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A solubility limited pyrene-4,5,9,10-tetraone-based covalent organic framework for high-performance aqueous zinc-organic batteries

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Nano Research 2024年第6期17卷 5095-5103页

作者： Min Cheng Shibing Zheng tianjiang sun Diantao Li Weijia Zhang Zhengtai Zha Qiong sun Jing Tian Kai Zhang Zhanliang Tao Frontiers Science Center for New Organic Matter State Key Laboratory of Advanced Chemical Power SourcesKey Laboratory of Advanced Energy Materials Chemistry(Ministry of Education)Collaborative Innovation Center of Chemical Science and Engineering(Tianjin)Renewable Energy Conversion and Storage CentreNankai UniversityTianjin 300071China Haihe Laboratory of Sustainable Chemical Transformations Tianjin 300192China

Pyrene-4,5,9,10-tetraone(PTO),with a high theoretical capacity of 408 mAh·g^(−1),is a promising candidate for rechargeable aqueous zinc-ion batteries(RAZIBs),but its zincated products during discharge process suffer from high solubility in ***,aβ-ketoenamine-linked two-dimensional(2D)covalent organic framework(COF)based on a 2,7-diaminopyrene-4,5,9,10-tetraone(4KT-BD)monomer and a 2,4,6-trihydroxy-benzene-1,3,5-tricarbaldehyde(Tp)node(4KT-Tp-COF)is synthesized to address the above *** well-designed 4KT-Tp-COF displays low solubility in 3 M Zn(CF3SO3)2 owing to the favorableπ-πstacking as well as extended ***,the ingenious structural design of the active molecule and the long-range ordered nano-channels alter the intramolecular electron distribution,which facilitates the ionic ***,the 4KT-Tp-COF cathode exhibits a stable capacity of 181 mAh·g^(−1)at 0.2 A·g^(−1),superior rate capability of 139 mAh·g^(−1)at 20 A·g^(−1),and a long lifetime of 1000 cycles without capacity loss at 30 A·g^(−1).Even at a low temperature of−20°C,the electrode also performs an ultralong cycling life of 9000 cycles with a capacity of 106 mAh·g^(−1)at 5 A·g^(−1).The comprehensive characterizations of ex-situ analyses together with the theoretical calculations validate that the groups of C=O can contribute highly accessible redox-active sites for Zn^(2+)*** ultra-stable 4KT-Tp-COF cathode provides important insights for designing robust organic electrodes for sustainable and large-scale electrochemical energy storage.

关键词： pyrene-4,5,9,10-tetraone solubility limited covalent organic framework zinc batteries

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Intramolecular Hydrogen Bond Improved Durability and Kinetics for Zinc‑Organic Batteries

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Nano-Micro Letters 2024年第3期16卷 138-148页

作者： tianjiang sun Jun Pan Weijia Zhang Xiaodi Jiang Min Cheng Zhengtai Zha Hong Jin Fan Zhanliang Tao Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Renewable Energy Conversion and Storage CenterCollege of ChemistryNankai UniversityHaihe Laboratory of Sustainable Chemical TransformationsTianjin 300071People’s Republic of China School of Physical and Mathematical Sciences Nanyang Technological UniversitySingapore 637371Singapore Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology School of Physics Science and EngineeringTongji UniversityShanghai 200092People’s Republic of China

Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic ***,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)*** intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in *** situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current ***,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular *** work provides an efficient approach toward insoluble organic electrode materials.

关键词： Zn-organic batteries H-PNADBQ polymer Intramolecular hydrogen bond Reduced solubility Improvedπ-conjugated level

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Synergistic Effect of Cation and Anion for Low-Temperature Aqueous Zinc-Ion Battery

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Nano-Micro Letters 2021年第12期13卷 301-310页

作者： tianjiang sun Shibing Zheng Haihui Du Zhanliang Tao Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Renewable Energy Conversion and Storage CenterCollege of ChemistryNankai UniversityTianjin 300071People’s Republic of China

Although aqueous zinc-ion batteries have gained great development due to their many merits,the frozen aqueous electrolyte hinders their practical application at low temperature ***,the synergistic e ect of cation and anion to break the hydrogen-bonds network of original water molecules is demonstrated by multi-perspective ***,an aqueous-salt hydrates deep eutectic solvent of 3.5 M Mg(ClO_(4))_(2)+1 M Zn(ClO_(4))_(2)is proposed and displays an ultralow freezing point of-121℃.A high ionic conductivity of 1.41 mS cm-1 and low viscosity of 22.9 mPa s at-70℃ imply a fast ions transport behavior of this *** the benefits of the low-temperature electrolyte,the fabricated Zn||Pyrene-4,5,9,10-tetraone(PTO)and Zn||Phenazine(PNZ)batteries exhibit satisfactory low-temperature *** example,Zn||PTO battery shows a high discharge capacity of 101.5 mAh g^(-1)at 0.5 C(200 mA g^(-1))and 71 mAh g^(-1)at 3C(1.2 A g^(-1))when the temperature drops to-70℃.This work provides an unique view to design anti-freezing aqueous electrolyte.

关键词： Low-temperature aqueous zinc-ion battery 3.5M Mg(ClO_4)_(2)+1M Zn(ClO_4)_(2)electrolyte Synergistic effect Pyrene-4 5 9 10-tetraone Phenazine

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Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery

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Nano-Micro Letters 2023年第3期15卷 98-111页

作者： tianjiang sun Weijia Zhang Qingshun Nian Zhanliang Tao Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) College of ChemistryHaihe Laboratory of Sustainable Chemical TransformationsRenewable Energy Conversion and Storage CenterNankai UniversityTianjin 300071People’s Republic of China CAS Key Laboratory of Materials for Energy Conversion Department of Materials Science and EngineeringHefei National Laboratory for Physical Science at the MicroscaleUniversity of Science and Technology of China HefeiHefei 230026AnhuiPeople’s Republic of China

Novel small sulfur heterocyclic quinones(6a,16adihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone(4S6Q)and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone(4S4Q))are developed by molecule structural design method and as cathode for aqueous zincorganic *** conjugated thioether(–S–)bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extendedπ-conjugated plane and constructed flexible molecular ***,the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1(M)Zn(ClO4)*** instance,the Zn//4S6Q battery obtains 240 and 208.6 mAh g^(-1)of discharge capacity at 150 mA g^(-1)and 30 A g^(-1),*** excellent rate capability is ascribed to the fast reaction *** system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g^(-1).Additionally,the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory ***,the battery can normally work at-60℃benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g^(-1),which is 86.2%of discharge capacity at 25℃.The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.

关键词： Aqueous Zn-organic battery Small sulfur heterocyclic quinones Conjugated thioether skeleton Superlong cycling life H+-involved mechanism -60℃

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Hollow tubular conjugated organic polymer for lithium batteries

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Nano Research 2023年第2期16卷 2474-2479页

作者： Weijia Zhang Shibing Zheng Tao Ma tianjiang sun Zhanliang Tao Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Renewable Energy Conversion and Storage CentreCollege of ChemistryNankai UniversityHaihe Laboratory of Sustainable Chemical TransformationsTianjin 300071China

Polymerization is a valid strategy to solve the dissolution issue of organic electrode materials in aprotic ***,conventional polymers usually with amorphous structures and morphology’s influence on electrochemistry have rarely been ***,a hollow tubular poly phenyl pyrene-4,5,9,10-tetraone(T-PPh-PTO)organic cathode material was designed and synthesized based on the concentration-gradient of the precursor(PTO-Br2)and asymmetrical internal diffusion during the *** unique hollow structure endowed T-PPh-PTO with a short Li+diffusion path accompanied by a high diffusion Li+coefficient(D≈10−8 cm^(2)·s^(−1)).Thus,T-PPh-PTO presented a capacitance-dominated redox pseudocapacitance action with an outstanding rate performance(173 mAh·g^(−1)at 2 A·g^(−1))and high cycle stability(capacity retention ratio is 91.7%after 2,000 cycles).Our study leads to further developments in designing unique organic structures for energy storage.

关键词： conjugated organic polymer hollow tubular structure lithium batteries ionic migration

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Alloxazine as anode material for high-performance aqueous ammonium-ion battery

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Nano Research 2022年第3期15卷 2047-2051页

作者： Yuan Ma tianjiang sun Qingshun Nian Shibing Zheng Tao Ma Qiaoran Wang Haihui Du Zhanliang Tao Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Renewable Energy Conversion and Storage CenterCollege of ChemistryNankai UniversityTianjin 300071China Hefei National Laboratory for Physical Science at the Microscale CAS Key Laboratory of Materials for Energy ConversionDepartment of Materials Science and EngineeringUniversity of Science and Technology of ChinaHefei 230026China

Aqueous ammonium-ion battery(AAIB)has attracted much attention due to its low cost,safety,and environmental friendliness,but its electrode materials have many ***,alloxazine(ALO)is introduced as the anode for the *** its pseudocapacitive effect and fast diffusion kinetics of NH4+,ALO anode shows excellent rate performance with a specific capacity of 120 mAh/g at 40 C(10 A/g).The full battery is further fabricated by ALO anode and Prussian white analogs *** specific capacity can reach 110 mAh/g and it can work up to 10,000 cycles with no obvious capacity fading at 20 C(5 A/g).In addition,the system delivers a high energy density of 122.5 Wh/kg and a power density of 5,055 W/*** work broadens the application prospect of the AAIB.

关键词： aqueous ammonium-ion battery alloxazine anode material pseudocapacitive effect

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A phenazine anode for high-performance aqueous rechargeable batteries in a wide temperature range

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Nano Research 2020年第3期13卷 676-683页

作者： tianjiang sun Chang Liu Jiayue Wang Qingshun Nian Yazhi Feng Yan Zhang Zhanliang Tao Jun Chen Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) College of ChemistryNankai UniversityTianjin300071China State Key Laboratory of Molecular Reaction Dynamics Dalian Institute of Chemical Physics(DICP)Chinese Academy of SciencesDalian116023China Institute of Molecular Sciences and Engineering Shandong UniversityQingdaoBinhai Road 72Qingdao266237China

Aqueous rechargeable batteries are a possible strategy for large-scale energy storage ***,limited choices of anode materials restrict their further *** we report phenazine(PNZ)as stable anode materials in different alkali-ion(Li+,Na+,K+)electrolyte.A novel full cell is assembled by phenazine anode,Na0.44MnO2 cathode and 10 M NaOH electrolyte to further explore the electrochemical performance of phenazine *** battery is able to achieve high capacity(176.7 mAh·g^−1 at 4 C(1.2·Ag^−1)),ultralong cycling life(capacity retention of 80%after 13,000 cycles at 4 C),and excellent rate capacity(92 mAh·g^−1 at 100 C(30 A·g^−1)).The reaction mechanism of PNZ during charge—discharge process is demonstrated by in situ Raman spectroscopy,in situ Fourier transform infrared(FTIR)spectroscopy,X-ray photoelectron spectroscopy(XPS)and density functional theory(DFT)***,the system is able to successfully operate at wide temperature range from−20 to 70°C and achieves remarkable electrochemical performance.

关键词： aqueous rechargeable batteries phenazine Na0.44MnO2 alkali-ion electrolyte wide temperature

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医药研发团队“分步式”激励方案设计--以扬子江药业集团为例

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中国人力资源开发 2015年第10期32卷 74-79页

作者：孙田江肖璐江苏吴中医药集团有限公司江苏大学管理学院

运用案例研究方法,借助期望理论、马斯洛需求层次等激励理论,在分析医药研发活动"高投入、长周期、高风险"等特点以及研发人才激励难点基础上,以扬子江药业集团为例,对医药研发团队的"分步式"激励方案进行了详细分析,实践证明该方案解... 详细信息

运用案例研究方法,借助期望理论、马斯洛需求层次等激励理论,在分析医药研发活动"高投入、长周期、高风险"等特点以及研发人才激励难点基础上,以扬子江药业集团为例,对医药研发团队的"分步式"激励方案进行了详细分析,实践证明该方案解决了企业在员工激励过程中的时效性难题,同时分解了激励的成本,实现了对激励的过程控制。最后指出了该方案对医药行业其他企业的借鉴意义。

关键词：医药研发激励方案 “分步式”激励

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高新技术企业研发部门关键绩效指标制定的实证研究——以医药企业为例

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科技管理研究 2012年第12期32卷 93-95,113页

作者：孙田江范明周云隆扬子江药业集团江苏泰州225321 江苏大学江苏镇江212013

以随机选择绩效管理优秀的三个不同级别的高新技术医药企业为例,对其研发人才、绩效管理人才进行问卷调研,运用SPSS16.0统计分析软件和KMO检验模型对调研数据进行标准化处理和相关性检验,采用多元统计分析中的因子分析法,找出累积贡献... 详细信息

以随机选择绩效管理优秀的三个不同级别的高新技术医药企业为例,对其研发人才、绩效管理人才进行问卷调研,运用SPSS16.0统计分析软件和KMO检验模型对调研数据进行标准化处理和相关性检验,采用多元统计分析中的因子分析法,找出累积贡献率大的公共因子,该公共因子就是评价高新技术医药企业研发部门综合业绩的主因子,由此制定高新技术医药企业研发部门的关键绩效指标。

关键词：研发部门关键绩效指标因子分析法高新技术企业

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钙钒青铜/碳纳米管复合材料的制备及电化学性能

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高等学校化学学报 2019年第12期40卷 2526-2533页

作者：刘建杜海会孙田将年庆舜李海霞陶占良南开大学化学学院先进能源材料化学教育部重点实验室

采用水热法制备了具有二维层状结构的钙钒青铜(CaxV2O5·n H2O,CVO)水系锌离子电池钒基正极材料,并通过调控前驱体溶液中碳纳米管的含量,得到3种钙钒青铜/碳纳米管复合材料(CVO@CNTs).利用X射线衍射、热重分析、扫描电子显微镜和透射电... 详细信息

采用水热法制备了具有二维层状结构的钙钒青铜(CaxV2O5·n H2O,CVO)水系锌离子电池钒基正极材料,并通过调控前驱体溶液中碳纳米管的含量,得到3种钙钒青铜/碳纳米管复合材料(CVO@CNTs).利用X射线衍射、热重分析、扫描电子显微镜和透射电子显微镜等对材料进行了表征.结果表明,所制备的CVO呈纳米带形貌,长约十几微米,宽约几百纳米,选区电子衍射测试表明所得材料为单晶结构.循环伏安测试结果表明,CVO和CVO@CNTs均具有多个氧化还原峰,储锌机制包括赝电容行为和电池行为.在放电倍率1C (1C=300 m A/g)测试条件下,CVO纳米带比容量稳定在210. 1 m A·h/g;与CNTs复合后,CVO@CNTs复合材料的电荷转移阻抗降低,在相同测试条件下表现出更高的比容量和优异的倍率性能.其中,CVO@CNTs-40表现出最高的比容量,在1C倍率测试条件下的比容量可达274. 3 m A·h/g,即使在20C的测试条件下放电比容量仍可达85. 2 m A·h/g,且循环1000次后容量保持率能达到92%.

关键词：水系锌离子电池正极材料钙钒青铜碳纳米管水热反应

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