Excellent Cycling Stability Research Articles

Oxygen-deficient NH4V4O10 cathode with Ag quantum dots and interlayer Ag+ towards high-performance aqueous zinc ion batteries

Herein, oxygen-deficient NH4V4O10 micro-flowers with loaded Ag quantum dots and pre-intercalated Ag+ (NVO-Ag) for aqueous zinc ion battery (AZIB) cathode materials were successfully synthesized by a one-step hydrothermal method. The reversible redox reaction between Ag+ and Ag quantum dots, and the abundant Zn2+ storage sites from oxygen vacancies provided capacity contributions for NVO-Ag. Meanwhile, the loaded Ag quantum dots, pre-intercalated Ag+ and introduced oxygen vacancies synergistically optimized the electronic structure and distribution of NVO-Ag, promoting the transport of electrons in NVO-Ag. The pre-intercalated Ag+ could also replace the NH4+ in the interlayer of NH4V4O10, weakening the repulsion between the interlayer NH4+ and Zn2+, which achieved rapid Zn2+ diffusion kinetics. Moreover, the abundant oxygen vacancies in NVO-Ag could alleviate the strong electrostatic interaction between Zn2+ and V-O framework, boosting the transmission of Zn2+ in NVO-Ag. Finally, the structural stability of NH4V4O10 micro-flowers was improved due to the high bonding strength between Ag+ and V-O layers. Benefiting from the above effects, NVO-Ag-100 achieved excellent capacity performance (387.2 mAh g−1 at 0.5 A g−1), rate performance (178.9 mAh g−1 at 12 A g−1) and cycle stability (91.7 % capacity retention after 1700 cycles at 8 A g−1). This work provided effective ideas to achieve high-performance AZIB cathode materials.

An organic cathode integrating carbonyl and imino groups for high-performance aqueous zinc-ion battery with air self-charging ability

Air-self-charging aqueous zinc-ion batteries (AZIBs) are a promising system applied in some special occasions, where no external power source can be provided to recharge the battery. Here, a new π-conjugated aromatic compound 2,7,12-tri(4H-1,2,4-triazol-4-yl)-1H-pyrrolo [3,4-b]pyrrolo[3′,4′:5,6]pyrazino[2,3f]pyrrolo[3′,4′:5,6]pyrazi-no[2,3−h]quinoxaline-1,3,6,8,11,13(2H,7H,12H)-hexaone (THQH) is reported. Because THQH contains multiple redox-active groups (CN and CO) and its insolubility in 2 M ZnSO4, as the cathode material of flexible/coin-type AZIBs, it owns outstanding discharge specific capacity, higher-rate performance and longer cycle life. Various ex-situ experiments and theoretical calculation revealed H+ and Zn2+ participated in the THQH cathode reaction. Notably, as the discharged flexible Zn//THQH battery is exposed to air, it can be self-recharged via the redox reaction between oxygen in air and the discharged THQH cathode, along with H+ ions removal. The flexible Zn//THQH battery can deliver a discharge capacity of up to 566 mA h g−1 at 0.5 A g−1, a higher-rate capability and an excellent self-charging cycle stability (31 cycles) after exposed to air for 28 h, displaying an excellent reusability. This work paves a way for the development of high-performance flexible air self-charging AZIBs.

Plasma-assisted surface modification of MXene/carbon nanofiber electrodes for electrochemical energy storage

Inferior ion diffusion and relatively low electrochemically active sites of MXene-based electrodes make them becoming a major challenge to develop advanced electrode. Surface modification of electrodes using non-thermal plasma is a great way to suppress these challenges through providing more space for energy storage and facilitating the diffusion of electrolyte ions. Herein, the effect of nitrogen and oxygen plasma treatments on MXene/carbon nanofiber electrode is reported to enhance the electrochemical performance. In this work, Ti3C2Tx MXene/CNF composites were fabricated using a hybrid needleless electrospinning/plasma method for the electrochemical energy storage. Surface modification of the composites was performed by a DBD plasma reactor under N2 and O2 gases at low-pressure glow discharge as a two-step plasma treatment process. The results revealed that total pore volume and the surface area of the plasma-treated Ti3C2Tx/CNF composite increased considerably due to the N2 and O2 plasma treatments. It was found that the electrochemical active surface area of the N2/O2-plasma-treated Ti3C2Tx/CNF electrode enhanced by approximately two times compared to the non-treated one, leading to the specific capacitance of 162 F/g at 1 A g−1 in a 2 M KOH electrolyte. The increase in electrochemical activity arises from separate doping of N2 and O2 plasma, which not only improves the pore structure and wettability, but also modifies the electrical conductivity and capacitance of the electrode. The N2/O2-plasma-treated Ti3C2Tx/CNF electrode achieved excellent cycling stability with 124 % capacitance retention after 10,000 cycles, while the capacitance retention of the pure N2 and O2-plasma-treated Ti3C2Tx/CNF electrodes as well as the non-treated one were 111 %, 105 % and 98 %, respectively. Additionally, an asymmetric supercapacitor N2/O2-plasma-treated Ti3C2Tx/CNF//AC based on the N2/O2-plasma-treated Ti3C2Tx/CNF as a positive electrode and activated carbon (AC) as a negative electrode was successfully constructed, which demonstrated an energy density of 26.3 Wh kg−1 with a power density of 750 W kg−1 at the current density of 1 A g−1 with excellent capacitance retention (102 %) after 5000 cycles. This work provides a highly efficient method for the surface modification of MXene-based electrodes through non-thermal plasma treatment.

Free‐Standing Si@C/CNFs Prepared by Simple Electrospinning as a Stable Anode for Lithium‐Ion Batteries

AbstractThe development of free‐standing and foldable electrodes with excellent electrochemical performance is paramount for flexible electronic devices. However, the silicon‐based free‐standing anodes lack a straightforward preparation process. Herein, we successfully designed a hierarchical Si@C/CNFs composite material by combining hydrothermal and electrospinning techniques, in which the carbon‐coated silicon (Si@C) is served as the primary nanostructure and carbon nanofibers (CNFs) from electrospinning are maintained as the network matrix, resulting in a free‐standing anode. Owing to the amorphous carbon coating on Si nanoparticles and the formation of a 3D network structure of CNFs, which tightly encases the primary Si@C nanostructure, the Si@C/CNFs electrode demonstrates exceptional conductivity and flexibility. This dual carbon‐layer structure further enhances kinetics and mitigates the volume expansion of Si nanoparticles. The Si@C/CNFs electrode exhibits a high specific capacity (1573 mAh g−1 at 0.1 A g−1), exceptional rate capability, and excellent cycling stability (78.5 % capacity retention after 100 cycles). Thus, Si@C/CNFs can be a promising material for the anode electrode in flexible lithium‐ion batteries.

Superior performance of asymmetric supercapacitor based on Cu doped bismuth ferrite electrode

Electrochemical energy storage devices, like supercapacitors and batteries, are needed to meet the constantly increasing demands of portable energy devices. Many types of supercapacitor electrodes were synthesized and reported which include carbon-based materials, polymers, oxides and perovskites. In this work, we report on the fabrication of Cu doped bismuth ferrite (Cu-BiFeO3, Cu-BFO) nanoparticles via sol-gel procedure. In most of the doping cases the costly rare earth elements like La, Nd, Sm, Ce and Yb are used to replace Bi. Electrodes of Bi1-xCuxFeO3 where x have the values 0.0, 0.025, 0.05, 0.075, 0.1 and 0.15 were deposited on graphitic sheets. Optimum Cu doping value was found to be at x = 0.05. Cu2+ ions doping in place of Bi3+ ions will reveal the roles of oxygen vacancies, as determined from XPS. The estimated values of specific capacitance was found to be 732 F/g at 0.5 A/g for the electrode at x = 0.05 in three electrode system. 5%Cu-BFO//Carbon black asymmetric supercapacitor (ASC) device can be charged and discharged reversibly at cell voltage of 0.0 up to 1.5 V when using a 0.5 M Na2SO4 aqueous electrolyte. This configuration allows the ASC device to deliver a great energy density of 37.25 Wh/kg at a power density of 752 W/kg. The ASC device demonstrates excellent cycling stability, retaining 88.64 % of its initial specific capacitance after 5000 cycles. Increasing the Cu content up to 15 % causes instability in the crystal structure of BFO resulting on phase segregation into Bi2Fe4O9 along with BFO and deterioration in the electrode overall performance. XPS showed that replacement of Cu2+ in place of Bi3+ disturbs the neutrality and the chemical environment of the compound. Hence to achieve neutrality and ionic balance, oxygen vacancies increase and the Fe2+/Fe3+ ratio increases as well. Both oxygen vacancies and the change in the Fe ions ratio reduce electrochemical impedance and give rise to charge density. The homogenous distribution of the pores at x = 0.05 contributed greatly to its fast electrolyte ion diffusion that improved the observed capacitive properties. One has to mention here, that despite doping that contains ions with different ionic size and/or different oxidation state is unfavorable, to some extent, due to the changes they produce in the electronic structure and the chemical environment, nevertheless it is sometimes beneficial in creating new parameters in the structure that promote specific application like in the case of the current work, oxygen vacancies, increase in surface area and the mixed state valency.

Flexible electrospun carbon nanofibers - Nickel disulfide@carbon nanofibers - Carbon nanofibers sandwich structure as binder-free anode for high performance lithium-ion batteries

People have recently shown increasing interest in wearable and flexible electronics. Due to their high electrical conductivity and flexibility, carbon nanofibers can be utilized for various flexible applications. However, pure carbon nanofibers have low capacity, which makes it challenging to achieve high capacity for flexible applications. Herein, sandwich-like nanofibers - nickel disulfide@carbon nanofibers - carbon nanofibers are obtained through a multi-step electrospinning process to serve as a flexible binder-free anode for lithium-ion batteries. This strategy stabilizes the structure well with two layers of carbon nanofibers, effectively accelerating the Li+diffusion and promoting the electrolyte infiltration. Accordingly, the electrode exhibits a discharge capacity of 551.8 mAh g-1 at 0.1 A g-1 after 100 cycles and achieves a discharge capacity of 523.8 mAh g-1 at 1 A g-1 after 1000 cycles, demonstrating excellent cyclic stability and high capacity for Li+ storage. The kinetic analysis also reveals that the sandwich structure provides a higher capacity contribution. This work introduces a novel approach for creating flexible binder-free anodes with high performance, effectively expanding the application of sulfides through electrospinning.

Dome structure nonwoven-based dual-mode pressure-humidity sensor: Enhancing sensitivity and breathability for human health monitoring

In the field of health monitoring and electronic skin, flexible wearable sensors have attracted considerable research interest. However, preparing a flexible multifunctional sensor that simultaneously possesses a rapid response time, stability, reliability, high breathability, as well as high sensitivity remains a significant challenge. Herein, a flexible pressure-humidity dual-mode sensor based on nonwoven fabrics is developed in this study, using hydroentangled nonwoven fabric with graphene oxide/carbon nanotube composite as the sensing layer and polyester plain nonwoven fabric with carbon nanotube printed interdigitated electrodes as the electrode layer. The sensor exhibits high permeability (649.2 mm/s), high sensitivity (2.72 kPa−1), wide sensing range (0–220 kPa), fast response/recovery time (24.4 /73.3 ms), and low detection limit (2.79 Pa). In addition, the sensor exhibits excellent cyclic stability (15,000 cycles) and can detect both weak body movements (pulses, swallowing) as well as large deformational movements (joint movements). Furthermore, the sensing layer of the sensor responds quickly to different humidity levels, which can be used to monitor humidity in real time, and human breathing and speech can be monitored by placing it inside a mask. This high-performance flexible pressure-humidity dual-mode sensor shows promising potential for applications in health monitoring and respiratory monitoring.

Long-Cycling Cellulose-Based Gel Polymer Electrolyte Utilizing Nanohydrotalcite as a Li+ Transport Redistributor.

The hydroxyl groups on the surface of the cellulose-based gel polymer electrolyte lead to poor interfacial compatibility due to side reactions with lithium sheets. In this paper, a novel cellulose-based gel polymer electrolyte was prepared by uniformly coating the surface of a cellulose membrane with a nanohydrotalcite/PVDF-HFP composite using electrospinning technology. This cellulose-based gel polymer electrolyte exhibits good interfacial compatibility and excellent cycling stability (91.7% specific capacity retention after 500 cycles at 0.5C). Theory and experiments have shown that nanohydrotalcite on the surface of cellulose membrane can effectively prevent the contact of hydroxyl groups with lithium sheets to reduce the side reactions. In addition, nanohydrotalcite can also act as a Li+ transport redistributor to facilitate the uniform deposition of Li+ and reduce the formation of lithium dendrites to extend the cycle life.

Deciphering the energy storage mechanism of CoS2 nanowire arrays for High-Energy aqueous copper-ion batteries

Transition metal sulfide (TMs) offers ultra-high specific capacity through multi-electron transfer, showing promise for aqueous batteries. However, the poor cycling performance and the uncleared energy storage mechanism are restricted from further development. Herein, CoS2 nanowire arrays grown on carbon cloth (CoS2/CC) are proposed as binder-free and self-supporting electrodes for aqueous copper-ion batteries. The energy storage mechanism is clarified by a series of ex-situ tests: a multi-electron electrode reaction through a three-step reaction of CoS2 → CuS → Cu7S4 → Cu2S. Electrochemical results suggest that the CoS2/CC cathode exhibits excellent long cycle stability (capacity retention of 99.7 % after 1000 cycles at 10 A/g) along with high specific capacity (762.3 mAh g−1 at 1 A/g). The carbon cloth with stable three-dimensional (3D) conductive structure can not only offer high-speed pathways to promote the transfer of electrons but also inhibit the volume change. Meanwhile, CoS2 nanowire arrays with high surface-to-volume ratios can improve wettability of electrolyte and promote redox reactions. Furthermore, an advanced Zn-CoS2/CC hybrid ion aqueous battery reveals an energy density of 724 Wh kg−1 and an output voltage of 1.24 V, providing a promising strategy for the establishment of transition metal sulfide cathode in high-energy aqueous batteries.

Preparation and photothermal properties of latent functional thermal fluid based on size-controllable phase change nanocapsules

To improve the solar heat utilization efficiency of working fluid in direct solar collector, a novel latent functional thermal fluid (LFTF) based on self-designed 1-octadecanol@silica phase change nanocapsules (NEPCMs) with excellent heat storage capacity and photothermal conversion efficiency were prepared. The NEPCMs prepared by sol–gel method were dispersed in water containing multi-walled carbon nanoparticles to prepare the LFTF. The prepared NEPCMs have high encapsulation efficiency (85.12 %) and melting phase change enthalpy (235.1 J/g), controllable particle size (27.13–167.30 nm), excellent thermal stability and cycle stability. The LFTF containing 10 wt% NEPCMs was considered the optimal choice for its excellent dispersion stability (zeta potential 35.63 mV), thermal storage capacity (peak specific heat capacity 5.11 J·g−1·K−1) and superior photothermal conversion efficiency (up to 98 %), which is roughly 3.29 times that of water. These results offer valuable insights for the future development of LFTF in the field of solar thermal applications.

In situ constructing 2D/2D layered BiOBr/Bi2O2CO3 heterostructure for efficient photocatalytic reduction CO2 to CO

Photocatalytic reduction of CO2 to valuable energy materials is necessary for sustainable development. It is a considerable challenge to prepare photocatalysts for CO2 photoreduction with excellent separation capability of carriers by simple way. Herein, the BiOBr/Bi2O2CO3 type-II heterostructure was constructed by in situ conversion at room temperature. Combining the advantages of the 2D/2D layered structure can form a close contact interface and the type-II heterostructure can facilitate the transport of photogenerated charges, the BiOBr/Bi2O2CO3 composite showed significant enhancement in photocatalytic CO2 reduction performance. The most obvious performance enhancement was observed for 2.0-BiOBr/Bi2O2CO3, where CO yield could reach 29.55 μmol·g−1 for 3 h under light irradiation, it is 11 and 4 times higher than Bi2O2CO3 and BiOBr, respectively. And the sample exhibits excellent cycling stability in photocatalytic tests. In situ Fourier Transform Infrared spectroscopy confirmed that the important intermediates of the reaction are *COOH and *CO. The photocatalytic reduction mechanism of CO2 to CO in the BiOBr/Bi2O2CO3 type-II heterostructure was further analyzed. This study provides feasible solutions for selecting photocatalytic materials and designing facile preparation of efficient 2D/2D catalysts for photocatalytic reduction of CO2.

Preparation of Zirconium-Based MOF-Derived Phosphide on GO/MXene Double Substrates for High-Performance Asymmetric Supercapacitors.

At present, it is very necessary to select and prepare suitable positive and negative electrode materials to fabricate high-performance asymmetric supercapacitors. Metal-organic frameworks (MOFs) have garnered significant attention in the energy storage field due to their high conductivity. As a branch, the zirconium organic framework (UIO-66) is a promising porous material due to its large specific surface area and abundant Zr centers. Graphene oxide (GO) and MXene are very suitable as substrate materials for conducting an MOF due to their abundant active sites and adjustable interlayer distance. The GO/MXene@NiZrP prepared through an in situ composite of GO and Mxene with the hydrothermal method and calcining method showed excellent electrochemical performance. Compared with the precursor UIO-66, the specific capacitance of the final product GO/MXene@NiZrP increases more than ten times, mainly because of its special layered porous structure, and GO/MXene@NiZrP has a larger specific surface area, pore volume, and surface defects caused by unstable Zr4+ than those of UIO-66. Using GO/MXene@NiZrP as the positive electrode and biochar (BC) as the negative electrode, an asymmetric supercapacitor, BC//GO/MXene@NiZrP, is assembled. After 10,000 cycles at a current density of 10 A g-1, the capacitance retention remains at 83.3%, showing excellent cycle stability.

Hierarchical 2D/1D MOFs/electrospun ZIF-67 modified carbon nanofibers heterostructure electrode for high-performance asymmetric supercapacitor

In this paper, a 2 dimensional (2D) metal–organic frameworks (MOFs) nanosheets grown on 1D ZIF-67 modified carbon nanofibers (CNFs) was designed and fabricated with a hierarchical heterostructure. The hierarchical 2D/1D MOFs/CCNF offers rich electrochemical active sites and favorable ion/electron diffusion pathways. The synergistic effect of Co, CNFs and MOFs from heterostructures contributes to superb electrochemical activities. Benefiting from the hierarchical heterostructures optimized by the mass ratio of ZIF-67/PAN and CCNF/NiMOF as well as the type of substrates, CCNF-20@MOF showed a specific capacity of 361.50 C g−1 at 0.5 A g−1, whose charge storage mechanism is dominated by diffusion control. Meanwhile, a bamboo-derived carbon material (BBC) was designed in the solid-state asymmetric supercapacitor (CCNF-20@MOF//BBC). The device exhibited an energy density of 38.89 Wh kg−1 at the power density of 800.02 W kg−1 and excellent cycling stability, that exceed many MOFs based devices. Moreover, it could be successfully used for LED light-emitting, demonstrating a good application prospect. This work provides a feasible strategy for the improved performance of MOFs and CNFs based materials in the field of energy storage.

Constructing stress-release layer on Si nanoparticles for high-performance lithium storage

Tailing structures of silicon anode to alleviate the mechanical stress has an important significance in the development of lithium-ion batteries (LIBs). Herein, the stress-released layer of N-doped cubic carbon on the surface of Si nanoparticles (Si@NCC) is explored to stabilize the electrode. Endowed with the unique superiority, the Si@NCC electrode delivers an impressive lithium storage performance with high specific capacity of 630 mAh/g at 0.1 A/g, excellent cycling stability (72.0 % capacity retention after 100 cycles at 0.1 A/g) and good rate capability (375 mAh/g at 2 A/g). It has been demonstrated that the N-doped cubic carbon shell with high conductivity can effectively limit the expansion and agglomeration of Si nanoparticles. Besides, the COMSOL simulations of the stress distributions in materials confirm that the N-doped cubic carbon layer could remarkably decrease the stress originated from the volume expansion of Si nanoparticles during the lithiation. Therefore, this work provides ideas for the mechanical effect of Si-based anodes for lithium storage and sheds lights on the designing advanced materials toward high-performance energy storage devices.

Dual Li ion transport channels in a dynamical supramolecular solid electrolyte toward safety and high-performance Li metal batteries

The polymer based quasi-solid electrolyte (QSE), which combines the high ionic conductivity of the liquid electrolytes with the excellent mechanical flexibility of the polymer matrix, is highly desired and most promising for Li metal batteries (LMBs). However, the Li+ transfer pathways in QSE is not clear enough, and the practical applications in LMBs are also hindered by safety hazards arising from risks of mechanical damage, flammability and high voltage instability. Here, a dynamical supramolecular QSE with abundant hydrogen bonds to fabricate stable and safety LMBs, is reported. In this designed electrolyte, both thermal stability and superior interface stability with anode/cathode electrodes were achieved. Notably, the dual Li+ transport channels in QSE were investigated using in-situ FTIR technology and DFT calculations, providing insights into both the “wet” liquid phase and “dry” polymer chain channels. Benefiting from this design, the Li||NCM622 full batteries based on this QSE exhibit excellent long-term cycling stability.

Highly stable aqueous Zn−I2 batteries enabled by the synergistic adsorption/conversion effect via porous graphitic iodine host

Aqueous zinc-iodide batteries (AZIBs) are considered to be the promising candidate after lithium-ion batteries due to their low cost and high safety. However, the poor electrical conductivity of iodine and the notorious shuttle effect brought about by resolvable polyiodides have seriously hindered the widespread application prospects of AZIBs. In this work, we develop a sample and effective strategy for synthesizing N-doped hierarchical porous graphitized carbon (CN-Mg-CaCO3) that shows great potential as a host material for iodine confinement. The unique porous structure with graphitic domains and synergistic effects of surface adsorption and efficient conversion contribute to the high performance of AZIBs, with notable specific capacity (185 mA h g−1 at 0.1 mA g−1), impressive rate capability (114 mA h g−1 at 10 A g−1), and excellent long-term cycling stability (85 % retention after 104 cycles at 5 A g−1). The elaborately constructed conductive carbon skeleton enhances iodine utilization, while the redox reaction of I2/I- occurs without the formation of intermediates I3-. Additionally, the presence of surface adsorbed Zn2+ leads to enhanced pseudo-capacitance. This research introduces innovative approaches and broadens new ideas for developing cathode materials for AZIBs.

Enhanced Vanadium Redox Flow Battery Performance with New Amphoteric Ion Exchange Membranes.

Vanadium redox flow batteries (VRFBs) depend on the separator membrane for their efficiency and cycle life. Herein, two amphoteric ion exchange membranes are synthesized, based on sulfonic acid group-grafted poly(p-terphenyl piperidinium), for VRFBs. Using ether-free poly(p-terphenyl piperidine) (PTP) as the polymer matrix, and sodium 2-bromoethanesulphonate (ES) and 1,4-butane sultone (BS) as grafting agents, We achieve quaternization of PTP through an environmentally friendly process without alkaline catalysts. PTP-ES and PTP-BS membranes exhibit low area resistance, high H+ permeability, and significantly reduced vanadium ion permeability, leading to exceptional ion selectivity, which is 3.06×106Smincm-3 and 4.34×106Smincm-3, respectively,three orders of magnitude higher than that of Nafion115 (0.27×104Smincm-3). The VRFB with PTP-BS achieves a self-discharge duration of 190h, compared to 86h for Nafion 115. Additionally, under current densities of 40-160mAcm-2, PTP-BS shows coulombic efficiencies of 98.1-99.1% and energy efficiencies of 92.0-82.1%, outperforming Nafion 115. The VRFB with PTP-BS also demonstrates excellent cycle stability and discharge capacity retention over 300 cycles at 100mAcm-2. Therefore, the amphoteric PTP-BS membrane shows remarkable performance, offering significant potential for VRFB applications.

Enhancing Reversibility and Kinetics of Anionic Redox in O3‐NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth

AbstractAnionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium‐ion batteries, O3‐NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27 % P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87 %, comparable to the state‐of‐the‐art Li‐rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X‐ray Diffraction. The as‐prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g−1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.

Entropy-Driven 60mol% Li Electrolyte for Li Metal-Free Batteries.

Highly Li-concentrated electrolytes are acknowledged for their compatibility with Li metal negative electrodes and high voltage positive electrodes to achieve high-energy Li metal batteries, showcasing stable and facile interfaces for Li deposition/dissolution and high anodic stability. This study aims to explore a highly concentrated electrolyte by adopting entropy-driven chemistry for Li metal-free (so-called anode-free) batteries. The combination of lithium bis(fluorosulfonyl)amide (LiFSA) and lithium trifluoromethanesulfonate (LiOTf)salts in a pyrrolidinium-based ionic liquid is found to significantly modify the coordination structure, resulting in an unprecedented 60mol% Li concentration and a low solvent-to-salt ratio of 0.67:1 in the electrolyte system. This novel 60mol% Li electrolyte demonstrates unique coordination stricture, featuring a high ratio of monodentate-anion structures and aggregates, which facilitates an enhanced Li+ transference number and improved anodic stability. Moreover, the developed electrolyte provides a facile de-coordination process and leads to the formation of an anion-based solid electrolyte interface, which enables stable Li deposition/dissolution properties and demonstrates excellent cycling stability in the Li metal-free full cell with a Li[Ni0.8Co0.1Mn0.1]O2 (NCM811) positive electrode.

Enhancing Reversibility and Kinetics of Anionic Redox in O3-NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth.

Anionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium-ion batteries, O3-NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27 % P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87 %, comparable to the state-of-the-art Li-rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X-ray Diffraction. The as-prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g-1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.