The development of high-performance battery technologies necessitates ultrathin separators with superior mechanical strength and electrochemical properties. We present an innovative 1 µm thick, pinhole-free zeolitic imidazolate framework-8 (ZIF-8) layer, cathodically deposited on an 8 µm thick commercial polypropylene (PP) film in a rapid process, resulting in a ZIF-8@8-µm PP flexible membrane. This crack-free ZIF-8 layer, featuring angstrom-scale pores and chemical polar groups, functions as a Li+ sieve, regulating Li+ transport, controlling Li deposition, and blocking dissolved active cathode materials. It also enhances Li+ diffusion and transference number, extending the Sand’s time for Li dendrite formation. Consequently, the ZIF-8@8-µm PP separator addresses polysulfide shuttling in Li-S batteries and Li dendrite formation in Li-metal batteries, significantly improving their performance compared to conventional separators. Our findings indicate that while the 8-μm PP alone is unsuitable as a battery separator, the ZIF-8@8-μm PP, possesses the mechanical strength and electrochemical properties necessary for developing both Li-S and Li-metal batteries, as well as application in conventional Li-ion batteries with enhanced volumetric energy densities. 
                        more » 
                        « less   
                    
                            
                            Polysulfides in Magnesium‐Sulfur Batteries
                        
                    
    
            Abstract Mg‐S batteries hold great promise as a potential alternative to Li‐based technologies. Their further development hinges on solving a few key challenges, including the lower capacity and poorer cycling performance when compared to Li counterparts. At the heart of the issues is the lack of knowledge on polysulfide chemical behaviors in the Mg‐S battery environment. In this Review, a comprehensive overview of the current understanding of polysulfide behaviors in Mg‐S batteries is provided. First, a systematic summary of experimental and computational techniques for polysulfide characterization is provided. Next, conversion pathways for Mg polysulfide species within the battery environment are discussed, highlighting the important role of polysulfide solubility in determining reaction kinetics and overall battery performance. The focus then shifts to the negative effects of polysulfide shuttling on Mg‐S batteries. The authors outline various strategies for achieving an optimal balance between polysulfide solubility and shuttling, including the use of electrolyte additives, polysulfide‐trapping materials, and dual‐functional catalysts. Based on the current understanding, the directions for further advancing knowledge of Mg polysulfide chemistry are identified, emphasizing the integration of experiment with computation as a powerful approach to accelerate the development of Mg‐S battery technology. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 2126923
- PAR ID:
- 10478601
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 36
- Issue:
- 7
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            In Li–S batteries, the insulating nature of sulfur and Li 2 S causes enormous challenges, such as high polarization and low active material utilization. The nucleation of the solid discharge product, Li 2 S, during the discharge cycle, and the activation of Li 2 S in the subsequent charge cycle, cause a potential challenge that needs to be overcome. Moreover, the shuttling of soluble lithium polysulfide intermediate species results in active material loss and early capacity fade. In this study, we have used thiourea as an electrolyte additive and showed that it serves as both a redox mediator to overcome the Li 2 S activation energy barrier and a shuttle inhibitor to mitigate the notorious polysulfide shuttling via the investigation of thiourea redox activity, shuttle current measurements and study of Li 2 S activation. The steady-state shuttle current of the Li–S battery shows a 6-fold drop when 0.02 M thiourea is added to the standard electrolyte. Moreover, by adding thiourea, the charge plateau for the first cycle of the Li 2 S based cathodes shifts from 3.5 V (standard ether electrolyte) to 2.5 V (with 0.2 M thiourea). Using this additive, the capacity of the Li–S battery stabilizes at ∼839 mA h g −1 after 5 cycles and remains stable over 700 cycles with a low capacity decay rate of 0.025% per cycle, a tremendous improvement compared to the reference battery that retains only ∼350 mA h g −1 after 300 cycles. In the end, to demonstrate the practical and broad applicability of thiourea in overcoming sulfur-battery challenges and in eliminating the need for complex electrode design, we study two additional battery systems – lithium metal-free cells with a graphite anode and Li 2 S cathode, and Li–S cells with simple slurry-based cathodes fabricated via blending commercial carbon black/S and a binder. We believe that this study manifests the advantages of redox active electrolyte additives to overcome several bottlenecks in the Li–S battery field.more » « less
- 
            The shuttling of polysulfides with sluggish redox kinetics has severely retarded the advancement of lithium–sulfur (Li–S) batteries. In this work oxygen-deficient titanium dioxide (TiO 2 ) has been investigated as a novel functional host for Li–S batteries. Experimental and first-principles density functional theory (DFT) studies reveal that oxygen vacancies help to reduce polysulfide shuttling and catalyze the redox kinetics of sulfur/polysulfides during cycling. Consequently, the resulting TiO 2 /S composite cathode manifests superior electrochemical properties in terms of high capacity (1472 mA h g −1 at 0.2C), outstanding rate capability (571 mA h g −1 at 2C), and excellent cycling properties (900 mA h g −1 over 100 cycles at 0.2C). The present strategy offers a viable way through vacancy engineering for the design and optimization of high-performance electrodes for advanced Li–S batteries and other electrochemical devices.more » « less
- 
            Abstract Metal‐sulfur batteries are a promising next‐generation energy storage technology, offering high theoretical energy densities with low cost and good sustainability. An active area of research is the development of electrolytes that address unwanted migration of sulfur and intermediate species known as polysulfides during operation of metal‐sulfur batteries, a phenomenon that leads to low energy efficiency and short life‐spans. A particular class of electrolytes, gel polymer electrolytes, are especially attractive for their ability to repel polysulfides on the basis of structure, electrostatics, and other polymer properties. Herein, within the context of magnesium‐ and lithium‐sulfur batteries, we investigate the impact of gel polymer electrolyte cation solvation capacity, a property related to network dielectric constant and chemistry, on sulfur/polysulfide‐polymer interactions, an understudied property‐performance relationship. Polymers with lower cation solvation capacity are found to permanently absorb less polysulfide active material, which increases sulfur utilization for Li−S batteries and significantly increases charge efficiency and life‐span for Li−S and Mg−S batteries.more » « less
- 
            Here we present a 1D model of a Li-Sulfur battery with physically derived geometric parameters and thermodynamically consistent electrochemical kinetics. The approach enables straightforward comparison of proposed Li-S mechanisms and provides insights into the influence of polysulfide intermediates on battery discharge. Comparing predictions from multiple mechanisms demonstrates the need for both lithiated and non-lithiated polysulfide species, and highlights the challenge of developing parameter estimates for complex electrochemical mechanisms. The model is also used to explore cathode design strategies. Discharge performance and polysulfide concentrations for electrolyte/sulfur ratios in the range 2–4μL mg−1identifies trade-offs that limit battery energy and power density, and highlights the risk of polysulfide precipitation. New cathode and electrolyte approaches must limit polysulfide concentrations in the electrolyte, both to unlock better rate capabilities in Li-S technology and to prevent capacity fade due to polysulfide precipitation.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
