Band Structure Engineering Promotes Anionic Redox Reversibility of Cobalt-Free Li-Rich Layered Oxides Cathodes.

Li-rich layered oxides cathodes (LLOs) have prevailed as the promising high-energy-density cathode materials due to their distinctive anionic redox chemistry. However, uncontrollable anionic redox process usually leads to structural deterioration and electrochemical degradation. Herein, a Mo/Cl co-doping strategy is proposed to regulate the relative position of energy band for modulating the anionic redox chemistry and strengthening the structural stability of Co-free Li1.16Mn0.56Ni0.28O2 cathodes. The incorporation of Mo with high d state orbit and Cl with low electronegativity can narrow the band energy gap between bonding and antibonding bands via increasing the filled lower-Hubbard band (LHB) and decreasing the non-bonding O 2p energy bands, promoting the anionic redox reversibility. In addition, strong covalent Mo─O and Mn─Cl bonding further increases the covalency of Mn─O band to further stabilize the O2 n- species and enhance the reversible distortion of MnO6 octahedron. The strengthening electronic conductivity, together with the epitaxial structure Li2MoO4 facilitates the fast Li+ kinetics. As a result, the dual doping material exhibits enhanced anionic redox reversibility and suppressed oxygen release with increased cyclic stability and excellent rate performance. This strategy provides some guidance to design high-energy-density LLOs with desirable anionic redox reversibility and stable crystal structure via band structure engineering.

Rational Design of an In-Situ Polymer-Inorganic Hybrid Solid Electrolyte Interphase for Realising Stable Zn Metal Anode under Harsh Conditions.

The in-depth understanding of the composition-property-performance relationship of solid electrolyte interphase (SEI) is the basis of developing a reliable SEI to stablize the Zn anode-electrolyte interface, but it remains unclear in rechargeable aqueous zinc ion batteries. Herein, a well-designed electrolyte based on 2 M Zn(CF3SO3)2-0.2 M acrylamide-0.2 M ZnSO4 is proposed. A robust polymer (polyacrylamide)-inorganic (Zn4SO4(OH)6.xH2O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO4 2- with Zn2+ and OH-. For the first time, the underlying SEI composition-property-performance relationship is systematically investigated and correlated. The results showed that the polymer-inorganic hybrid SEI, which integrates the high modulus of the inorganic component with the high toughness of the polymer ingredient, can realize high reversibility and long-term interfacial stability, even under ultrahigh areal current density and capacity (30 mA cm-2~30 mAh cm-2). The resultant Zn||NH4V4O10 cell also exhibits excellent cycling stability. This work will provide a guidance for the rational design of SEI layers in rechargeable aqueous zinc ion batteries.

Stabilized Anionic Redox by Rational Structural Design from Surface to Bulk for Long-Life Fast-Charging Li-Rich Oxide Cathodes.

On account of high capacity and high voltage resulting from anionic redox, Li-rich layered oxides (LLOs) have become the most promising cathode candidate for the next-generation high-energy-density lithium-ion batteries (LIBs). Unfortunately, the participation of oxygen anion in charge compensation causes lattice oxygen evolution and accompanying structural degradation, voltage decay, capacity attenuation, low initial columbic efficiency, poor kinetics, and other problems. To resolve these challenges, a rational structural design strategy from surface to bulk by a facile pretreatment method for LLOs is provided to stabilize oxygen redox. On the surface, an integrated structure is constructed to suppress oxygen release, electrolyte attack, and consequent transition metals dissolution, accelerate lithium ions transport on the cathode-electrolyte interface, and alleviate the undesired phase transformation. While in the bulk, B doping into Li and Mn layer tetrahedron is introduced to increase the formation energy of O vacancy and decrease the lithium ions immigration barrier energy, bringing about the high stability of surrounding lattice oxygen and outstanding ions transport ability. Benefiting from the specific structure, the designed material with the enhanced structural integrity and stabilized anionic redox performs an excellent electrochemical performance and fast-charging property..

High-Entropy Doping Boosts Ion/Electronic Transport of Na4 Fe3 (PO4 )2 (P2 O7 )/C Cathode for Superior Performance Sodium-Ion Batteries.

Fe-based mixed phosphate cathodes for Na-ion batteries usually possess weak rate capacity and cycle stability challenges resulting from sluggish diffusion kinetics and poor conductivity under the relatively low preparation temperature. Here, the excellent sodium storage capability of this system is obtained by introducing the high-entropy doping to enhance the electronic and ionic conductivity. As designed high-entropy doping Na4 Fe2.85 (Ni,Co,Mn,Cu,Mg)0.03 (PO4 )2 P2 O7 (NFPP-HE) cathode can release 122 mAh g-1 at 0.1 C, even 85 mAh g-1 at ultrahigh rate of 50 C, and keep a high retention of 82.3% after 1500 cycles at 10 C. Besides, the cathode also exhibits outstanding fast charge capacity in terms of the cyclability and capacity with 105 mAh g-1 at 5 C/1 C, corresponding 94.3% retention after 500 cycles. The combination of in situ X-ray diffraction, density functional theory, conductive-atomic force microscopy, and galvanostatic intermittent titration technique tests reveal that the reversible structure evolution with optimized Na+ migration path and energy barrier boost the Na+ kinetics and improve the interfacial electronic transfer, thus improving performance.

The wetting characteristics of aluminum droplets on rough surfaces with molecular dynamics simulations.

In the present study, the impact of surface roughness on the wettability behavior of Al droplets has been investigated via molecular dynamics (MD) simulations. In this work, amorphous carbon (AC) and graphite substrates with different depths and widths were considered. The results show that the increased width of grooves causes the transition of the wetting state from Cassie to Wenzel. Thermodynamic property analysis results indicate that the solid-liquid adhesion and the work done for the removal of the Al droplet from the solid surface decrease as the roughness increases. However, the adhesion in the Wenzel wetting state is better than that in the Cassie wetting state. Therefore, the contact angle increases with the increased roughness in the Cassie wetting systems, while in the Wenzel wetting systems, the contact angle is less than that in other rough systems. In addition, due to the heterogeneity of the surfaces, the density of Al droplets in the solid-liquid interface is decreased with the increased roughness. The anisotropic spreading of Al liquid can be explained by the MSD curves along the X and Y directions.

Coalescence and wetting mechanism of Al droplets on different types of carbon for developing wettable cathodes: a molecular dynamics simulation.

So far, there have been few studies on the microscopic wetting behavior of aluminum liquid on cathode surfaces, which is critical for developing wettable cathode materials. In the present study, an investigation on the coalescence and wetting mechanism of Al droplets on different carbonaceous substrates has been performed via molecular dynamics (MD) simulation for developing wettable cathodes. The growth rate of liquid bridge, the mean squared displacement, the balanced contact angle, and the time of full coalescence were calculated to describe the coalescence and wetting of the Al droplets. The results illustrate the sequence of full coalescence time for the Al droplets: DG < HCNT < VCNT ≈ AC and the corresponding balanced contact angles were 47.98°, 53.32°, 55.02°, and 63.12°, respectively. Furthermore, the presence of defects on DG will increase the time of coalescence and the contact angle but the directions of defects have little influence. The free energy analysis indicates that the defects reduce the solid-liquid interaction and the work done for removing the Al droplet from the substrates so that the wettability is weaker than that for perfect graphene, which also explains the balanced wettability of Al droplets on the other substrates. In addition, the surface roughness increases the contact angle of Al liquid on AC (from 62° to 113°-120°) and hence, the wettability is changed from good to poor. In general, our results can improve the understanding of the wetting of AC and graphene by Al liquid at the atomic level, which can provide direction and theoretical guidance for further research on wettable cathodes.

Ionic micro-structure and transport properties of low-temperature aluminium electrolytes containing potassium cryolite and sodium cryolite.

Nowadays, low-temperature aluminium electrolytes are reported to have good prospects for application in the industrial process of aluminium production. In this paper, low-temperature electrolytes containing potassium cryolite and sodium cryolite with a cryolite ratio of 1.3 were investigated by using first-principles molecular dynamics simulation. This calculation reproduces the ionic structure of low-temperature 1.3(KF + NaF)-AlF3 electrolytes, indicating that [AlF4]-, [AlF5]2- and [AlF6]3- are the fundamental aluminum-fluoro clusters and [AlF5]2- is the predominant species. The calculated results for the ionic structure indicate that molten 1.3(KF + NaF)-AlF3 electrolytes have a high ionic polymerization degree, which is unfavorable for the transport properties of low-temperature 1.3(KF + NaF)-AlF3 electrolytes. Fortunately, increasing the mass fraction of NaF can effectively reduce the polymerization degree of ionic structure and thus improve the ionic conductivity of low-temperature 1.3(KF + NaF)-AlF3 electrolytes, which is an important guiding factor for the component selection of low-temperature electrolytes in future. Also, DFT calculations were adopted to further analyse the small aluminum-fluoro complexes. The calculated Raman spectrum of the aluminum-fluoro complexes is excellently consistent with literature results. Our calculated ionic conductivity falls in between the estimated value of the empirical equation of different literature studies, demonstrating that our results may be more precise than the literature results. This further proves the practicability of our modified N-E equation.

Association of Matrix Metalloproteinase-1 and Matrix Metalloproteinase-3 Gene Variants with Ischemic Stroke and Its Subtype.

BACKGROUND: Genetic variations in the genes of matrix metalloproteinases (MMPs) may play an important role in the pathogenesis of ischemic stroke (IS). Here we investigate the association between MMP-1 -1607 1G/2G and MMP-3 -1171 5A/6A genetic polymorphisms and etiological subtypes of IS in the Han Chinese population. METHODS: A total of 640 eligible patients with IS and 637 age- and gender-matched apparently healthy volunteers were enrolled. Subtypes of IS were classified by Trial of Org 10172 in Acute Stroke Treatment criteria. MMP-1 (-1607 1G/2G) and MMP-3 (-1171 5A/6A) polymorphisms were evaluated using polymerase chain reaction-restriction fragment length polymorphism. RESULTS: The frequencies of the 5A/6A + 5A/5A genotypes and 5A allele were significantly higher in patients with IS than in controls (P <.001, P <.001, respectively). No association was found between MMP-1 1G/2G polymorphism and overall IS. In subgroup analyses, MMP-1 1G/2G and 2G/2G genotypes increased the risk of small-artery occlusion (SAO) subtype (multivariate-adjusted, P <.001, P = .002, respectively), and MMP-3 5A/6A + 5A/5A genotypes were related with large-artery atherosclerosis (LAA) subtype (multivariate-adjusted, P <.001). Haplotype analyses indicated that 2G-6A and 1G-5A increased the risk of SAO (multivariate-adjusted, P = .029) and LAA (multivariate-adjusted, P <.001), respectively. CONCLUSIONS: MMP-1 (-1607 1G/2G) and MMP-3 (-1171 5A/6A) polymorphisms may contribute to different subtypes of IS susceptibility.

Impact of 5A/6A polymorphism of matrix metalloproteinase-3 on recurrent atherosclerotic ischemic stroke in Chinese.

Little is known about the impact of the 5A/6A polymorphism of matrix metalloproteinase-3 (MMP-3) on recurrence of atherosclerotic ischemic stroke in Chinese. The aim of this study was to investigate the association of MMP-3 serum level and 5A/6A genetic polymorphism with the recurrence of atherosclerotic ischemic stroke in the Chinese Han population. We analyzed 106 large artery atherosclerosis (LAA) recurrent ischemic stroke patients and 545 LAA first onset ischemic stroke patients from January 2009 to June 2014. Serum MMP-3 concentrations were measured with an enzyme-linked immunosorbent assay. The genotypes of MMP-3 promoter polymorphism (-1171 5A/6A) were determined using polymerase chain reaction-restriction fragment length polymorphism. The frequencies of MMP-3 5A/6A+5A/5A (32.08% vs. 21.47%, p = 0.02) genotype and 5A (16.98% vs. 11.01%, p = 0.01) allele in the recurrent group was significantly higher than those in the first onset group. After adjustment for vascular risk factors, multivariate logistic regression analysis suggested that the MMP-3 5A/6A+5A/5A genotype was an independent risk factor for LAA recurrent ischemic stroke (odds ratio [OR], 1.74; 95% confidence interval [CI], 1.09-2.79, p = 0.021). No significant difference was observed for the MMP-3 serum concentrations between the recurrent group and the first onset group (22.23 ± 8.31 vs. 21.49 ± 7.89 ng/ul, t = 0.88, p = 0.38). The MMP-3 (-1171 5A/6A) polymorphism may contribute to LAA recurrent ischemic stroke susceptibility. Analysis of 5A/6A polymorphism in MMP-3 may identify patients at higher risk for LAA ischemic stroke recurrence, who may be selected for intensive preventive therapy.

Anion Substitution Strategy toward an Advanced NASICON-Na4Fe3(PO4)2P2O7 Cathode for Sodium-Ion Batteries.

Superior sodium-ion batteries (SIBs) greatly need cathode materials with higher capacity and better durability. Herein, the anion group substitution strategy is proposed to design a cathode material with extraordinary Na+ storage performance, NASICON-Na4Fe3(PO4)1.9(SiO4)0.1P2O7 (NFPP-Si0.1). The experimental and theoretical research revealed that modification in the local structure by anion substitution significantly boosts the ionic/electronic transfer kinetics via optimizing the electronic conductivity and reducing the Na+ diffusion energy barrier. Furthermore, the SiO44- substitution generates a slight expansion of the crystal lattice to broaden the Na+ diffusion channel. Specifically, the custom-designed NFPP-Si0.1 could deliver a high rate capability of 77.6 mAh g-1 at constant 50 C charge-discharge and excellent recyclability of 79.4% retention rate after 7000 cycles at 10 C. Besides, it also possesses outstanding low temperature reversible capacity of 95.5 mAh g-1 at 0.1 C and long-term cyclability of 93.6% capacity retention after 1000 cycles at 5 C in -10 °C. This strategy of heterogeneous and isostructural anion group substitution provides a method for unlocking high-rate and long-life-span mixed polyanionic cathodes.

Double S-scheme Cu2-xSe/twinned-Cd0.5Zn0.5S homo-heterojunctions with surface plasmon effects for efficient photocatalytic H2 evolution.

The enhancement of charge separation and utilization efficiency in both the bulk phase and interface of semiconductor photocatalysts, as well as the expansion of light absorption range, are crucial research topics in the field of photocatalysis. To address this issue, twinned Cd0.5Zn0.5S (T-CZS) homojunctions consisting of wurtzite Cd0.5Zn0.5S (WZ-CZS) and zinc blende Cd0.5Zn0.5S (ZB-CZS) were synthesized via a hydrothermal method to facilitate the bulk-phase charge separation. Meanwhile, Cu2-xSe with localized surface plasmon resonance effect (LSPR) generated by Cu vacancies was also obtained through a hydrothermal process. Due to their opposite electronegativity, a solvent evaporation strategy was employed to combine Cu2-xSe and T-CZS by intermolecular electrostatic. After optimization, the photocatalytic hydrogen (H2) evolution rate of 5 wt% Cu2-xSe/T-CZS reached an impressive value of 60 mmol∙h-1∙g-1, which was 4.6 and 66.6 times higher than that of pure Cu2-xSe and T-CZS, respectively. Furthermore, this composites demonstrated a remarkable rate of 0.46 mmol∙h-1∙g-1 under near-infrared (NIR) wavelength (>800 nm). The enhanced performance observed in Cu2-xSe/T-CZS can be attributed to its unique and efficient double S-scheme charge transfer mechanism which effectively suppresses rapid recombination of electron-hole pairs both within the bulk phase and at the surface interfaces; this conclusion is supported by Density Functional Theory (DFT) calculations as well as electron paramagnetic resonance spectroscopy analysis. Moreover, incorporation of Cu2-xSe enables effective utilization ultraviolet visible-near infrared (UV-Vis-NIR) light by the composites while facilitating injection "hot electrons" into T-CZS for promoting photocatalytic reactions. This study provides a potential strategy for achieving efficient solar energy conversion through synergistic integration of non-stoichiometric plasmonic materials with photocatalysts with twinned-twinned structures.

Rational design of intergrowth P2/O3 biphasic layered structure with reversible anionic redox chemistry and structural evolution for Na-ions batteries.

Layered oxides have attracted unprecedented attention for their outstanding performance in sodium-ion battery cathodes. Among them, the two typical candidates P2 and O3 type materials generally demonstrate large diversities in specific capacity and cycling endurance with their advantages. Thus, composite materials that contain both P2 and O3 have been widely designed and constructed. Nevertheless, the anionic/cationic ions' behavior and structural evolution in such complex structures remain unclear. In this study, a deep analysis of an advanced Na0.732Ni0.273Mg0.096Mn0.63O2 material that contains 78.39 wt% P2 phase and 21.61 wt% O3 phase is performed based on two typical cathodes P2 Na0.67Ni0.33Mn0.67O2 and O3 NaNi0.5Mn0.5O2 that have the same elemental constitution but different crystal structures. Structural analysis and density functional theory (DFT) calculations suggest that the composite is preferred to form a symbiotic structure at the atomic level, and the complex lattice texture of the biphase structure can block unfavorable ion and oxygen migration in the electrode process. Consequently, the biphase structure has significantly improved the electrochemical performance and kept preferable anionic oxygen redox reversibility. Furthermore, the hetero-epitaxy-like structure of the intergrowth of P2 and O3 structures share multi-phase boundaries, where the inconsistency in electrochemical behavior between P2 and O3 phases leads to an interlocking effect to prevent severe structural collapse and relieves the lattice strain from Na+ de/intercalation. Hence, the symbiotic P2/O3 composite materials exhibited a preferable capacity and cyclability (∼130 mAh g-1 at 0.1 C, 73.1% capacity retention after 200 cycles at 1 C), as well as reversible structural evolution. These findings confirmed the advantages of using the bi/multi-phase cathode for high-energy Na-ion batteries.

Trace Amounts of Triple-Functional Additives Enable Reversible Aqueous Zinc-Ion Batteries from a Comprehensive Perspective.

Although their cost-effectiveness and intrinsic safety, aqueous zinc-ion batteries suffer from notorious side reactions including hydrogen evolution reaction, Zn corrosion and passivation, and Zn dendrite formation on the anode. Despite numerous strategies to alleviate these side reactions have been demonstrated, they can only provide limited performance improvement from a single aspect. Herein, a triple-functional additive with trace amounts, ammonium hydroxide, was demonstrated to comprehensively protect zinc anodes. The results show that the shift of electrolyte pH from 4.1 to 5.2 lowers the HER potential and encourages the in situ formation of a uniform ZHS-based solid electrolyte interphase on Zn anodes. Moreover, cationic NH4+ can preferentially adsorb on the Zn anode surface to shield the "tip effect" and homogenize the electric field. Benefitting from this comprehensive protection, dendrite-free Zn deposition and highly reversible Zn plating/stripping behaviors were realized. Besides, improved electrochemical performances can also be achieved in Zn//MnO2 full cells by taking the advantages of this triple-functional additive. This work provides a new strategy for stabilizing Zn anodes from a comprehensive perspective.

Insights into the mechanism of fluoride adsorption over different crystal phase alumina surfaces.

Activated alumina is the most common adsorbent for purifying fluoride in water, however, little is known so far about the adsorption mechanisms and comparison of adsorption behaviors for F on different crystal phase alumina surfaces, which seriously obstacles the development of high-performance sorbents. Herein, employing the density functional theory approach, we have studied F adsorbed on α-Al2O3(0001), γ-Al2O3(110), and θ-Al2O3(010) surfaces. Results accentuate that the θ-Al2O3 (010) is the most reactive than ɑ-Al2O3 (0001) and γ-Al2O3 (110) for F adsorption and the high reactivity is mainly attributed to the high unsaturation level of Al atoms. Detailly, the most stable adsorption sites are top of Al1 site, bridge of Al6 and adjacent Al atom, and bridge of AlⅢ atoms for α, γ, θ-alumina, respectively. The bonding picture shows that the bonding between F and alumina surface is attributed to the hybridization between F-p orbitals and Al-s,p orbitals. In addition, the alumina surfaces are hydroxylated with water molecules when exposing to the atmosphere, exhibiting a great impact on the performance of purifying F element. Results suggest that the hydroxylated θ-Al2O3 (010) adsorbs F with the smallest adsorption energy than other hydroxylated alumina surfaces, exhibiting the lowest performance of purifying F element.

Boosting potassium-storage performance via confining highly dispersed molybdenum dioxide nanoparticles within N-doped porous carbon nano-octahedrons.

The development of durable and stable metal oxide anodes for potassium ion batteries (PIBs) has been hampered by poor electrochemical performance and ambiguous reaction mechanisms. Herein, we design and fabricate molybdenum dioxide (MoO2)@N-doped porous carbon (NPC) nano-octahedrons through metal-organic frameworks derived strategy for PIBs with MoO2 nanoparticles confined within NPC nano-octahedrons. Benefiting from the synergistic effect of nanoparticle level of MoO2 and N-doped carbon porous nano-octahedrons, the MoO2@NPC electrode exhibits superior electron/ion transport kinetics, excellent structural integrity, and impressive potassium-ion storage performance with enhanced cyclic stability and high-rate capability. The density functional theory calculations and experiment test proved that MoO2@NPC has a higher affinity of potassium and higher conductivity than MoO2 and N-doped carbon electrodes. Kinetics analysis revealed that surface pseudocapacitive contributions are greatly enhanced for MoO2@NPC nano-octahedrons. In-situ and ex-situ analysis confirmed an intercalation reaction mechanism of MoO2@NPC for potassium ion storage. Furthermore, the assembled MoO2@NPC//perylenetetracarboxylic dianhydride (PTCDA) full cell exhibits good cycling stability with 72.6 mAh g-1 retained at 100 mA g-1 over 200 cycles. Therefore, this work present here not only evidences an effective and viable structural engineering strategy for enhancing the electrochemical behavior of MoO2 material in PIBs, but also gives a comprehensive insight of kinetic and mechanism for potassium ion interaction with metal oxide.

Robust Artificial Interphases Constructed by a Versatile Protein-Based Binder for High-Voltage Na-Ion Battery Cathodes.

The multiple issues of unstable electrode/electrolyte interphases, sluggish reaction kinetics, and transition-metal (TM) dissolution have long greatly affected the rate and cycling performance of cathode materials for Na-ion batteries. Herein, a multifunctional protein-based binder, sericin protein/poly(acrylic acid) (SP/PAA), is developed, which shows intriguing physiochemical properties to address these issues. The highly hydrophilic nature and strong H-bond interaction between crosslinking SP and PAA leads to a uniform coating of the binder layer, which serves as an artificial interphase on the high-voltage Na4 Mn2 Fe(PO4 )2 P2 O7 cathode material (NMFPP). Through systematic experiments and theoretical calculations, it is shown that the SP/PAA binder is electrochemically stable at high voltages and possesses increased ionic conductivity due to the interaction between sericin and electrolyte anion ClO4 - , which can provide additional sodium-migration paths with greatly reduced energy barriers. Besides, the strong interaction force between the binder and the NMFPP can effectively protect the cathode from electrolyte corrosion, suppress Mn-dissolution, stabilize crystal structure, and ensure electrode integrity during cycling. Benefiting from these merits, the SP/PAA-based NMFPP electrode displays enhanced rate and cycling performance. Of note, the universality of the SP/PAA binder is further confirmed on Na3 V2 (PO4 )2 F3 . It is believed that the versatile protein-based binder is enlightening for the development of high-performance batteries.

Stabilization of Multicationic Redox Chemistry in Polyanionic Cathode by Increasing Entropy.

Polyanionic compounds have large compositional flexibility, which creates a growing interest in exploring the property limits of electrode materials of rechargeable batteries. The realization of multisodium storage in the polyanionic electrodes can significantly improve capacity of the materials, but it often causes irreversible capacity loss and crystal phase evolution, especially under high-voltage operation, which remain important challenges for their application. Herein, it is shown that the multisodium storage in the polyanionic cathode can be enhanced and stabilized by increasing the entropy of the polyanionic host structure. The obtained polyanionic Na3.4 Fe0.4 Mn0.4 V0.4 Cr0.4 Ti0.4 (PO4 )3 cathode exhibits multicationic redox property to achieve high capacity with good reversibility under the high voltage of 4.5 V (vs Na/Na+ ). Exploring the underlying mechanism through operando characterizations, a stable trigonal phase with reduced volume change during the multisodium storage process is disclosed. Besides, the enhanced performance of the HE material also derives from the synergistic effect of the diverse TM species with suitable molarity. These results reveal the effectiveness of high-entropy concept in expediting high-performance polyanionic cathodes discovery.

Heteroatom-Substituted P2-Na2/3Ni1/4Mg1/12Mn2/3O2 Cathode with {010} Exposing Facets Boost Anionic Activity and High-Rate Performance for Na-Ion Batteries.

As an attractive cathode candidate for sodium-ion batteries, P2-type Na2/3Ni1/3Mn2/3O2 is famous for its high stability in humid air, attractive capacity, and high operating voltage. However, the low Na+ transport kinetics, oxygen-redox reactions, and irreversible structural evolution at high-voltage areas hinder its practical application. Herein, a comprehensive study of a microbar P2-type Ni2/3Ni1/4Mg1/12Mn2/3O2 material with {010} facets is presented, which exhibits high reversibility of structural evolution and anionic redox activity, leading to outstanding rate capability and cyclability. The notable rate performance (53 mA h g-1 at 20 C, 2.0-4.3 V) contributed to the high exposure of {010} facets via controlling the growth orientation of the precursor, which is certified by density functional theory calculation and lattice structural analysis. Mg substitution strengthens the reversibility of anionic oxygen redox and structural evolution in high-voltage areas that was confirmed by the in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy tests, leading to outstanding cyclic reversibility (68.9% after 1000 cycles at 5 C) and slowing down the voltage fading. This work provides new insights into constructing electrochemically active planes combined with heteroatom substitution to improve the Na+ transport kinetics and structural stability of layered oxide cathodes for sodium storage.

[Quality of life, personality, coping style in the patients with advanced laryngeal cancer].

OBJECTIVE: To evaluate the relationship between the life quality of advanced laryngeal squamous cell cancer patients and their personality, coping style and other psychological factors. METHODS: The life quality were measured for 2 sub-groups of advanced laryngeal cancer patients and the normal control group. The Eysenck personality questionnaire (EPQ), coping style questionnaires (CSQ) and University of Washington-quality of life (UW-QOL) were used for life quality evaluation. The 2 sub-groups of the patients on the worse speech, job and ability (group I), the better speech, job and ability (group II), and normal control. RESULTS: (1) UW-QOL score: the total, activity, recreation, job and speech scores of group II were significantly higher than those of group I (P < 0.01). Group II was better than group I in appearance (P < 0.05). (2) EPQ score: the P and N scores in group II were lower than that in group I (P < 0.05). The E scores in group II were significantly higher than that in group I (P < 0.01). (3) CSQ score: the problem-saving factor and help-seeking factor in group II were more significantly lower than that in group I (P < 0.01). The self-blaming factor in group II were higher than that in group I (P < 0.05). (4) There was positive correlation between total scores of QOL and the problem-saving factor, help-seeking factor of CSQ, the E scores of EPQ (P < 0.05), there was negative correlation between total scores of QOL and the P scores, the N scores of EPQ (P < 0.05). CONCLUSIONS: The advanced laryngeal cancer patients of group II have better life quality, and their personalities showed more extroversive, stable feeling, adaptable, mature coping styles. The above characteristics may have good effects on the prognosis of advanced laryngeal cancer.