ABSTRACT
Since sodium-ion batteries (SIBs) have become increasingly commercialized in recent years, Na3V2(PO4)2O2F (NVPOF) offers promising economic potential as a cathode for SIBs because of its high operating voltage and energy density. According to reports, NVPOF performs poorly in normal commercial poly(vinylidene fluoride) (PVDF) binder systems and performs best in combination with aqueous binder. Although in line with the concept of green and sustainable development for future electrode preparation, aqueous binders are challenging to achieve high active material loadings at the electrode level, and their relatively high surface tension tends to cause the active material on the electrode sheet to crack or even peel off from the collector. Herein, a cross-linkable and easily commercial hybrid binder constructed by intermolecular hydrogen bonding (named HPP) has been developed and utilized in an NVPOF system, which enables the generation of a stable cathode electrolyte interphase on the surface of active materials. According to theoretical simulations, the HPP binder enhances electronic/ionic conductivity, which greatly lowers the energy barrier for Na+ migration. Additionally, the strong hydrogen-bond interactions between the HPP binder and NVPOF effectively prevent electrolyte corrosion and transition-metal dissolution, lessen the lattice volume effect, and ensure structural stability during cycling. The HPP-based NVPOF offers considerably improved rate capability and cycling performance, benefiting from these benefits. This comprehensive binder can be extended to the development of next-generation energy storage technologies with superior performance.
ABSTRACT
Flexible quasi-solid-state sodium ion batteries featuring their low-cost, high safety and excellent mechanical strength have attracted widespread interest in the field of wearable electronic devices. However, the development of such batteries faces great challenges including the construction of interfacial compatible flexible electrode materials and addressing the high safety demands of electrolyte. Here selenium-vacancies regulated bimetallic selenide heterojunctions anchored on waste cotton cloth-derived flexible carbon cloth (FCC) with robust interfacial C-Se-Co/Fe chemical bonds as a flexible anode material (CCFSF) is proposed by ultrafast microwave pyrolysis method. Rich selenium vacancies and CoSe2 /FeSe2-x heterostructures are synchronously formed that can significantly improve ionic and electronic diffusion kinetics. Additionally, a uniform carbon layer coating on the surface of Se-deficient heterostructures endows it with outstanding structural stability. The flexible cathode (PB@FCC) is also fabricated by directly growing Prussian blue nanoparticles on the FCC. Furthermore, an advanced flexible quasi-solid-state Na-ion pouch cell is assembled by coupling CCFSF anode, PB@FCC cathode with P(VDF-HFP)-based gel polymer electrolyte. The full cell not only demonstrates excellent energy storage performance but also robust mechanical flexibility and safety. The present work offers an effective avenue to achieve high safety flexible energy storage device, promoting the development of flexible wearable electronic devices.
ABSTRACT
Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries, the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers. Herein, by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether, the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ. This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport. Consequently, the graphite anode retained a prolonged cycling capability of up to 1400cycles (245 mA h g-1, remaining above 12mon) with an excellent capacity retention of as high as 92.4%. This is superior to those of conventional and high-concentration electrolytes. Thus, the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite, providing a potential application prospect for K-storage evolution.
ABSTRACT
Impossible voltage plateau regulation for the cathode materials with fixed active elemental center is a pressing issue hindering the development of Na-superionic-conductor (NASICON)-type Na3 V2 (PO4 )2 F3 (NVPF) cathodes in sodium-ion batteries (SIBs). Herein, a high-entropy substitution strategy, to alter the detailed crystal structure of NVPF without changing the central active V atom, is pioneeringly utilized, achieving simultaneous electronic conductivity enhancement and diffusion barrier reduction for Na+ , according to theoretical calculations. The as-prepared carbon-free high-entropy Na3 V1.9 (Ca,Mg,Al,Cr,Mn)0.1 (PO4 )2 F3 (HE-NVPF) cathode can deliver higher mean voltage of 3.81 V and more advantageous energy density up to 445.5 Wh kg-1 , which is attributed by the diverse transition-metal elemental substitution in high-entropy crystalline. More importantly, high-entropy introduction can help realize disordered rearrangement of Na+ at Na(2) active sites, thereby to refrain from unfavorable discharging behaviors at low-voltage region, further lifting up the mean working voltage to realize a full Na-ion storage at the high voltage plateau. Coupling with a hard carbon (HC) anode, HE-NVPF//HC SIB full cells can deliver high specific energy density of 326.8 Wh kg-1 at 5 C with the power density of 2178.9 W kg-1 . This route means the unlikely potential regulation in NASICON-type crystal with unchangeable active center becomes possible, inspiring new ideas on elevating the mean working voltage for SIB cathodes.
ABSTRACT
There are still many problems that hinder the development of sodium-ion batteries (SIBs), including poor rate performance, short-term cycle lifespan, and inferior low-temperature property. Herein, excellent Na-storage performance in fluorophosphate (Na3 V2 (PO4 )2 F3 ) cathode is achieved by lattice regulation based on charge balance theory. Lattice regulation of aliovalent Mn2+ for V3+ increases both electronic conductivity and Na+ -migration kinetics. Because of the maintaining of electrical neutrality in the material, aliovalent Mn2+ -introduced leads to the coexistence of V3+ and V4+ from charge balance theory. It decreases the particle size and improves the structural stability, suppressing the large lattice distortion during cathode reaction processes. These multiple effects enhance the specific capacity (123.8 mAh g-1 ), outstanding high-rate (68% capacity retention at 20 C), ultralong cycle (only 0.018% capacity attenuation per cycle over 1000 cycles at 1 C) and low-temperature (96.5% capacity retention after 400 cycles at -25 °C) performances of Mn2+ -induced Na3 V1.98 Mn0.02 (PO4 )2 F3 when used as cathode in SIBs. Importantly, a feasible sodium-ion full battery is assembled, achieving outstanding rate capability and cycle stability. The strategy of aliovalent ion-induced lattice regulation constructs cathode materials with superior performances, which is available to improve other electrode materials for energy storage systems.
ABSTRACT
Sodium-ion batteries (SIBs) are heralded as promising candidates for grid-scale energy storage systems due to their low cost and abundant sodium resources. Excellent rate capacity and outstanding cycling stability are always the goals for SIBs. Up to now, nearly all attention has been focused on the control of morphology and structure of electrode materials, but the influence of binders on their performance is neglected, especially in cathode materials. Herein, using Na3V2(PO4)2O2F (NVPOF) as a cathode material, the influence of four different binders (sodium alginate, SA; carboxymethylcellulose sodium, CMC; poly(vinylidene fluoride), PVDF; and poly(acrylic latex), LA133) on its electrochemical performance is studied. As a result, when using SA as the binder, the electrochemical performance of the NVPOF electrode is improved significantly, which is mainly because of the high water solubility, rich carboxyl and hydroxyl groups, and high adhesive and cohesive properties of the SA binder, leading to the uniform distribution of active materials NVPOF and carbon black in electrodes, good integrity, low polarization, and superior kinetic properties of the NVPOF electrodes, as demonstrated by scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic intermittent titration technique. More importantly, when coupled with a hard carbon anode, the fabricated sodium-ion full cells also exhibit excellent rate performance, thus providing a preview of their practical application. This work shows that the battery performance can be improved by matching suitable binder systems, which is believed to have great importance for the further optimization of the electrochemical performance of SIBs.
ABSTRACT
One main challenge for phosphate cathodes in sodium-ion batteries (SIBs) is to increase the working voltage and energy density to promote its practicability. Herein, an advanced Na3V2(PO4)2F3@C cathode is prepared successfully for sodium-ion full cells. It is revealed that, carbon coating can not only enhance the electronic conductivity and electrode kinetics of Na3V2(PO4)2F3@C and inhibit the growth of particles (i.e., shorten the Na+-migration path), but also unexpectedly for the first time adjust the dis-/charging plateaux at different voltage ranges to increase the mean voltage (from 3.59 to 3.71 V) and energy density (from 336.0 to 428.5 Wh kg-1) of phosphate cathode material. As a result, when used as cathode for SIBs, the prepared Na3V2(PO4)2F3@C delivers much improved electrochemical properties in terms of larger specifc capacity (115.9 vs. 93.5 mAh g-1), more outstanding high-rate capability (e.g., 87.3 vs. 60.5 mAh g-1 at 10 C), higher energy density, and better cycling performance, compared to pristine Na3V2(PO4)2F3. Reasons for the enhanced electrochemical properties include ionicity enhancement of lattice induced by carbon coating, improved electrode kinetics and electronic conductivity, and high stability of lattice, which is elucidated clearly through the contrastive characterization and electrochemical studies. Moreover, excellent energy-storage performance in sodium-ion full cells further demonstrate the extremely high possibility of Na3V2(PO4)2F3@C cathode for practical applications.
