RESUMO
Lithium-oxygen (Li-O2) batteries, renowned for their high theoretical energy density, have garnered significant interest as prime candidates for future electric device development. However, their actual capacity is often unsatisfactory due to the passivation of active sites by solid-phase discharge products. Optimizing the growth and storage of these products is a crucial step in advancing Li-O2 batteries. Here, a fluorine-doped bimetallic cobalt-nickel oxide (CoNiO2- xFx/CC) with an interlaced catalytic surface (ICS) and a corncob-like structure is proposed as an oxygen electrode. Unlike conventional oxide electrodes with a "single adsorption catalytic mechanism," the ICS of CoNiO2- xFx/CC offers a "competitive adsorption catalytic mechanism," where oxygen sites facilitate oxygen conversion while fluorine sites contribute to the growth of Li2O2. This results in a change in Li2O2 morphology from a surface film to toroidal particles, effectively preventing the burial of active sites. Additionally, the unique open architecture aids in the capture and release of oxygen and the formation of well-contacted Li2O2/electrode interfaces, which benefits the complete decomposition of Li2O2 products. Consequently, the Li-O2 battery with a CoNiO2- xFx/CC cathode demonstrates a high specific capacity of up to 30923 mAh g-1 and a lifespan exceeding 580 cycles, surpassing most reported metal oxide-based cathodes.
RESUMO
Since the introduction of poly(ethylene oxide) (PEO)-based polymer electrolytes more than 50 years, few other real polymer electrolytes with commercial application have emerged. Due to the low ion conductivity at room temperature, the PEO-based electrolytes cannot meet the application requirements. Most of the polymer electrolytes reported in recent years are in fact colloidal/composite electrolytes with plasticizers and fillers, not genuine electrolytes. Herein, we designed and synthesized a cross-linked polymer with a three-dimensional (3D) mesh structure which can dissolve the Li bis(trifluoromethylsulfonyl)imide (LiTFSI) salt better than PEO due to its unique 3D structure and rich oxygen-containing chain segments, thus forming an intrinsic polymer electrolyte (IPE) with ionic conductivity of 0.49â mSâ cm-1 at room temperature. And it can hinder the migration of large anions (e.g. TFSI-) in the electrolyte and increase the energy barrier to their migration, achieving Li+ migration numbers (tLi+) of up to 0.85. At the same time, IPE has good compatibility with lithium metal cathode and LiFePO4 (LFP) cathode, with stable cycles of more than 2,000 and 700â h in Li//Li symmetric batteries at 0.2 and 0.5â mAhâ cm-2 current densities, respectively. In addition, the Li/IPE/LFP batteries show the capacity retention >90% after 300 cycles at 0.5â C current density. This polymer electrolyte will be a pragmatic way to achieve commercializing all-solid-state, lithium-based batteries.
RESUMO
The usage of flame retardants in flammable polymers has been an effective way to protect both lives and material goods from accidental fires. Phosphorus flame retardants have the potential to be follow-on flame retardants after halogenated variants, because of their low toxicity, high efficiency and compatibility. Recently, the emerging allotrope of phosphorus, two-dimensional black phosphorus, as a flame retardant has been developed. To further understand its performance in flame-retardant efficiency among phosphorus flame retardants, in this work, we built model materials to compare the flame-retardant performances of few-layer black phosphorus, red phosphorus nanoparticles, and triphenyl phosphate as flame-retardant additives in cellulose and polyacrylonitrile. Aside from the superior flame retardancy in polyacrylonitrile, few-layer black phosphorus in cellulose showed the superior flame-retardant efficiency in self-extinguishing, ~1.8 and ~4.4 times that of red phosphorus nanoparticles and triphenyl phosphate with similar lateral size and mass load (2.5~4.8 wt%), respectively. The char layer in cellulose coated with the few-layer black phosphorus after combustion was more continuous and smoother than that with red phosphorus nanoparticles, triphenyl phosphate and blank, and the amount of residues of cellulose coated with the few-layer black phosphorus in thermogravimetric analysis were 10 wt%, 14 wt% and 14 wt% more than that with red phosphorus nanoparticles, triphenyl phosphate and blank, respectively. In addition, although exothermic reactions, the combustion enthalpy changes in the few-layer black phosphorus (-127.1 kJ mol-1) are one third of that of red phosphorus nanoparticles (-381.3 kJ mol-1). Based on a joint thermodynamic, spectroscopic, and microscopic analysis, the superior flame retardancy of the few-layer black phosphorus was attributed to superior combustion reaction suppression from the two-dimensional structure and thermal nature of the few-layer black phosphorus.
Assuntos
Retardadores de Chama , Fósforo/química , Celulose/química , Polímeros/químicaRESUMO
Solid-state lithium metal batteries are hindered from practical applications by insufficient room-temperature ionic conductivity and poor electrode/electrolyte interfaces. Herein, we designed and synthesized a high ionic conductivity metal-organic-framework-based composite solid electrolyte (MCSE) with the synergy of high DN value ligands from Uio66-NH2 and succinonitrile (SN). XPS and FTIR reveal that the amino group (-NH2) of Uio66-NH2 and the cyano group (-C≡N) of SN have a stronger solvated coordination with Li+, which can promote the dissociation of crystalline LiTFSI, achieving an ionic conductivity of 9.23 × 10-5 S cm-1 at RT. Afterward, a flexible polymer electrolyte membrane (FPEM) with admirable ionic conductivity (1.56 × 10-4 S cm-1 at RT) and excellent electrode/electrolyte interfaces (86.2 Ω for the Li|20% FPEM|Li cell and 303.1 Ω for the LiFePO4|20% FPEM|Li cell) was successfully obtained after compounding the MCSE with polyethylene oxide (PEO). Moreover, a stable solid electrolyte layer (SEI) was formed in situ on the surface of the lithium metal, which enables the Li|20% FPEM|Li cell to exhibit remarkable cycling stability (1000 h at a current density of 0.05 mA cm-2). At the same time, the assembled LiFePO4|20% FPEM|Li cell offers a discharge-specific capacity of 155 mAh g-1 at 0.1 C and a columbic efficiency of 99.5% after 200 cycles. This flexible polymer electrolyte provides a possibility for operating long lifespan solid-state electrochemical energy storage systems at RT.
RESUMO
As a holy grail in electrochemistry, both high-power and high-energy electrochemical energy storage system (EES) has always been a pursued dream. To simultaneously achieve the "both-high" EES, a rational design of structure and composition for storage materials with characteristics of battery-type and capacitor-type storage is crucial. Herein, fluorine-nitrogen co-implanted carbon tubes (FNCT) have been designed, in which plentiful active sites and expanded interlayer space have been created benefiting from the heteroatom engineering and the fluorine-nitrogen synergistic effect, thus the above two-type storage mechanism can get an optimal balance in the FNCT. The implanted fluorine heteroatoms can not only amplify interlayer spacing, but also induce the transformation of nitrogen configuration from pyrrole nitrogen to pyridine nitrogen, further promoting the activity of the carbon matrix. The extraordinary electrochemical performance as results can be witnessed for FNCT, which exhibit fast lithium-ion storage capability with a high energy density of 119.4 Wh kg-1 at an ultrahigh power density of 107.5 kW kg-1 .
RESUMO
The urgent demand for high energy and safety storage devices is pushing the development of lithium metal batteries. However, unstable solid electrolyte interface (SEI) formation and uncontrollable lithium dendrite growth are still huge challenges for the practical use of lithium metal batteries. Herein, a composite polymer electrolyte (CPE) endowed with designated ion channels is fabricated by constructing nanoscale Uio66-NH2 layer, which has uniformly distributed pore structure to regulate reversible Li plating/stripping in lithium metal batteries. The regular channels within the Uio66-NH2 layer work as an ion sieve to restrict larger TFSI- anions inside its channels and extract Li+ across selectively, which result in a high Li-ion transference number ( t Li + ${t_{{\rm{L}}{{\rm{i}}^{\bm{ + }}}}}$ ) of 0.6. Moreover, CPE provides high ion conductivity (0.245 mS cm-1 at room temperature) and expanded oxidation window (5.1 V) and forms a stable SEI layer. As a result, the assembled lithium metal batteries with CPE exhibit outstanding cyclic stability and capacity retention. The Li/CPE/Li symmetric cell continues plating/stripping over 500 h without short-circuiting. The Li/CPE/LFP cell delivers a reversible capacity of 149.3 mAh g-1 with a capacity retention of 99% after 100 cycles.
Assuntos
Eletrólitos , Lítio , Condutividade Elétrica , Canais Iônicos , PolímerosRESUMO
Glymes are the most widely used electrolyte solvents in lithium-oxygen batteries (LOBs) due to their relatively high stability. However, their associated LOBs have long been plagued by large charge overpotential, which is closely related to the sluggish two-electron Li2 O2 oxidation mechanism. Here, we report a new electrolyte solvent-1,1,3,3-tetramethylurea (TMU) for LOBs with high performance and an alternative mechanism, where a kinetically favorable one-electron Li2 O2 oxidation pathway can happen in the urea electrolyte system, thus leading to a much lower charge overpotential (≈0.51â V) compared to the tetraglyme-based LOBs (≈1.27â V). Besides, TMU also exhibits good stability since it does not contain any α-hydrogen atoms that are vulnerable to be attacked by superoxide species, thus suppressing the hydrogen abstraction side reactions. Consequently, the TMU-based LOBs can stably work for more than 135â cycles, which is four times that of the tetraglyme-based LOBs (≈28â cycles).
RESUMO
Because of their high theoretical energy density and low cost, lithium-sulfur (Li-S) batteries are promising next-generation energy storage devices. The electrochemical performance of Li-S batteries largely depends on the efficient reversible conversion of Li polysulfides to Li2S in discharge and to elemental S during charging. Here, we report on our discovery that monodisperse cobalt atoms embedded in nitrogen-doped graphene (Co-N/G) can trigger the surface-mediated reaction of Li polysulfides. Using a combination of operando X-ray absorption spectroscopy and first-principles calculation, we reveal that the Co-N-C coordination center serves as a bifunctional electrocatalyst to facilitate both the formation and the decomposition of Li2S in discharge and charge processes, respectively. The S@Co-N/G composite, with a high S mass ratio of 90 wt %, can deliver a gravimetric capacity of 1210 mAh g-1, and it exhibits an areal capacity of 5.1 mAh cm-2 with capacity fading rate of 0.029% per cycle over 100 cycles at 0.2 C at S loading of 6.0 mg cm-2 on the electrode disk.
RESUMO
Lithium-sulfur batteries are widely seen as a promising next-generation energy-storage system owing to their ultrahigh energy density. Although extensive research efforts have tackled poor cycling performance and self-discharge, battery stability has been improved at the expense of energy density. We have developed an interlayer consisting of two-layer chemical vapor deposition (CVD)-grown graphene supported by a conventional polypropylene (PP) separator. Unlike interlayers made of discrete nano-/microstructures that increase the thickness and weight of the separator, the CVD-graphene is an intact film with an area of 5 × 60 cm2 and has a thickness of â¼0.6 nm and areal density of â¼0.15 µg cm-2, which are negligible to those of the PP separator. The CVD-graphene on PP separator is the thinnest and lightest interlayer to date and is able to suppress the shuttling of polysulfides and enhance the utilization of sulfur, leading to concurrently improved specific capacity, rate capability, and cycle stability and suppressed self-discharge when assembled with cathodes consisting of different sulfur/carbon composites and electrolytes either with or without LiNO3 additive.