Engineering Configuration Compatibility and Electronic Structure in Axially Assembled Metal–Organic Framework Nanowires for High-Performance Lithium Sulfur Batteries

Xiao, Yingbo; Guo, Sijia; Xiang, Yucui; Li, Dixiong; Zheng, Cheng; Ouyang, Yuan; Cherevan, Alexey; Gan, Liyong; Eder, Dominik; Zhang, Qi; Huang, Shaoming

doi:10.1021/acsenergylett.3c01698

Cited by 13 publications

(6 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The solution of Li 2 S 6 containing MIL‐125(Ti) and SC‐MOF‐Ti remained dark yellow, while the solution containing MIL‐125(Ti)‐NH 2 and MSC‐MOF‐Ti turned almost transparent. The UV/Vis spectra in Figure S12 indicate that their adsorption ability follows the sequence of MSC‐MOF‐Ti>MIL‐125(Ti)‐NH 2 >SC‐MOF‐Ti>MIL‐125(Ti), which corroborates that −NH 2 can effectively preconcentrate polysulfides inside nanopores of MOFs and matches well with the DFT calculations in Figure 2f [18] …”

Section: Resultssupporting

confidence: 80%

“…The UV/Vis spectra in Figure S12 indicate that their adsorption ability follows the sequence of MSC-MOF-Ti > MIL-125(Ti)-NH 2 > SC-MOF-Ti > MIL-125(Ti), which corroborates that À NH 2 can effectively preconcentrate polysulfides inside nanopores of MOFs and matches well with the DFT calculations in Figure 2f. [18] Besides, XPS analyses of MOFs before and after Li 2 S 6 adsorption were performed to investigate the chemical interactions between LiPSs and different MOFs (Figure S13). The Li 1s spectra in MSC-MOF-Ti and MIL-125(Ti)-NH 2 after Li 2 S 6 adsorption reveal a chemical interaction between Li + and À NH 2 .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Multimodal Engineering of Catalytic Interfaces Confers Multi‐Site Metal‐Organic Framework for Internal Preconcentration and Accelerating Redox Kinetics in Lithium‐Sulfur Batteries

Lu,

Zeng,

et al. 2024

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

The development of highly efficient catalysts to address the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium‐sulfur batteries (LSBs) remains a formidable challenge. In this study, a series of multi‐site catalytic metal‐organic frameworks (MSC‐MOFs) were elaborated through multimodal molecular engineering to regulate both the reactant diffusion and catalysis processes. MSC‐MOFs were crafted with nanocages featuring collaborative specific adsorption/catalytic interfaces formed by exposed mixed‐valence metal sites and surrounding adsorption sites. This design facilitates internal preconcentration, a coadsorption mechanism, and continuous efficient catalytic conversion toward polysulfides concurrently. Leveraging these attributes, LSBs with an MSC‐MOF‐Ti catalytic interlayer demonstrated a 62% improvement in discharge capacity and cycling stability. This resulted in achieving a high areal capacity (11.57 mAh cm−2) at a high sulfur loading (9.32 mg cm−2) under lean electrolyte conditions, along with a pouch cell exhibiting an ultra‐high gravimetric energy density of 350.8 Wh kg−1. Lastly, this work introduces a universal strategy for the development of a new class of efficient catalytic MOFs, promoting SRR and suppressing the shuttle effect at the molecular level. The findings shed light on the design of advanced porous catalytic materials for application in high‐energy LSBs.

show abstract

Section: Resultssupporting

confidence: 80%

Section: Methodsmentioning

confidence: 99%

Multimodal Engineering of Catalytic Interfaces Confers Multi‐Site Metal‐Organic Framework for Internal Preconcentration and Accelerating Redox Kinetics in Lithium‐Sulfur Batteries

Lu,

Zeng,

et al. 2024

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

show abstract

“…The adsorption energy of Li 2 S 6 with p-NCMO is −4.17 eV, which is much lower than that of NCMO (−11.89 eV), indicating that NCMO has a strong chemical interaction with Li 2 S 6 . However, very strong adsorption of NCMO is not conducive to the fast electrochemical conversion and the subsequent desorption of LiPS, which is confirmed by the Sabatier principle. , Consequently, the moderate adsorption of p-NCMO can accelerate the catalytic conversion of LiPS more effectively.…”

Section: Resultsmentioning

confidence: 98%

“…However, very strong adsorption of NCMO is not conducive to the fast electrochemical conversion and the subsequent desorption of LiPS, which is confirmed by the Sabatier principle. 38,39 Consequently, the moderate adsorption of p-NCMO can accelerate the catalytic conversion of LiPS more effectively.…”

Section: Morphology and Structuralmentioning

confidence: 99%

Surface-Phosphided Metal Oxide Microspheres as Catalytic Host of Sulfur to Enhance the Performance of Lithium–Sulfur Batteries

Gao,

Tian,

Wang

et al. 2024

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Lithium−sulfur (Li−S) batteries are one of the most promising high-energy density secondary batteries due to their high theoretical energy density of 2600 Wh kg −1 . However, the sluggish kinetics and severe "shuttle effect" of polysulfides are the well-known barriers that hinder their practical applications. A carefully designed catalytic host of sulfur may be an effective strategy that not only accelerates the conversion of polysulfides but also limit their dissolution to mitigate the "shuttle effect." Herein, in situ surface-phosphided Ni 0.96 Co 0.03 Mn 0.01 O (p-NCMO) oxide microspheres are prepared via gas-phase phosphidation as a catalytic host of sulfur. The as-prepared unique heterostructured microspheres, with enriched surface-coated metal phosphide, exhibit superior synergistic effect of catalytic conversion and absorption of the otherwise soluble intermediate polysulfides. Correspondingly, the sulfur cathode exhibits excellent electrochemical performance, including a high initial discharge capacity (1162 mAh g s −1 at 0.1C), long cycling stability (491 mAh g s −1 after 1000 cycles at 1C), and excellent rate performance (565 mAh g s −1 at 5C). Importantly, the newly prepared sulfur cathode shows a high areal capacity of 4.0 mAh cm −2 and long cycle stability under harsh conditions (high sulfur loading of 5.3 mg cm −2 and lean electrolyte/sulfur ratio of 5.8 μL mg −1 ). This work proposes an effective strategy to develop the catalytic hosts of sulfur for achieving high-performance Li−S batteries via surface phosphidation.

show abstract

“…However, the transfer of long-chain LiPSs in microporous channels of MOFs is normally suppressed, which is possible to limit the use of inner catalytic sites and lower the whole catalytic efficiency . As a result, constructing MOFs featuring both rapid mass transfer ability and high-density catalytic sites holds great potential for achieving highly efficient catalysts. − However, this has not been fully realized and understood due to the lack of strategies for addressing the contradictory relationship between pore apertures and catalytic site density.…”

Section: Introductionmentioning

confidence: 99%

Balanced Mass Transfer and Active Sites Density in Hierarchical Porous Catalytic Metal–Organic Framework for Enhancing Redox Reaction in Lithium–Sulfur Batteries

Xie,

Xiao,

Zeng

et al. 2024

ACS Nano

Self Cite

View full text Add to dashboard Cite

Developing highly efficient catalysts, characterized by controllable pore architecture and effective utilization of active sites, is paramount in addressing the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium–sulfur batteries (LSBs), which, however, remains a formidable challenge. In this study, a hierarchical porous catalytic metal–organic framework (HPC-MOF) with both appropriate porosity and abundant exposed catalytic sites is achieved through time-controlled precise pore engineering. It is revealed that the evolution of the porous structure and catalytic site density is time-dependent during the etching processes. The moderately etched HPC-MOF-M attains heterogeneous pores at various scales, where large apertures ensure fast mass transfer and micropores inherit high-density catalytic sites, enhancing utilization and catalytic kinetics at internal catalytic sites. Capitalizing on these advantages, LSB incorporating the HPC-MOF-M interlayer demonstrates a 164.6% improvement in discharge capability and an 83.3% lower decay rate over long-term cycling at 1.0C. Even under high sulfur loading of 7.1 mg cm–2 and lean electrolyte conditions, the LSB exhibits stable cycling for over 100 cycles. This work highlights the significance of balancing the relationship between mass transfer and catalytic sites through precise chemical regulation of the porous structure in catalytic MOFs, which are anticipated to inspire the development of advanced catalysts for LSBs.

show abstract

Engineering Configuration Compatibility and Electronic Structure in Axially Assembled Metal–Organic Framework Nanowires for High-Performance Lithium Sulfur Batteries

Cited by 13 publications

References 38 publications

Multimodal Engineering of Catalytic Interfaces Confers Multi‐Site Metal‐Organic Framework for Internal Preconcentration and Accelerating Redox Kinetics in Lithium‐Sulfur Batteries

Multimodal Engineering of Catalytic Interfaces Confers Multi‐Site Metal‐Organic Framework for Internal Preconcentration and Accelerating Redox Kinetics in Lithium‐Sulfur Batteries

Surface-Phosphided Metal Oxide Microspheres as Catalytic Host of Sulfur to Enhance the Performance of Lithium–Sulfur Batteries

Balanced Mass Transfer and Active Sites Density in Hierarchical Porous Catalytic Metal–Organic Framework for Enhancing Redox Reaction in Lithium–Sulfur Batteries

Contact Info

Product

Resources

About