Next Article in Journal
Decision Matrix in an Autonomous Power System for Agro-Industrial Complexes with Renewable Energy Sources
Previous Article in Journal
Structural Effects of Economic Shocks on the Macroeconomic Economy–Electricity–Emissions Nexus in India via Long-Term Cointegration Approach
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Energies
Volume 17
Issue 17
10.3390/en17174356
energies-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Scalable Ni12P5-Coated Carbon Cloth Cathode for Lithium–Sulfur Batteries

by
Artur M. Suzanowicz
1,
Thulitha M. Abeywickrama
1,
Hao Lin
1,2,
Dana Alramahi
1,2,
Carlo U. Segre
2,3 and
Braja K. Mandal
1,*
1
Department of Chemistry, Illinois Institute of Technology, Chicago, IL 60616, USA
2
Center for Synchrotron Radiation Research and Instrumentation, Illinois Institute of Technology, Chicago, IL 60616, USA
3
Department of Physics, Illinois Institute of Technology, Chicago, IL 60616, USA
*
Author to whom correspondence should be addressed.
Energies 2024, 17(17), 4356; https://doi.org/10.3390/en17174356
Submission received: 21 June 2024 / Revised: 3 August 2024 / Accepted: 29 August 2024 / Published: 31 August 2024
(This article belongs to the Section D2: Electrochem: Batteries, Fuel Cells, Capacitors)
Browse Figures
Versions Notes

Abstract

:
As a better alternative to lithium-ion batteries (LIBs), lithium–sulfur batteries (LSBs) stand out because of their multi-electron redox reactions and high theoretical specific capacity (1675 mA h g−1). However, the long-term stability of LSBs and their commercialization are significantly compromised by the inherently irreversible transition of soluble lithium polysulfides (LiPS) into solid short-chain S species (Li2S2 and Li2S) and the resulting substantial density change in S. To address these issues, we used activated carbon cloth (ACC) coated with Ni12P5 as a porous, conductive, and scalable sulfur host material for LSBs. ACC has the benefit of high electrical conductivity, high surface area, and a three-dimensional (3D) porous architecture, allowing for ion transport channels and void spaces for the volume expansion of S upon lithiation. Ni12P5 accelerates the breakdown of Li2S to increase the efficiency of active materials and trap soluble polysulfides. The highly effective Ni12P5 electrocatalyst supported on ACC drastically reduced the severity of the LiPS shuttle, affected the abundance of adsorption–diffusion–conversion interfaces, and demonstrated outstanding performance. Our cells achieved near theoretical capacity (>1611 mA h g−1) during initial cycling and superior capacity retention (87%) for >250 cycles following stabilization with a 0.05% decay rate per cycle at 0.2 C.

1. Introduction

Lithium–sulfur batteries (LSBs) are potential substitutes for lithium-ion batteries (LIBs) because of their impressive theoretical specific capacity (1675 mA h g−1) and energy density (2600 Wh kg−1), which far surpass the limited energy storage capabilities of LIBs (~300 mA h g−1 and 240 Wh kg−1, respectively) [1,2,3]. Elemental sulfur is a cost-effective option, with a price of USD 150 per ton, compared to approximately USD 10,000 per ton for LiCoO2. It is also widely available and environmentally friendly, unlike cathode materials used in lithium-ion batteries [4]. Although LIB technology is widely recognized for its documented capacity retention, LSB technology lacks the same level of understanding and established track record. The effective commercialization of LSBs relies on the resolution of three primary difficulties. The primary difficulty lies in the ongoing depletion of active material from the cathode due to the movement of electrolyte-soluble lithium polysulfide (LiPS) intermediates (Li2Sx, 4 ≤ x < 8), as well as the accumulation of non-recoverable Li2S and Li2S2 on the cathode surface. The “polysulfide shuttle” (PSS) effect refers to a troublesome phenomenon that reduces the number of electrochemical reaction sites and leads to a decline in capacity [5]. Furthermore, both elemental sulfur and the reduced/discharged product Li2S have low electronic conductivity. For example, sulfur has an electrical conductivity of 10−15 S/m [6]. The third concern is the substantial increase and decrease in volume that occur throughout the process of sulfur reduction and oxidation. Sulfur undergoes approximately 80% expansion during discharge (lithiation) and contraction during charge (delithiation) as a result of the lower density of Li2S (1.66 g cm3 compared to sulfur’s 2.03 g cm3) [1,2,7].
In order to tackle the PSS problem, our lab has investigated many resistive materials, including MnO2, g-C3N4, TiO2, and AlF3. These chemicals mitigate the effects of PSS by forming chemical bonds with polysulfides, hence improving the long-term stability of cycling. Occasionally, they have yielded favorable outcomes, with a 10% to 30% increase in capacity and over 20% capacity retention compared to cathodes without PSS resistive materials [1,2,8,9]. One example is the adsorption of polysulfides by MnO2 through surface chemical trapping mechanisms. In this process, soluble polysulfides are converted into insoluble thiosulfate species on the surface of MnO2 by oxidation [2]. Graphitic carbon nitride (g-C3N4), with its abundant nitrogen content, provides active sites for the attachment of polysulfides and facilitates the catalytic conversion of lithium polysulfides through graphene [10]. TiOx has unsaturated Ti-centers that form strong Lewis acid-based interactions to anchor polysulfides [11]. AlF3 has significant polarity and electronegativity as a result of the presence of fluorine. This property allows it to effectively hinder the dissolution of polysulfides by chemical bonding and generate strong polar anchoring effects. Consequently, it enhances the chemisorption of lithium polysulfides [12].
In order to enhance the conductivity of sulfur and maximize its capacity, it is necessary to reduce the particle size of sulfur to the nanoscale. Nanomaterials often possess a diameter that is less than 100 nm. The characteristics of the objects vary considerably compared to larger objects because of their high-surface-area-to-volume ratio and potential quantum effects [13]. Decreasing the dimensions of the active particles from micrometers to nanometers reduces resistance by enhancing the contact area between ionic species. It reduces the time for dissemination by a factor of 106 [14]. In recent decades, different methods of nanofabrication have been used to address the issue of sulfur’s insulating qualities by including carbonaceous conductive elements [15]. For instance, extensive research has been conducted on porous carbon materials such as high-surface-area carbons (HSACs), multi-walled carbon nanotubes (CNTs), and reduced graphene oxides (rGOs) due to their capacity to contain sulfur and improve conductivity. These materials possess adjustable pore sizes that can be tailored to achieve certain results, including micro-, meso-, or macropores, with diameters less than 2 nm, ranging from 2 nm to 50 nm, and above 50 nm, respectively [16].
The fluctuations in volume of S during reduction and oxidation lead to the fragmentation of active materials, resulting in the undesired rapid deterioration of capacity. One often used approach to deal with volume expansion is to utilize a carbonaceous material with a high specific surface area (SSA) and high porosity as the host for sulfur [1]. Carbon is a cost-effective material that is lightweight and capable of maintaining a close electrical connection with sulfur. Greater surface area and pore capacity result in improved interaction between the active material and higher sulfur loading [8].
In addition, the carbon structure has the ability to physically trap polysulfides and prevent them from diffusing outwards, while still enabling the movement of Li+ ions in and out if the pores have a diameter of up to 0.9 nm [9,17,18]. Conversely, it can be readily obstructed if the pore diameter is not large enough. Moreover, an inadequate pore capacity will restrict the quantity of sulfur that can be integrated into the carbon host, leading to the formation of a sulfur layer on the external surface [7]. Under these circumstances, the electrically conductive carbon matrix will be divided by an insulating sulfur layer, resulting in internal resistance and the reduced speed of redox processes [1]. If a high pore volume host is partially filled with sulfur, it can theoretically tolerate the volume expansion of sulfur while still physically trapping LiPS intermediates [1,12]. Hence, it is imperative to have an adequate amount of pore space in order to accommodate the substantial alterations in sulfur volume that occur during charge/discharge cycles, thus preventing any harm to the structural integrity of the host material [9]. In addition, porosity facilitates effective electrolyte penetration by necessitating the presence of surplus electrolytes to occupy the pores and establish interconnected channels for the transfer of Li+ ions across particles [10].
Carbon cloth (CC), composed of amorphous carbon fibers with varying sizes, presents a superior option compared to the previously described carbon forms. More precisely, it possesses the advantages of being simple and scalable because it does not necessitate nano-synthesis, rendering it appropriate for industrial manufacturing [18,19,20,21,22]. Moreover, it exhibits excellent electrical conductivity and flexibility, allowing for the movement of ions and giving sufficient empty space for the expansion of sulfur during the process of lithiation. When CC is activated, it has a significant surface area and a three-dimensional microporous structure, which enables sufficient loading of sulfur and active material [23]. Tian et al. employed molybdenum-doped CC. The cathodes were fabricated by growing MoS2 nanosheets on carbon cloth using a hydrothermal method, and then subjecting them to a two-step melt diffusion procedure. After 10 cycles, the Coulombic efficiency showed a significant improvement compared to the control cells, and the cyclic voltammetry (CV) scans exhibited excellent stability, with the peaks overlapping perfectly. SEM testing confirmed that the polar nanosheets effectively facilitated the permeation of sulfur and exhibited a robust adsorption action that suppressed the PSS. Furthermore, it was shown that the polysulfides formed connections with the carbon fibers after 300 cycles, suggesting that CC has the potential to serve as a very effective current collector [24].
Transition-metal phosphides are currently generating significant scientific attention due to their unique semiconducting properties and possible applications in domains such as electricity, catalysis, and magnetism [25]. Ni12P5 is a highly efficient catalyst for the breakdown of Li2S, leading to the enhanced usage of active materials [26,27]. In addition, Ni12P5 exhibits excellent conductivity as a result of its lack of band-gap energy, enabling efficient electron transmission and enhancing the rate performance and reversible capacity of Li+ [28]. Liu et al. synthesized Ni12P5 nanoparticles on a reduced graphene oxide framework using a self-template and recrystallization-self-assembly method. The researchers discovered that the Ni12P5 nanoparticles acted as active sites, enhancing the speed of the sulfur redox reaction and effectively capturing polysulfides by polar contact when applied to the separator. When subjected to a current density of 1 C for 500 cycles, the system exhibited excellent cycling stability and experienced a capacity loss of only 0.074% per cycle [27].
In this study, we present a simple technique for activating CC and performing a two-step synthesis of Ni12P5 from Ni(OH)2. We employed carbon cloth as the sulfur host and applied a coating of Ni12P5 to create (S@ACC@Ni12P5). The unique cathode structure we developed provides an interconnected three-dimensional porous architecture for loading active materials [18]. Ni12P5 may effectively capture soluble polysulfides by polar interactions [26,27]. This simple design can also be expanded for large-scale production.

2. Experimental Section

2.1. Materials

Na2S2O3, KCl, NiSO4·6H2O, K2S2O8, NH4OH, MeOH, NaH2PO2·H2O, and sublimed sulfur (~100 mesh, 99.5%) were purchased from Alfa Aesar (Haverhill, MA, USA). Carbon cloth was purchased from MSE Supplies (Tucson, AZ, USA). All reagents were used as received without further purification.

2.2. Activation of CC and Preparation of ACC@Ni(OH)2

Carbon cloth was soaked in an aqueous solution containing 1:1 wt.% of Na2S2O3 and KCl, pyrolyzed at 800 °C under Ar, followed by a wash in DI/MeOH and overnight drying at 80 °C. One eq. of NiSO4·6H2O and 0.2 eq. of K2S2O8 were dissolved in 40 mL of H2O and 5 mL of NH4OH. ACC was submerged in the solution and left undisturbed for 2 h, followed by a DI/MeOH wash and overnight drying at 80 °C, gaining 10.46 wt.% of Ni(OH)2.

2.3. Preparation of ACC@Ni12P5 and S@ACC@Ni12P5

ACC@Ni(OH)2 was placed over glass wool and 0.5 g of NaH2PO2·H2O in a ceramic boat and heated under Ar at 300 °C for 2 h to make ACC@Ni12P5, followed by sulfur infiltration at 155 °C for 12 h under Ar.

2.4. Characterization

The identification of active substances was conducted through the utilization of scanning electron microscopy (SEM) and X-ray diffraction (XRD). A scanning electron microscope (SEM) was utilized, namely, the JEOL JSM-5900LV model (Joel USA, Peabody, MA, USA). The X-ray diffraction (XRD) patterns of ACC@Ni(OH)2 and ACC@Ni12P5 materials were collected using a Rigaku ATX-G instrument (Rigaku Instruments, The Woodlands, TX, USA). The measurements were performed in Bragg–Brentano geometry, with Cu Kα1 radiation. The scanning parameters included a step size of 0.05° and a scan rate of 2°/min, covering a range of 10–80°. The XRD measurements were conducted at an X-ray tube voltage of 50 kV and a current of 240 mA.
The sulfur content of the cathode samples was determined using thermogravimetric analysis (TGA) using a Mettler Toledo TGA2 instrument. The material was heated from ambient temperature to 600 °C at a rate of 10 °C per minute, while a constant flow of N2 gas was maintained. The galvanostatic charge–discharge test was conducted utilizing the Neware battery testing system within a potential range of 1.7–2.8 V compared to Li+/Li.

2.5. Electrochemical Measurements

Slurries with high viscosity were created by combining 80% by weight of active material, 10% by weight of Super P carbon, and 10% by weight of polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP). The liquid was vigorously stirred using a vortex mixer for the whole duration of the night. The cathode composite film was applied onto Al foil, which functioned as the cathode current collector. The foil that had been covered with a layer of material was subjected to a drying process for a duration of one night at a temperature of 60 °C. Once the cathodes were dried, they were divided into disks measuring 7/16″ (1.11 cm) in diameter. The weight of the active substance (sulfur) in the composite film ranged from 0.95 to 1.5 mg/cm2. In order to assess the electrochemical capabilities of our cathode, we created CR2032-type coin cells. These cells were produced in a glove box filled with Ar gas, ensuring that the O2 level was less than 1 part per million. The cells consisted of a Li metal chip serving as both the counter and reference electrode, with a Celgard® (Celgard, LLC, Charlotte, NC, USA) porous membrane acting as the separator. Each cell was supplemented with 40 μL of electrolyte solution containing a 1 M concentration of lithium bis (trifluoromethane sulfonyl)imide salt (LiTFSI) in a 1:1 volume ratio of 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL), along with 2 wt% of LiNO3. The cells were constructed within an environment containing less than 1 part per million of O2, utilizing a glove box filled with Ar gas.

3. Results and Discussion

Figure 1 illustrates the schematic depiction of the synthesis procedure for obtaining S@ACC@Ni12P5, as stated in the experimental section. The activation of CC involved the use of Na2S2O3. as the activating agent, along with the use of KCl to help control the process. The activation process develops porosity (micropores and mesopores) in the fibers of the cloth by etching carbon. Sodium thiosulfate decomposes to sodium sulfate, which reacts with carbon at a high temperature to create porous structures. The potassium chloride seems to contribute to the widening of the pores, a significant increase in carbon yield, and superior textural properties by providing an ionic medium that can enhance the interaction between thiosulfate and carbon [15].
4Na2S2O3 → 3Na2SO4 + Na2S5
Na2SO4 + 4C → Na2S + 4CO
The cloth was subjected to heat treatment in an atmosphere of Ar gas at a temperature of 800 °C for a duration of 2 h, which led to the formation of a cloth with a porous structure made of carbon. The process of applying a conformal coating of Ni(OH)2 onto ACC was performed in situ by immersing the fabric in a solution containing NiSO4, K2S2O8, and NH4OH. K2S2O8 oxidizes Ni2+ to Ni3+ where it then reacts with NH4OH to make Ni(OH)2 [29].
2Ni2+ + S2O82− → 2Ni3+ + 2SO42−
2Ni3+ + 6NH4OH → 2Ni(OH)3 + 6NH4+
2Ni(OH)3 → 2Ni(OH)2 + H2O + O2
In order to create the ultimate nickel-rich phosphide host material, we utilized NaH2PO2 as the phosphine gas source and ACC@Ni(OH)2 as the Ni2+ source. We then subjected the mixture to thermal reaction under an Ar atmosphere at a temperature of 300 °C, resulting in the conversion to Ni12P5 through the phosphorization of Ni by phosphine resulting from sodium hypophoshite.
2NaH2PO2 → Na2HPO4 + PH3
12Ni + 5PH3 → Ni12P5 + 7.5H2
The last stage involved the incorporation of elemental sulfur into ACC@Ni12P5 via the widely used melt-diffusion method, resulting in the formation of S@ACC@Ni12P5.
Figure 2 displays the SEM images of powdered ACC@Ni12P5 at various stages of production. SEM pictures revealed no discernible variations at the micron scale among ACC, ACC@Ni(OH)2, and ACC@Ni12P5 after each consecutive chemical modification step. However, as elaborated in the publication, X-ray diffraction (XRD) provided more comprehensive insights into the alterations occurring when the activated carbon cloth (ACC) initially underwent a reaction with Ni(OH)2 and subsequently formed a bond with Ni12P5 (Figure 3).
Figure 3 illustrates the XRD patterns of ACC@Ni12P5 and ACC@Ni(OH)2. The X-ray diffraction (XRD) pattern of ACC@Ni(OH)2 (represented by the blue line) exhibits prominent peaks at 19, 33, 38, and 51.5°, which correspond to the diffraction from the (001), (100), (101), and (102) crystal planes, respectively. These peaks indicate a strong similarity with the XRD pattern of Ni(OH)2, which has a trigonal crystal structure and belongs to the P-3m1 space group. The XRD pattern of Ni(OH)2 used for comparison is documented in the ICDD PDF card number 00-014-0117. Moreover, every peak detected in the XRD pattern of ACC@Ni12P5 exhibited a perfect correspondence with the tetragonal crystal structure of Ni12P5 (ICDD PDF card number 04-007-1033) and the I4/m space group. This suggests that the conversion of Ni(OH)2 into Ni12P5 was fully achieved during the phosphination process utilizing NaH2PO2·H2O and PH3. The prominent peak detected at an angle of 29° in both samples is indicative of the presence of activated carbon cloth (ACC).
Figure 4 depicts the extended cycling and coulombic efficiency of the S@ACC@Ni12P5 carbon cloth electrode material at a rate of 0.2 C for a total of 350 cycles. The cathode material was expected to have a sulfur concentration of 70 wt.%. All specific capacities were adjusted to account for the sulfur level, with 1 C equal to 1675 mA h g−1. The initial discharge capacity was approximately 1610 mA h g−1, which is almost 99% of sulfur’s theoretical capability. Nevertheless, the duration of this phenomenon was brief and experienced a substantial decrease to approximately 635 mA h g−1, ultimately stabilizing after around 100 cycles. Nevertheless, throughout the course of more than 350 cycles, the cells consistently retained over 80% of their original capacity, ultimately reaching a value of approximately 515 mA h g−1. It is important to highlight that the majority of LSB investigations have observed a significant decrease following the initial cycle [15,29,30]. The rapid and irreversible deterioration of capacity occurs due to the incomplete formation of a strong solid–electrolyte interface (SEI) layer in the initial cycles, giving rise to fast capacity fading. Numerous Li-S battery studies have displayed comparable performance [31,32,33]. Furthermore, as a result of sulfur spillover from the cathode region, S is no longer available for the electrochemical reactions needed to produce energy. This results in a direct loss of capacity [34]. In addition, agglomeration results in specific sulfur particles that have not yet undergone complete activation to engage in the lithiation/delithiation reaction [31].
Figure 5 presents the rate capacity of the S@ACC@Ni12P5 carbon cloth at various rates, including 0.2 C, 0.5 C, 1 C, 2 C, and 3 C, followed by a return to 0.2 C. Every individual cell underwent 10 cycles while operating at the specified current density. The cathode made of S@ACC@Ni12P5 achieved an initial specific capacity of approximately 1662 mA h g−1 at a rate of 0.2 C. Following the initial cycles, the cell reached a stable state with a capacity of approximately 581 mA h g−1. As the current rate was progressively raised from 0.5 C to 1 C, 2 C, and 3 C, the specific discharge capacities exhibited a decline as the current density grew. At a C-rate of 0.2 C, the cathode material showed a reversible capacity of around 560 mA h g−1, demonstrating its great reversibility and resilience. It was able to regain more than 96% of its prior capacity.

4. Conclusions

We have effectively produced a sulfur cathode for lithium–sulfur batteries by coating a carbon cloth with Ni12P5. The porous carbon fabric allowed for ample accommodation of the substantial fluctuations in sulfur volume during the charge and discharge cycles. The transition metal phosphide efficiently immobilized soluble polysulfides and effectively promoted the breakdown of Li2S, thereby enhancing the usage of active materials. Due to its improved performance, our cathode material has the potential to attain theoretical capacity and is suitable for large-scale production. This makes it an attractive option for the commercialization of lithium–sulfur batteries. The Ni12P5 electrocatalyst, when supported on activated carbon cloth, effectively mitigated the negative impacts of the LiPS shuttle, enhanced the interfaces for adsorption, diffusion, and conversion, and demonstrated outstanding performance. Following stabilization, the S@ACC@Ni12P5 cell had a 0.05% decay rate per cycle at 0.2 C after obtaining near-theoretical capacity (>1611 mA h g−1) during initial cycling.

Author Contributions

A.M.S.: methodology, conceptualization, characterization, and writing—original draft; T.M.A.: characterization; H.L.: cell fabrication and cell testing; D.A.: cell fabrication and cell testing. C.U.S.: data interpretation, writing—review and editing, and supervision; B.K.M.: methodology, conceptualization, writing—review and editing, and supervision. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Data are contained within the article.

Acknowledgments

We thank the Wanger Institute for Sustainable Energy Research (WISER# 6-1-22) Foundation for the partial financial support of this research work.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Ashuri, M.; Dunya, H.; Yue, Z.; Alramahi, D.; Mei, X.; Kucuk, K.; Aryal, S.; Segre, C.U.; Mandal, B.K. Enhancement in Electrochemical Performance of Lithium-Sulfur Cells through Sulfur Encapsulation in Hollow Carbon Nanospheres Coated with Ultra-Thin Aluminum Fluoride Layer. ChemistrySelect 2019, 4, 12622–12629. [Google Scholar] [CrossRef]
  2. Dunya, H.; Ashuri, M.; Alramahi, D.; Yue, Z.; Kucuk, K.; Segre, C.U.; Mandal, B.K. MnO2-Coated Dual Core–Shell Spindle-Like Nanorods for Improved Capacity Retention of Lithium–Sulfur Batteries. ChemEngineering 2020, 4, 42. [Google Scholar] [CrossRef]
  3. Ye, H.; Li, M.; Liu, T.; Li, Y.; Lu, J. Activating Li2S as the Lithium-Containing Cathode in Lithium–Sulfur Batteries. ACS Energy Lett. 2020, 5, 2234–2245. [Google Scholar] [CrossRef]
  4. Pang, Q.; Shyamsunder, A.; Narayanan, B.; Kwok, C.Y.; Curtiss, L.A.; Nazar, L.F. Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li–S batteries. Nat. Energy 2018, 3, 783–791. [Google Scholar] [CrossRef]
  5. Yan, J.; Liu, X.; Li, B. Capacity fade analysis of sulfur cathodes in lithium–sulfur batteries. Adv. Sci. 2016, 3, 101. [Google Scholar] [CrossRef] [PubMed]
  6. Periodictable.com. Available online: https://periodictable.com/Elements/016/data.html (accessed on 5 January 2021).
  7. Yue, Z.; Dunya, H.; Kucuk, K.; Aryal, S.; Ma, Q.; Antonov, S.; Ashuri, M.; Alabbad, B.; Lin, Y.; Segre, C.U.; et al. MnO2-Coated Sulfur-Filled Hollow Carbon Nanosphere-Based Cathode Materials for Enhancing Electrochemical Performance of Li-S Cells. J. Electrochem. Soc. 2019, 166, A1355–A1362. [Google Scholar] [CrossRef]
  8. Dunya, H.; Ashuri, M.; Yue, Z.; Kucuk, K.; Lin, Y.; Alramahi, D.; Segre, C.U.; Mandal, B.K. Rational design of titanium oxide-coated dual Core–Shell sulfur nanocomposite cathode for highly stable lithium–sulfur batteries. J. Phys. Chem. Solids 2021, 149, 109791. [Google Scholar] [CrossRef]
  9. Dunya, H.; Yue, Z.; Ashuri, M.; Mei, X.; Lin, Y.; Kucuk, K.; Aryal, S.; Segre, C.U.; Mandal, B.K. A new graphitic carbon nitride-coated dual Core–Shell sulfur cathode for highly stable lithium–sulfur cells. Mater. Chem. Phys. 2020, 246, 122842. [Google Scholar] [CrossRef]
  10. Wang, M.; Liang, Q.; Han, J.; Tao, Y.; Liu, D.; Zhang, C.; Lv, W.; Yang, Q.H. Catalyzing polysulfide conversion by g-C3N4 in a graphene network for long-life lithium-sulfur batteries. Nano Res. 2018, 11, 3480–3489. [Google Scholar] [CrossRef]
  11. Wang, R.; Wang, K.; Tao, H.; Zhao, W.; Jiang, M.; Yan, J.; Jiang, K. Controllable electrolytic formation of Ti2O as an efficient sulfur host in lithium-sulfur (Li-S) batteries. J. Mater. Chem. A 2020, 8, 11224–11232. [Google Scholar] [CrossRef]
  12. Luo, Z.; Lei, W.; Wang, X.; Pan, J.; Pan, Y.; Xia, S. AlF3 coating as sulfur immobilizers in cathode material for high performance lithium-sulfur batteries. J. Alloys Compd. 2020, 812, 152132. [Google Scholar] [CrossRef]
  13. Wang, X.-Y.; Narita, A.; Müllen, K. Precision synthesis versus bulk-scale fabrication of graphenes. Nat. Rev. Chem. 2018, 2, 100. [Google Scholar] [CrossRef]
  14. Julien, C.M.; Mauger, A. Nanostructured MnO2 as electrode materials for energy storage. Nanomaterials 2017, 7, 396. [Google Scholar] [CrossRef] [PubMed]
  15. Fuertes, A.B.; Ferrero, G.A.; Diez, N.; Sevilla, M. A Green Route to High-Surface Area Carbons by Chemical Activation of Biomass-Based Products with Sodium Thiosulfate. ACS Sustain. Chem. Eng. 2018, 6, 16323–16331. [Google Scholar] [CrossRef]
  16. Knoop, J.E.; Ahn, S. Review recent advances in nanomaterials for high-performance Li–S batteries. J. Energy Chem. 2020, 47, 86–106. [Google Scholar] [CrossRef]
  17. Peng, B.; Xu, Y.; Wang, X.; Shi, X.; Mulder, F.M. The electrochemical performance of super P carbon black in reversible Li/Na ion uptake. Sci. China Phys. Mech. Astron. 2017, 60, 064611. [Google Scholar] [CrossRef]
  18. Fu, Y.; Hu, J.; Wang, Q.; Lin, D.; Li, K.; Zhou, L. Thermally etched porous carbon cloth catalyzed by metal organic frameworks as sulfur hosts for lithium–sulfur batteries. Carbon 2019, 150, 76–84. [Google Scholar] [CrossRef]
  19. Dong, C.; Gao, W.; Jin, B.; Jiang, Q. Advances in Cathode Materials for High-Performance Lithium-Sulfur Batteries. iScience 2018, 6, 151–198. [Google Scholar] [CrossRef]
  20. Song, M.K.; Zhang, Y.; Cairns, E.J. A long-life, high-rate lithium/sulfur cell: A multifaceted approach to enhancing cell performance. Nano Lett. 2013, 13, 5891–5899. [Google Scholar] [CrossRef]
  21. Xu, F.; Tang, Z.; Huang, S.; Chen, L.; Liang, Y.; Mai, W.; Zhong, H.; Fu, R.; Wu, D. Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage. Nat. Commun. 2015, 6, 7221. [Google Scholar] [CrossRef]
  22. Cho, I.; Choi, J.; Kim, K.; Ryou, M.H.; Lee, Y.M. A comparative investigation of carbon black (Super-P) and vapor-grown carbon fibers (VGCFs) as conductive additives for lithium-ion battery cathodes. RSC Adv. 2015, 5, 95073–95078. [Google Scholar] [CrossRef]
  23. Song, J.-Y.; Lee, H.-H.; Hong, W.G.; Huh, Y.S.; Lee, Y.S.; Kim, H.J.; Jun, Y.-S. A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium–Sulfur Batteries. Nanomaterials 2018, 8, 90. [Google Scholar] [CrossRef] [PubMed]
  24. Tian, C.; Wu, J.; Ma, Z.; Li, B.; Zhang, X.; Zu, X.; Xiang, X.; Li, S. A melt diffusion strategy for tunable sulfur loading on CC@MoS2 for lithium–sulfur batteries. Energy Rep. 2020, 6, 172–180. [Google Scholar] [CrossRef]
  25. Ni, Y.; Liao, K.; Li, J. In situ template route for synthesis of porous Ni12P5 superstructures and their applications in environmental treatments. CrystEngComm 2010, 12, 1568–1575. [Google Scholar] [CrossRef]
  26. Yuan, H.; Chen, X.; Zhou, G.; Zhang, W.; Luo, J.; Huang, H.; Gan, Y.; Liang, C.; Xia, Y.; Zhang, J.; et al. Efficient Activation of Li2S by Transition Metal Phosphides Nanoparticles for Highly Stable Lithium-Sulfur Batteries. ACS Energy Lett. 2017, 2, 1711–1719. [Google Scholar] [CrossRef]
  27. Liu, G.; Zhang, Z.; Tian, W.; Chen, W.; Xi, B.; Li, H.; Feng, J.; Xiong, S. Ni12P5 nanoparticles bound on graphene sheets for advanced lithium-sulfur batteries. Nanoscale 2020, 12, 10760–10770. [Google Scholar] [CrossRef]
  28. Gan, Y.; Wang, C.; Chen, X.; Liang, P.; Wan, H.; Liu, X.; Tan, Q.; Wu, H.; Rao, H.; Wang, H.; et al. High conductivity Ni12P5 nanowires as high-rate electrode material for battery-supercapacitor hybrid devices. Chem. Eng. J. 2020, 392, 123661. [Google Scholar] [CrossRef]
  29. Mandal, S.; Bera, T.; Dubey, G.; Saha, J.; Laha, J.K. Uses of K2S2O8 in Metal-Catalyzed and Metal-Free Oxidative Transformations. ACS Catal. 2018, 8, 5085–5144. [Google Scholar] [CrossRef]
  30. Liu, Z.; Huang, X.; Zhu, Z.; Dai, J. A simple mild hydrothermal route for the synthesis of nickel phosphide powders. Ceram. Int. 2010, 36, 1155–1158. [Google Scholar] [CrossRef]
  31. Li, Q.; Liu, J.; Bai, A.; Li, P.; Li, J.; Zhang, X.; Yu, M.; Wang, J.; Sun, H. Preparation of a Nitrogen-Doped Reduced Graphene Oxide-Modified Graphite Felt Electrode for VO2+/VO2+ Reaction by Freeze-Drying and Pyrolysis Method. J. Chem. 2019, 2019, 8958946. [Google Scholar] [CrossRef]
  32. Chen, L.; Liu, Y.; Zhang, F.; Liu, C.; Shaw, L.L. PVP-Assisted Synthesis of Uniform Carbon Coated Li2S/CB for High-Performance Lithium–Sulfur Batteries. ACS Appl. Mater. Interfaces 2015, 7, 25748–25756. [Google Scholar] [CrossRef] [PubMed]
  33. Wang, S.; Yang, Z.; Zhang, H.; Tan, H.; Yu, J.; Wu, J. Mesoporous β-MnO2/sulfur composite as cathode material for Li–S batteries. Electrochim. Acta 2013, 106, 307–311. [Google Scholar] [CrossRef]
  34. Medenbach, L.; Escher, I.; Köwitsch, N.; Armbrüster, M.; Zedler, L.; Dietzek, B.; Adelhelm, P. Sulfur Spillover on Carbon Materials and Possible Impacts on Metal–Sulfur Batteries. Angew. Chem. Int. Ed. 2018, 57, 13666–13670. [Google Scholar] [CrossRef] [PubMed]
Energies 17 04356 g001
Figure 1. Synthetic scheme for S@ACC@Ni12P5.
Figure 1. Synthetic scheme for S@ACC@Ni12P5.
Energies 17 04356 g001
Energies 17 04356 g002
Figure 2. SEM images of (A) activated carbon cloth (ACC), (B) ACC@Ni(OH)2, and (C) ACC@Ni12P5.
Figure 2. SEM images of (A) activated carbon cloth (ACC), (B) ACC@Ni(OH)2, and (C) ACC@Ni12P5.
Energies 17 04356 g002
Energies 17 04356 g003
Figure 3. X-ray diffraction (XRD) patterns for ACC@Ni(OH)2 (shown in blue) and ACC@Ni12P5 (shown in red).
Figure 3. X-ray diffraction (XRD) patterns for ACC@Ni(OH)2 (shown in blue) and ACC@Ni12P5 (shown in red).
Energies 17 04356 g003
Energies 17 04356 g004
Figure 4. Long-term discharge capacity and Coulombic efficiency of S@ACC@Ni12P5 at 0.2 C for 350 cycles.
Figure 4. Long-term discharge capacity and Coulombic efficiency of S@ACC@Ni12P5 at 0.2 C for 350 cycles.
Energies 17 04356 g004
Energies 17 04356 g005
Figure 5. Rate capabilities of S@ACC@Ni12P5 at different rates.
Figure 5. Rate capabilities of S@ACC@Ni12P5 at different rates.
Energies 17 04356 g005
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Suzanowicz, A.M.; Abeywickrama, T.M.; Lin, H.; Alramahi, D.; Segre, C.U.; Mandal, B.K. Scalable Ni12P5-Coated Carbon Cloth Cathode for Lithium–Sulfur Batteries. Energies 2024, 17, 4356. https://doi.org/10.3390/en17174356

AMA Style

Suzanowicz AM, Abeywickrama TM, Lin H, Alramahi D, Segre CU, Mandal BK. Scalable Ni12P5-Coated Carbon Cloth Cathode for Lithium–Sulfur Batteries. Energies. 2024; 17(17):4356. https://doi.org/10.3390/en17174356

Chicago/Turabian Style

Suzanowicz, Artur M., Thulitha M. Abeywickrama, Hao Lin, Dana Alramahi, Carlo U. Segre, and Braja K. Mandal. 2024. "Scalable Ni12P5-Coated Carbon Cloth Cathode for Lithium–Sulfur Batteries" Energies 17, no. 17: 4356. https://doi.org/10.3390/en17174356

APA Style

Suzanowicz, A. M., Abeywickrama, T. M., Lin, H., Alramahi, D., Segre, C. U., & Mandal, B. K. (2024). Scalable Ni12P5-Coated Carbon Cloth Cathode for Lithium–Sulfur Batteries. Energies, 17(17), 4356. https://doi.org/10.3390/en17174356

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop