Lithium-ion Sulfur Battery Research Articles

Communication—A Simple and Scalable Pre-Lithiation Approach for High Energy and Low Cost Lithium Ion Sulfur Batteries

Pre-lithiation is an essential technique for development of Li-ion sulfur batteries (LISBs), which have lower cost and higher durability than conventional Li-ion batteries. Herein, a simple and scalable pre-lithiation approach by direct contact with lithium foil is applied to a sulfur-polyacrylonitrile (S-PAN) cathode to construct LISBs, which exhibit an initial capacity of 1367 mAh g−1 and maintain 1192 mAh g−1 after 100 cycles. Moreover, we demonstrate the feasibility of proposed method on both electrodes for performance enhancement. The theoretical estimation further demonstrates the potential of the system for achieving high specific capacity and good cycle life at low cost.

Building high performance silicon–oxygen and silicon–sulfur battery by in-situ lithiation of fibrous Si/C anode

Using Li metal-free anodes for lithium-ion oxygen and lithium-ion sulfur batteries is considered as a promising solution to resolve the hazard of Li metal anode. Although Si anode exhibits high capacity and low electrochemical potential, it cannot match with oxygen (or sulfur) cathode, because both lack cycleable lithium ions. In this work, a free-standing and fibrous Si/C anode is prepared by electrospinning and its simple but effective lithiation is proposed. When assembling the cells, the free-standing Si/C anode was put between mass-controlled lithium metal foil and separator, and then the Si/C anode could be lithiated after adding electrolytes. By optimizing a LiFSI based ether electrolyte, the Si/C anode could achieve good cycleablity comparable to that in carbonate electrolytes. The lithiated Si–O2 cells exhibit better cycling stability than the lithium oxygen cells with gel polymer electrolye. Moreover, because both Si anode and S@pPAN cathode are compatible with carbonate electrolytes, exceptional cycling performance has been achieved for the lithiated Si–S cells. This simple method could pave the way to commercial applications of lithium-ion oxygen and lithium-ion sulfur batteries.

Advanced Lithium Ion Sulfur Battery Based on Spontaneous Electrochemical Exfoliation/Lithiation of Graphite in Nonaqueous Electrolytes

An advanced lithium ion sulfur battery is constructed on the foundation of spontaneous electrochemical exfoliation and lithiation of graphite in nonaqueous electrolytes, in which to produce a high-quality graphene matrix for the sulfur cathode and lithiated graphite for the anode, respectively. On one hand, the high-quality graphene, obtained via spontaneous electrochemical exfoliation of graphite in propylene-carbonate-based electrolyte, works as a matrix to improve the conductivity of sulfur and trap the polysulfides. On the other hand, the lithiated graphite anode, obtained by spontaneous electrochemical lithiation of graphite in ethylene-carbonate-based electrolyte with 5 wt % fluoroethylene-carbonate additive, provides ample lithium ion sources and increases the safety coefficient of the lithium ion sulfur battery. Meanwhile, the fluoroethylene-carbonate additive can derive a LiF-rich solid electrolyte interphase on a lithiated graphite anode, which can in turn mitigate the notorious “shuttle effect”...

Engineering Rice Husk into a High-Performance Electrode Material through an Ecofriendly Process and Assessing Its Application for Lithium-Ion Sulfur Batteries

High-capacity and cycle-stable SiOx/C composite anodes for Li-ion batteries (LIBs) were synthesized from rice husk (RH) using an ecofriendly, one-step pyrolysis process that takes full advantage of...

Enabling High-Rate and Safe Lithium Ion-Sulfur Batteries by Effective Combination of Sulfur-Copolymer Cathode and Hard-Carbon Anode.

Fabrication and high-rate performance of a safe lithium ion-sulfur battery (LISB) with sulfur-copolymer [poly(S-co-divinylbenzene (DVB)] cathode having a sulfur content higher than 90 wt %, a carbon-fiber interlayer, and a prelithiated hard-carbon (Li-HC) anode are reported, which mitigates problems of lithium-sulfur cells such as performance fade and safety issues due to dissolution of polysulfides and lithium-dendrite growth. The poly(S-co-DVB) cathode offers scalability owing to the abundance and low cost of DVB. The Li-HC anode, the surface of which is passivated by a solid electrolyte interphase, inhibits the deposition of polysulfides. As a result, the LISB exhibits reversible and stable cycling performance at high rates up to 3 C, which enables quick charging within 20 min, and delivers a reversible capacity of approximately 400 mAh g-1 at 3 C for 500 cycles. The results give insight into the design principle of promising, quickly charged, and safe LISBs.

A new high-capacity and safe energy storage system: lithium-ion sulfur batteries.

Lithium-ion sulfur batteries as a new energy storage system with high capacity and enhanced safety have been emphasized, and their development has been summarized in this review. The lithium-ion sulfur battery applies elemental sulfur or lithium sulfide as the cathode and lithium-metal-free materials as the anode, which can be divided into two main types. One is anode-type, where elemental sulfur is applied as the cathode, and the anode provides lithium ions. The other one is cathode-type, where lithium sulfide as the cathode provides lithium ions, and lithium-metal-free materials (e.g., graphite, silicon/carbon) function as the anode. Recently, some new lithium-ion sulfur battery systems have also been proposed, and are discussed in this review as well. The lithium-ion sulfur batteries not only maintain the advantage of high energy density because of the high capacities of sulfur and lithium sulfide, but also exhibit the improved safety of the batteries due to a non-lithium-metal in the anode. This review paper aims to track the recent progress in the development of lithium-ion sulfur batteries and summarize the challenges and the approaches for improving their electrochemical performances, including the lithiation methods to prepare lithium-metal-free anodes in anode-type lithium-ion sulfur batteries and the lithium sulfide cathode modification approaches in cathode-type lithium-ion sulfur batteries. Furthermore, the challenges and perspectives for future research and commercial applications have also been enumerated.

Trace ethanol as an efficient electrolyte additive to reduce the activation voltage of the Li2S cathode in lithium-ion-sulfur batteries.

Trace ethanol is applied as a cheap and effective electrolyte additive for reducing the activation voltage of Li2S cathodes in lithium-ion-sulfur batteries. Because Li2S can dissolve in ethanol, the solid-solid phase reaction in the first stage of the activation process converts into a liquid-solid phase reaction, which expedites the transport of electrons and lithium ions and reduces the activation voltage of Li2S. This strategy can be extended to other solvents that can dissolve Li2S.

Minimizing Polysulfide Shuttle Effect in Lithium-Ion Sulfur Batteries by Anode Surface Passivation.

Lithium-ion sulfur batteries use nonlithium materials as the anode for extended cycle life. However, polysulfide shuttle reactions still occur on the nonmetal anodes (such as graphite and Si), and result in undesirable low Coulombic efficiency. In this work, we used Al2O3 layers coated by atomic layer deposition (ALD) technique to suppress the shuttle reactions. With the optimal thickness of 2 nm Al2O3 coated on graphite anode, the Coulombic efficiency of the sulfur cathode was improved from 84% to 96% in the first cycle, and from 94% to 97% in the subsequent cycles. As a result, the discharge capacity of the sulfur cathode was increased to 550 mAh g-1 in the 100th cycle, as compared with 440 mAh g-1 when the pristine graphite anode was used. The Al2O3 passivation layer minimizes the formation of insoluble sulfide (Li2S2, Li2S) on the surface of graphite anode and improves the efficiency and capacity retention of the graphite-sulfur batteries. The surface passivation strategy could also be used in other sulfur based battery systems (with Li, Si, and Sn anodes), to minimize side reactions and enable high-performance sulfur batteries.

An efficient Li2S-based lithium-ion sulfur battery realized by a bifunctional electrolyte additive

Previous investigations have shown that high-energy lithium-ion sulfur batteries could be directly assembled with lithium sulfide (Li2S) cathode and a non-lithium anode. However, the existing lithium-ion sulfur battery suffers from the multistep sophisticated preparation process, high activation potential and also polysulfides corrosion to the anode. In this work, we propose and prepare a facile and feasible Li2S-based lithium-ion sulfur battery system, which is enabled by a bifunctional electrolyte additive. At first, Li2S particles were loaded on the low-cost carbonized commercial wipes by a solution-based infiltration method. Interestingly, for the first time, it is found that the well-designed indium triiodide (InI3) electrolyte additive not only performed as a cathodic redox mediator, reducing the activation potential of Li2S cathode, but also resulted in a passivation layer, preventing the anode from corrosion due to the shuttle effect. The obtained SnO2/Li2S full cell exhibits a stable electrochemical performance (983, 878, 746 and 675mAh/g at 0.2, 0.4, 0.8, and 1.5C, 647mAh/g after 200 cycles at 0.5C). Moreover, the manageable amount of lithium ions and the voltage cooperation between the cathode and anode in the full cell rendered the battery with a strong recovery ability against the abusive conditions test, such as over-charge, over-discharge and short-circuit, showing a great potential for practical use.

High-safety lithium-ion sulfur battery with sulfurized polyacrylonitrile cathode, prelithiated SiOx/C anode and carbonate-based electrolyte

In this work, a lithium-ion sulfur battery has been constructed by employing the sulfurized polyacrylonitrile (S@pPAN) cathode, prelithiated SiOx/C anode and commercial carbonate-based electrolyte. Compared with the traditional lithium-sulfur battery, the replacement of lithium metal with prelithiated SiOx/C anode and the use of commercial carbonate-based electrolyte ensure the high safety of the new battery. Meanwhile, the lithium-ion sulfur battery also possesses the advantage of high energy density. It delivers a high reversible capacity of 616 mA h g−1 after 100 cycles with an average working voltage of about 1.6 V, corresponding to a high energy density of 661 W h kg−1, which is more than double that of the commercial lithium-ion batteries. The fabrication of the lithium-ion sulfur battery provides an effective way to solve the safety problems of the available lithium-sulfur batteries.

Study on Lithium-Sulfur Batteries

Lithium-Sulfur (Li-S) batteries have recently raised worldwide attention owning to the high specific theoretical energy density of sulfur (2600Wh kg-1), the low cost and the wide availability of sulfur. However, the practical application of lithium-sulfur batteries has been hindered by several challenges, such as the shuttling of polysulfide intermediates, the large volume expansion of sulfur during charge/discharge and the dendrites formation on Li-anode. In this talk, we will introduce our recent investigation about Li-S batteries, including physical and chemical immobilization of sulfur to improve cycling stability, segregator optimization to minimize the shuttling effect and design of ionic liquids based electrolyte system to reduce the self-discharge. Finally, we introduce a lithium-ion sulfur battery based on a Li2S cathode using a dual-phase electrolyte (Li2S/electrolyte-1/LISICON/electrolyte-2/Li) and then replaced the Li anode with Al and graphite, which demonstrates a proof of concept of metal Li free Li-ion Sulfur battery. Reference [1] S.Y. Yuan, Z.Y. Guo, L.N. Wang, S. Hu, Y. G. Wang*, Y.Y. Xia*, Adv. Sci. 2015, 2: 1500071. [2] S.Y. Yuan, J.W. Bao, L.N. Wang, Y.Y. Xia, D.G. Truhlar*, Y.G. Wang*, Adv. Energy Mater., 2015 , 1501733. [3] L.N. Wang, J.Y. Liu, S. Haller, Y.G. Wang*, Y.Y. Xia*, Chem. Commun., 2015, 51: 6996. [4] L.N. Wang, J.Y. Liu, S.Y. Yuan, Y.G. Wang*, Y.Y. Xia*, Energy Environ. Sci., 2016, 9: 224. [5] L.N. Wang, Y.G. Wang*, Y.Y. Xia*, Energy Environ. Sci., 2015, 8: 1551.

A highly-safe lithium-ion sulfur polymer battery with SnO2 anode and acrylate-based gel polymer electrolyte

Safety is a prime concern associated with the use of metallic lithium in high-capacity Li–S batteries. Recent studies have shown that replacing lithium metal with other high performance anodes and assembling as lithium-ion sulfur battery (LISB) are effective methods to enhance the safety coefficient of the battery. However, the volume expansion of anodic active materials and gradual thickening of solid electrolyte interface (SEI) on the anode, as well as the ever-existing detrimental shuttle effect of sulfur cathode still limit the performance of LISBs. In this work, we propose and prepare a lithium-ion sulfur polymer battery (LISPB) that employs a stable SnO2 anode and a bi-functional gel polymer electrolyte (GPE). We demonstrate that graphene and carboxymethyl cellulose (CMC) are able to form a robust anode structure and simultaneously maintain a stable SEI in ether-based electrolyte, while the acrylate-based GPE immobilizes the polysulfides and protects the anodic SEI from side deposition reactions. The LISPB renders a superior high rate capability (608.2mAhg−1 at 5C), while maintaining excellent retention at both high and low current densities (83.3% after 300 cycles at 0.3C and 82.1% after 500 cycles at 1C). This novel and simple LISPB system represents a significant advancement of high-safety sulfur-based batteries.

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

Dual Nature Embedded Electrode Investigated through Deis Technique for Lithium Ion Sulfur Battery

The development of new energy storage technology has become an essential part to sustain the growth and progress of the society. In this respect, lithium ion batteries are one of the promising candidates to alleviate the growing energy crises and are attractive from the stability point of view but it is lacking the high power density and energy density. Lithium sulfur battery has high theoretical energy density of 2600 Wh/kg, and the abundance of sulfur open the scope of the battery to meet the market requirements. We report the lithium ion sulfur characteristics of the battery by using a versatile technique called dynamic electrochemical impedance spectroscopy analysis (DEIS). The cell configuration based on partially exfoliated carbon nanotube, graphene, and sulfur composite used as cathode and lithium foil as anode in LiTFSI, DOL/DME electrolyte, shows dual electrochemical behavior. The morphological features of the electrode material are probed by transmission electron microscopy as well as scanning electron microscopy. Through analysis of DEIS, cyclic voltammetry and galvanostatic cycling reveal dual nature of Li-ion and Li-S batteries. The cell operated in Li-ion battery condition shows a stable capacity of about 900mAh/g.

A Dual-Phase Cathode and a Si/SiOx Anode for Li-Sulfur Batteries

The lithium-sulfur battery is one of the most promising high-energy-density electrochemical energy storage systems for emerging applications such as power storage systems for renewable energy plants and the powering of sustainable electric vehicles.1 The natural abundance and low cost of sulfur, coupled with the high theoretical energy density of sulfur-based cathodes, namely, 1675 mAh g-1 and 3500 Wh kg-1, are the major advantages of this sulfur battery.2 However, the insulating nature of sulfur, leads to low active material utilization, and sulfur electrodes have low stability, arising from the formation of soluble lithium polysulfide during cell operation; these problems, have so far limited the commercialization of this battery.3 There has been consistent progress recently toward optimizing the sulfur electrode.4 Recently, several research groups have reported that the addition of lithium polysulfide to the electrolyte could improve the performance of the Li/S battery in terms of cycle performance and energy density.5 Another major concern regarding the lithium-sulfur battery system is its use of a lithium metal anode, which is well known to have some critical problems including chemical reactivity in commonly used organic electrolytes and dendritic growth of lithium during cycling, leading to poor cycle performance and safety problems. In addition, when coupled with a sulfur cathode, the lithium metal anode reacts with lithium polysulfide to form an insoluble Li2S phase on the lithium surface, leading to the loss of lithium metal and eventually causing poor cycle performance of the system. It should be also noted that an excess amount of lithium metal is needed to construct the full cell to secure its long cycle life, which might lead to degradation of both the energy density and the safety of the full cell. Herein, we demonstrated a lithium-ion sulfur cell configuration using a newly designed dual-type sulfur cathode and a lithiate Si/SiOx nanosphere anode with optimized liquid electrolyte. Our dual-type sulfur cathode system delivered maximum capacity on the order of 1,300 mAh g-1as referred to the mass of the overall sulfur content; that is to say, the mass of sulfur both in the solid cathode and in the dissolved lithium polysulfide. The lithiated Si/SiOx nanosphere anode used showed highly stable cycling behavior over 100 cycles, with a capacity as high as 800 mAh g-1and cycling efficiency approaching 100%. The full lithium-ion sulfur cell presented herein delivered a capacity on the order of about 750mAhg-1. We believe that these results might advance the practical development of the lithium-ion sulfur battery, particularly for use in emerging markets including electric vehicles and large-scale power storage systems for use with renewable energy systems.

A lithium-ion sulfur battery using a polymer, polysulfide-added membrane.

In this paper we report the performances of a lithium-ion sulfur battery characterized by a polymer configuration. The cell, based on a sulfur-carbon cathode, a Li-Sn-C nanostructured anode and a PEO-based, polysulfide-added electrolyte, shows very good electrochemical performances in terms of stability and delivered capacity. The remarkable cell performances are ascribed to the mitigation of the cathode dissolution process due to the buffer action ensured by the polysulfide added to the polymer electrolyte. This electrolyte configuration allows the achievement of a stable capacity ranging from 500 to 1500 mAh gS-1, depending on the cycling rate. The use of a polymer electrolyte and the replacement of the lithium metal with a Li-Sn-C nanostructured alloy are expected to guarantee high safety content, thus suggesting the battery here studied as advanced energy storage system.

A long-life lithium ion sulfur battery exploiting high performance electrodes.

A novel lithium ion sulfur battery is formed by coupling an activated ordered mesoporous carbon-sulfur (AOMC-S) cathode and a nanostructured tin-carbon anode. The lithium ion cell has improved reversibility, high energy content and excellent cycle life.

A high performance lithium-ion sulfur battery based on a Li2S cathode using a dual-phase electrolyte

Li2S is efficiently used for a Li-ion sulfur battery with a dual-phase electrolyte, in which the parasitic polysulfide shuttle process is eliminated.

A Lithium-Ion Sulfur Battery Based on a Carbon-Coated Lithium-Sulfide Cathode and an Electrodeposited Silicon-Based Anode

In this paper, we report a lithium-ion battery employing a lithium sulfide cathode and a silicon-based anode. The high capacity of the silicon anode and the high efficiency and cycling rate of the lithium sulfide cathode allowed optimal full cell balance. We show in fact that the battery operates with a very stable capacity of about 280 mAh g(-1) at an average voltage of 1.4 V. To the best of our knowledge, this battery is one of the rare examples of lithium-metal-free sulfur battery. Considering the high theoretical capacity of the employed electrodes, we believe that the battery here reported may be of potential interest as high-energy, safe, and low-cost power source for electric vehicles.

Rechargeable lithium sulfide electrode for a polymer tin/sulfur lithium-ion battery

In this work we investigate the electrochemical behavior of a new type of carbon–lithium sulfide composite electrode. Results based on cyclic voltammetry, charge (lithium removal)-discharge (lithium acceptance) demonstrate that this electrode has a good performance in terms of reversibility, cycle life and coulombic efficiency. XRD analysis performed in situ in a lithium cell shows that lithium sulfide can be converted into sulfur during charge and re-converted back into sulfide during the following discharge process. We also show that this electrochemical process can be efficiently carried out in polymer electrolyte lithium cells and thus, that the Li 2S–C composite can be successfully used as cathode for the development of novel types of rechargeable lithium-ion sulfur batteries where the reactive and unsafe lithium metal anode is replaced by a reliable, high capacity tin–carbon composite and the unstable organic electrolyte solution is replaced by a composite gel polymer membrane that is safe, highly conductive and able to control dendrite growth across the cell. This new Sn–C/Li 2S polymer battery operates with a capacity of 600 mAh g −1 and with an average voltage of 2 V, this leading to a value of energy density amounting to 1200 Wh kg −1.