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Energy & Environmental Materials 2024年第3期7卷 72-83页

作者： Sheng Liu chaozhu shu Yu Yan Dayue Du Longfei Ren Ting Zeng Xiaojuan Wen Haoyang Xu Xinxiang Wang Guilei Tian Ying Zeng College of Materials and Chemistry&Chemical Engineering Chengdu University of Technology1#DongsanluErxianqiaoChengdu 610059China Institute of Fundamental and Frontier Sciences University of Electronic Science and Technology of ChinaChengdu 611731China State Key Laboratory of Polymer Materials Engineering Polymer Research InstituteSichuan UniversityChengdu 610065China

The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the ***,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li *** on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 *** addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.

关键词： electric double layer electrolyte additives intermolecular hydrogen bonds Li metal batteries p-Hydroxybenzoic acid

Active site synergy of the mixed-phase cobalt diselenides with slight lattice distortion for highly reversible and stable lithium oxygen batteries

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Journal of Materials Science & Technology 2021年第33期92卷 159-170页

作者： Minglu Li chaozhu shu Anjun Hu Yu Yan Miao He Jianping Long College of Materials and Chemistry&Chemical Engineering Chengdu University of TechnologyChengdu 610059China State Key Laboratory of Electronic Thin Films and Integrated Devices University of Electronic Science and Technology of ChinaChengdu 610054China

Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application,which leads to poor *** this work,we propose c-CoSe_(2)/o-CoSe_(2)as the oxygen electrode of lithium-oxygen batteries(LOBs)to improve its cycle *** heterogeneous interface inside c-CoSe_(2)/o-CoSe_(2)leads to an increase in the covalence bonds between Co and Se ions,which greatly enhances the robustness of the crystal lattice,thereby improving the stability of the *** addition,the strong interaction between the mixed phases is favorable for adjusting the electron density around the active sites and boosting oxygen electrode ***,the epitaxial growth of o-CoSe_(2)on c-CoSe_(2)will cause abundant heterogeneous interfaces and slight lattice distortion along the interfaces,thereby providing sufficient catalytic reaction *** DFT calculation results show that the optimized adsorption of intermediates at the heterogeneous interface plays an important role in boosting oxygen electrode reactions and improving the electrochemical performance of *** experimental results show that LOBs with the c-CoSe_(2)/o-CoSe_(2)electrodes exhibit outstanding performance,including large specific capacity of about 23,878 m A h g^(-1),high coulombic efficiency of up to 93.66%,and excellent stability of over 176 cycles(1410 h).

关键词： Li-O_(2)battery Oxygen electrode Structure design Lattice distortion Jahn-Teller effect

Long-cycling lithium-oxygen batteries enabled by tailoring Li nucleation and deposition via lithiophilic oxygen vacancy in Vo-TiO_(2)/Ti_(3)C_(2)Tx composite anodes

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Journal of Energy Chemistry 2022年第2期31卷 654-665页

作者： Yu Yan chaozhu shu Ruixin Zheng Minglu Li Zhiqun Ran Miao He Longfei Ren Dayue Du Ying Zeng College of Materials and Chemistry&Chemical Engineering Chengdu University of TechnologyChengdu 610059SichuanChina

Uncontrollable Li dendrite growth and infinite volume fluctuation during durative plating and stripping process gravely hinder the application of metallic Li electrode in lithium-oxygen ***,oxygen vacancy-rich TiO_(2)(Vo-TiO_(2))nanoparticles(NPs)uniformly dispersing on Ti_(3)C_(2)T_(x)(Vo-TiO_(2)/Ti_(3)C_(2) T_(x))with excellent lithiophilicity feature are presented as effective composite anodes,on which a dense and uniform Li growth behavior is *** on electrochemical studies,mutiphysics simulation and theoretical calculation,it is found that Vo-TiO_(2) coupling with three dimensional(3 D)conductive Ti_(3)C_(2) T_(x) MXene forms highly ordered lithiophilic sites which succeed in guiding Li ions flux and adsorption,thus modulating the uniform Li nucleation and *** a result,this composite electrode is capable of preserving Li with high areal capacity of~10 mAh cm^(-2) without the presence of dendrites and large volume ***,the as-prepared Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anode shows outstanding performance including low voltage hysteresis(~19 mV)and superior durability(over 750 h).When assembling with the Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anodes,lithium-oxygen batteries also deliver enhanced cycling stability and improved rate *** work demonstrates the effectiveness of oxygen vacancies in guiding Li nucleating and plating behavior at initial stage and brings a promising strategy for promoting the development of advanced Li metal-based batteries.

关键词： Lithium-oxygen batteries Electrode materials Vo-TiO_(2)/Ti_(3)C_(2)Tx composite Oxygen vacancies Adsorption energy

Modulating Sand’s time by ion-transport-enhancement toward dendrite-free lithium metal anode

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Nano Research 2022年第4期15卷 3150-3160页

作者： Yu Yan chaozhu shu Ruixin Zheng Minglu Li Zhiqun Ran Miao He Anjun Hu Ting Zeng Haoyang Xu Ying Zeng College of Materials and Chemistry&Chemical Engineering Chengdu University of Technology1#DongsanluErxianqiaoChengdu 610059China

Metallic lithium is deemed as the“Holy Grail”anode in high-energy-density secondary *** lithium dendrite growth and related issues originated from uneven concentration distribution of Li+in the vicinity of the anode,however,induce severe safety concerns and poor cycling efficiency,dragging lithium metal anode out of practical *** we address these issues by using cross-linked lithiophilic amino phosphonic acid resin as the effective host with the ion-transportenhancement *** on theoretical calculations and multiphysics simulation,it is found that this ion-transportenhancement feature is capable of facilitating the self-concentration kinetics of Li+and accelerating Li^(+)transfer at the electrolyte/electrode interface,leading to uniform bulk lithium *** results show that the proposed lithiumhosting resin decreases the irreversible lithium capacity and improves lithium utilization(with the Coulombic efficiency(CE)of 98.8%over 130 cycles).Our work demonstrates that inducing the self-concentrating distribution of Li+at the interface can be an effective strategy for improving the interfacial ion concentration gradient and optimizing lithium deposition,which opens a new avenue for the practical development of next-generation lithium metal batteries.

关键词： lithium-oxygen batteries electrode materials lithiophilic resin electrode structure stability

Manipulating the ion-transference and deposition kinetics by regulating the surface chemistry of zinc metal anodes for rechargeable zinc-air batteries

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Green Energy & Environment 2023年第1期8卷 318-330页

作者： Miao He chaozhu shu Ruixing Zheng Wei Xiang Anjun Hu Yu Yan Zhiqun Ran Minglu Li Xiaojuan Wen Ting Zeng Jianping Long College of Materials and Chemistry&Chemical Engineering Chengdu University of Technology1#DongsanluErxianqiaoChengduSichuan610059China State Key Laboratory of Electronic Thin Films and Integrated Devices University of Electronic Science and Technology of ChinaChengduSichuan610054China

Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental ***,the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ***,the N-doped carbon cloth(NC)prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite *** show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn^(2+)by boosting the desolvation process of Zn^(2+),eventually reducing the nucleation ***,theoretical calculation results confirm the zincophilicity of N-containing functional group(such as pyridine N and pyrrole N),which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn^(2+) in the vicinity of the surface and enhancing its interaction with zinc *** a result,the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8%and long-term stability of over 500 cycles at 0.2 mA cm^(-2).And the Coulombic efficiency reached about 99.5%at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm^(-2).The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 *** addition,the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh g_(Zn)^(-1) and a long life of over 430 *** effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn^(2+) presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.

关键词： Zinc metal anodes Dendrite-free Surface chemical regulation Ion-transference kinetics Aqueous zinc-air battery

Cationic vanadium vacancy-enriched V_(2−x)O_(5)on V_(2)C MXene as superior bifunctional electrocatalysts for Li-O_(2) batteries

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Science China Materials 2022年第7期65卷 1761-1770页

作者： Haoyang Xu Ruixin Zheng Dayue Du Longfei Ren Runjing Li Xiaojuan Wen Chuan Zhao Ting Zeng Bo Zhou chaozhu shu College of Materials and Chemistry&Chemical Engineering Chengdu University of TechnologyChengdu 610059China

The development of cationic vacancies has been extensively examined as an effective strategy to improve the activity of ***,it is a challenge to effectively introduce cationic vacancies on the material *** specific effects on the electrochemical performance of lithium-oxygen(Li-O_(2))batteries are rarely *** this work,vanadium pentoxide with abundant vanadium vacancies(V_(2-x)O_(5))is in situ prepared on the V_(2)C MXene(V_(2-x)O_(5)@V_(2)C MXene)surface,and their bifunctional catalytic activity toward the oxygen electrode reaction in Li-O_(2)batteries is systematically *** results show that the V_(2-x)O_(5)@V_(2)C MXene-based Li-O_(2)battery exhibits excellent *** delivers a high energy efficiency of 83.4%at 100 mA g^(-1) and excellent cycling performance of more than 500 ***,density functional theory calculations confirm that the presence of cationic vanadium vacancies can provide abundant active sites to reduce the reaction barrier and optimize the adsorption of reactants,increasing the oxygen electrode reactions in the Li-O_(2)*** work provides a meaningful view that modulating the electronic structure by creating cationic metal vacancies can improve the electrocatalytic activity of transition metal oxides.

关键词： Li-O_(2)batteries oxygen electrode electrocatalyst transition metal oxide vanadium vacancy

过渡金属碳氮化合物(MXenes)在能量储存装置的研究进展

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电子元件与材料 2020年第2期39卷 1-9页

作者：郑瑞鑫舒朝龙剑平成都理工大学材料与化学化工学院

层状过渡金属碳化物和/或氮化物(MXenes)凭借其特有的结构和性能成为了新型储能装置电极催化剂的重要候选材料。MXenes的表达式一般为Mn+1 Xn Tx,其中“M”代表早期的过渡金属元素,“x”表示C、N或CN,而“Tx”为“-OH”、“-F”等基团,... 详细信息

层状过渡金属碳化物和/或氮化物(MXenes)凭借其特有的结构和性能成为了新型储能装置电极催化剂的重要候选材料。MXenes的表达式一般为Mn+1 Xn Tx,其中“M”代表早期的过渡金属元素,“x”表示C、N或CN,而“Tx”为“-OH”、“-F”等基团,n的值一般为1,2或3。MXenes具有比表面积高、离子电导率大、亲水性好等优良特性,有利于其在离子电池、超级电容器等储能装置中应用推广。本文综述了近几年MXenes在能源储存装置中的应用及研究现状,归纳总结了MXenes的结构及能量储存机制,指出了目前研究过程中存在的短板,并对其发展方向进行展望。

关键词：二维材料 MXenes 综述储能装置电催化剂超级电容器

农户分化、示范引领对农户农业绿色生产意愿与行为的影响

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中国农机化学报 2024年第5期45卷 279-288,319页

作者：孙前路李朝柱周口师范学院经济与管理学院河南周口466001 清华大学中国农村研究院北京市100084

农户农业绿色生产对农业生态耕种具有重要意义。从农户分化和示范引领的视角,基于7省857户调查数据,利用半非参数估计对农户农业绿色生产意愿、行为及意愿行为一致性的影响因素进行实证分析。研究发现:农户农业绿色生产意愿较高,但生产... 详细信息

农户农业绿色生产对农业生态耕种具有重要意义。从农户分化和示范引领的视角,基于7省857户调查数据,利用半非参数估计对农户农业绿色生产意愿、行为及意愿行为一致性的影响因素进行实证分析。研究发现:农户农业绿色生产意愿较高,但生产行为发生概率不高。职业分化对农户农业绿色生产意愿均存在正向影响,回归系数分别为0.085 7、0.131 6和0.220 0,且均在1%统计水平上显著。干部灌溉引领行为外,干部示范对农户农业绿色生产意愿和行为均存在显著的正向影响,村民引领对农户化肥减量化意愿和行为、新型灌溉方式行为和低毒农药施用意愿存在显著的正向影响。被调查者年龄越高,采用新型灌溉方式、施用低毒农药的意愿越强,影响系数分别为0.034 0和0.033 4,且均在1%统计水平上显著。因而,在农村农业绿色生产推进中,提高基层干部威信,提高农户非农收入水平,加强农业绿色生产研发,提高绿色生产补贴,扩大耕地生态宣传等能从不同层面提高农户农业绿色生产意愿和行为。

关键词：农业绿色生产农户分化半非参数估计意愿与行为示范引领

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锂-空气电池MnO_2和Co_3O_4正极催化剂的研究进展

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电子元件与材料 2017年第12期36卷 47-57页

作者：胡安俊舒朝龙剑平成都理工大学材料与化学化工学院四川成都610059

锂-空气电池因具有超高的理论能量密度,被认为是最具发展前景的新一代储能系统。然而,正极缓慢的电极反应成为制约其发展的关键因素之一。催化剂的加入可以有效降低锂-空气电池的过电位,进而提高正极反应的速率。本文首先简要介绍了锂-... 详细信息

锂-空气电池因具有超高的理论能量密度,被认为是最具发展前景的新一代储能系统。然而,正极缓慢的电极反应成为制约其发展的关键因素之一。催化剂的加入可以有效降低锂-空气电池的过电位,进而提高正极反应的速率。本文首先简要介绍了锂-空气电池的基本结构和工作原理,随后详细综述了近年来用于锂-空气电池正极的过渡金属氧化物(二氧化锰和四氧化三钴)催化剂的研究进展,最后根据目前所存在的问题指出未来的研究方向。

关键词：锂-空气电池正极综述二氧化锰四氧化三钴催化剂

具有可调界面电子结构的金属硫化物异质结构作为锂-氧气电池的高效催化剂

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Science China Materials 2023年第4期66卷 1341-1351页

作者：田桂雷任龙飞徐浩洋曾婷王鑫翔温晓娟杜大越严羽刘盛舒朝 College of Materials and Chemistry&Chemical Engineering Chengdu University of TechnologyChengdu 610059China

设计和制备具有优异稳定性和高活性的催化剂对于提高锂-氧气电池的性能至关重要.由于其可调节的结构及促进氧还原反应和析氧反应动力学的有效性,异质结构催化剂引起了广泛的研究兴趣.在这项工作中,CuCo_(2)S_(4)/CoS_(1.097)多元金属硫... 详细信息

设计和制备具有优异稳定性和高活性的催化剂对于提高锂-氧气电池的性能至关重要.由于其可调节的结构及促进氧还原反应和析氧反应动力学的有效性,异质结构催化剂引起了广泛的研究兴趣.在这项工作中,CuCo_(2)S_(4)/CoS_(1.097)多元金属硫化物被证明是锂-氧气电池氧电极反应的有效电催化剂.密度泛函理论计算表明,CuCo_(2)S_(4)/CoS_(1.097)的电子结构在异相界面处受到调控,有利于优化氧电极反应过程中间体的吸附,最终加速氧电极反应动力学.实验结果表明,基于CuCo_(2)S_(4)/CoS_(1.097)的锂-氧气电池在100 m A g^(-1)下具有26,727.8 m A h g^(-1)的高比容量和超过267次循环的出色耐久性.该工作为锂-氧气电池高性能正极材料的设计和构造提供了新视角.

关键词：氧还原反应氧电极电催化剂正极材料异质结构密度泛函理论计算金属硫化物高比容量