Probing the Origin of Viscosity of Liquid Electrolytes for Lithium Batteries.

Viscosity is an extremely important property for ion transport and wettability of electrolytes. Easy access to viscosity values and a deep understanding of this property remain challenging yet critical to evaluating the electrolyte performance and tailoring electrolyte recipes with targeted properties. We proposed a screened overlapping method to efficiently compute the viscosity of lithium battery electrolytes by molecular dynamics simulations. The origin of electrolyte viscosity was further comprehensively probed. The viscosity of solvents exhibits a positive correlation with the binding energy between molecules, indicating viscosity is directly correlated to intermolecular interactions. Salts in electrolytes enlarge the viscosity significantly with increasing concentrations while diluents serve as the viscosity reducer, which is attributed to the varied binding strength from cation-anion and cation-solvent associations. This work develops an accurate and efficient method for computing the electrolyte viscosity and affords deep insight into viscosity at the molecular level, which exhibits the huge potential to accelerate advanced electrolyte design for next-generation rechargeable batteries.

Lithiophilicity chemistry of heteroatom-doped carbon to guide uniform lithium nucleation in lithium metal anodes.

The uncontrollable growth of lithium (Li) dendrites seriously impedes practical applications of Li metal batteries. Various lithiophilic conductive frameworks, especially carbon hosts, are used to guide uniform Li nucleation and thus deliver a dendrite-free composite anode. However, the lithiophilic nature of these carbon hosts is poorly understood. Herein, the lithiophilicity chemistry of heteroatom-doped carbon is investigated through both first principles calculations and experimental verifications to guide uniform Li nucleation. The electronegativity, local dipole, and charge transfer are proposed to reveal the lithiophilicity of doping sites. Li bond chemistry further deepens the understanding of lithiophilicity. The O-doped and O/B-co-doped carbons exhibit the best lithiophilicity among single-doped and co-doped carbons, respectively. The excellent lithiophilicity achieved by O-doping carbon is further validated by Li nucleation overpotential measurement. This work uncovers the lithiophilicity chemistry of heteroatom-doped carbons and affords a mechanistic guidance to Li metal anode frameworks for safe rechargeable batteries.

Lithium Bond Chemistry in Lithium-Sulfur Batteries.

The lithium-sulfur (Li-S) battery is a promising high-energy-density storage system. The strong anchoring of intermediates is widely accepted to retard the shuttle of polysulfides in a working battery. However, the understanding of the intrinsic chemistry is still deficient. Inspired by the concept of hydrogen bond, herein we focus on the Li bond chemistry in Li-S batteries through sophisticated quantum chemical calculations, in combination with 7 Li nuclear magnetic resonance (NMR) spectroscopy. Identified as Li bond, the strong dipole-dipole interaction between Li polysulfides and Li-S cathode materials originates from the electron-rich donors (e.g., pyridinic nitrogen (pN)), and is enhanced by the inductive and conjugative effect of scaffold materials with π-electrons (e.g., graphene). The chemical shift of Li polysulfides in 7 Li NMR spectroscopy, being both theoretically predicted and experimentally verified, is suggested to serve as a quantitative descriptor of Li bond strength. These theoretical insights were further proved by actual electrochemical tests. This work highlights the importance of Li bond chemistry in Li-S cell and provides a deep comprehension, which is helpful to the cathode materials rational design and practical applications of Li-S batteries.

A Quinonoid-Imine-Enriched Nanostructured Polymer Mediator for Lithium-Sulfur Batteries.

The reversible formation of chemical bonds has potential for tuning multi-electron redox reactions in emerging energy-storage applications, such as lithium-sulfur batteries. The dissolution of polysulfide intermediates, however, results in severe shuttle effect and sluggish electrochemical kinetics. In this study, quinonoid imine is proposed to anchor polysulfides and to facilitate the formation of Li2 S2 /Li2 S through the reversible chemical transition between protonated state (NH+ ) and deprotonated state (N). When serving as the sulfur host, the quinonoid imine-doped graphene affords a very tiny shuttle current of 2.60 × 10-4 mA cm-2 , a rapid redox reaction of polysulfide, and therefore improved sulfur utilization and enhanced rate performance. A high areal specific capacity of 3.72 mAh cm-2 is achieved at 5.50 mA cm-2 on the quinonoid imine-doped graphene based electrode with a high sulfur loading of 3.3 mg cm-2 . This strategy sheds a new light on the organic redox mediators for reversible modulation of electrochemical reactions.

Topological Defects in Metal-Free Nanocarbon for Oxygen Electrocatalysis.

A bifunctional graphene catalyst with abundant topological defects is achieved via the carbonization of natural gelatinized sticky rice to probe the underlying oxygen electrocatalytic mechanism. A nitrogen-free configuration with adjacent pentagon and heptagon carbon rings is revealed to exhibit the lowest overpotential for both oxygen reduction and evolution catalysis. The versatile synthetic strategy and novel insights on the activity origin facilitate the development of advanced metal-free carbocatalysts for a wide range of electrocatalytic applications.

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.

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)).

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.