High energy density lithium–sulfur batteries (LSBs) are a potential replacement for lithium-ion batteries (LIBs). However, practical lifetimes are inhibited by lithium polysulfide (LiPS) shuttling. Concurrently, plastic waste accumulation worldwide threatens our ecosystems. Herein, a fast and facile strategy to upcycle polyethylene terephthalate (PET) waste into useful materials is investigated. Dilithium terephthalate (Li2TP) and dipotassium terephthalate (K2TP) salts were synthesized from waste soda bottles via microwave depolymerization and solution coated onto glass fiber paper (GFP) separators. Salt-functionalized separators with Li2TP@GFP and K2TP@GFP mitigated LiPS shuttling and improved electrochemical performance in cells. Pore analysis and density functional theory (DFT) calculations indicate the action mechanism is synergistic physical blocking of bulky LiPS anions in nanopores and diffusion inhibition via electrostatic interactions with abundant carboxylate groups. LSBs with K2TP@GFP separator showing highest LiPS affinity and smallest pore size demonstrated enhanced initial capacity as compared to non-modified GFP by 5.4% to 648 mAh g−1, and increased cycle 100 capacity by 23% to 551 mAh g−1. Overall, K2TP@GFP retained 85% of initial capacity after 100 cycles with an average capacity fading of 0.15% per cycle. By comparison, GFP retained only 73% of initial capacity after 100 cycles with 0.27% average capacity loss, demonstrating effective LiPS retention.
more »
« less
High Specific Capacity of Lithium–Sulfur Batteries with Carbon Black/Chitosan- and Carbon Black/Polyvinylidene Fluoride-Coated Separators
In this research, the shuttle effect and the low sulfur activation of lithium–sulfur batteries were mitigated by coating the cathode side of Celgard 2400 separators with mixtures of carbon black/chitosan or carbon black/polyvinylidene fluoride using the simple slurry technique. Carbon nanoparticles and the polar groups of the polymers were responsible for boosting the reaction kinetics of sulfur and the chemical and physical trapping of lithium polysulfides. The adsorption of sulfur species in the coated separators was confirmed by the morphologic changes observed in the AFM and SEM images and by the new elements presented in the EDX spectra after 100 charge/discharge cycles. The high intensity of the peaks in the cyclic voltammograms and the long plateaus in the discharge profiles support the improvement in the reaction kinetics. The batteries with the carbon black/chitosan- and carbon black/polyvinylidene fluoride-coated separators reached high specific discharge capacities of 833 and 698 mAhg−1, respectively, after 100 cycles at 0.5 C. This is promising for this kind of technology, and detailed results are presented in the article.
more »
« less
- Award ID(s):
- 1849243
- PAR ID:
- 10407113
- Date Published:
- Journal Name:
- Energies
- Volume:
- 15
- Issue:
- 6
- ISSN:
- 1996-1073
- Page Range / eLocation ID:
- 2183
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Lithium–sulfur (Li–S) batteries are regarded as one of the most promising next-generation electrochemical cells. However, shuttling of lithium polysulfide intermediates and sluggish kinetics in random deposition of lithium sulfide (Li 2 S) have significantly degraded their capacity, rate and cycling performance. Herein, few-layered MoS 2 nanosheets enriched with sulfur vacancies are anchored inside hollow mesoporous carbon (MoS 2−x /HMC) via S–C bonding and proposed as a novel functional mediator for Li–S batteries. Ultrathin MoS 2 sheets with abundant sulfur vacancies have strong chemical affinity to polysulfides and in the meantime catalyze their fast redox conversion with enhanced reaction kinetics as proved by experimental observations and first-principles density functional theory (DFT) calculations. At a current density of 1C, the MoS 2−x /HMC-S composite cathode exhibits a high initial capacity of 945 mA h g −1 with a high retained capacity of 526 mA h g −1 and a coulombic efficiency of nearly 100% after 500 cycles. The present work sheds light on the design of novel functional electrodes for next-generation electrochemical cells based on a simple yet effective vacancy engineering strategy.more » « less
-
In this study, we are reporting the impact of the incorporation of ferroelectric nanoparticles (FNPs), such as BaTiO3 (BTO), BiFeO3 (BFO), Bi4NdTi3Fe0.7Ni0.3O15 (BNTFN), and Bi4NdTi3Fe0.5Co0.5O15 (BNTFC), as well as the mass loading of sulfur to fabricated solvent-free sulfur/holey graphene-carbon black/polyvinylidene fluoride (S/FNPs/CBhG/PVDF) composite electrodes to achieve high areal capacity for lithium-sulfur (Li-S) batteries. The dry-press method was adopted to fabricate composite cathodes. The hG, a conductive and lightweight scaffold derived from graphene, served as a matrix to host sulfur and FNPs for the fabrication of solvent-free composites. Raman spectra confirmed the dominant hG framework for all the composites, with strong D, G, and 2D bands. The surface morphology of the fabricated cathode system showed a homogeneous distribution of FNPs throughout the composites, confirmed by the EDAX spectra. The observed Li+ ion diffusion coefficient for the composite cathode started at 2.17 × 10−16 cm2/s (S25(CBhG)65PVDF10) and reached up to the highest value (4.15 × 10−15 cm2/s) for S25BNTFC5(CBhG)60PVDF10. The best discharge capacity values for the S25(CBhG)65PVDF10 and S25BNTFC5(CBhG)60PVDF10 composites started at 1123 mAh/gs and 1509 mAh/gs and dropped to 612 mAh/gs and 572 mAh/gs, respectively, after 100 cycles; similar behavior was exhibited by the other composites that were among the best. These are better values than those previously reported in the literature. The incorporation of ferroelectric nanoparticles in the cathodes of Li-S batteries reduced the rapid formation of polysulfides due to their internal electric fields. The areal capacity for the S25(CBhG)65PVDF10 composites was 4.84 mAh/cm2 with a mass loading of 4.31 mgs/cm2, while that for the S25BNTFC5(CBhG)60PVDF10 composites was 6.74 mAh/cm2 with a mass loading of 4.46 mgs/cm2. It was confirmed that effective FNP incorporation within the S cathode improves the cycling response and stability of cathodes, enabling the high performance of Li-S batteries.more » « less
-
Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1more » « less
-
Doron Aurbach (Ed.)Rechargeable Li-CO2 batteries have emerged as promising candidates for next generation batteries due to their low cost, high theoretical capacity, and ability to capture the greenhouse gas CO2. However, these batteries still face challenges such as slow reaction kinetic and short cycle performance due to the accumulation of discharge products. To address this issue, it is necessary to design and develop high efficiency electrocatalysts that can improve CO2 reduction reaction. In this study, we report the use of NiMn2O4 electrocatalysts combined with multiwall carbon nanotubes as a cathode material in the Li-CO2 batteries. This combination proved effective in decomposing discharge products and enhancing cycle performance. The battery shows stable discharge–charge cycles for at least 30 cycles with a high limited capacity of 1000 mAh/g at current density of 100 mA/g. Furthermore, the battery with the NiMn2O4@CNT catalyst exhibits a reversible discharge capacity of 2636 mAh/g. To gain a better understanding of the reaction mechanism of Li-CO2 batteries, spectroscopies and microscopies were employed to identify the chemical composition of the discharge products. This work paves a pathway to increase cycle performance in metal-CO2 batteries, which could have significant implications for energy storage and the reduction of greenhouse gas emissions.more » « less
An official website of the United States government

