Project description:Realizing efficient immobilization of lithium polysulfides (LiPSs) as well as reversible catalytic conversion between LiPSs and the insoluble Li2S is vital to restrain the shuttle effect, which requires highly reactive catalysts for high-performance Li-S batteries. Here, three-dimensional ordered porous Mo-based metal phosphides (3DOP Mo3P/Mo) with heterogeneous structures were fabricated and utilized as separator-modified coatings for Li-S batteries to catalyze the conversion of LiPSs. The adsorption, catalytic and electrochemical performance of the corresponding cells were compared among 3DOP Mo3P/Mo and 3DOP Mo, by kinetic and electrochemical performance measurements. It was found that the cell with 3DOP Mo3P/Mo modified separator deliver better electrochemical performance, with a high specific capacity of 469.66 mAh g-1 after 500 cycles at a high current density of 1°C. This work provides an idea and a guideline for the design of the separator modification for high-performance Li-S batteries.
Project description:Lithium-sulfur batteries are anticipated to be the next generation of energy storage devices because of their high theoretical specific capacity. However, the polysulfide shuttle effect of lithium-sulfur batteries restricts their commercial application. The fundamental reason for this is the sluggish reaction kinetics between polysulfide and lithium sulfide, which causes soluble polysulfide to dissolve into the electrolyte, leading to a shuttle effect and a difficult conversion reaction. Catalytic conversion is considered to be a promising strategy to alleviate the shuttle effect. In this paper, a CoS2-CoSe2 heterostructure with high conductivity and catalytic performance was prepared by in situ sulfurization of CoSe2 nanoribbon. By optimizing the coordination environment and electronic structure of Co, a highly efficient CoS2-CoSe2 catalyst was obtained, to promote the conversion of lithium polysulfides to lithium sulfide. By using the modified separator with CoS2-CoSe2 and graphene, the battery exhibited excellent rate and cycle performance. The capacity remained at 721 mAh g-1 after 350 cycles, at a current density of 0.5 C. This work provides an effective strategy to enhance the catalytic performance of two-dimensional transition-metal selenides by heterostructure engineering.
Project description:We design the Janus-like interlayer with two different functional faces for suppressing the shuttle of soluble lithium polysulfides (LPSs) in lithium-sulfur batteries (LSBs). At the front face, the conductive functionalized carbon fiber paper (f-CFP) having oxygen-containing groups i.e., -OH and -COOH on its surface was placed face to face with the sulfur cathode serving as the first barrier accommodating the volume expansion during cycling process and the oxygen-containing groups can also adsorb the soluble LPSs via lithium bonds. At the back face, a crystalline coordination network of [Zn(H2PO4)2(TzH)2]n (ZnPTz) was coated on the back side of f-CFP serving as the second barrier retarding the left LPSs passing through the front face via both physical confinement and chemical adsorption (i.e. Li bonding). The LSB using the Janus-like interlayer exhibits a high reversible discharge capacity of 1,416 mAh g-1 at 0.1C with a low capacity fading of 0.05% per cycle, 92% capacity retention after 200 cycles and ca. 100% coulombic efficiency. The fully charged LSB cell can practically supply electricity to a spinning motor with a nominal voltage of 3.0 V for 28 min demonstrating many potential applications.
Project description:Rechargeable room temperature sodium-sulfur (RT Na-S) batteries are seriously limited by low sulfur utilization and sluggish electrochemical reaction activity of polysulfide intermediates. Herein, a 3D "branch-leaf" biomimetic design proposed for high performance Na-S batteries, where the leaves constructed from Co nanoparticles on carbon nanofibers (CNF) are fully to expose the active sites of Co. The CNF network acts as conductive "branches" to ensure adequate electron and electrolyte supply for the Co leaves. As an effective electrocatalytic battery system, the 3D "branch-leaf" conductive network with abundant active sites and voids can effectively trap polysulfides and provide plentiful electron/ions pathways for electrochemical reaction. DFT calculation reveals that the Co nanoparticles can induce the formation of a unique Co-S-Na molecular layer on the Co surface, which can enable a fast reduction reaction of the polysulfides. Therefore, the prepared "branch-leaf" CNF-L@Co/S electrode exhibits a high initial specific capacity of 1201 mAh g-1 at 0.1 C and superior rate performance.
Project description:Lithium-sulfur battery possesses high energy density but suffers from severe capacity fading due to the dissolution of lithium polysulfides. Novel design and mechanisms to encapsulate lithium polysulfides are greatly desired by high-performance lithium-sulfur batteries towards practical applications. Herein, we report a strategy of utilizing anthraquinone, a natural abundant organic molecule, to suppress dissolution and diffusion of polysulfides species through redox reactions during cycling. The keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding. This mechanism leads to a long cycling stability of sulfur-based electrodes. With a high sulfur content of ~73%, a low capacity decay of 0.019% per cycle for 300 cycles and retention of 81.7% over 500 cycles at 0.5 C rate can be achieved. This finding and understanding paves an alternative avenue for the future design of sulfur-based cathodes toward the practical application of lithium-sulfur batteries.
Project description:Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.
Project description:Sodium-sulfur (Na-S) batteries provide lithium-free alternatives to lithium-sulfur (Li-S) batteries. Na-S chemistry has been less studied. Thus, the types of polysulfides (PS) and their evolution during charge-discharge of Na-S batteries are not as well understood as those in the Li-S system. We, therefore, study the formation of different PS in tetraethylene glycol dimethyl ether-based electrolyte during battery operation using in situ Raman and ex situ ultraviolet-visible (UV-vis) spectroscopies. We start by making reference solutions with different ratios of sodium sulfide (Na2S) to sulfur, ranging from pure Na2S to Na2S:7S, with the sulfur ratio increasing by one integer per solution. We then correlate the UV-vis and Raman peaks to PS species. Our galvanostatic charge-discharge (GCD) and cyclic voltammetry measurements show a total of ten features. Using ex situ UV-vis on aliquots and in situ Raman spectra from PS solutions at GCD voltage plateaus, we map out sodium polysulfide (NaPS) species at key stages of the charge-discharge cycle. We identify Na2S8, Na2S4, and Na2S2 as intermediates and Na2S as the final product. We find that intermediate Na2S6 forms from disproportionation of Na2S8 and Na2S4. We also observe that intermediate PS can also dissociate into S3•- radical species, which contributes to loss of active material. Our results provide detailed insights into Na-S chemistry that will be helpful for the development of high performance and stable batteries.
Project description:Although the rechargeable lithium-sulfur battery is an advanced energy storage system, its practical implementation has been impeded by many issues, in particular the shuttle effect causing rapid capacity fade and low Coulombic efficiency. Herein, we report a conductive porous vanadium nitride nanoribbon/graphene composite accommodating the catholyte as the cathode of a lithium-sulfur battery. The vanadium nitride/graphene composite provides strong anchoring for polysulfides and fast polysulfide conversion. The anchoring effect of vanadium nitride is confirmed by experimental and theoretical results. Owing to the high conductivity of vanadium nitride, the composite cathode exhibits lower polarization and faster redox reaction kinetics than a reduced graphene oxide cathode, showing good rate and cycling performances. The initial capacity reaches 1,471 mAh g-1 and the capacity after 100 cycles is 1,252 mAh g-1 at 0.2 C, a loss of only 15%, offering a potential for use in high energy lithium-sulfur batteries.
Project description:Room-temperature sodium-sulfur (RT Na-S) batteries are arousing great interest in recent years. Their practical applications, however, are hindered by several intrinsic problems, such as the sluggish kinetic, shuttle effect, and the incomplete conversion of sodium polysulfides (NaPSs). Here a sulfur host material that is based on tungsten nanoparticles embedded in nitrogen-doped graphene is reported. The incorporation of tungsten nanoparticles significantly accelerates the polysulfides conversion (especially the reduction of Na2 S4 to Na2 S, which contributes to 75% of the full capacity) and completely suppresses the shuttle effect, en route to a fully reversible reaction of NaPSs. With a host weight ratio of only 9.1% (about 3-6 times lower than that in recent reports), the cathode shows unprecedented electrochemical performances even at high sulfur mass loadings. The experimental findings, which are corroborated by the first-principles calculations, highlight the so far unexplored role of tungsten nanoparticles in sulfur hosts, thus pointing to a viable route toward stable Na-S batteries at room temperatures.
Project description:Lithium-sulfur batteries have attracted great attention because of their high energy density, environmental friendliness, natural abundance and intrinsically low cost of sulfur. However, their commercial applications are greatly hindered by rapid capacity decay due to poor conductivity of electrode, fast dissolution of the intermediate polysulfides into the electrolyte, and the volume expansion of sulfur. Herein, we report a novel composite MWCNTs@TiO2-S nanostructure by grafting TiO2 onto the surface of MWCNTs, followed by incorporating sulfur into the composite. The inner MWCNTs improved the mechanical strength and conductivity of the electrode and the outer TiO2 provided the adsorption sites to immobilize polysulfides due to bonding interaction between TiO2 and polysulfides. The MWCNTs@TiO2-S composite with a mass ratio of 50% (MWCNTs in MWCNTs@TiO2) exhibited the highest electrochemistry performance among all compositing ratios of MWCNTs/TiO2. The performance improvement might be attributed to the downward shift of the apparent Fermi level to a more positive potential and electron rich space region at the interface of MWCNTs-TiO2 that facilitates the reduction of lithium polysulfide at a higher potential. Such a novel hybrid structure can be applicable for electrode design in other energy storage applications.