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Science China Chemistry 2024年第3期67卷 751-752页

作者： Xiong Liu chaojiang niu School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China

关键词： lithium electrolyte layer

Atomic engineering promoted electrooxidation kinetics of manganese-based cathode for stable aqueous zinc-ion batteries

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Nano Research 2022年第9期15卷 8603-8612页

作者： Hao Luo Lipeng Wang Penghui Ren Jiahuang Jian Xiong Liu chaojiang niu Dongliang Chao School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China Laboratory of Advanced Materials Fudan UniversityShanghai 200433China MHT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbin 150001China

Rechargeable zinc-based batteries with near-neutral media are standing in the middle of the energy storage field by virtue of their high safety and low cost.However,it is still imperative for Mn-based cathode to improve rate capacity by facilitating ions/electron transfer and long-cycle stability by suppressing Mn dissolution.Herein,promoting electrooxidation kinetics is proposed and employed to construct advanced Mn-Zn battery.The formation of carbon-protected birnessite-MnO_(2)is promoted via inducing the electron-donating capability of the heterointerface between the N-C coating and the defective MnO.Moreover,density functional theory calculations also demonstrate that N-C protected birnessite-MnO_(2)is more hydrophobic than pure birnessite-MnO_(2),which is beneficial to prohibiting Mn dissolution and other side reactions.As a result,the elaborate design realizes effective transformation from low valence to high valence Mn for high capacity(291 mAh·g^(−1))and protective bambooslike structure for rate capacity(126 mAh·g^(−1)at 5 A·g^(−1))and cycling stability(89%capacity retention after 2,000 cycles).The assembled flexible quasi-solid-state Mn-Zn pouch batteries display application prospects for wearable and implantable electronic devices.The atomic engineering promoting electrooxidation kinetics strategy will be instructive in activating other cathode materials and maximizing their capacity.

关键词： atomic engineering Mn-based cathode electrooxidation Zn-ion battery long lifespan

Bilayer solid-electrolyte interphase structure enables a 440 Wh kglithium metal pouch cell to achieve 130 cycles

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Science China Chemistry 2023年

作者： Xiong Liu chaojiang niu School of Materials Science and Engineering Zhengzhou University

Lithium (Li) metal has been considered one of the most promising anodes due to its high theoretical capacity, lightweight and low electrochemical potential. The cell-level energy density of rechargeable lithium metal batteries(LMBs) is expected to surpass 500 Wh kg-1after replacing the graphite anode in lithium-ion batteries [1]. However, the development and application of LMBs have been mainly hindered by serious issues from the lithium metal anode.During the cycling, the uneven repeated lithium plating/stripping processes cause the continuous break and reconstruction of solid-electrolyte interphase (SEI)(Figure1a), constant consumption of active lithium and depletion of limited electrolyte, thus leading to a rapid expansion of cell volume and a sudden drop in cell capacity.

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Interface-modulated fabrication of hierarchical yolk-shell Co3O4/C dodecahedrons as stable anodes for lithium and sodium storage

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Nano Research 2017年第7期10卷 2364-2376页

作者： Yuzhu Wu Jiashen Meng Qi Li chaojiang niu Xuanpeng wang Wei Yang Wei Li Liqiang Mai State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan 430070 China Department of Chemistry University of California Berkeley California 94720 USA

Transition-metal oxides （TMOs） have gradually attracted attention from resear- chers as anode materials for lithium-ion batteries （LIBs） and sodium-ion batteries （SIBs） because of their high theoretical capacity. However, their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic con- ductivity limit their applications. To solve the problems of TMOs, carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks （MOFs） have emerged as promising electrode materials for LIBs and SIBs. In this study, we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imida- zolate frameworks. This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process. The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation, and the carbon matrix improves the electrical conductivity of the electrode. As an anode for LIBs, the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability （1,100 mAh.g-1 after 120 cycles at 200 mA-g-1）. As an anode for S1Bs, the composites exhibit an outstand- ing rate capability （307 mAh-g-1 at 1,000 mA-g-1 and 269 mAh.g-1 at 2,000 mA-g-1）. Detailed electrochemical kinetic analysis indicates that the energy storage for Li＋ and Na＋ in yolk-sheU Co3O4/C dodecahedrons shows a dominant capacitive behavior. This work introduces an effective approach for fabricating carbon- based metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.

关键词： carbon-based metal oxide,metal--organicframeworks （MOFs）,yolk-shell structure,lithium-ion batteries （LIBs）,sodium-ion batteries（SIBs）

Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

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Nano Research 2016年第8期9卷 2445-2457页

作者： Jiashen Meng chaojiang niu Xiong Liu Ziang Liu Hongliang Chen Xuanpeng Wang Jiantao Li Wei Chen Xuefeng Guo Liqiang Mai State Key Laboratory of Advcrnced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan 430070 China Center for Nanochemistry Beijing National Laboratory for Molecular Sciences State Key Laboratory for Structural Chemistry of Unstable and Stable Species College of Chemistry and Molecular Engineering Peking University Beijing 100871 China

Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis, chemical sensing, drug delivery, and energy storage. However, the controlled synthesis of multilevel nanotubes remains a great challenge. Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment. This versatile strategy can be effectively applied to fabricate wire-in-tube and tube- in-tube nanotubes of various metal oxides. These multilevel nanotubes possess a large specific surface area, fast mass transport, good strain accommodation, and high packing density, which are advantageous for lithium-ion batteries （LIBs） and the oxygen reduction reaction （ORR）. Specifically, shrinkable CoMn204 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of -565 mAh-g-1 at a high rate of 2 A.g-~, maintaining 89% of the latter after 500 cycles. Further, as an oxygen reduction reaction catalyst, these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s, which is higher than that of commercial Pt/C （81%）. Therefore, this feasible method may push the rapid development of one-dimensional （1D） nanomaterials. These multifunctional nanotubes have great potential in many frontier fields.

关键词： interface-modulatedapproach,multilevel nanotubes,metal oxide,lithium-ion battery （LIB~,~,oxygen reduction reaction（ORR）

Niobium oxyphosphate nanosheet assembled two-dimensional anode material for enhanced lithium storage

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Journal of Energy Chemistry 2021年第2期30卷 268-275,I0009页

作者： Bo Wen Ruiting Guo Xiong Liu Wen Luo Qiu He chaojiang niu Jiashen Meng Qi Li Yan Zhao Liqiang Mai State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070HubeiChina State Key Laboratory of Silicate Materials for Architectures Wuhan University of TechnologyWuhan 430070HubeiChina Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory Foshan 528216GuangdongChina

The development of high-capacity and high-rate anodes has become an attractive endeavor for achieving high energy and power densities in lithium-ion batteries(LIBs).Herein,a new-type anode material of reduced graphene oxide(rGO) supported niobium oxyphosphate(NbOPO_4) nanosheet assembled twodimensional composite material(NbOPO_4/rGO) is firstly fabricated and presented as a promising highperformance LIB anode material.In-depth electrochemical analyses and in/ex situ characterizations reveal that the intercalation-conversion reaction takes place during the first discharge process,followed by the reversible redox process between amorphous NbPO_4 and Nb which contributes to the reversible capacity in the subsequent cycles.Meanwhile,the lithiation-generated Li3 PO_4,behaving as a good lithium ion conductor,facilitates ion transport.The rGO support further regulates the structural and electron/ion transfer properties of NbOPO_4/rGO composite compared to neat NbOPO_4, resulting in greatly enhanced electrochemical performances.As a result,NbOPO_4/rGO as a new-type LIB anode material achieves a high capacity of 502.5 mAh g^(-1) after 800 cycles and outstanding rate capability of 308.4 mAh g^(-1) at 8 A g^(-1).This work paves the way for the deep understanding and exploration of phosphate-ba sed high-efficiency anode materials for LIBs.

关键词： 2D nanomaterials Niobium oxyphosphate High-rate anode Lithium storage mechanism Lithiation-induced amorphization

Carbon-supported and nanosheet-assembled vanadium oxide microspheres for stable lithium-ion battery anodes

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Nano Research 2016年第1期9卷 128-138页

作者： chaojiang niu Meng Huang Peiyao Wang Jiashen Meng Xiong Liu Xuanpeng Wang Kangning Zhao Yang Yu Yuzhu Wu Chao Lin Liqiang Mai State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan430070 China

Naturally abundant transition metal oxides with high theoretical capacity have attracted more attention than commercial graphite for use as anodes in lithium-ion batteries. Lithium-ion battery electrodes that exhibit excellent electrochemical performance can be efficiently achieved via three-dimensional （3D） architectures decorated with conductive polymers and carbon. As such, we developed 3D carbon-supported amorphous vanadium oxide microspheres and crystalline V203 microspheres via a facile solvothermal method. Both samples were assembled with ultrathin nanosheets, which consisted of uniformly distributed vanadium oxides and carbon. The formation processes were clearly revealed through a series of time-dependent experiments. These microspheres have numerous active reaction sites, high electronic conductivity, and excellent structural stability, which are all far superior to those of other lithium-ion battery anodes. More importantly, 95% of the second-cycle discharge capacity was retained after the amorphous microspheres were subjected to 7,000 cycles at a high rate of 2,000 mA/g. The crystalline microspheres also exhibited a high-rate and long-life performance, as evidenced by a 98% retention of the second-cycle discharge capacity after 9,000 cycles at a rate of 2,000 mA/g. Therefore, this facile solvothermal method as well as unique carbon-supported and nanosheet-assembled microspheres have significant potential for the synthesis of and use in, respectively, lithium-ion batteries.

关键词： vanadium oxide,microspheres,amorphous,lithium-ion battery,anodes

P-doped Germanium Nanowires with Fanobroadening in Raman Spectrum

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Journal of Wuhan University of Technology(Materials Science) 2016年第1期31卷 52-57页

作者：何亮 xiong biao zhou peng luo wen song peishuai wang xukun hao zhimeng yang xiao niu chaojiang tian xiaocong yan mengyu 麦立强 State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan 430070 China

The optimized growth conditions for high density germanium（Ge） nanowires and P-doped Ge nanowires on Si（111） substrate were investigated,the phosphorus（P）-doping in Ge nanowires was also characterized.Vapor liquid solid-low pressure chemical vapor deposition（VLS-LPCVD） of Ge nanowires was conducted with different thicknesses of Au film as catalyst,different flow rates of GeH4 as precursor and PH3/Ar as co-flow.The morphologies of the Ge nanowires were characterized by scanning electron microscopy（SEM）,the P-doping was verified by micro Raman spectroscopy via measuring the P local vibrational peak（342-345 cm^（-1）） and asymmetric broadening of Ge-Ge vibrational peak（about 300 cm^（-1）,respectively.The characterization results show that 1 run thickness of Au catalyst is the most suitable condition among thicknesses of 0.1,1,5,and 10 nm for the growth of high density Ge nanowires at 300 and 350℃,and 0.5 sccm is the best flow rate of PH3/Ar to grow high density and large scale P-doped Ge nanowires among flow rates of 0.5,1 and 2sccm.The P impurity can be doped into Ge nanowires effectively during LPCVD process at 350 ℃.

关键词： germanium nanowires LPCVD doping VLS

Nanowire based Electrochemical Devices for Energy Storage

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Nanowire based Electrochemical Devices for Energy Storage

pyrG基因缺失对黑曲霉中赭曲霉毒素A生物合成的影响

2011中国材料研讨会

作者： Liqiang Mai,1,2,Fei Dong 1,Xu Xu 1,Yunlong Zhao 1,chaojiang niu 1,Lin Xu 1,Chunhua Han 1 1.State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan,430070,China 2.Department of Chemistry and Chemical Biology,Harvard University,Cambridge,Massachusetts 02138,USA

Li-ion batteries for portable electronic devices and hybrid electric vehicles have gained great importance for energy storage today [1-3].However,how to prepare cathode materials with higher energy density,high potentials,and longer cycle life is still a challenge.Recently,oxide nanowire electrodes are found to have excellent cycling performance because they have higher surface area,shorter Li ion diffusion lengths,and facile strain relaxation upon electrochemical cycling [4-6].In the previous work,bulk materials made of nanowires were usually used as the battery electrodes.Although the electrochemical properties of these materials were improved,aggregation and disorder make the advantage of nanowires not prominent.Meanwhile,it is difficult to know whether fast capacity fading is due to intrinsic nature of nanowires or extrinsic reason such as the contact of nanowires,binders,and conductive additives.To understand intrinsic reason of capacity fading,we design the single nanowire electrochemical devices which may push the fundamental limits of the nanowire materials for energy storage applications [7].In this device,single vanadium oxide nanowire or single Si/a-Si core/shell nanowire was used as working electrode,and electrical transport of the single nanowire was recorded in situ to detect the evolution of the nanowire during charging and discharging.Our results show that conductivity of the nanowire electrode decreased reversibly （for vanadium oxide nanowire by shallow discharge/charge） or irreversibly （for vanadiumoxide nanowire by deep discharge/charge,or silicon nanowire） during the electrochemical reaction,which limits the cycle life of the devices.Based on the above conclusion,to improve the cycling performance of electrochemical devices,we used prelithiation to restrain the conductivity decrease of the electrode materials [8-9].Lithiated single MoO 3 nanowire device was achieved by secondary hydrothermal reaction followed by e-beam lithiography.The conductivity of a lithiated single MoO 3 nanowire （10-2 Sc

关键词： Vanadium Oxide Nanowire Lithiation Energy Storage Electrochemical Properties

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河南工业大学学报（自然科学版） 2022年第4期43卷 1-8页

作者：胡朝江张艺格张智慧牛志鹏吕扬勇翟焕趁魏闪胡元森河南工业大学生物工程学院河南郑州450001

黑曲霉在食品工业中广泛应用,但近年来发现该菌群可产生赭曲霉毒素A(OTA)等强致癌真菌毒素,对食品安全造成严重威胁。为了研究黑曲霉中OTA合成调控机理,构建了乳清酸核苷-5′-磷酸脱羧酶基因pyrG缺失菌株及回补菌株,利用HPLC-FLD检测该... 详细信息

黑曲霉在食品工业中广泛应用,但近年来发现该菌群可产生赭曲霉毒素A(OTA)等强致癌真菌毒素,对食品安全造成严重威胁。为了研究黑曲霉中OTA合成调控机理,构建了乳清酸核苷-5′-磷酸脱羧酶基因pyrG缺失菌株及回补菌株,利用HPLC-FLD检测该基因对OTA生物合成的影响,通过添加不同浓度尿嘧啶核苷及荧光定量PCR,初步探索该基因调控OTA合成的机理,并检测玉米粒上该基因缺失菌株中OTA含量的变化。结果表明:与野生型菌株及回补菌株相比,pyrG基因缺失菌株OTA含量分别降低77.8%和75.7%;该基因调控OTA合成不依赖尿嘧啶核苷的浓度;与野生型菌株相比,pyrG基因缺失菌株OTA合成基因簇中基因pks、p450、nrps、hal和bZIP基因的表达水平分别下调52.0%、36.0%、84.0%、46.0%、74.0%,与回补菌株相比,分别下调55.7%、42.1%、85.1%、50.3%、76.0%;pyrG基因缺失后导致玉米粒上的黑曲霉菌株几乎不产生OTA。pyrG基因缺失影响黑曲霉中OTA合成基因pks、p450、nrps、hal及bZIP的表达,从而降低了OTA的合成水平。

关键词：黑曲霉赭曲霉毒素A pyrG OTA合成基因簇玉米粒