Electrochemical Enhancement of Lithium-Ion Diffusion in Polypyrrole-Modified Sulfurized Polyacrylonitrile Nanotubes for Solid-to-Solid Free-Standing Lithium-Sulfur Cathodes.

The energy density of lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries has chronically suffered from low sulfur content. Although a free-standing electrode can significantly reduce noncapacity mass contribution, the slow bulk reaction kinetics still constrain the electrochemical performance. In this regard, a novel electrochemically active additive, polypyrrole (PPy), is introduced to construct PAN nanotubes as a sulfur carrier. This hollow channel greatly facilitates charge transport within the electrode and increases the sulfur content. Both electrochemical tests and simulations show that the SPANPPy-1% cathode possesses a larger lithium-ion diffusion coefficient and a more homogeneous phase interface than the SPAN cathode. Consequently, significantly improved capabilities and rate properties are achieved, as well as decent exportations under high-sulfur-loading or lean-electrolyte conditions. In-situ and semi-situ characterizations are further performed to demonstrate the nucleation growth of lithium sulfide and the evolution of the electrode surface structure. This type of electrochemically active additive provides a well-supported implementation of high-energy-density Li-S batteries.

Synthesis of orthogonal push-pull chromophores via click reaction of arylynamines.

Herein, we report a catalyst-free 'click' reaction: metal-free [2 + 2] cycloaddition-retro-electrocyclisation (CA-RE) of arylynamines with the sluggish acceptor tetracyanoquinodimethane (TCNQ) to provide orthogonal electron-push-pull light-harvesting small molecules: N-heterocyclic dicyanoquinodimethane-substituted methylene malononitriles. Ynamines are reactive alkynes and tend to induce over-reactions with the CA-RE adducts. The reactivity of arylynamines was balanced properly by ensuring the electron-density of the nitrogen atom was delocalised more over the aromatic rings than the triple bond.

Few-Layer Boron Nitride with Engineered Nitrogen Vacancies for Promoting Conversion of Polysulfide as a Cathode Matrix for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have become one of the most promising candidates as next-generation batteries, owing to their high specific capacity, low cost, and environmental benignity. Although many strategies have been proposed to restrain the shuttle of lithium polysulfides (LiPSs) through physical trapping and chemical binding, the sluggish kinetics of PS conversion still degrade the capacity, rate, and cycling performance of Li-S batteries. Herein, a novel kind of few-layer BN with engineered nitrogen vacancies (v-BN) has been developed as a cathode matrix for Li-S batteries. The positive vacancies in the BN nanosheets not only promote the immobilization and conversion of LiPSs, but also accelerate the lithium ion diffusion in cathode electrodes. Compared with pristine BN, the v-BN cathodes exhibit higher initial capacities from 775 mA h g-1 to 1262 mA h g-1 at 0.1 C and a high average coulombic efficiency of over 98 % during 150 cycles. Upon increasing the current density to 1 C, the cell still preserves a capacity of 406 mA h g-1 after 500 cycles, exhibiting a capacity decay of only 0.084 % per cycle. The new vacancy-engineered material provides a promising method for achieving excellent performance in Li-S batteries.

In Situ Polymerized Zwitterionic Copolymer Ionic Gel Electrolytes with High Performance for Lithium-Ion Batteries.

Gel electrolytes are a promising research direction due to their high safety. However, its poor room temperature conductivity along with complex preparation process hinder its practical application. In this article, a type of zwitterionic gel electrolyte is prepared by in situ polymerization. The introduction of charged but nonmigrating zwitterionic copolymer in the polymer chain is beneficial to the dissociation of the lithium salt, improving the ion transport of the electrolyte on this account. At room temperature, the conductivity of lithium ion reaches 9.1 × 10-4 S cm-1, which contributes to achieve excellent electrochemical performance at high rates. The assembled Li|LiFePO4 cell also shows a capacity retention rate of 90.5% after 150 cycles at 0.5 C at room temperature as well as remarkable cycle stability at 1 C. These offer a novel tactic for the efficient and safe commercial application of lithium-ion batteries.

Weak Solvation Chemistry in Fluorinated Nonflammable Electrolytes Achieves Stable Cycling in High-Voltage Lithium Metal Batteries.

High-voltage (>4.35 V) lithium nickel-cobalt-manganese batteries are star candidates due to their higher energy density for next-generation power batteries. This poses higher demands for electrolyte design, including compatibility with lithium metals, stability on high-voltage cathodes, speedy interfacial ion transport kinetics, and appropriate concentration. However, electrolytes at the current level of research struggle to balance these demands. Here, we took advantage of the reduced affinity with Li+ and enhanced oxidative stability of three fluorinated linear carbonates to design a series of weakly solvating electrolytes (WSEs) at a low salt concentration of 1 M, which contain abundant ionic cluster structures, leading to the optimization of interfacial chemistry. As a result, WSEs can support the stable cycling of 4.6 V high-voltage Li||NCM811 cells for 300 cycles with a capacity retention of nearly 80%. Moreover, benefiting from the lower desolvation energy of Li+, WSEs achieve superior cycling stability and low polarization under -20 °C. Our work extends the application of WSEs for high-voltage LMBs, providing a promising solution in electrolytes for high-specific-energy lithium batteries.

Improving Fast-Charging Capability of High-Voltage Spinel LiNi0.5 Mn1.5 O4 Cathode under Long-Term Cyclability through Co-Doping Strategy.

Co-free spinel LiNi0.5 Mn1.5 O4 (LNMO) is emerging as a promising contender for designing next generation high-energy-density and fast-charging Li-ion batteries, due to its high operating voltage and good Li+ diffusion rate. However, further improvement of the Li+ diffusion ability and simultaneous resolution of Mn dissolution still pose significant challenges for their practical application. To tackle these challenges, a simple co-doping strategy is proposed. Compared to Pure-LNMO, the extended lattice in resulting LNMO-SbF sample provides wider Li+ migration channels, ensuring both enhanced Li+ transport kinetics, and lower energy barrier. Moreover, Sb creating structural pillar and stronger TM─F bond together provides a stabilized spinel structure, which stems from the suppression of detrimental irreversible phase transformation during cycling related to Mn dissolution. Benefiting from the synergistic effect, the LNMO-SbF material exhibits a superior reversible capacity (111.4 mAh g-1 at 5C, and 70.2 mAh g-1 after 450 cycles at 10C) and excellent long-term cycling stability at high current density (69.4% capacity retention at 5C after 1000 cycles). Furthermore, the LNMO-SbF//graphite full cell delivers an exceptional retention rate of 96.9% after 300 cycles, and provides a high energy density at 3C even with a high loading. This work provides valuable insight into the design of fast-charging cathode materials for future high energy density lithium-ion batteries.

A Metal-Organic Framework Based Quasi-Solid-State Electrolyte Enabling Continuous Ion Transport for High-Safety and High-Energy-Density Lithium Metal Batteries.

Solid-state lithium metal batteries are promising next-generation rechargeable energy storage systems. However, the poor compatibility of the electrode/electrolyte interface and the low lithium ion conductivity of solid-state electrolytes are key issues hindering the practicality of solid-state electrolytes. Herein, rational designed metal-organic frameworks (MOFs) with the incorporation of two types of ionic liquids (ILs) are fabricated as quasi-solid electrolytes. The obtained MOF-IL electrolytes offer continuous ion transport channels with the functional sulfonic acid groups serving as lithium ion hopping sites, which accelerate the Li+ transport both in the bulk and at the interfaces. The quasi-solid MOF-IL electrolytes exhibit competitive ionic conductivities of over 3.0 × 10-4 S cm-1 at room temperature, wide electrochemical windows over 5.2 V, and good interfacial compatibility, together with greatly enhanced Li+ transference numbers compared to the bare IL electrolyte. Consequently, the assembled quasi-solid Li metal batteries show either superior stability at low C rates or improved rate performance, related to the species of ILs. Overall, the quasi-solid MOF-IL electrolytes possess great application potential in high-safety and high-energy-density lithium metal batteries.

Graphdiyne-like Porous Organic Framework as a Solid-Phase Sulfur Conversion Cathodic Host for Stable Li-S Batteries.

As a unique branch of Li-S batteries, solid-phase sulfur conversion polymer cathodes have shown superior stability with fast ion-transfer kinetics and high discharge capacities owing to the mere existence of short-chain sulfur species during charging/discharging. However, representative compounds such as sulfurized polyacrylonitrile (SPAN) and polyaniline (SPANI) suffer from low sulfur contents and poor cycling performances under large current densities due to the sulfurization occurring only on polymers' surface. Here, a graphdiyne-like porous organic framework, denoted as GPOF, is synthesized and used as a host for enabling solid-phase sulfur conversion. Plenty of unsaturated bonds in GPOF provide sufficient reaction sites to bind sulfur chains, resulting in a high active sulfur content in the cathode. Moreover, the microporous GPOF possesses suitable cavities to accommodate the volume expansion, leading to favorable long-term cycling stability. As a result, the sulfurized GPOF cathode (SGPOF-320) displays outstanding electrochemical stability with negligible capacity decline after 250 cycles at 0.2 C with an average discharge capacity of 925 mA h g-1. Our work applies a facile procedure to produce sulfur conversion porous polymer cathodes, which could provide a proper way for exploring more suitable cathode materials for high-performance Li-S batteries.

Enhanced Cycling Performance for Lithium-Sulfur Batteries by a Laminated 2D g-C3 N4 /Graphene Cathode Interlayer.

Decay in electrochemical performance resulting from the "shuttle effect" of dissolved lithium polysulfides is one of the biggest obstacles for the realization of practical applications of lithium-sulfur (Li-S) batteries. To meet this challenge, a 2D g-C3 N4 /graphene sheet composite (g-C3 N4 /GS) was fabricated as an interlayer for a sulfur/carbon (S/KB) cathode. It forms a laminated structure of channels to trap polysulfides by physical and chemical interactions. The thin g-C3 N4 /GS interlayer significantly suppresses diffusion of the dissolved polysulfide species (Li2 Sx ; 2

High-Charge Density Polymerized Ionic Networks Boosting High Ionic Conductivity as Quasi-Solid Electrolytes for High-Voltage Batteries.

Solid-state electrolytes are actively sought for their potential application in energy storage devices, especially lithium metal rechargeable batteries. However, one of the key challenges in the development of solid-state electrolytes is their lower ionic conductivity compared with that of liquid electrolytes (10-2 S cm-1 at room temperature), where a large gap still exists. Therefore, the pursuit of high ionic conductivity equal to that of liquid electrolytes remains the main objective for the design of solid-state electrolytes. Here, we show a series of high-charge density polymerized ionic networks as solid-state electrolytes that take inspiration from poly(ionic liquid)s. The obtained quasi-solid electrolyte slice displays an astonishingly high ionic conductivity of 5.89 × 10-3 S cm-1 at 25 °C (the highest conductivity among those of the state-of-art polymer gel electrolytes and polymer solid electrolytes) and ultrahigh decomposition potential, >5.2 V versus Li/Li+, which are attributed to the continuous ion transport channel formed by an ultrahigh ion density and an enhanced chemical stability endowed by highly cross-linked networks. The Li/LiFePO4 and Li/LiCoO2 batteries (3.0-4.4 V) assembled with the solid electrolytes show high stable capacities of around 155 and 130 mAh g-1, respectively. In principle, our work breaks new ground for the design and fabrication of the solid-state electrolytes in various energy conversion devices.

Space-Confined Polymerization: Controlled Fabrication of Nitrogen-Doped Polymer and Carbon Microspheres with Refined Hierarchical Architectures.

The construction of refined architectures plays a crucial role in performance improvement and application expansion of advanced materials. The synthesis of carbon microspheres with a refined hierarchical structure is still a problem in synthetic methodology, because it is difficult to achieve the necessary delicate control of the interior structure and outer shell across the microscale to nanoscale. Nitrogen-doped multichamber carbon (MCC) microspheres with a refined hierarchical structure are realized here via a surfactant-directed space-confined polymerization strategy. The MCC precursor is not the traditional phenolic resol but a new kind of 2,6-diaminopyridine-based multichamber polymer (MCP) with a high nitrogen content up to 20 wt%. The morphology and sizes of MCP microspheres can be easily controlled by a dual-surfactant system. The as-synthesized MCC with a highly microporous shell, a multichamber inner core, and beneficial N-doping can serve as a promising supercapacitor material.