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Energy & Environmental Materials 2022年第1期5卷 285-294页

作者： Zhiheng Wu Xiangdan Zhang Lijun Deng Yongshang Zhang Zhuo Wang yonglong shen Guosheng Shao State Center for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) School of Materials Science and EngineeringZhengzhou University100 Kexue AvenueZhengzhou 450001China Zhengzhou Materials Genome Institute(ZMGI) Building 2ZhongyuanzhiguXingyangZhengzhou 450100China Center for Advanced analysis&Gene Sequencing Zhengzhou UniversityZhengzhou 450001China

Heteroatom doped graphene materials are considered as promising anode for high-performance sodium-ion batteries(SIBs).Defective and porous structure especially with large specific surface area is generally considered as a feasible strategy to boost reaction kinetics;however,the unwanted side reaction at the anode hinders the practical application of SIBs.In this work,a precisely controlled Al_(2)O_(3)coated nitrogen doped vertical graphene nanosheets(NVG)anode material has been proposed,which exhibits excellent sodium storage capacity and cycling stability.The ultrathin Al_(2)O_(3)coating on the NVG is considered to help construct an advantageous interface between electrode and electrolyte,both alleviating the electrolyte decomposition and enhancing sodium adsorption ability.As a result,the optimal Al_(2)O_(3)coated NVG materials delivers a high reversible capacity(835.0 mAh g^(-1))and superior cycling stability(retention of 92.3%after 5000 cycles).This work demonstrates a new way to design graphene-based anode materials for highperformance sodium-ion batteries.

关键词： Al_(2)O_(3) nitrogen doped vertical graphene nanosheets reaction kinetics sodium-ion batteries

Enabling High-Performance Sodium Battery Anodes by Complete Reduction of Graphene Oxide and Cooperative In-Situ Crystallization of Ultrafine SnO_(2)Nanocrystals

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Energy & Environmental Materials 2023年第3期6卷 356-365页

作者： Junwu Sang Kangli Liu Xiangdan Zhang Shijie Zhang Guoqin Cao yonglong shen Guosheng Shao School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China State Centre for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001China Zhengzhou Materials Genome Institute(ZMGI) XingyangZhengzhou 450100China Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education School of Chemical EngineeringZhengzhou UniversityZhengzhou 450001China

The main bottleneck against industrial utilization of sodium ion batteries(SIBs)is the lack of high-capacity electrodes to rival those of the benchmark lithium ion batteries(LIBs).Here in this work,we have developed an economical method for in situ fabrication of nanocomposites made of crystalline few-layer graphene sheets loaded with ultrafine SnO_(2)nanocrystals,using short exposure of microwave to xerogel of graphene oxide(GO)and tin tetrachloride containing minute catalyzing dispersoids of chemically reduced GO(RGO).The resultant nanocomposites(SnO_(2)@MWG)enabled significantly quickened redox processes as SIB anode,which led to remarkable full anode-specific capacity reaching 538 mAh g^(−1)at 0.05 A g^(−1)(about 1.45 times of the theoretical capacity of graphite for the LIB),in addition to outstanding rate performance over prolonged charge–discharge cycling.Anodes based on the optimized SnO_(2)@MWG delivered stable performance over 2000 cycles even at a high current density of 5 A g^(−1),and capacity retention of over 70.4%was maintained at a high areal loading of 3.4 mg cm^(−2),highly desirable for high energy density SIBs to rival the current benchmark LIBs.

关键词： in situ compositing microwave reduced graphene oxide sodium ion battery sodium ion battery anode ultrafine SnO_(2)nanocrystals

Enabling Argyrodite Sulfides as Superb Solid-State Electrolyte with Remarkable Interfacial Stability Against Electrodes

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Energy & Environmental Materials 2022年第3期5卷 852-864页

作者： Hongjie Xu Guoqin Cao yonglong shen Yuran Yu Junhua Hu Zhuo Wang Guosheng Shao School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China State Centre for International Cooperation on Designer Low-Carbon&Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001China Zhengzhou Materials Genome Institute(ZMGI) Building 2Zhongyuanzhigu Xingyang 450100China

While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.

关键词： al oying chemistry argyrodite sulfide compatibility with high-voltage cathode and lithium anode fast solid lithium ion conductor resilience to humid air

Seamless Stitching of Redox Windows to Enable High-Voltage Resilient Solid Sodium Ion Batteries

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Energy & Environmental Materials 2023年第6期6卷 445-454页

作者： Xiangdan Zhang Yuanyuan Huang Xiaoyi Hu Ruxin Guo Yongshang Zhang Zhiheng Wu Guoqin Cao Yuran Yu Zhuo Wang yonglong shen Guosheng Shao School of Materials Engineering Henan International Joint Laboratory of Rare Earth Composite MaterialsHenan University of EngineeringZhengzhou 451191China School of Material Science and Engineering Zhengzhou UniversityZhengzhou 450001China Zhengzhou Materials Genome Institute Building 2ZhongyuanzhiguXingyang 450100China

While sulfide solid electrolytes such as Na_(11)Sn_(2)PS_(12)can allow fast transport of Na+ions,their utilization in solid sodium ion batteries is rather unsuccessful since they are not electrochemically compatible to both high-voltage cathodes and sodium metal anode.In this work,we devise an effective approach toward realizing solid sodium ion batteries,using the Na_(11)Sn_(2)PS_(12)electrolyte and slurry-coated NASICON-type Na_(3)MnTi(PO_(4))_(3)@C as high-voltage cathode,highly beneficial for low processing cost and high content/loading of active cathode matter.We report that through significantly improved integrity of electrolyte-cathode interface,such solid sodium ion batteries can deliver outstanding cycling and rate performance,with a charge voltage resilience up to 4.1 V,a high cathode discharge capacity of 128.7 mAh g^(-1)against the Na_(3)MnTi(PO_(4))_(3)@C in cathode is achieved at 0.05 C,and capacity retention ratio of 82%with a rate of 0.1 C is realized after prolonged cycling at room temperature.Besides,we demonstrate that such a solid sodium ion battery can even perform at a sub-zero Celsius temperature of-10℃,when the conventional control cell using liquid electrolyte completely fail to function.This work is to offer a dependable avenue in engineering next generation of safe solid ion batteries based on highly sustainable and much cheaper material resources.

关键词： C-coated NASICON nanocrystals electrolyte-electrode interface full-cathode capacity Na_(11)Sn_(2)PS_(12) solid sodium-ion battery

Significant performance enhancement of all-inorganic CsPbBr_(3)perovskite solar cells enabled by Nb-doped SnO_(2)as effective electron transport layer

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Energy & Environmental Materials 2021年第4期4卷 671-680页

作者： Ruxin Guo Yan Zhao Yongshang Zhang Quanrong Deng yonglong shen Wei Zhang Guosheng Shao State Centre for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) School of Materials Science and EngineeringZhengzhou UniversityZhengzhou 450001China Zhengzhou Materials Genome Institute(ZMGI) Building 2ZhongyuanzhiguXingyangZhengzhou 450100China Hubei Key Laboratory of Plasma Chemistry and Advanced Materials Wuhan Institute of TechnologyWuhan 430205China Advanced Technology Institute(ATI) University of SurreyGuildford Surrey GU27XHUK

All-inorganic CsPbBr_(3)-based perovskite solar cells(PSCs)have attracted great attention because of their high chemical and thermal stabilities in ambient air.However,the short-circuit current density(J_(sc))of CsPbBr_(3)-based PSCs is inadequate under solar illumination because of the wide bandgap,inefficient charge extraction and recombination loss,leading to lower power-conversion efficiencies(PCEs).It is envisaged that in addition to narrowing the bandgap by alloying,J_(sc)of the PSCs could be enhanced by effective improvement of electron transportation,suppression of charge recombination at the interface between the perovskite and electron transporting layer(ETL),and tuning of the space charge field in the device.In this work,Nb-doped SnO_(2)films as ETLs in the CsPbBr_(3)-based PSCs have been deposited at room temperature by high target utilization sputtering(Hi TUS).Through optimizing the Nb doping level alone,the J_(sc)was increased by nearly 19%,from 7.51 to 8.92 mA·cm^(-2)and the PCE was enhanced by 27%from 6.73%to 8.54%.The overall benefit by replacing the spin-coated SnO_(2)with sputtered SnO_(2)with Nb doping was up to 39%increase in J_(sc)and 62%increase in PCE.Moreover,the PCE of the optimized device showed negligible degradation over exposure to ambient environment(T~25°C,RH~45%),with 95.4%of the original PCE being maintained after storing the device for 1200 h.

关键词： sputter Nb-doped SnO_(2) perovskite solar cell short-circuit current density long-term stability

Stable all-solid-state battery enabled with Li_(6.25)PS_(5.25)Cl_(0.75) as fast ion-conducting electrolyte

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Journal of Energy Chemistry 2021年第2期30卷 147-154,I0006页

作者： Weidong Xiao Hongjie Xu Minjie Xuan Zhiheng Wu Yongshang Zhang Xiangdan Zhang Shijie Zhang yonglong shen Guosheng Shao School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001HenanChina Centre for International Cooperation on Designer Low-carbon Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001HenanChina Zhengzhou Materials Genome Institute(ZMGI) Zhengzhou 450100HenanChina

All-solid-state batteries(ASSB) with lithium anode have attracted ever-increasing attention towards developing safer batteries with high energy densities.While great advancement has been achieved in developing solid electrolytes(SE) with superb ionic conductivity rivalling that of the current liquid technology,it has yet been very difficult in their successful application to ASSBs with sustaining rate and cyclic performances.Here in this work,we have realized a stable ASSB using the Li_(6.25)PS_(5.25)Cl_(0.75) fast ionconducting electrolyte together with LiNbO_3 coated LiCoO_2 as cathode and lithium foil as the anode.The effective diffusion coefficient of Li-ions in the battery is higher than 10^(-12) cm~2 s^(-1),and the significantly enhanced electrochemical matching at the cathode-electrolyte interface was essential to enable long-term stability against high oxidation potential,with the LCO@LNO/Li_(6.25)PS_(5.25)Cl_(0.75)/Li battery to retain 74.12% capacity after 430 cycles at 100 μA cm-2 and 59.7% of capacity after 800 cycles at 50 μA cm^(-2),at a high charging cut-off voltage of 4.2 V.This demonstrates that the Li_(6.25)PS_(5.25)Cl_(0.75) can be an excellent electrolyte for the realization of stable ASSBs with high-voltage cathodes and metallic lithium as anode,once the electrochemical compatibility between cathode and electrolyte can be addressed with a suitable buffer coating.

关键词： All-solid-state batteries Sulfide electrolyte Li_(6.25)PS_(5.25)Cl_(0.75) LiNbO_(3)coating Lithium anode Long-term stability

Influence of Halide Choice on Formation of Low-Dimensional Perovskite Interlayer in Efficient Perovskite Solar Cells

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Energy & Environmental Materials 2022年第2期5卷 670-682页

作者： Xueping Liu Thomas Webb Linjie Dai Kangyu Ji Joel A.Smith Rachel C.Kilbride Mozhgan Yavari Jinxin Bi Aobo Ren Yuanyuan Huang Zhuo Wang yonglong shen Guosheng Shao Stephen J.Sweeney Steven Hinder Hui Li David G.Lidzey Samuel D.Stranks Neil C.Greenham S.Ravi P.Silva Wei Zhang State Center for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001China Advanced Technology Institute Department of Electrical and Electronic EngineeringUniversity of SurreyGuildford GU27XHUK Cavendish Laboratory University of CambridgeCambridge CB30HEUK Department of Chemical Engineering and Biotechnology University of CambridgeCambridge CB30ASUK Department of Physics and Astronomy University of SheffieldSheffield S37RHUK Department of Physics University of OxfordClarendon LaboratoryOxford OX13PUUK Advanced Technology Institute and Department of Physics University of SurreyGuildford GU27XHUK The Surface Analysis Laboratory Department of Mechanical Engineering SciencesUniversity of SurreyGuildford GU27XHUK Institute of Electrical Engineering Chinese Academy of SciencesBeijing 100190China

Recent advances in heterojunction and interfacial engineering of perovskite solar cells(PSCs)have enabled great progress in developing highly efficient and stable devices.Nevertheless,the effect of halide choice on the formation mechanism,crystallography,and photoelectric properties of the lowdimensional phase still requires further detailed study.In this work,we present key insights into the significance of halide choice when designing passivation strategies comprising large organic spacer salts,clarifying the effect of anions on the formation of quasi-2D/3D heterojunctions.To demonstrate the importance of halide influences,we employ novel neo-pentylammonium halide salts with different halide anions(neoPAX,X=I,Br,or Cl).We find that regardless of halide selection,iodide-based(neoPA)_(2)(FA)_((n-1))PbnI_((3n+1))phases are formed above the perovskite substrate,while the added halide anions diffuse and passivate the perovskite bulk.In addition,we also find the halide choice has an influence on the degree of dimensionality(n).Comparing the three halides,we find that chloride-based salts exhibit superior crystallographic,enhanced carrier transport,and extraction compared to the iodide and bromide analogs.As a result,we report high power conversion efficiency in quasi-2D/3D PSCs,which are optimal when using chloride salts,reaching up to 23.35%,and improving long-term stability.

关键词： carrier dynamics halide anions(I Br Cl) neo-pentylammonium halides perovskite solar cells quasi-2D/3D heterojunction

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盐度对瘤背石磺消化系统组织结构的影响

水产科学 2015年第4期34卷 240-244页

作者：沈永龙黄金田戈贤平盐城工学院江苏省滩涂底栖生物重点试验室江苏盐城224051 南京农业大学无锡渔业学院江苏无锡214081

以瘤背石磺为研究对象，通过在不同盐度（5、15、25、35和45）环境下饲养，研究盐度对瘤背石磺消化系统的组织结构和超微结构的影响。试验显示：盐度能显著影响瘤背石磺幽门胃、贲门胃、肝胰腺以及肠道结构组织。随着盐度的升高，幽门... 详细信息

以瘤背石磺为研究对象，通过在不同盐度（5、15、25、35和45）环境下饲养，研究盐度对瘤背石磺消化系统的组织结构和超微结构的影响。试验显示：盐度能显著影响瘤背石磺幽门胃、贲门胃、肝胰腺以及肠道结构组织。随着盐度的升高，幽门胃和贲门胃细胞均出现不同程度的萎缩，而肝胰腺在低盐度时部分被溶解，出现“空泡化现象”，而高盐度时细胞损伤严重。另外，通过扫描电镜观察，高盐度对肠道绒毛细胞有破坏作用，随着盐度的升高，瘤背石磺前肠褶皱高度逐渐降低，至盐度35～45时表面逐渐呈现扁平化，消化吸收面积显著降低。试验结果表明，盐度对瘤背石磺消化系统组织结构有显著影响，盐度过高对消化系统组织损伤严重，消化吸收率显著降低。从组织学角度分析可见，盐度15左右是瘤背石磺适宜的养殖盐度。

关键词：瘤背石磺盐度消化系统组织结构

盐度对瘤背石磺(Onchidium struma)消化酶活性的影响

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动物营养学报 2012年第9期24卷 1839-1846页

作者：沈永龙戈贤平黄金田王爱民吕富南京农业大学无锡渔业学院无锡214081 盐城工学院江苏省滩涂底栖生物重点实验室盐城224051

为探讨盐度对瘤背石磺(Onchidium struma)不同消化器官蛋白酶、淀粉酶和纤维素酶活性的影响,试验选用1 200只个体均一的瘤背石磺[初均重(16.82±2.14)g]随机分成5组,分别置于不同盐度梯度(5、15、25、35和45)下饲养,期间用海泥与螺旋藻... 详细信息

为探讨盐度对瘤背石磺(Onchidium struma)不同消化器官蛋白酶、淀粉酶和纤维素酶活性的影响,试验选用1 200只个体均一的瘤背石磺[初均重(16.82±2.14)g]随机分成5组,分别置于不同盐度梯度(5、15、25、35和45)下饲养,期间用海泥与螺旋藻粉(m∶m=5∶1)拌饲投喂。每组设置3个重复,每个重复80只,饲养30 d后测定消化道不同器官蛋白酶、淀粉酶和纤维素酶活性。试验结果显示:1)各消化酶在幽门胃、贲门胃、肝胰腺和肠中均有分布,但各消化器官之间酶活性差异显著(P<0.05)。不同消化器官中蛋白酶活性由大到小依次为幽门胃[(91.46±0.57)U/g]、肝胰腺[(72.63±0.59)U/g]、肠[(44.78±0.66)U/g]和贲门胃[(40.12±0.45)U/g];淀粉酶活性由大到小依次为肝胰腺[(87.11±1.31)U/mg]、幽门胃[(45.72±1.06)U/mg]、肠[(26.52±1.05)U/mg]和贲门胃[(23.68±0.82)U/mg];纤维素酶活性以肝胰腺[(2.02±0.01)U/mg]最高,其次是肠[(1.01±0.01)U/mg],最低的是幽门胃[(0.53±0.01)U/mg]。2)盐度对各种消化酶活性的影响差异显著(P<0.05)。除肝胰腺中的蛋白酶以外,幽门胃、贲门胃、肝胰腺和肠中各消化酶活性随盐度升高均呈先上升后下降的趋势,且淀粉酶和纤维素酶分别在盐度15和25时活性最高,盐度45时活性最低。试验结果表明,低盐度(盐度5～25)对各消化器官消化酶活性均具有激活作用;其中,盐度15～25时消化酶活性最高,有利于瘤背石磺对饵料的消化吸收;而当盐度高于25时,则会抑制消化酶活性。

关键词：瘤背石磺盐度蛋白酶淀粉酶纤维素酶

基于Merkle哈希树的电网数据隐私防护建模研究

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电子设计工程 2024年第11期32卷 160-163,168页

作者：李渊文康健郑伟宁永龙申新远国网宁夏电力有限公司宁夏银川750000 国网中卫供电公司宁夏银川750000

为了对数据隐私存储区域进行合理防护,解决电网数据隐私性不高的问题,研究了基于Merkle哈希树的电网数据隐私防护建模方法。根据Merkle哈希树架构连接标准,创建电网数据隐私序列表达式,完善数据样本之间的索引关系,完成电网数据隐私性... 详细信息

为了对数据隐私存储区域进行合理防护,解决电网数据隐私性不高的问题,研究了基于Merkle哈希树的电网数据隐私防护建模方法。根据Merkle哈希树架构连接标准,创建电网数据隐私序列表达式,完善数据样本之间的索引关系,完成电网数据隐私性的检验。确定电网数据分析结果,通过分析防护作用范围求解,映射建模条件的数值计算结果,完成电网数据隐私防护建模。实验结果表明,在Merkle哈希树作用下,电网主机对于隐私存储区域内数据样本的有效防护时间可达150 h,可以保证提升电网数据隐私性。

关键词： Merkle哈希树电网数据隐私防护隐私序列数据索引映射建模