Deciphering the Lithium-Ion Conduction Mechanism of LiH in Solid-Electrolyte Interphase.

Lithium hydride (LiH) has been widely recognized as the critical component of the solid-electrolyte interphase (SEI) in Li batteries. Although the formation mechanism and structural model of LiH in SEI have been extensively reported, the role in electro-performance of LiH in SEI is still ambiguous and has proven challenging to explored due to the complicated structure SEI and the lack of advanced in situ experimental technology. In this study, the isotopic exchange experiments combined with isotopic tracer experiments is applied to solidly illustrate the superior conductivity and Li+ conduction behavior of the LiH in natural SEI. Importantly, in situ transmission electron microscopy analysis is utilized to visualize the self-electrochemical decomposition of LiH, which is significantly distinctive from LiF and Li2O. The critical experimental evidence discovered by the work demonstrates ion transport behaviors of key components in the SEI, which is imperative for designing novel SEI and augurs a new area in optimizing the performance of lithium batteries.

Fusion Bonding Technique for Solvent-Free Fabrication of All-Solid-State Battery with Ultrathin Sulfide Electrolyte.

For preparing next-generation sulfide all-solid-state batteries (ASSBs), the solvent-free manufacturing process has huge potential for the advantages of economic, thick electrode, and avoidance of organic solvents. However, the dominating solvent-free process is based on the fibrillation of polytetrafluoroethylene, suffering from poor mechanical property and electrochemical instability. Herein, a continuously solvent-free paradigm of fusion bonding technique is developed. A percolation network of thermoplastic polyamide (TPA) binder with low viscosity in viscous state is constructed with Li6PS5Cl (LPSC) by thermocompression (≤5 MPa), facilitating the formation of ultrathin LPSC film (≤25 µm). This composite sulfide film (CSF) exhibits excellent mechanical properties, ionic conductivity (2.1 mS cm-1), and unique stress-dissipation to promote interface stabilization. Thick LiNi0.83Co0.11Mn0.06O2 cathode can be prepared by this solvent-free method and tightly adhered to CSF by interfacial fusion of TPA for integrated battery. This integrated ASSB shows high-energy-density feasibility (>2.5 mAh cm-2 after 1400 cycles of 9200 h and run for more than 10 000 h), and energy density of 390 Wh kg-1 and 1020 Wh L-1. More specially, high-voltage bipolar cell (≥8.5 V) and bulk-type pouch cell (326 Wh kg-1) are facilely assembled with good cycling performance. This work inspires commercialization of ASSBs by a solvent-free method and provides beneficial guiding for stable batteries.

Oxygen vacancy chemistry in oxide cathodes.

Secondary batteries are a core technology for clean energy storage and conversion systems, to reduce environmental pollution and alleviate the energy crisis. Oxide cathodes play a vital role in revolutionizing battery technology due to their high capacity and voltage for oxide-based batteries. However, oxygen vacancies (OVs) are an essential type of defect that exist predominantly in both the bulk and surface regions of transition metal (TM) oxide batteries, and have a crucial impact on battery performance. This paper reviews previous studies from the past few decades that have investigated the intrinsic and anionic redox-mediated OVs in the field of secondary batteries. We focus on discussing the formation and evolution of these OVs from both thermodynamic and kinetic perspectives, as well as their impact on the thermodynamic and kinetic properties of oxide cathodes. Finally, we offer insights into the utilization of OVs to enhance the energy density and lifespan of batteries. We expect that this review will advance our understanding of the role of OVs and subsequently boost the development of high-performance electrode materials for next-generation energy storage devices.

A PF6 - -Permselective Polymer Electrolyte with Anion Solvation Regulation Enabling Long-Cycle Dual-Ion Battery.

Graphitic carbon that allows reversible anion (de)intercalation is a promising cathode material for cost-efficient and high-voltage dual-ion batteries (DIBs). However, one notorious but overlooked issue is the incomplete interfacial anion desolvation, which not only reduces the oxidative stability of electrolytes, but also results in solvent co-intercalation into graphite layers. Here, an "anion-permselective" polymer electrolyte with abundant cationic quaternary ammonium motif is developed to weaken the PF6 - -solvent interaction and thus facilitates PF6 - desolvation. This strategy significantly inhibits solvent co-intercalation as well as enhances the oxidation resistance of electrolyte, ensuring the structural integrity of graphite. As a result, the as-assembled graphite||Li cell achieves a superior cyclability with an average Coulombic efficiency of 99.0% (vs 95.7% for baseline electrolyte) and 87.1% capacity retention after 2000 cycles even at a high cutoff potential of 5.4 V versus Li+ /Li. Besides, this polymer also forms a robust cathode electrolyte interface, working together to enable a long-life DIB. This strategy of tuning anion coordination environment provides a promising solution to regulate solvent co-intercalation chemistry for DIBs.

Uncovering LiH Triggered Thermal Runaway Mechanism of a High-Energy LiNi0.5 Co0.2 Mn0.3 O2 /Graphite Pouch Cell.

The continuous energy density increase of lithium ion batteries (LIBs) inevitably accompanies with the rising of safety concerns. Here, the thermal runaway characteristics of a high-energy 5 Ah LiNi0.5 Co0.2 Mn0.3 O2 /graphite pouch cell using a thermally stable dual-salt electrolyte are analyzed. The existence of LiH in the graphite anode side is innovatively identified in this study, and the LiH/electrolyte exothermic reactions and H2 migration from anode to cathode side are proved to contribute on triggering the thermal runaway of the pouch cell, while the phase transformation of lithiated graphite anode and the O2 -releasing from cathode are just accelerating factors for thermal runaway. In addition, heat determination during cycling at two boundary scenarios of adiabatic and isothermal environment clearly states the necessity of designing an efficient and smart battery thermal management system for avoiding heat accumulation. These findings will shed promising lights on thermal runaway route map depiction and thermal runaway prevention, as well as formulation of electrolyte for high energy safer LIBs.

Anion Solvation Reconfiguration Enables High-Voltage Carbonate Electrolytes for Stable Zn/Graphite Cells.

Conventional carbonate solvents with low HOMO levels are theoretically compatible with the low-cost, high-voltage chemistry of Zn/graphite batteries. However, the nucleophilic attack of the anion on carbonates induces an oxidative breakdown at high potentials. Here, we restore the inherent anodic stability of carbonate electrolytes by designing a micro-heterogeneous anion solvation network. Based on the addition of a strongly electron-donating solvent, trimethyl phosphate (TMP), the oxidation-vulnerable anion-carbonate affinities are decoupled because of the preferential sequestration of anions into solvating TMP domains around the metal cations. The hybridized electrolytes elevate the electrochemical window of carbonate electrolytes by 0.45 V and enable the operation of Zn/graphite dual-ion cells at 2.80 V with a long cycle life (92 % capacity retention after 1000 cycles). By inheriting the non-flammability from TMP and the high ion-transport kinetics from the carbonate systems, this facile strategy provides cells with the additional benefits of fire retardancy and high-power capability.

Highly Reversible Cuprous Mediated Cathode Chemistry for Magnesium Batteries.

Sluggish kinetics and poor reversibility of cathode chemistry is the major challenge for magnesium batteries to achieve high volumetric capacity. Introduction of the cuprous ion (Cu+ ) as a charge carrier can decouple the magnesiation related energy storage from the cathode electrochemistry. Cu+ is generated from a fast equilibrium between copper selenide electrode and Mg electrolyte during standing time, rather than in the electrochemical process. A reversible chemical magnesiation/de-magnesiation can be driven by this solid/liquid equilibrium. During a typical discharge process, Cu+ is reduced to Cu and drives the equilibrium to promote the magnesiation process. The reversible Cu to Cu+ redox promotes the recharge process. This novel Cu+ mediated cathode chemistry of Mg battery leads to a high reversible areal capacity of 12.5 mAh cm-2 with high mass loading (49.1 mg cm-2 ) of the electrode. 80 % capacity retention can be achieved for 200 cycles after a conditioning process.

A High-Energy 5 V-Class Flexible Lithium-Ion Battery Endowed by Laser-Drilled Flexible Integrated Graphite Film.

Due to its highly in-plane oriented crystal structure, the flexible graphite film (GF) possesses excellent electrochemical corrosion resistance, high planar electrical conductivity, and considerable mechanical strength. In this work, the laser-drilled integrated graphite film (porous-GF, PGF) is unprecedentedly used as a key to fabricate a high-performance high-energy 5 V-class flexible PGF/PGF-LiNi0.5Mn1.5O4 full cell, where the flexible PGF is a self-standing flexible graphite anode for lithium-ion intercalation/deintercalation and a high-voltage resistance cathode current collector. This unique design based on the flexible PGF will endow the future flexible batteries with excellent characteristics of thin, lightweight, simple fabrication, and high energy. More encouragingly, unlike previously reported flexible electrodes using carbon nanomaterials as the nonmetal current collector, the mass production and processability of the flexible GF and PGF are feasible with the aid of commercially available roll-to-roll laser drilling technology.

Coaxial Ni(x)Co(2x)(OH)(6x)/TiN nanotube arrays as supercapacitor electrodes.

NixCo2x(OH)6x, as a precursor of intensively studied NiCo2O4, has been directly deposited into self-standing titanium nitride nanotube array (TiN NTA) grid monolithic supports to form a coaxial nanostructured electrode for supercapacitors. With TiN NTA substrates providing a large surface area, fast electron transport, and enhanced structure stability, this NixCo2x(OH)6x/TiN electrode exhibits superior pseudocapacitive performance with a high specific capacitance of 2543 F g(-1) at 5 mV s(-1), remarkable rate performance of 660 F g(-1) even at 500 mV s(-1), and promising cycle performance (about 6.25% capacitance loss for 5000 cycles). Interestingly, the NixCo2x(OH)6x/TiN NTA electrode outperforms the NiCo2O4/TiN NTA electrode, indicating that this self-standing NixCo2x(OH)6x/TiN NTA monolith is a promising candidate for high-performance supercapacitor applications.

1D coaxial platinum/titanium nitride nanotube arrays with enhanced electrocatalytic activity for the oxygen reduction reaction: towards Li-air batteries.

CAT ON A HOT TIN SUPPORT: Coaxial Pt/TiN nanotube arrays are used to achieve a superior electrocatalytic activity of platinum towards the oxygen reduction reaction (ORR). Compared to a commercial Pt/C catalyst, the Pt/TiN NTA materials delivers a higher mass activity and specific activity for the ORR. Hence, these materials are useful as cathodes for hybrid electrolyte Li-air batteries, as demonstrated.

Nanostructured titanium nitride/PEDOT:PSS composite films as counter electrodes of dye-sensitized solar cells.

The composite films of titanium nitride in conjunction with polystyrenesulfonate-doped poly (3,4-ethylene-dioxythiophene) (PEDOT:PSS) were prepared by a simple mechanical mixture of TiN and PEDOT:PSS under ultrasonication, which was demonstrated to deliver an effectively combined network of both high electrical conductivity and superior electrocatalytic activity. The composite films have been explored as an alternative for the counter electrodes of dye-sensitized solar cells. It was manifested that these nanostructured TiN-PEDOT:PSS composite films displayed excellent performance comparable to Pt-FTO counter electrode due to the combined network endowing more favorable and efficient interfacial active sites. Among them, the energy conversion efficiency of the cell with TiN(P)-PEDOT:PSS as counter electrode reached 7.06%, which was superior to 6.57% of the cell with Pt-FTO counter electrode under the same experimental conditions.

Synthesis of nitrogen-doped MnO/graphene nanosheets hybrid material for lithium ion batteries.

Nitrogen-doped MnO/graphene nanosheets (N-MnO/GNS) hybrid material was synthesized by a simple hydrothermal method followed by ammonia annealing. The samples were systematically investigated by X-ray diffraction analysis, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and atomic force microscopy. N-doped MnO (N-MnO) nanoparticles were homogenously anchored on the thin layers of N-doped GNS (N-GNS) to form an efficient electronic/ionic mixed conducting network. This nanostructured hybrid exhibited a reversible electrochemical lithium storage capacity as high as 772 mAh g(-1) at 100 mA g(-1) after 90 cycles, and an excellent rate capability of 202 mA h g(-1) at a high current density of 5 A g(-1). It is expected that N-MnO/GNS hybrid could be a promising candidate material as a high capacity anode for lithium ion batteries.

Molybdenum nitride based hybrid cathode for rechargeable lithium-O2 batteries.

Molybdenum nitride/nitrogen-doped graphene nanosheets (MoN/NGS) are synthesized and used as an alternative O(2) electrode for Li-O(2) batteries. In comparison with electrocatalysts proposed previously, this hybrid cathode exhibits a high discharge potential (around 3.1 V) and a considerable specific capacity (1490 mA h g(-1), based on carbon + electrocatalyst).

Mesoporous coaxial titanium nitride-vanadium nitride fibers of core-shell structures for high-performance supercapacitors.

In this study, titanium nitride-vanadium nitride fibers of core-shell structures were prepared by the coaxial electrospinning, and subsequently annealed in the ammonia for supercapacitor applications. These core-shell (TiN-VN) fibers incorporated mesoporous structure into high electronic conducting transition nitride hybrids, which combined higher specific capacitance of VN and better rate capability of TiN. These hybrids exhibited higher specific capacitance (2 mV s(-1), 247.5 F g(-1)) and better rate capability (50 mV s(-1), 160.8 F g(-1)), which promise a good candidate for high-performance supercapacitors. It was also revealed by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) characterization that the minor capacitance fade originated from the surface oxidation of VN and TiN.

A biocompatible titanium nitride nanorods derived nanostructured electrode for biosensing and bioelectrochemical energy conversion.

In this study, a facile method is proposed to fabricate biocompatible TiN nanorod arrays through solvent-thermal synthesis and subsequent nitridation in ammonia atmosphere. The TiN nanorod arrays are potential excellent nanostructured electrodes owing to their good electronic conductivity and large surface area. These nanostructured electrodes not only deliver superior electrocatalytic activity (the limit of detection, LOD is 0.5 µM) and highly selective sensing towards H(2)O(2), but also exhibit excellent biocompatibility with horseradish peroxidase (HRP) in a highly sensitive enzymatic biosensor for H(2)O(2) (the LOD can reach to 0.05 µM). Furthermore, a novel biocatalytic cathode based Li air fuel cell (bio-Li-air fuel cell) is explored based on the combination of TiN nanorod arrays and laccase (LAC) for electrochemical energy conversion. These results demonstrate that TiN nanorod arrays can be served as excellent nanostructured electrodes for multifunctional bioelectrochemical applications.

Facile preparation of mesoporous titanium nitride microspheres for electrochemical energy storage.

In this study, mesoporous TiN spheres with tunable diameter have been fabricated via a facile template-free strategy. Under ammonia atmosphere, mesoporous TiO2 spheres are directly converted into mesoporous TiN spheres with the addition of cyanamide to retain the original morphology. The electrochemical performance of the resultant mesoporous TiN spheres demonstrates that this material can be a promising electrode material for nonaqueous supercapacitors with high energy densities.