Frontispiece: Bis(aryl) Tetrasulfides as Cathode Materials for Rechargeable Lithium Batteries

Guo, Wei; Wawrzyniakowski, Zachary D.; Cerda, Matthew M.; Bhargav, Amruth; Pluth, Michael D.; Ma, Ying; Fu, Yongzhu

doi:10.1002/chem.201786763

Cited by 7 publications

(9 citation statements)

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“…In recent years, some new organopolysulfide molecules and polymers with long sulfur chains have been developed and investigated in rechargeable lithium batteries. For example, dimethyl trisulfide, diphenyl trisulfide, and tetrasulfides have been proven to be promising cathode materials. Trithiocyanuric acid with three nitrogen atoms was used to prepare three‐dimensionally interconnected sulfur‐rich polymers .…”

Section: Methodsmentioning

confidence: 99%

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Wang

Guo

et al. 2019

Advanced Science

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Organic compounds with active sites for lithiation can be used as electrode materials for lithium batteries. Their tunable structures allow a variety of materials to be made and investigated. Herein, a spectrum of dipyridyl polysulfides (Py2Sx, 3 ≤ x ≤ 8) is prepared in electrolyte by a one‐pot synthesis method from dipyridyl disulfide (Py2S2) and elemental sulfur. It renders up to seven dipyridyl polysulfides (i.e., Py2S3, Py2S4, Py2S5, Py2S6, Py2S7, and Py2S8) which show fully reversible electrochemical behavior in lithium batteries. In the discharge, the initial lithiation occurs at 2.45 V leading to the breakage of SαSβ bonds in Py2Sx and formation of lithium 2‐pyridinethiolate, in which lithium is coordinated in between N and S atoms. The left sulfur species act as elemental sulfur, showing two voltage plateaus at 2.3 and 2.1 V. The molecular dynamics simulations show the attraction between pyridyl groups and lithium polysulfides/sulfide via N···Li···S bonds, which enable good retention of soluble discharge products within electrodes and stable cycling performance. In the recharge, low‐order Py2Sx (e.g., Py2S3, Py2S4, and Py2S5) remain as the charged products. The mixture catholyte exhibits superlong cycle life at 1C rate with 1200 cycles and 70.5% capacity retention.

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Section: Methodsmentioning

confidence: 99%

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Wang

Guo

et al. 2019

Advanced Science

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“…The organic functional group has been shown to have a significant impact on the morphology. [ 14 ] The uniform nucleation and growth of the discharge product crystals confirm the favorable interactions the xanthogen groups possess with CNT substrate. This result demonstrates that CNT can effectively confine the discharge products while accommodating the volume expansion at the cathode.…”

Section: Resultsmentioning

confidence: 79%

“…[ 13 ] Finally, the bulkiness and polarity of the organic functional groups can be used to alter their solubility in the electrolyte, thus minimizing parasitic shuttle effects. [ 12,14 ]…”

Section: Introductionmentioning

confidence: 99%

Xanthogen Polysulfides as a New Class of Electrode Material for Rechargeable Batteries

Bhargav

Manthiram

2020

Advanced Energy Materials

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electrochemical reversibility. In addition to their favorable redox behavior, these compounds are also naturally abundant, environmentally friendly, inexpensive, and easy to process into battery electrodes. [12] While sulfur offers a high energy density exceeding 2500 W h kg −1 , it is beleaguered by three major issues. First, the electrical conductivity of sulfur is extremely low, necessitating the addition of a large amount of conductive hosts (e.g., carbon) in the battery electrode. Second, the difference in density between sulfur and its discharge product, Li 2 S, is quite large. This results in a volume change of nearly 80% during cycling, thus requiring a cathode structure to accommodate the large volume fluctuation and the resulting stresses generated. Third, the lithium polysulfides formed during cycling are electrolyte-soluble and thus shuttle between the electrodes. This "shuttle effect" results in a loss of active material, poor Coulombic efficiency, and short cycle life. [8] On the other hand, organic compounds (e.g., carbonyls, organosulfides, imines, and nitriles) present three distinct advantages. First, the functional groups in the organic moieties can alter the physical properties of these materials including their electrical conductivity. [9] Second, the difference in density between the delithiated and the lithiated forms of these compounds is low, resulting in a smaller volume change and stress in the cathode. [13] Finally, the bulkiness and polarity of the organic functional groups can be used to alter their solubility in the electrolyte, thus minimizing parasitic shuttle effects. [12,14] Organosulfur compounds combine the multi-electron, highenergy-density characteristics of sulfur with the distinct advantages of organic compounds. Specifically, the ability to tune the physical and chemical properties of organosulfur materials with various functional groups allows for optimization of their conductivity, solubility, and density. [9,15-17] Recognizing these advantages, various organosulfur compounds have been reported since the late 1980s. [18,19] Early reports of such materials focused on polymers that functioned according to the disulfide-thiolate redox behavior. [19,20] More recently, polymers containing multiple SS bonds that have been synthesized through inverse vulcanization, [21,22] incorporation of covalent frameworks, [22-25] and condensation reactions have been reported. [26-29] In addition to polymers, linear compounds, [15,30,31] cyclics, [32] hybrids, [33,34] and compounds with unique functional groups have also been reported. [35-37] Organosulfides are an emerging class of alternative sulfur-based cathode materials. This work explores a new member in this family of active materials, viz., xanthogen polysulfides. Diisopropyl xanthogen polysulfide (DIXPS) is used as a model compound in a lithium battery to understand the chemical changes and the unique electrochemical behavior of this class of materials by employing various materials characterization methodologies. As a cathode ma...

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“…Organosulfur, as a kind of organic electrode material, owns sulfur chain and tunable functional groups, resulting in high theoretical capacity, structural diversity, and flexibility. [ 2 ] In addition, they have great potential in rechargeable lithium batteries due to their low molecular weights and multiple electron transformation. [ 3 ] This series of organosulfur cathode materials is based on the reversibility of SS bonds breaking and reforming in rechargeable batteries for lithium storage, and the theoretical capacity increases with the increase of sulfur atoms.…”

Section: Introductionmentioning

confidence: 99%

Anchoring and Catalytic Effects of rGO Supported VS₂ Nanosheets Enable High‐Performance Li–Organosulfur Battery

Zhang

Guo

2023

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on the reversibility of SS bonds breaking and reforming in rechargeable batteries for lithium storage, and the theoretical capacity increases with the increase of sulfur atoms. [4] For example, diphenyl tetrasulfide (PhS 4 Ph, PTS) possesses six electrons transfer, owning a theoretical capacity of 570 mAh g −1 . [5] However, as a lithium-sulfur-based battery, there are still some drawbacks to the cathode that hinder its practical application, including the electronic/ionic insulation and sluggish redox kinetics. [6] Drawing on lithium-sulfur (Li-S) battery, there are many strategies exist to solve the problems on the cathode. The general strategy is to encapsulate active materials with porous carbonaceous nanomaterials, such as carbon nanotubes, porous carbon spheres, and graphene, which could enhance electrode conductivity. [7] But it is insufficient to adsorb active materials due to weak van der Waals interaction. [8] Later, polar nanomaterials (e.g., transition metal oxides, sulfides, and nitrides) were introduced into host materials, which could chemisorb and catalyze active materials. [9] However, it is easy to agglomerate, and the conductivity is not as good as carbonaceous nanomaterials. [10] Hence, like Li-S batteries, it is critical to select an appropriate host material to improve the electrochemical performance of lithium−organosulfur batteries.As a typical family member of transition metal sulfides, vanadium disulfide (VS 2 ) consists of a vanadium layer sandwiched between the two sulfur layers as SVS. These triple layers stack together by weak Van der Waals force. [11] The theoretical study revealed that the VS 2 monolayer was metallic with a spin-polarized ground state and had a faster Li + diffusion rate than MoS 2 and graphite, which makes it widely used in energy storage devices. [12] Moreover, the weak van der Waals interlayer interaction provides practical feasibility for VS 2 to be exfoliated into ultrathin nanosheets with highly catalytic active edges. [13] In addition, nano-morphology has a great influence on the properties of VS 2 . Like 2D nanoarchitecture, which provides a large available surface area for its catalytic ability. These merits are needed to improve the performance of Li-organosulfur batteries. [11b] Previous studies report that VS 2 was widely applied in Li-S batteries as a host material. [14] Cui reported that Li-S/VS 2 -based cathodes exhibit the highest capacity, lowest overpotential, and best cycling stability compared with the As a high-energy-density cathode material, organosulfur has great potential for lithium batteries. However, their practical application is plagued by electronic/ionic insulation and sluggish redox kinetics. Hence, our strategy is to design a self-weaving, freestanding host material by introducing reduced graphene oxide-supported VS 2 nanosheets (VS 2 -rGO) and carbon nanotubes (CNTs) for lithium-phenyl tetrasulfide (Li-PTS) batteries. Unique host materials not only provide physicochemical confinement of active materials to boost the util...

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Frontispiece: Bis(aryl) Tetrasulfides as Cathode Materials for Rechargeable Lithium Batteries

Cited by 7 publications

References 0 publications

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Xanthogen Polysulfides as a New Class of Electrode Material for Rechargeable Batteries

Anchoring and Catalytic Effects of rGO Supported VS₂ Nanosheets Enable High‐Performance Li–Organosulfur Battery

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Frontispiece: Bis(aryl) Tetrasulfides as Cathode Materials for Rechargeable Lithium Batteries

Cited by 7 publications

References 0 publications

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Long Cycle Life Organic Polysulfide Catholyte for Rechargeable Lithium Batteries

Xanthogen Polysulfides as a New Class of Electrode Material for Rechargeable Batteries

Anchoring and Catalytic Effects of rGO Supported VS2 Nanosheets Enable High‐Performance Li–Organosulfur Battery

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Anchoring and Catalytic Effects of rGO Supported VS₂ Nanosheets Enable High‐Performance Li–Organosulfur Battery