Hong-Jie Peng

Unstacked double-layer templated graphene for high-rate lithium–sulphur batteries

Preventing the stacking of graphene is essential to exploiting its full potential in energy-storage applications. The introduction of spacers into graphene layers always results in a change in the intrinsic properties of graphene and/or induces complexity at the interfaces. Here we show the synthesis of an intrinsically unstacked double-layer templated graphene via template-directed chemical vapour deposition. The as-obtained graphene is composed of two unstacked graphene layers separated by a large amount of mesosized protuberances and can be used for high-power lithium-sulphur batteries with excellent high-rate performance. Even after 1,000 cycles, high reversible capacities of ca. 530 mA h g(-1) and 380 mA h g(-1) are retained at 5 C and 10 C, respectively. This type of double-layer graphene is expected to be an important platform that will enable the investigation of stabilized three-dimensional topological porous systems and demonstrate the potential of unstacked graphene materials for advanced energy storage, environmental protection, nanocomposite and healthcare applications.

Nitrogen‐Doped Aligned Carbon Nanotube/Graphene Sandwiches: Facile Catalytic Growth on Bifunctional Natural Catalysts and Their Applications as Scaffolds for High‐Rate Lithium‐Sulfur Batteries

Nitrogen-doped aligned CNT/graphene sandwiches are rationally designed and in-situ fabricated by a facile catalytic growth on bifunctional natural catalysts that exhibit high-rate performances as scaffolds for lithium-sulfur batteries, with a high initial capacity of 1152 mA h g(-1) at 1.0 C. A remarkable capacity of 770 mA h g(-1) can be achieved at 5.0 C. Such a design strategy for materials opens up new perspectives to novel advanced functional composites, especially interface-modified hierarchical nanocarbons for broad applications.

Powering Lithium–Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries

Lithium–sulfur batteries attract great attention due to their high energy density, while their real applications are still hindered by the rapid capacity degradation. Despite great efforts devoted to solving the polysulfide shuttle between the cathode and anode electrodes, it remains a serious challenge to build highly-stable lithium–sulfur batteries. Herein we demonstrate a strategy of introducing an ion selective membrane to improve the stability and coulombic efficiency of lithium–sulfur batteries. The sulfonate-ended perfluoroalkyl ether groups on the ionic separators are connected by pores or channels that are around several nanometers in size. These SO3− groups-coated channels allow ion hopping of positively charged species (Li+) but reject hopping of negative ions, such as polysulfide anions (Sn2−) in this specific case due to the coulombic interactions. Consequently, this cation permselective membrane acts as an electrostatic shield for polysulfide anions, and confines the polysulfides on the cathode side. An ultra-low decay rate of 0.08% per cycle is achieved within the initial 500 cycles for the membrane developed in this work, which is less than half that of the routine membranes. Such an ion selective membrane is versatile for various electrodes and working conditions, which is promising for the construction of high performance batteries.

Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium–Sulfur Batteries

Lithium-sulfur batteries hold great promise for serving as next generation high energy density batteries. However, the shuttle of polysulfide induces rapid capacity degradation and poor cycling stability of lithium-sulfur cells. Herein, we proposed a unique lithium-sulfur battery configuration with an ultrathin graphene oxide (GO) membrane for high stability. The oxygen electronegative atoms modified GO into a polar plane, and the carboxyl groups acted as ion-hopping sites of positively charged species (Li(+)) and rejected the transportation of negatively charged species (Sn(2-)) due to the electrostatic interactions. Such electrostatic repulsion and physical inhibition largely decreased the transference of polysulfides across the GO membrane in the lithium-sulfur system. Consequently, the GO membrane with highly tunable functionalization properties, high mechanical strength, low electric conductivity, and facile fabrication procedure is an effective permselective separator system in lithium-sulfur batteries. By the incorporation of a permselective GO membrane, the cyclic capacity decay rate is also reduced from 0.49 to 0.23%/cycle. As the GO membrane blocks the diffusion of polysulfides through the membrane, it is also with advantages of anti-self-discharge properties.

Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries.

Li dendrite-free growth is achieved by employing glass fiber with large polar functional groups as the interlayer of Li metal anode and separator to uniformly distribute Li ions. The evenly distributed Li ions render the dendrite-free Li deposits at high rates (10 mA cm(-2)) and high lithiation capacity (2.0 mAh cm(-2)).

Design Principles for Heteroatom‐Doped Nanocarbon to Achieve Strong Anchoring of Polysulfides for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries have been intensively concerned to fulfill the urgent demands of high capacity energy storage. One of the major unsolved issues is the complex diffusion of lithium polysulfide intermediates, which in combination with the subsequent paradox reactions is known as the shuttle effect. Nanocarbon with homogeneous nonpolar surface served as scaffolding materials in sulfur cathode basically cannot afford a sufficient binding and confining effect to maintain lithium polysulfides within the cathode. Herein, a systematical density functional theory calculation of various heteroatoms-doped nanocarbon materials is conducted to elaborate the mechanism and guide the future screening and rational design of Li-S cathode for better performance. It is proved that the chemical modification using N or O dopant significantly enhances the interaction between the carbon hosts and the polysulfide guests via dipole-dipole electrostatic interaction and thereby effectively prevents shuttle of polysulfides, allowing high capacity and high coulombic efficiency. By contrast, the introduction of B, F, S, P, and Cl monodopants into carbon matrix is unsatisfactory. To achieve the strong-couple effect toward Li2 Sx , the principles for rational design of doped carbon scaffolds in Li-S batteries to achieve a strong electrostatic dipole-dipole interaction are proposed. An implicit volcano plot is obtained to describe the dependence of binding energies on electronegativity of dopants. Moreover, the codoping strategy is predicted to achieve even stronger interfacial interaction to trap lithium polysulfides.

Dual-Phase Lithium Metal Anode Containing a Polysulfide-Induced Solid Electrolyte Interphase and Nanostructured Graphene Framework for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries, with a theoretical energy density of 2600 Wh kg(-1), are a promising platform for high-energy and cost-effective electrochemical energy storage. However, great challenges such as fast capacity degradation and safety concerns prevent it from widespread application. With the adoption of Li metal as the anode, dendritic and mossy metal depositing on the negative electrode during repeated cycles leads to serious safety concerns and low Coulombic efficiency. Herein, we report a distinctive graphene framework structure coated by an in situ formed solid electrolyte interphase (SEI) with Li depositing in the pores as the anode of Li-S batteries. The graphene-based metal anode demonstated a superior dendrite-inhibition behavior in 70 h of lithiation, while the cell with a Cu foil based metal anode was short-circuited after only 4 h of lithiation at 0.5 mA cm(-2). The graphene-modified Li anode with SEI induced by the polysulfide-containing electrolyte improved the Coulombic efficiency to ∼97% for more than 100 cycles, while the control sample with Cu foil as the current collector exhibited huge fluctuations in Coulombic efficiency. The unblocked ion pathways and high electron conductivities of frameworks in the modified metal anode led to the rapid transfer of Li ions through the SEI and endowed the anode framework with an ion conductivity of 7.81 × 10(-2) mS cm(-1), nearly quintuple that of the Cu foil based Li metal anode. Besides, the polarization in the charge-discharge process was halved to 30 mV. The stable and efficient Li deposition was maintained after 2000 cycles. Our results indicated that nanoscale interfacial electrode engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes, thus improving the safety of Li-S cells.

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries have been recognized as promising substitutes for current energy-storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long-life Li-S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid-liquid polysulfide interconversion and liquid-solid precipitation of lithium sulfides more than non-polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm-2 , the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance.

Rational Integration of Polypropylene/Graphene Oxide/Nafion as Ternary-Layered Separator to Retard the Shuttle of Polysulfides for Lithium-Sulfur Batteries.

The reversible electrochemical transformation from lithium (Li) and sulfur (S) into Li2 S through multielectron reactions can be utilized in secondary Li-S batteries with very high energy density. However, both the low Coulombic efficiency and severe capacity degradation limits the full utilization of active sulfur, which hinders the practical applications of Li-S battery system. The present study reports a ternary-layered separator with a macroporous polypropylene (PP) matrix layer, graphene oxide (GO) barrier layer, and Nafion retarding layer as the separator for Li-S batteries with high Coulombic efficiency and superior cyclic stability. In the ternary-layered separator, ultrathin layer of GO (0.0032 mg cm(-2) , estimated to be around 40 layers) blocks the macropores of PP matrix, and a dense ion selective Nafion layer with a very low loading amount of 0.05 mg cm(-2) is attached as a retarding layer to suppress the crossover of sulfur-containing species. The ternary-layered separators are effective in improving the initial capacity and the Coulombic efficiency of Li-S cells from 969 to 1057 mAh g(-1) , and from 80% to over 95% with an LiNO3 -free electrolyte, respectively. The capacity degradation is reduced from 0.34% to 0.18% per cycle within 200 cycles when the PP separator is replaced by the ternary-layered separators. This work provides the rational design strategy for multifunctional separators at cell scale to effective utilizing of active sulfur and retarding of polysulfides, which offers the possibility of high energy density Li-S cells with long cycling life.