively. This leads to 'endless' red-ox shuttle, often referred to as the 'polysulfide shuttle '. 4,7 In addition, a part of the dissolved polysulfides can also be fully reduced at the negative electrode, forming an insulating layer; as a result, part of the active material is irreversibly lost and at the same time the resistance of the negative electrode is increased. The polysulfide shuttle therefore lowers the efficiency of the cell, reduces its specific charge and compromises its lifetime. [8][9][10][11][12] In recent years, numerous solutions have been proposed to reduce the effects of polysulfide shuttle and to control it. These approaches include encapsulation by or addition of adsorbing inorganic materials, polymers and their...

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Viability of Polysulfide-Retaining Barriers in Li–S Battery

Berg

Trabesinger

2017

J. Electrochem. Soc.

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“…[33] In poly-sulfide redox flow systems PIMs have been shown to inhibit poly-sulfide crossover. [34,35,36,37,38] Selective permeability to small ionic species was shown in many cases to provide excellent separator performance based on PIMs. Initial exploratory studies have addressed applications of PIMs also as self-healing films and in corrosion science.…”

Section: Electrochemical Methods Based On Pim-modified Electrodes Andmentioning

confidence: 99%

Polymers of Intrinsic Microporosity in Triphasic Electrochemistry: Perspectives

et al. 2019

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Polymers of intrinsic microporosity (PIMs) as molecularly rigid polymers have emerged as a new class of gas‐permeable glassy materials. They offer excellent processability and a range of potential applications also in electrochemical processes. Particularly interesting is the ability of some PIM films to remain gas‐permeable/binding even in the presence of (aqueous) liquid electrolyte to give triphasic interfacial reactivity. Gaseous reagents or products (such as hydrogen or oxygen) are bound probably into hydrophobic regions in the wet PIM film to avoid macroscopic bubble formation and to enhance both the surface reactivity and the apparent activity of the gas solute close to the electrode/catalyst surface. The photoelectrochemical formation of hydrogen gas close to a platinum electrode is enhanced by PIM‐1, which is presented as an example of energy harvesting through molecular H2 “energy carrier” transport.

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“…This undesirable chemically was recently mitigated by cross-linking the membranes, showing that the relationship between membrane chemical reactivity and selectivity are critical for developing membranes for the next generation of Li-S batteries [232]. Other conductive polymers can be used as a shell, like polythiophene (Pth) [233].…”

Section: Other Polymersmentioning

confidence: 99%

Advances in lithium—sulfur batteries

Zhang

Xie

Kim

et al. 2017

Materials Science and Engineering: R: Reports

110

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International audienceThis review is focused on the state-of-the-art of lithium-sulfur batteries. The great advantage of these energy storage devices in view of their theoretical specific capacity (2500 Wh kg−1, 2800 Wh L−1, assuming complete reaction to Li2S) has been the motivation for a huge amount of works. However, these batteries suffer of disadvantages that have restricted their applications such as high electrical resistance, capacity fading, self-discharge, mainly due to the so-called shuttle effect. Strategies have been developed with the recent modifications that have been proposed as a remedy to the shuttle effect, and the insulating nature of the polysulfides. All the elements of the battery are concerned and the solution, as we present herewith, is a combination of modification of the cathode, of the separator, of the electrolyte, including the choice of binder, even though few binder-free architectures have now been proposed

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Understanding and controlling the chemical evolution and polysulfide-blocking ability of lithium–sulfur battery membranes cast from polymers of intrinsic microporosity

Abstract: By understanding how PIM-1 membrane reactivity affects its ion-transport selectivity, it’s possible to intervene to stabilize it in a Li–S battery.

Cited by 46 publications

References 41 publications

Viability of Polysulfide-Retaining Barriers in Li–S Battery

Viability of Polysulfide-Retaining Barriers in Li–S Battery

Polymers of Intrinsic Microporosity in Triphasic Electrochemistry: Perspectives

Advances in lithium—sulfur batteries

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