A robust 2D organic polysulfane nanosheet with grafted polycyclic sulfur for highly reversible and durable lithium-organosulfur batteries

Hu, Hao; Zhao, Bote; Cheng, Haoyan; Dai, Shuge; Kane, Nicholas; Yu, Ying; Liu, Meilin

doi:10.1016/j.nanoen.2018.12.092

Cited by 77 publications

(44 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…To meet the challenge, a vulcanization strategy was proposed to prepare a novel organic polysulfane with high sulfur content as the cathode for Li–S battery. [ 109 ] Through sulfur‐radical‐promoted decarboxylation, sulfur was grafted onto the carbon frame of the poly(acrylic acid) (PAA), resulting in the organic polysulfane nanosheets (OPNS) (Figure 6c). In situ Raman study reveals that the OPNS are highly reversible and no elemental sulfur is formed during cycling.…”

Section: Suppressing Shuttling Of the Intermediatesmentioning

confidence: 99%

Strategies toward High‐Loading Lithium–Sulfur Battery

Chen

Lei

et al. 2020

Advanced Energy Materials

313

176

View full text Add to dashboard Cite

despite all these promises, three intrinsic drawbacks need to be resolved before fulfilling the promise of the market potential.First, the most stable but electronically insulating S 8 (≈10 −14 S cm −2 ) with cyclic configuration is used as the starting material in Li-S cathode, significantly limiting the full utilization of the active materials to reach the theoretical capacity. Therefore, it is the first priority to design the cathode that ensures the maximum usage of the starting materials, which sets the upper limit of the capacity performance. Second, the muti-step reduction process releases highly soluble lithium polysulfides (LiPSs) intermediates (Li 2 S x , where x = 4-8) into the organic electrolyte. [6] Unlike the batteries based on ion-insertion mechanism, [7,8] Li-S battery possesses unique and complex electrochemical/chemical processes during operation. During galvanostatic discharge process, two distinct plateaus can be verified at about 2.4 and 2.1 V in the voltage profile, corresponding to the reduction of sulfur into long-chain polysulfides and subsequent reaction from short-chain polysulfides to Li 2 S, respectively. [9] Further investigations about the reaction mechanism of Li-S battery based on experimental and theoretical studies reveal that the existence of various intermediates during electrochemical processes, indicating much more complex battery chemistry compared to the simple stepwise reaction model. [10,11] As a result, the soluble intermediates can diffuse through the polymeric separator to the anode surface, causing the loss of active materials and degradation of anode. Third, the density difference between the starting material (sulfur, 2.07 g cm −3 ) and discharge product (Li 2 S, 1.66 g cm −3 ) causes significant volumetric change during continuous cycling, damaging the integrity of the cathode structure and leading to serious capacity fading. [12] Besides above problems concerning the cathode side of the Li-S battery, other issues arose on the anode side, such as the unstable solid-electrolyte interphase (SEI), surface passivation, and uncontrolled lithium dendrite growth. [13][14][15] Stemmed from the basic problems mentioned above from the very beginning of the designed Li-S battery systems, various derivative problems were gradually unraveled during persistent efforts for improving the battery performance to approach the ultimate goal for commercialization. In the past decade, fundamental studies about Li-S battery were carried in laboratories all over the world, and it gradually put the puzzle together while brought promising performance improvement. [11,[16][17][18][19][20] However, to date, most of the lab-scale progresses have been based on batteries with sulfur loading lower than 2 mg cm −2 , Lithium-sulfur (Li-S) batteries, due to the high theoretical energy density, are regarded as one of the most promising candidates for breaking the limitations of energy-storage system based on Li-ion batteries. Tremendous efforts have been made to meet the challenge of high-performan...

show abstract

Section: Suppressing Shuttling Of the Intermediatesmentioning

confidence: 99%

Strategies toward High‐Loading Lithium–Sulfur Battery

Chen

Lei

et al. 2020

Advanced Energy Materials

313

176

View full text Add to dashboard Cite

show abstract

“…For example, Hu et al developed an STM using KCl as a template to synthesize 2D organic polysulfane which was constructed by polycyclic sulfur grafted on the polymer carbon chain. [ 95 ] The as‐prepared 2D organic polysulfane demonstrated excellent stability as electrode materials for Li‐S battery with a capacity retention of 91% after 620 cycles at 1 C rate. Huang et al reported a facile STM to fabricate polymers nanosheets by using CuCl 2 as template and oxidant through a vapor phase polymerization way.…”

Section: Stmmentioning

confidence: 99%

Salt‐Assisted Synthesis of 2D Materials

Huang

Jin

et al. 2020

Adv Funct Materials

136

112

View full text Add to dashboard Cite

2D materials have demonstrated good chemical, optical, electrical, and magnetic characteristics, and offer great potential in numerous applications. Corresponding synthesis technologies of 2D materials that are highquality, high-yield, low-cost, and time-saving are highly desired. Salt-assisted methods are emerging technologies that can meet these requirements for the fabrication of 2D materials. Herein, the recent process for the salt-assisted synthesis of 2D materials and their typical applications are summarized. First, the properties of salt crystals and molten salts are briefly introduced, and then some examples of 2D materials synthesis with the assistance of salt as well as their representative applications are presented. The underlying mechanisms of salts with different states on the formation of 2D morphology are discussed to aid in the rational design of synthetic route of 2D materials. At last, the challenges and future perspectives for salt-assisted methods are briefly described. This review provides guidance for the controllable synthesis of 2D materials based on the salt-assisted approaches.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adfm.201908486.MoO 3 , and LaNb 2 O 7 ), [14][15][16] layered double hydroxides (LDHs, e.g., Mg 6 Al 2 (OH) 16 CO 3 •4H 2 O), [17] hexagonal-boron nitride (h-BN), [2,18] transition metal halides (such as MoCl 2 and CrCl 3 ), [19] black phosphorus, [20] graphitic carbon nitride (g-C 3 N 4 ), [5] MXene (such as Ti 2 C and Ti 3 CN), [21][22][23][24][25] and clays (for instance, [(Mg 3 )(Si 2 O 5 ) 2 (OH) 2 ] and [(Al 2 )(Si 3 Al) O 10 (OH) 2 ]K). [19] Notably, many nonlayered structure species can also form 2D morphology with specific synthetic methods, largely expanding the 2D family (such as hexagonal-MoO 3 (h-MoO 3 ), hexagonal-WO 3 (h-WO 3 ), [15] transition metal nitrides (TMNs), [26,27] and transition metal phosphides (TMPs)). [28] To exploit the applications of 2D materials, the development of a synthetic method should be prioritized. Currently, synthesis processes of 2D materials could be divided into two categories, naming the top-down and bottom-up approaches. [29][30][31] Generally, exfoliation is the most common top-down method to produce monolayer or few-layer 2D materials. [19,32] Graphene was first prepared by mechanical exfoliation of highly oriented pyrolytic graphite with sellotape in 2004. [33] The exfoliation can weaken the interlayer Van der Waals force for bulk materials with layered crystal structures while maintain the covalent bonding in plane to produce monolayer or few-layer nanosheets. Although the productivity based on this method is limited due to the low efficiency, the exfoliation approach provides a new synthesis methodology for 2D materials. A series of studies on liquid exfoliation have been conducted by Coleman and co-workers. [19,34,35] By sonicating the bulk material in an appropriate solvent with similar interface energy, 2D material ink can be prepared. After the liq...

show abstract

“…It is clearly seen from Figure a that there are two distinct discharge platforms at 2.3 and 2.1 V. The high‐voltage platform at 2.3 V is attributed to poly(S‐ co ‐DVIMBr) reduced to high Li 2 S x ( x ≥8) and Li 2 S 8 . Another plateau at 2.1 V can be assigned to the formation of Li 2 S x (4≤ x ≤6) . Upon further discharge, these Li 2 S x (4≤ x ≤6) are finally reduced to fully discharged Li 2 S 2 /Li 2 S .…”

Section: Resultsmentioning

confidence: 96%

Trapping of Polysulfides with Sulfur‐Rich Poly Ionic Liquid Cathode Materials for Ultralong‐Life Lithium–Sulfur Batteries

Liu

Zeng

et al. 2020

ChemSusChem

View full text Add to dashboard Cite

Sulfur‐rich polymers synthesized by inverse vulcanization are promising cathodes for Li–S batteries and can suppress the shuttle effect to improve the cycling properties of Li–S batteries. However, developing a sulfur‐rich copolymer with new chemical functionality to enhance performance of Li–S batteries remains a huge challenge. In this report, a sulfur‐rich polymer cathode containing ionic liquid segments named poly(sulfur‐co‐1‐vinyl‐3‐allylimidazolium bromide) [poly(S‐co‐DVIMBr)] was obtained by the inverse vulcanization of S8 with DVIMBr and used as cathode for the first time. This sulfur‐rich poly ionic liquid cathode showed effective suppression of the shuttle effect through joint effects of the stable chemical bonding of C−S and strong cation absorption for lithium polysulfides, which was confirmed by DFT calculations. In particular, the Li–S cell with poly(S‐co‐DVIMBr) cathode delivered high capacity retention of 90.22 % even over 900 cycles. Developing sulfur‐rich poly ionic liquids may provide a new strategy of introducing the functional groups with cations into the cathode materials for suppressing the shuttle effect and improving the performance of Li–S batteries.

show abstract

A robust 2D organic polysulfane nanosheet with grafted polycyclic sulfur for highly reversible and durable lithium-organosulfur batteries

Cited by 77 publications

References 49 publications

Strategies toward High‐Loading Lithium–Sulfur Battery

Strategies toward High‐Loading Lithium–Sulfur Battery

Salt‐Assisted Synthesis of 2D Materials

Trapping of Polysulfides with Sulfur‐Rich Poly Ionic Liquid Cathode Materials for Ultralong‐Life Lithium–Sulfur Batteries

Contact Info

Product

Resources

About