Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries

Earth abundant O3-type NaFe_(0.5)Mn_(0.5)O_(2)layered oxide is regarded as one of the most promising cathodes for sodium ion batteries due to its low cost and high energy density.However,its poor structural stability and cycle life strongly impede the practical application.Herein,the dynamic phase evolution as well as charge compensation mechanism of O3-type NaFe_(0.5)Mn_(0.5)O_(2)cathode during sodiation/desodiation are revealed by a systemic study with operando X-ray diffraction and X-ray absorption spectroscopy,high resolution neutron powder diffraction and neutron pair distribution functions.The layered structure experiences a phase transition of O3→P3→OP2→ramsdellite during the desodiation,and a new O3’phase is observed at the end of the discharge state(1.5 V).The density functional theory(DFT)calculations and nPDF results suggest that depletion of Na^(+)ions induces the movement of Fe into Na layer resulting the formation of an inert ramsdellite phase thus causing the loss of capacity and structural integrity.Meanwhile,the operando XAS clarified the voltage regions for active Mn^(3+)/Mn^(4+)and Fe^(3+)/Fe^(4+)redox couples.This work points out the universal underneath problem for Fe-based layered oxide cathodes when cycled at high voltage and highlights the importance to suppress Fe migration regarding the design of high energy O3-type cathodes for sodium ion batteries.

Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon

N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.

Glancing incidence x-ray fluorescence spectrometry based on a single-bounce parabolic capillary

Glancing incidence x-ray fluorescence spectrometry using a single-bounce parabolic capillary is proposed for the analysis of layered samples.The divergence of the x-ray beam was 0.33 mrad.In this paper,we used this instrumental setup to analyze a Si single crystal and a 50 nm HfO_(2) single-layer film deposited on a Si substrate.

Identification and comparison of the local physicochemical structures of transition metal-based layered double hydroxides for high performance electrochemical oxygen evolution reactions

Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.

Experimental study on boundary lubricity of superficial area of articular cartilage and synovial fluid

The boundary lubrication mechanism at the articulating surface of natural synovial joints has been the subject of much discussion in tribology.In this study,to elucidate the lubricating function of the superficial area of articular cartilage and synovial fluid(SF),cartilage specimens were processed with four different treatments:gentle and severe washing with detergent,incubation in NaCl solution,and trypsin digestion to selectively remove certain constituents from the cartilage surface.Subsequently,the frictional characteristics were examined in phosphate-buffered saline(PBS)and SF against glass.Angularly reciprocating sliding tests with a spherical glass probe and square articular cartilage specimens were performed at low contact loads in the mN range to extract the frictional behavior in the superficial area of the cartilage specimens.Meanwhile,the cartilage surface was observed to confirm the effects of treatments on the morphology of the cartilage surface using a fluorescence microscope and water-immersion methods.The coefficient of friction(COF)of the prepared cartilage specimens was varied from 0.05 to over 0.3 in PBS.However,a certain group of cartilage specimens exhibited a low COF of less than 0.1 with limited variation.For the low COF group of specimens,all four treatments increased the COF in PBS to different extents,and fluorescence microscopy revealed that the integrity of the cartilage surface was deteriorated by treatments.This means that the intact cartilage surface had lubricating constituents to maintain low friction,and the removal of such constituents resulted in the loss of the intrinsic boundary lubricity of the cartilage surface.The variation in the COF of the cartilage specimens was suppressed in SF because it had a clear boundary lubrication effect on the cartilage surface.The lubricating effect of SF could be confirmed even after degenerative treatment.

中药热敷联合微针刀浅筋膜层松解术治疗膝关节骨性关节炎寒湿痹阻型疗效观察

目的:观察中药热敷联合微针刀浅筋膜层松解术治疗膝关节骨性关节炎(KOA)寒湿痹阻型的疗效。方法:92例以随机数字表法分为两组各46例。对照组用微针刀浅筋膜层松解术治疗,联合组用微针刀浅筋膜层松解术及中药热敷治疗。结果:联合组治愈率高于对照组(P<0.05),治疗后联合组WOMAC、VAS及证候评分低于对照组而Lysholm评分高于对照组(P<0.05),治疗后联合组关节间隙角、股骨内侧髁高宽比、股骨外侧髁高宽比高于对照组而股骨角低于对照组(P<0.05),治疗后联合组IL-1β、TWEAK、CTX-Ⅰ、TRACP低于对照组(P<0.05)。结论:中药热敷与微针刀浅筋膜层松解术联合治疗KOA寒湿痹阻型效果较好。

Role of Ion Beam Irradiation and Annealing Efect on the Deposition of AlON Nanolayers by Using Plasma Focus Device

AlON nanolayers are synthesized on Al substrate by the irradiation of energetic nitrogen ions using plasma focusing. Samples are exposed to multiple （5, 10, 15, 20 and 25） focus shots. Ion energy and ion number density range from 80 keV to 1.4 MeV and 5.6×10^19 m^- 3 to 1.3×10^19 m ^-3, respectively. Moreover, the effect of continuous annealing （473 K and 523 K） on an AlN surface layer synthesized with 25 focus shots is also examined. The main features of the X-ray diffraction （XRD） patterns with increasing focus shots are： （i） variation in the crystallinity of AlN along （111）, （200） and （311） planes, （ii） increasing average crystallite size of AlN （111） plane, and （iii） stress relaxation observed in AlN （111） and （200） planes. The crystallinity of AlN surface layer is comparatively better at 473 K annealing temperature. A broadened diffraction peak related to an aluminium oxide phase showing weak crystallinity is observed for 15 focus shots while non-bounded oxides are present in all other deposited layers. Raman and Fourier transform infrared spectroscopy （FTIR） analysis confirm the presence of AlN and Al203 for the surface layer annealed at 473 K temperature. Raman analysis shows that the overlapping of AlN and Al2Oa results in the development of residual stresses. Scanning electron microscope （SEM） results demonstrate that the formation of rounded grains （range from 20 nm to 200 nm） and variations in their microstructures features depend on the increasing number of focus shots. Decomposition of larger clusters into smaller ones is observed.

A New Organo-templated Layered Zincophosphate Synthesized from a Solvothermal System Containing Racemic 1,2-Diaminopropane

A new layered zincophosphate was synthesized under solvothermal conditions by employing racemic 1,2-diaminopropane as the structure-directing agent. The structure of the compound was solved by means of single-crystal X-ray diffraction analysis. It crystallized in the monoclinic space group P2_1/c (No. 14) with a= 1.047 0(3) nm, b=0.787 31(18) nm, c=0.662 68(16) nm, β=103.120(5)°, V=0.532 0(2) nm 3 and Z=4. The structure is made up of anionic zincophosphate sheets stacked in an AAAA sequence. The individual sheet contains three- and four-membered rings and the infinite Zn-O-Zn chains can also be envisaged in the sheet. The charge-balancing diprotonated racemic 1,2-diaminopropane cations are sandwiched between the layers, whereas the inorganic layers are stabilized by strong H-bonds formed between the N atoms of the amine and the O atoms in the inorganic sheets.

The interface of SiO_2/ZnS films studied by high resolution X-ray photoluminescence

Sharp interfaces in optoelectronic devices are key for proper band alignment. Despite its benefits as buffer layer, ZnS deposited via atomic layer deposition(ALD) renders intermixed interfaces to its substrate, which can be detrimental for device performance. Here, we are attempting to elucidate the chemical species deriving from this metal-oxide to metal-sulfide transition studying ultrathin film ZnS on SiO_2 using high resolution X-ray photoluminescence spectroscopy(XPS).Regarding the S 2p spectra after a deposition of only three cycles of ZnS, we discover the many different chemical species in which S is present. These include intermediate oxides such as SO_4^(2-).These species become more obvious as we tilt the sample in the XPS chamber to shallower angles.Comparing the Si 2p and S 2p high resolution peaks in the depth profile, one can clearly uncover the confinement of SO_4^(2-) to the interface of the underlying substrate. This may indicate that SiO_2/ZnS interfaces contain interfacial sulphates that likely alter the electronic configuration of this interface.

Interface Reaction of Ta/NiFe and NiFe/Ta and the Dead Layer

The structures of Ta/Ni81Fe19 and Ni81Fe19/Ta are commonly used in magnetoresistance multilayers. It is found that the thickness of dead layer in Ta/Ni81Fe19/Ta was about 1.6±0.2nm. X-ray photoelectron spectroscopy (XPS) was used to study the interfaces of Ta/Ni81Fe19 and Ni81Fe19/Ta. The results show that there is a reaction at the two interfaces: 2Ta+Ni=NiTa2, which caused the thinning of the effective NiFe layer. Furthermore, this reaction could also explain the phenomenon that the dead layer thickness of spin valves multilayers prepared by MBE is thinner than those prepared by magnetron sputtering.

Characterization and application in XRF of HfO_(2)-coated glass monocapillary based on atomic layer deposition

Coating a glass monocapillary x-ray optics with high-density film is a promising way to improve transmission characteristics. For a long time, it has been a challenge to coat a high-density film in the inside of monocapillary with an extremely high length-to-diameter ratio. In this work, Hf O2 film is deposited on the inner wall of a tapered glass monocapillary with length 9.9 cm, entrance diameter 596.4 μm, and exit diameter 402.3 μm by atomic layer deposition. The coated and uncoated monocapillaries are studied by the transmission process of x-rays with energy from 5 ke V to 100 ke V and the x-ray fluorescence(XRF) spectra of a Mo sample are detected. Improved transmission characteristics have been obtained for the Hf O2-coated monocapillary. The energy upper limit of focused x-rays increases from 18.1 ke V to 33.0 ke V and the ‘penetration halo’ is suppressed to some extent. The XRF spectrum presents two stronger peaks at ~ 17.4 ke V and~ 19.6 ke V which are considered as the characteristic x-rays of Mo Kα and Mo Kβ. These results reveal that more higher energy x-rays from the W x-ray tube are totally reflected on the inner wall of the Hf O2-coated glass monocapillary due to the increase of total reflection critical angle. This work is significant for more applications of monocapillary in higher energy x-ray field.

四肢及脊柱浅筋膜中间筋膜层MRI特点及其对脂肪瘤屏障作用的临床观察

目的探讨四肢脊柱浅筋膜中间筋膜层对肿瘤的屏障作用。方法回顾117例共121部位(男48例,女69例)四肢脊柱脂肪瘤患者MRI、手术及病理结果,对肿瘤所在部位深筋膜、浅筋膜中间筋膜层的形态及肿瘤形态相关性进行观察。结果病人平均年龄52.2岁(15~82岁);脂肪瘤所在部位侧别:左侧44.4%(52例),右侧48.7%(57例),双侧5.1%(6例),中线1.7%(2例);部位:颈后部7.5%(9),胸背部5.8%(7),肩部23.1%(28),上臂15.7%(19),前臂7.4%(9),手3.3%(4),股部34.7%(42),小腿2.5%(3);肿瘤位置:肌内40.2%(47例),深筋膜深面17.9%(21例),浅筋膜中间筋膜深面23.9%(28例),浅筋膜中间筋膜浅面5.9%(7例),肌间隙11.9%(14例)。肿瘤形态:脂肪瘤均与正常组织存在边界,分叶状48.7%(57例),椭圆状41.9%(49例),扁平状9.4%(11例)。病理类型:棕色瘤3.4%(4例),血管脂肪瘤1.7%(2例),普通型86.3%(101例),纤维脂肪瘤8.4%(10例)。皮下脂肪瘤多位于深筋膜与中间筋膜层之间,呈分叶状,深筋膜深面及肌内肿瘤多为椭圆形,肿瘤形态与中间筋膜及深筋膜、肌外膜的形态相关。结论浅筋膜中间筋膜层是一层较致密的纤维结缔组织,位于深筋膜和皮肤之间,中间筋膜层对脂肪瘤增殖有一定的阻挡作用,是自然屏障结构,深筋膜和肌间隔同样是肿瘤屏障结构。

Improving superficial microstructure and properties of the laser-processed ultrathin kerf in Ti-6Al-4V alloy by water-jet guiding

In the present research,the gas-assisted laser(GAL)and water-jet guided laser(WGL)processing technologies were applied to machine the ultrathin kerf in the wrought Ti-6Al-4V alloy.The microstructure,microhardness,and wear properties of the superficial layer were investigated.The results reveal that the GAL processing could machine the kerf with a high depth-to-width ratio of 12–15,but the increased processing times enhance the depth little.Due to the oxygen entrainment and relatively low heat and mass transferring efficiency,the assisted gas promotes the formation of a scaled recast layer containingβ-Ti phase and oxides,which increases the roughness to 20μm.The WGL processed kerf has a low depth-to-width ratio with a value of 1.9–2.5 and the depth could be increased by increasing the WGL processing times.With the assistance of the water jet,the remelted debris and heat could be eliminated immediately,which restrains the formation of the recast layer and heat-affected zone.The ultrathin oxide outer layer with hundreds of nanometers and ultrafineα-Ti grain inner layer are formed on the surface,which decreases the roughness to 12μm.Compared with the as-received Ti-6Al-4V alloy,the microhardness of GAL processed kerf surface is increased to 382.8 HV accompanied by residual tensile stress,while the microhardness of WGL processed kerf surface is increased to 481.6 HV accompanying with residual compressive stress.In addition,the GAL processing increases the wear rate at room temperature but decreases the wear rate at high temperatures.Comparatively,the WGL processing decreases the wear rate at room and high temperatures,simultaneously.Such wear behaviors could be ascribed to their different superficial microstructures and phase constituents.

Application of high energy X-ray diffraction and Rietveld refinement in layered lithium transition metal oxide cathode materials

Layered lithium transition metal oxide(LTMO)cathode materials have attracted much attention for lithium-ion batteries and are shining in the current market.Establishing a clear structure-performance relationship is necessary for the performance improvement of LTMO cathode materials.The combination of synchrotron X-ray diffraction(XRD)with high intensity and XRD Rietveld refinement is powerful for revealing the structural characteristics of LTMO cathode materials.This review summarizes the application of high energy XRD and Rietveld refinement in LTMO cathode materials,including the brief introduction of synchrotron XRD and Rietveld refinement and their applications in understanding the structural evolution related to the synthetic,thermal runaway,cycling,and high-rate charge/discharge process of LTMO cathode materials.Synchrotron XRD can provide insights into the intermediates and reaction paths in the synthesis process,the origin of thermal runaway,the mechanism of structural decay during cycles,and the structural evolution during high-rate charging/discharging.Future works should focus on the development of higher intensity X-rays to gain more in-depth insights into the intrinsic relationship between their structural characteristics and properties.

光学相干断层血管造影成像应用于非增殖期糖尿病视网膜病变微血管的临床筛查

目的探讨光学相干断层血管造影成像(OCTA)应用于非增殖期糖尿病视网膜病变(NPDR)患者视网膜微血管筛查中的临床效果。方法选取在苏州大学附属第三医院确诊的30例NPDR患者(NPDR组)和30例健康志愿者(对照组)行OCTA检查,对其黄斑中心凹无血管区(FAZ)的面积、周长、圆度变化以及黄斑区视网膜浅层毛细血管层(SCP)和视盘盘周放射状毛细血管层(RPC)上侧、下侧、鼻侧、颞侧4个象限的血流密度进行量化分析。结果NPDR组患者黄斑区SCP和视盘RPC 4个象限的血流密度较对照组均显著下降(43.68±3.03vs.46.98±3.04、42.79±3.17vs.50.45±2.25、43.21±2.67vs.47.44±2.42、44.21±3.22vs.51.72±5.32、46.43±3.54vs.53.02±2.62、45.97±3.67vs.52.53±2.82、44.63±2.73vs.48.19±3.67、41.73±3.15vs.45.12±3.31),差异均有统计学意义(均P<0.01)。NPDR组患者FAZ面积和周长较正常对照组均明显增大[(0.50±0.06vs.0.43±0.47)mm2、(3.10±0.21vs.2.87±0.22)mm],圆度较对照组明显变小[(0.63±0.05vs.0.67±0.05)%],差异也均有统计学意义(均P<0.01)。结论OCTA可检测出NPDR的早期视网膜微结构改变,可作为NPDR的辅助筛查,为早期诊治提供信息。

High-performance 110 kVp hard x-ray detector based on all-crystalline-surface passivated perovskite single crystals

Halide perovskite single crystals(SCs)have attracted much attention for their application in high-performance x-ray detectors owing to their desirable properties,including low defect density,high mobility–lifetime product(μτ),and long carrier diffusion length.However,suppressing the inherent defects in perovskites and overcoming the ion migration primarily caused by these defects remains a challenge.This study proposes a facile process for dipping Cs0.05FA0.9MA0.05PbI3 SCs synthesized by a solution-based inverse temperature crystallization method into a 2-phenylethylammonium iodide(PEAI)solution to reduce the number of defects,inhibit ion migration,and increase x-ray sensitivity.Compared to conventional spin coating,this simple dipping process forms a two-dimensional PEA2PbI4 layer on all SC surfaces without further treatment,effectively passivating all surfaces of the inherently defective SCs and minimizing ion migration.As a result,the PEAI-treated perovskite SC-based x-ray detector achieves a record x-ray sensitivity of 1.3×10^(5)μC Gyair^(-1) cm^(-2) with a bias voltage of 30 V at realistic clinical dose rates of 1–5 mGy s^(-1)(peak potential of 110 kVp),which is 6 times more sensitive than an untreated SC-based detector and 3 orders of magnitude more sensitive than a commercialα-Se-based detector.Furthermore,the PEAI-treatedperovskite SC-based x-ray detector exhibits a low detection limit(73 nGy s^(-1)),improved x-ray response,and clear x-ray images by a scanning method,highlighting the effectiveness of the PEAI dipping approach for fabricating next-generation x-ray detectors.

非淬硬钢磨削表面硬化层的试验研究

在平面磨床上对非淬硬钢进行了磨削硬化处理,研究了磨削方式和冷却条件对表面硬化层的影响。结果表明:硬化层完全硬化区均由细小的孪晶马氏体和板条马氏体组成,且硬化层的组织形貌及显微硬度无显著变化,但硬化层略粗马氏体相的出现位置有所差异;在磨削用量恒定时,顺磨硬化层的深度以及最大残余压应力均大于逆磨硬化层;在磨削功率恒定时,采用逆磨方式可以获得更深的硬化层;与干磨相比,湿磨硬化层表面残余压应力有所提高,但其硬化层深度减少了约30%。

热轧钢板典型压入式氧化铁皮的分类及其形成机理

热轧钢板表面形成的典型压入式氧化铁皮可分为浅层压入式和嵌入式两种,分别对两种类型的压入式缺陷进行了分析和研究.结果表明,在钢坯再加热过程中,粘附在钢坯表面的保护渣与炉生氧化铁皮粘合在一起;粗除鳞后,残留的相互粘合的保护渣与炉生氧化铁皮在粗轧过程中被压入到钢板较深的位置,形成嵌入式的氧化铁皮;若连铸坯表面粘附保护渣颗粒,经粗除鳞未除完全后,残留的保护渣与新生的一次氧化铁皮包覆到一起,在粗轧过程中被压入到钢板较浅的位置,形成浅层压入式的氧化铁皮.

近30年南京市浅层地温场变化规律研究

在收集南京市单一观测站点近50年气温资料和近30年浅层地温数据的基础上,对南京市地温变化趋势及其与气温变化的相关性进行了分析,对不同深度定时地温变化、日均地温全年变化、地温日较差变化等进行了比较,同时也对地温变化对城市浅层土工程性质可能带来的影响进行了分析。结果表明：地温场与气温场变化规律基本一致,但存在一定的滞后现象;南京市月均地温变化规律基本相同,最高值出现在7,8月份,最低值出现在1,2月份;近30年来浅层地温场总体呈现上升趋势,其中地表上升最大值达2.8℃,0-20cm土层温度变化幅度比较接近,上升最大值达2.0℃,40cm处最大值达1.75℃;30年来地表最大温差高达84.5℃,40cm深度最大地温差也超过27.5℃,因此多年地温变化对城市浅层土工程性质的影响不容忽视。

不同分期糖尿病视网膜病变患者黄斑区结构和微血管改变定量分析

目的:通过光相干断层扫描(OCT)和光相干断层扫描血管造影(OCTA)检查,观察不同分期糖尿病视网膜病变(DR)患者黄斑区神经节细胞-内丛状层(GCIPL)厚度及各象限视网膜浅层毛细血管密度特征并作定量分析。方法:回顾性病例对照研究。选取2019-12/2020-05我院确诊DR患者33例54眼,并根据眼底情况分为无糖尿病视网膜病变(NDR)组6例8眼、非增殖型糖尿病视网膜病变(NPDR)组18例28眼和增殖型糖尿病视网膜病变(PDR)组9例18眼。选取同期与患者年龄相匹配的健康志愿者18例26眼作为对照组。观察并定量分析不同分期DR患者黄斑区GCIPL厚度及各象限视网膜浅层毛细血管线性密度(VD)和血管灌注密度(PD)。结果:DR组患者黄斑区各象限视网膜浅层毛细血管VD、PD及GCIPL厚度最小值均小于对照组(P<0.05)。不同分期DR患者黄斑区GCIPL厚度最小值及各象限视网膜浅层毛细血管VD组间比较均有差异(P<0.05),下方视网膜浅层毛细血管VD对DR的诊断价值最高(AUC=0.807、最佳诊断界限值为18.60mm^(-1)、灵敏度为0.923、特异度为0.648)。DR患者黄斑区GCIPL厚度最小值与各象限视网膜浅层毛细血管VD均呈正相关(r=0.342、0.480、0.384、0.342,均P<0.05)。结论:OCT结合OCTA检查为早期评估及定期随访DR的进展提供了可重复、可定量的检测方法和监测指标。