Thermal treatment induced transition from Zn3(OH)2(BDC)2 (MOF-69c) to Zn4O(BDC)3 (MOF-5)

Ren, Jianwei; Rogers, Dave E. C.; Segakweng, Tshiamo; Langmi, Henrietta W.; North, Brian C; Mathe, Mkhulu; Bessarabov, Dmitri

doi:10.3139/146.110994

Cited by 15 publications

(6 citation statements)

References 25 publications

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“…These values are in accordance with the values reported in the literature for MOF materials [90][91][92] shown in Table 1, though the values are somewhat lower than the Langmuir surface areas [80] reported for pure MOF-5 materials due to the transformation into MOF-5W It is however, noteworthy that these specific surface areas are greater than those of most carbonaceous host materials that have reportedly been used as sulfur hosts in Li -S batteries [18,49,50,65]. The large pore volume of the MOF materials is expected to facilitate in ensuring larger amounts of sulfur encapsulation and thus, resulting in high sulfur loading in the electrodes.…”

Section: B) Materials Characterization and Electrochemical Measurementssupporting

confidence: 92%

Understanding the Origin of Irreversible Capacity loss in Non-Carbonized Carbonate − based Metal Organic Framework (MOF) Sulfur hosts for Lithium − Sulfur battery

Shanthi

Hanumantha

Gattu

et al. 2017

Electrochimica Acta

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Li-Sulfur (Li-S) batteries are emergent next-generation energy storage devices due to their very high specific energy density (~2567 Wh g-1) but are limited by polysulfide dissolution issues. In this work, chemically synthesized sulfur containing non-carbonized metal organic framework (S-MOF) cathodes show initial specific capacities of 1476 mAh g-1 stabilizing at ~609 mAh g-1 with almost no fade for over 200 cycles. Post-cycled separators of the S-MOF cathodes display complete absence of polysulfides after cycle 1, 20 and 200. It was identified that the occurrence of carbonate species in the MOF structure resulted in the formation of C-S bonded species causing retention of polysulfide at the electrode surface ensuring long-term stability. However, this observed capacity drop during the first 10 cycles is attributed to the oxidation of some of the infiltrated sulfur by the MOF as determined by electrochemical and X-ray photoelectron spectroscopy (XPS) analyses. Nevertheless, the negligible fade rate (0.0014% cycle-1) and complete prevention of polysulfide dissolution renders these cathodes most promising candidates for Li-S batteries. Understanding of this transformation behavior in sulfur-containing MOF is essential to engineer chemically-bonded host-structures capable of efficient polysulfide trapping, a key pathway to establishing novel platforms for achieving high power Li-S batteries.

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Section: B) Materials Characterization and Electrochemical Measurementssupporting

confidence: 92%

Understanding the Origin of Irreversible Capacity loss in Non-Carbonized Carbonate − based Metal Organic Framework (MOF) Sulfur hosts for Lithium − Sulfur battery

Shanthi

Hanumantha

Gattu

et al. 2017

Electrochimica Acta

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“…was confirmed by XRD spectra as previously reported [17,18]. The SEM images showed nearly regular cube shaped crystals.…”

Section: Characterizationsupporting

confidence: 67%

“…The procedure for the synthesis of MOF-5 is the same as reported previously [17]. Typically, experiments were conducted using a 250 ml round-bottom flask and an oil bath to provide constant reaction temperature.…”

Section: Synthesis Of Mof-5mentioning

confidence: 99%

Comparison of MOF-5- and Cr-MOF-derived carbons for hydrogen storage application

et al. 2015

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Nanoporous carbons which possess high surface areas and narrow pore size distributions have become one of the most important classes of porous materials with potential to be utilized for hydrogen storage. In recent times, several Metal-organic frameworks (MOFs) have been shown to be promising precursors for creating nanoporous carbons due to their high surface areas and tunable pore sizes. The pore structure and surface area of the resultant carbon materials can be tuned simply by changing the calcination temperature.In this work, a zinc based MOF (MOF-5) and chromium based MOF (MIL-101) were both used as precursors for syntheses of nanoporous carbons structures by direct carbonization technique at different temperatures. The resultant carbon structures possessed high surface areas and differing hydrogen storage capacities.

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“…The experimentally determined specific surface area values are comparable with the specific surface area corresponding to conventional CFMs or MOFs studied and reported for gas storage and energy storage applications for Li -S batteries. 40,41,[64][65][66][67][68] The small average pore diameter of the SCFM (∼3.2 nm) is expected to aid in preventing polysulfide dissolution by facilitating improved trapping of the polysulfides formed during electrochemical cycling. The sulfur infiltrated CFM derived S-SCFM, on the other hand, shows a drastic reduction in surface area (12.36 m 2 g −1 ) which is clearly indicative of the pores being filled by sulfur and is thus, attributed to sulfur infiltration into the porous channels of the chemically derived CFM based SCFM which results in filling up of the pores.…”

Section: Resultsmentioning

confidence: 99%

Sulfonic Acid Based Complex Framework Materials (CFM): Nanostructured Polysulfide Immobilization Systems for Rechargeable Lithium–Sulfur Battery

Shanthi

Hanumantha

Kuruba

et al. 2019

J. Electrochem. Soc.

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Lithium-sulfur (Li-S) secondary batteries with sulfur cathodes and theoretical energy density of ∼2600 Wh/kg, are promising high energy-density system for next-generation electric-vehicles (EVs) potentially mitigating the gravimetric and volumetric energy density limitations of existing lithium-ion (Li-ion) batteries. Herein, a chemically synthesized sulfonic acid-based complex framework material (CFM) termed as (SCFM), was used as sulfur host (S-SCFM) to prevent polysulfide dissolution in Li-S batteries. The S-SCFM based CFM cathodes show an initial capacity of 1190 mAh/g and a capacity of 1044 mAh/g after 100 cycles. In addition, the S-SCFM based CFM cathodes exhibited good cycling stability with a minimal fade rate of ∼0.0012% per cycle. XPS analysis of the cycled separators with the S-SCFM electrodes shows complete absence of polysulfide species after 100 charge-discharge cycles. It was also identified that the SCFM based CFM chemically binds sulfur via -C-S-linkages thereby exhibiting an affinity for the polysulfide species formed during the charge-discharge cycles. As a result, the SCFM based CFM prevent polysulfide species from dissolving and diffusing into the electrolyte. A thorough understanding of these engineered SCFM based CFM sulfur host in Li-S battery outlined herein will be vital in designing promising sulfur hosts for next generation sulfur cathodes in Li-S batteries.

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Thermal treatment induced transition from Zn₃(OH)₂(BDC)₂ (MOF-69c) to Zn₄O(BDC)₃ (MOF-5)

Cited by 15 publications

References 25 publications

Understanding the Origin of Irreversible Capacity loss in Non-Carbonized Carbonate − based Metal Organic Framework (MOF) Sulfur hosts for Lithium − Sulfur battery

Understanding the Origin of Irreversible Capacity loss in Non-Carbonized Carbonate − based Metal Organic Framework (MOF) Sulfur hosts for Lithium − Sulfur battery

Comparison of MOF-5- and Cr-MOF-derived carbons for hydrogen storage application

Sulfonic Acid Based Complex Framework Materials (CFM): Nanostructured Polysulfide Immobilization Systems for Rechargeable Lithium–Sulfur Battery

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