A thin multifunctional coating on a separator improves the cyclability and safety of lithium sulfur batteries.
ABSTRACT: Lithium-sulfur batteries are one of the most promising next-generation batteries due to their high theoretical specific capacity, but are impeded by the low utilization of insulating sulfur, unstable morphology of the lithium metal anode, and transport of soluble polysulfides. Here, by coating a layer of nano titanium dioxide and carbon black onto a commercial polypropylene separator, we demonstrate a new composite separator that can confine the polysulfides on the cathode side, forming a catholyte chamber, and at the same time block the dendritic lithium on the anode side. Lithium-sulfur batteries using this separator show a high initial capacity of 1206 mA h g-1 and a low capacity decay rate of 0.1% per cycle at 0.5C. Analyses reveal the electrocatalytic effect and the excellent dendrite-blocking capability of the ?7 µm thick coating.
Project description:Lithium-sulfur batteries are paid much attention owing to their high specific capacity and energy density. However, their practical applications are impeded by poor electrochemical performance due to the dissolved polysulfides. The concentration of soluble polysulfides has a linear relationship with the internal heat generation. The issue of heat transport inside lithium-sulfur batteries is often overlooked. Here, we designed a functional separator that not only had a high thermal conductivity of 0.65 W m-1 K-1 but also alleviated the diffusion of dissolved active materials to the lithium anode, improving the electrochemical performance and safety issue. Lithium-sulfur batteries with the functional separator have a specific capacity of 1,126.4 mAh g-1 at 0.2 C, and the specific capacity can be remained up to 893.5 mAh g-1 after 100 cycles. Pouch Cells with high sulfur loading also showed a good electrochemical performance under a lean electrolyte condition of electrolyte/sulfur (E/S) = 3 ?L mg-1.
Project description:The lithium-sulfur battery is one of the most promising battery technologies with high energy density that exceeds the presently commercialized ones. The shuttle effect caused by the migration of soluble polysulfides to the lithium anode is known as one of the crucial issues that prevent the Li-S batteries from practical application. Modification of the separator is regarded as a convenient yet efficient strategy to alleviate the shuttle effect. In this report, we use a thermally stable and chemically robust metal-organic framework (MOF), UiO-66, as a physical and chemical barrier for soluble polysulfides to functionalize the commercial polypropylene separator. The Li-S cell assembled with such a separator shows a significantly improved cycling stability with an average specific capacity of ca. 720 mA h g-1 at a current rate of 0.5 C for 500 cycles. Experimental and theoretical investigations indicate that the cell performance enhancement results from the physical restriction of the MOF barrier layer and strong chemical interaction between UiO-66 and polysulfides. The excellent thermal stability and chemical robustness (in acid/alkali solutions, conventional organic solvents, and polysulfide electrolytes) of UiO-66 make it highly competitive among various materials developed for separator modification in Li-S batteries.
Project description:The practical application of lithium/sulfur (Li/S) batteries is hindered by the migration of soluble polysulfides (Li2Sn, 4 ≤ n ≤ 8) from cathode to anode, leading to poor electrochemical stability of the cell. To address this issue, in the present study, a TiO2/porous carbon (TiO2/PC) composite-coated Celgard 2400 separator was successfully fabricated and used as a polysulfide barrier for the Li/S battery. In TiO2/PC, the highly conductive PC with three-dimensional ordered porous structure physically constrains polysulfides and at the same time serves as an additional upper current collector. On the other hand, the TiO2 on the surface of PC chemically adsorbed polysulfides during the charge/discharge process. Due to the physical and chemical adsorption properties of TiO2/PC composite coating layer, an initial discharge capacity of 926 mAh g-1 at 0.1 C and a low fading rate (75% retention after 150 cycles) were achieved. Moreover, in the rate capability test, the discharge capacity for the TiO2/PC-modified Li/S battery was recovered to 728 mAh g-1 at 0.1 C after high-rate cycling and remained ~ 88% of the initial reversible capacity.
Project description:To enhance the electrochemical performance of the lithium/sulfur batteries, a novel interlayer was prepared by coating the slurry of PPy/ZnO composite onto the surface of a separator. Owing to a three-dimensional hierarchical network structure, PPy/ZnO composite serves as a polysulfide diffusion absorbent that can intercept the migrating soluble polysulfides to enhance the electrochemical performance of the Li/S batteries. The specific capacity of the cell with PPy/ZnO interlayer remained at 579 mAh g-1 after 100 cycles at 0.2 C. This interlayer can provide novel avenues for the commercial applications of Li/S batteries.
Project description:In lithium-sulfur cells, the dissolution and relocation of the liquid-state active material (polysulfides) lead to fast capacity fading and low Coulombic efficiency, resulting in poor long-term electrochemical stability. To solve this problem, we synthesize a composite using a gel polymer electrolyte and a separator as a functional membrane, coated with a layer of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The PEO/LiTFSI-coated polypropylene membrane slows the diffusion of polysulfides and stabilizes the liquid-state active material within the cathode region of the cell, while allowing smooth lithium-ion transfer. The lithium-sulfur cells with the developed membrane demonstrate a high charge-storage capacity of 1212 mA?h g<sup>-1</sup>, 981 mA?h g<sup>-1</sup>, and 637 mA?h g<sup>-1</sup> at high sulfur loadings of 2 mg cm<sup>-2</sup>, 4 mg cm<sup>-2</sup>, and 6 mg cm<sup>-2</sup>, respectively, and maintains a high reversible capacity of 534 mA?h g<sup>-1</sup> after 200 cycles, proving its ability to block the irreversible diffusion of polysulfides and to maintain the stabilized polysulfides as the catholyte for improved electrochemical utilization and stability. As a comparison, reference and control cells fabricated using a PEO-coated polypropylene membrane and a regular separator, respectively, show a poor capacity of 662 mA?h g<sup>-1</sup> and a short cycle life of 50 cycles.
Project description:Owing to the conversion chemistry of the sulfur cathode, the lithium-sulfur (Li-S) batteries exhibit high theoretical energy density. However, the intrinsic mobile redox centers during the sulfur/Li2S-to-lithium polysulfides solid-to-liquid phase transition induce low sulfur utilization and poor cycling life. Herein, the Janus separator of mesoporous cellular graphene framework (CGF)/polypropylene membrane to promote the utilization of sulfur cathode is introduced. The porous polypropylene membrane serves as an insulating substrate in contact with lithium anode while CGFs that possess high electrical conductivity of 100 S cm-1, a large mesopore volume of 3.1 cm3 g-1, and a huge surface area of 2120 m2 g-1 are adhered on cathode side to reactivate the shuttling-back polysulfides and to preserve the ion channels. Therefore, the Li-S cell with the "two-face" CGF Janus separator exhibit a high initial capacity of 1109 mAh g-1 and superior capacity preserved upon 800 mAh g-1 after 250 cycles at 0.2 C, which is 40% higher on sulfur utilization efficiency than the corresponding results with routine polypropylene separators. There are significant improvements on capacity as well as electrochemical kinetics. A very high areal capacity of 5.5 mAh cm-2 combined with high sulfur content of 80% and areal loading amount of 5.3 mg cm-2 is achieved for such advanced configuration. The negative impact of shuttle mechanism on lowering the utilization of sulfur and overall energy density of a Li-S battery is well eliminated by applying CGF separators. Consequently, employing carbonaceous materials as Janus face of separators enlightens new opportunities for improving the utilization of active materials and energy density of devices that involve complex phase evolution and conversion electrochemistry.
Project description:Lithium-sulfur (Li-S) batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg-1. However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC) to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m² g-1), high pore volume (1.78 cm³ g-1), good conductivity, and in situ nitrogen (1.86 at %) and sulfur (5.26 at %) co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li? ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g-1 at 0.2 C), excellent rate capability (596.6 mAh g-1 at 5 C), and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle). Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm-2 (70 wt. % sulfur), the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g-1, which is quite beneficial to commercialized applications.
Project description:Although the lithium-sulfur battery exhibits high capacity and energy density, the cycling performance is severely retarded by dendrite formation and side-reactions of the lithium metal anode and the shuttle effect of polysulfides. Therefore, exploring lithium rich-alloy (or compound) anodes and suppressing the shuttling of polysulfides have become practical technical challenges for the commercialization of lithium-sulfur batteries. Here, a lithium ion sulfur full battery system combining a lithium-rich Li-Si alloy anode and sulfurized polyacrylonitrile (S@pPAN) cathode has been proposed. The free-standing CNF matrix supported Li-Si alloy anode is prepared by a simple and effective method, which is practical for scale-up production. The obtained Li-Si alloy anode demonstrates high cycling stability without dendrite growth, while the use of the S@pPAN cathode avoids the shuttle effect in carbonate electrolytes. The constructed Li-Si/S@pPAN battery could be cycled more than 1000 times at 1C and 3000 times at 3C, with a capacity fading rate of 0.01% and 0.03% per cycle. The exceptional performance should originate from the stable integrated anode structure and the excellent compatibility of the S@pPAN cathode and Li-Si alloy anode with carbonate electrolytes.
Project description:Organic compounds with active sites for lithiation can be used as electrode materials for lithium batteries. Their tunable structures allow a variety of materials to be made and investigated. Herein, a spectrum of dipyridyl polysulfides (Py2S x , 3 ? x ? 8) is prepared in electrolyte by a one-pot synthesis method from dipyridyl disulfide (Py2S2) and elemental sulfur. It renders up to seven dipyridyl polysulfides (i.e., Py2S3, Py2S4, Py2S5, Py2S6, Py2S7, and Py2S8) which show fully reversible electrochemical behavior in lithium batteries. In the discharge, the initial lithiation occurs at 2.45 V leading to the breakage of S?-S? bonds in Py2S x and formation of lithium 2-pyridinethiolate, in which lithium is coordinated in between N and S atoms. The left sulfur species act as elemental sulfur, showing two voltage plateaus at 2.3 and 2.1 V. The molecular dynamics simulations show the attraction between pyridyl groups and lithium polysulfides/sulfide via N···Li···S bonds, which enable good retention of soluble discharge products within electrodes and stable cycling performance. In the recharge, low-order Py2S x (e.g., Py2S3, Py2S4, and Py2S5) remain as the charged products. The mixture catholyte exhibits superlong cycle life at 1C rate with 1200 cycles and 70.5% capacity retention.
Project description:Lithium nitrate (LiNO3) is known as an important electrolyte additive in lithium-sulfur (Li-S) batteries. The prevailing understanding is that LiNO3 reacts with metallic lithium anode to form a passivation layer which suppresses redox shuttles of lithium polysulfides, enabling good rechargeability of Li-S batteries. However, this view is seeing more challenges in the recent studies, and above all, the inability of inhibiting polysulfide reduction on Li anode. A closely related issue is the progressive reduction of LiNO3 on Li anode which elevates internal resistance of the cell and compromises its cycling stability. Herein, we systematically investigated the function of LiNO3 in redox-shuttle suppression, and propose the suppression as a result of catalyzed oxidation of polysulfides to sulfur by nitrate anions on or in the proximity of the electrode surface upon cell charging. This hypothesis is supported by both density functional theory calculations and the nitrate anions-suppressed self-discharge rate in Li-S cells. The catalytic mechanism is further validated by the use of ruthenium oxide (RuO2, a good oxygen evolution catalyst) on cathode, which equips the LiNO3-free cell with higher capacity and improved capacity retention over 400 cycles.