Insights into the effect of the interlayer spacings of bilayer graphene on the desolvation of H+, Li+, Na+, and K+ ions with water as a solvent: a first-principles study

Zhang, Xu; Yang, Shaobin; Shan, Xu; Li, Sinan; Tang, Shuwei

doi:10.1039/c9cp02922b

Cited by 13 publications

(15 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As previously reported, the aperture size of carbon materials displays an ionic-sieving effect on the solvated Na + and the pore size has a great influence on the electron distribution inside the pore [ 46 – 50 ]. Specifically, the desolvation will happen around the aperture when the aperture size is smaller than the solvated Na + [ 47 – 49 , 51 – 53 ]. In addition, according to the previous theoretical results, the Na + concentration inside the pore increases with the decreasing pore inner diameter [ 46 , 50 ].…”

Section: Introductionmentioning

confidence: 99%

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

et al. 2021

View full text Add to dashboard Cite

Highlights Hard-carbon anode dominated with ultra-micropores (< 0.5 nm) was synthesized for sodium-ion batteries via a molten diffusion–carbonization method. The ultra-micropores dominated carbon anode displays an enhanced capacity, which originates from the extra sodium-ion storage sites of the designed ultra-micropores. The thick electrode (~ 19 mg cm−2) with a high areal capacity of 6.14 mAh cm−2 displays an ultrahigh cycling stability and an outstanding low-temperature performance. Abstract Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries (SIBs). Ultra-micropores (< 0.5 nm) of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na+ but allow the entrance of naked Na+ into the pores, which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics. Herein, a molten diffusion–carbonization method is proposed to transform the micropores (> 1 nm) inside carbon into ultra-micropores (< 0.5 nm). Consequently, the designed carbon anode displays an enhanced capacity of 346 mAh g−1 at 30 mA g−1 with a high ICE value of ~ 80.6% and most of the capacity (~ 90%) is below 1 V. Moreover, the high-loading electrode (~ 19 mg cm−2) exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm−2 at 25 °C and 5.32 mAh cm−2 at − 20 °C. Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results, the designed ultra-micropores provide the extra Na+ storage sites, which mainly contributes to the enhanced capacity. This proposed strategy shows a good potential for the development of high-performance SIBs.

show abstract

Section: Introductionmentioning

confidence: 99%

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Consequently, we selected 1 × 1 × 1 as the K -point for structural optimization, and the K -point 2 × 2 × 1 for calculating the electronic structures. Through a comprehensive review of the literature , and analysis of previous studies, , it had been determined that these choices for the cutoff energy and K -point yield accurate results. During the optimization, all of the atomic positions were relaxed simultaneously.…”

Section: Computational Detailsmentioning

confidence: 99%

“…We discovered that the carbon layers in these materials are equivalent to a single layer of graphene, while the pores in the carbon materials can be seen as being composed of two relatively distant layers of graphene (Figure S1b). Thus, our group proposed the use of a double-layer graphene model to simulate nanopores and obtained the sizes for the complete desolvation of Na + and Li + . In 2022, a theoretical study was conducted to investigate the effect of nitrogen doping on the modification of doping in EDLCs .…”

Section: Introductionmentioning

confidence: 99%

Why Can Phosphorus-Doped Nanopores Improve the Capacitance of Electrochemical Double-Layer Capacitors Using Alkaline Electrolytes? A First-Principles Study

Zhang,

Hao,

Tang

et al. 2023

ACS Appl. Nano Mater.

Self Cite

View full text Add to dashboard Cite

To investigate how phosphorus-doped carbon micropores can significantly enhance the capacitance of electrochemical double-layer capacitors (EDLCs), we performed first-principles calculations on phosphorus-doped monolayer (MGP) and bilayer graphene (BGP-x, x = 4–8), simulating macropores or mesopores and micropores, respectively. In addition, we studied the stable structure, relative capacitance, and reaction characteristics of Na+, Li+, and their hydrated ion structures {[Na(H2O) n ]+, [Li(H2O) n ]+, n = 1–4} on MGP, as well as their insertion behavior in BGP-x. Surprisingly, we observed a desolvation phenomenon within the phosphorus-doped carbon micropores. The calculation results suggest that the adsorption of [Na(H2O)4]+ and [Li(H2O)4]+ on MGP is primarily attributed to the stronger OH–π interaction compared to the Na+–π and Li+–π interactions. On the other hand, the stability of the structure after embedding [Na(H2O) n ]+ and [Li(H2O) n ]+ in BGP-x can be explained by the opposite scenario. The equilibrium between these two interactions and the continuous reduction in interlayer spacing facilitate the desolvation of [Na(H2O) n ]+ and [Li(H2O) n ]+. A decrease in the number of water molecules bound to Na+ and Li+ ions leads to a maximum increase in relative capacitance of 2.7 and 3.0 times, respectively. This indicates that desolvation can significantly enhance the capacitance of EDLCs. The complete desolvation size for Na+ is less than 4 Å, while for Li+, it is 4.3 Å. Based on these calculations, when using phosphorus-doped carbon materials as electrode materials, selecting an electrolyte containing Li+ rather than Na+ would result in a higher capacitance. The calculation results reveal the mysterious mechanism behind the significant increase in capacitance caused by phosphorus-doped carbon micropores. In addition to this, they also provide us with a magical key to optimize the perfect combination of electrolyte composition and carbon material pore size/type.

show abstract

“…[13][14][15][16][17] The use of MFI type zeolites such as ZSM-5 and silicalite-1 have been of great interest due to a three-dimensional lattice structure with an internal pore size of 0.51 nm to 0.56 nm (5.1 Åto 5.6 Å). [18,19] The pentasil structure of silicalite-1 leads to a large internal microporous network with high surface area which is conducive to favourable adsorption capacity. The internal aperture of silicalite-1 is larger than the kinetic diameter of the studied gases: 0.26 nm, 0.33 nm, 0.36 nm, and 0.38 nm for He, CO 2 , N 2 , and CH 4 respectively.…”

Section: Introductionmentioning

confidence: 99%

Pore plugging synthesis and characterization of silicalite‐1 membranes using tubular TiO₂ supports: Effect of support pore size on membrane performance

et al. 2018

View full text Add to dashboard Cite

In this study, we present a detailed synthesis procedure and characterization of porous inorganic silicalite‐1 membranes. The membranes were synthesized in‐situ using a pore plugging method with the inclusion of a 12 h thermal break promoting secondary growth within the active layer pores of the tubular TiO2 supports. The effect of the support pore size on membrane performance was examined with pore sizes ranging from 0.3 μm to 1.4 μm. Characterization using SEM and EDS analysis confirm the penetration and formation of silicalite‐1 crystals within porous supports up to a depth of 10–12 µm for all membranes. With the exception of the membranes synthesized on the support with 1.4 μm pore size, all membranes were more permeable to probe gas N2 compared to He. The highest ideal N2/He selectivity of 2.3 ± 0.5 was observed for the membranes synthesized on supports with 0.8 μm pore size. Single gas permeance for the membranes was high, ranging between 3.7 × 10−7 and 1.3 × 10−5 mol/m2sPa, and was independent of gas kinematic diameter with the order of permeation being CH4 > CO2 > N2 > He. Binary equimolar CO2/N2 separation experiments show better membrane CO2/N2 permselectivity compared to the ideal selectivity calculated from the single gas experiments. Comparing the observed membrane gas diffusivity and the adsorbate gas uptake rate within the zeolite material alone shows that these favourable selective properties are the result of adsorption surface diffusion and that Knudsen diffusion is minimized.

show abstract

Insights into the effect of the interlayer spacings of bilayer graphene on the desolvation of H⁺, Li⁺, Na⁺, and K⁺ ions with water as a solvent: a first-principles study

Abstract: Reasonable control of the pore sizes of supercapacitor electrode materials ensures the desolvation of electrolyte ions to significantly improve the capacitance.

Cited by 13 publications

References 32 publications

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

Why Can Phosphorus-Doped Nanopores Improve the Capacitance of Electrochemical Double-Layer Capacitors Using Alkaline Electrolytes? A First-Principles Study

Pore plugging synthesis and characterization of silicalite‐1 membranes using tubular TiO₂ supports: Effect of support pore size on membrane performance

Contact Info

Product

Resources

About

Insights into the effect of the interlayer spacings of bilayer graphene on the desolvation of H+, Li+, Na+, and K+ ions with water as a solvent: a first-principles study

Abstract: Reasonable control of the pore sizes of supercapacitor electrode materials ensures the desolvation of electrolyte ions to significantly improve the capacitance.

Cited by 13 publications

References 32 publications

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

Why Can Phosphorus-Doped Nanopores Improve the Capacitance of Electrochemical Double-Layer Capacitors Using Alkaline Electrolytes? A First-Principles Study

Pore plugging synthesis and characterization of silicalite‐1 membranes using tubular TiO2 supports: Effect of support pore size on membrane performance

Contact Info

Product

Resources

About

Insights into the effect of the interlayer spacings of bilayer graphene on the desolvation of H⁺, Li⁺, Na⁺, and K⁺ ions with water as a solvent: a first-principles study

Pore plugging synthesis and characterization of silicalite‐1 membranes using tubular TiO₂ supports: Effect of support pore size on membrane performance