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Journal of Energy Chemistry 2022年第12期75卷 478-485,I0012页

作者： Huanqing Liu Xu Gao Jun Chen Jinqiang Gao Haoji Wang Yu Mei Huan Liu Wentao Deng Guoqiang Zou Hongshuai Hou Xiaobo Ji State Key Laboratory of Powder Metallurgy College of Chemistry and Chemical EngineeringCentral South UniversityChangsha 410083HunanChina School of Materials Science and Engineering Hunan Provincial Key Lab of Advanced Materials for New Energy Storage and ConversionHunan University of Science and TechnologyXiangtan 411201HunanChina

P2-type Mn-based layered oxides are viewed as promising cathode materials for sodium ion battery by virtue of their high theoretical *** that pure Na_(2/3)MnO_(2)suffers from poor cycling performances,Cu-substitution strategy is proposed to effectively alleviate this ***,the structural evolution mechanism of the Cu-containing samples still remains ***,we propose that CuSubstitution P2-type Na_(0.66)Mn_(1-x)Cu_(x)O_(2)with enlarged lattice parameters are conducive to improving the interlayer structure stability through mitigating TMO_(2)slabs *** by synchrotron XAS spectra and ex/in situ XRD,the expansion/contraction of MnO_6 octahedron is dramatically reduced with the increased Cu content,showing the facilitated Na ion ***,when the ratio of Cu to Mn reaches 1:4,the phase transition from P2 to P'2 type at the end of discharge can be suppressed,resulting in the improved interlayer skeleton *** Cu-containing samples with stable interlayer structure exhibit high capacity retention and outstanding rate performances(a capacity of 79.9 m Ah g^(-1)at 5C).This Cu-substitution strategy provides a promising approach to designing highly stable cathodes.

关键词： Sodium-ion battery Manganese-based cathode Cu-substitution In-plane distortion jahn-teller effect

Ultrasonic Study on jahn-teller Distortions in La1/3Sr2/3CoO3

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Chinese Journal of Chemical Physics 2008年第2期21卷 136-140页

作者： Jian-xing Yi Hui Kong Chang-fei Zhu Laboratory of Advanced Functional Materials and Devices Department of Materials Science and Engineering University of Science and Technology of China Hefei 230025 China

The longitudinal ultrasonic velocity （V1）, attenuation （α1）, magnetization and resistivity of single phase polycrystalline La1/3Sr2/3CoO3 were measured as a function of temperature from 20 K to 300 K. The resistivity shows metallic behavior in the whole temperature range and a kink at 235 K was observed, which coincides with the ferromagnetic transition temperature （Tc）. As the temperature cools down from Tc, the V1 softens conspicuously at beginning and reaches a minimum at 120 K. After that the V1 dramatically stiffens below 120 K accompanied by a wide attenuation peak. The analysis of the results suggests that these ultrasonic anomalies ;nay correspond to local lattice distortions via the jahn-teller effect of intermediate spin Co^3＋.

关键词： La1/3Sr2/3CoO3 Ultrasonic velocity and attenuation jahn-teller effect

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

jahn-teller distortion assisted interstitial nitrogen engineering:Enhanced oxygen dehydrogenation activity of N-doped Mn_(x)Co_(3-x)O_(4) hierarchical micro-nano particles

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Nano Research 2021年第8期14卷 2637-2643页

作者： Yangxin Jin Fengfeng Li Peixin Cui Yun Yang Qingping Ke Minh Ngoc Ha Wangcheng Zhan Fei Ruan Chao Wan Zhao Lei Van Noi Nguyen Wei Chen Jun Tang College of Chemistry and Chemical Engineering Anhui University of Technology Maanshan 243002China College of Chemistry and Materials Engineering Wenzhou University Wenzhou 325035China Key Laboratory of Soil Environment and Pollution Remediation Institute of Soil ScienceChinese Academy of SciencesNanjing 210008China VNU Key Laboratory of Advanced Material for Green Growth VNU University of ScienceVietnam National UniversityHanoi 100000Vietnam Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis School of Chemistry and Molecular EngineeringEast China University of Science and TechnologyShanghai 200237China

Rational design of earth-abundant transition metal oxides catalysts is highly desirable for developing sustainable chemical ***,we demonstrate a prospective interstitial nitrogen engineering for fabricating oxygen vacancies(OVs)-rich nitrogen-doped-Mn_(x)Co_(3-x)O_(4)(N-Mn_(x)Co_(3-x)O_(4))oxide catalyst,in which the ratio of OVs concentration of N-Mn_(x)Co_(3-x)O_(4)to Mn species is as high as 1:1,according to the characterizations of X-ray absorption(XAS)and X-ray photoelectron(XPS)*** promising strategy of interstitial nitrogen engineering through lattice distortion caused by the jahn-teller effect can significantly increase the amount of interstitial *** resulting catalyst enables an additive-free aerobic dehydrogenation coupling of aromatic amine to afford azo compounds with>99%yield and>99%selectivity at 60☆.We observed the superb catalytic activity is promoted by the enhanced oxygen mobility in OVs,which were created by the interstitial nitrogen in the catalyst *** presence of interstitial nitrogen in transition metal oxides in this study shows how the manipulation of catalyst matrix can increase the OV sites to promote aerobic oxidation reaction.

关键词： transition metal oxides jahn-teller effect interstitial nitrogen engineering MnxCo_(3-x)O_(4) dehydrogenation

Insights into Ti doping for stabilizing the Na_(2/3)Fe_(1/3)Mn_(2/3)O_(2)cathode in sodium ion battery

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Journal of Energy Chemistry 2022年第10期31卷 542-548,I0013页

作者： Tingting Yang Yalan Huang Jian Zhang He Zhu Jincan Ren Tianyi Li Leighanne C.Gallington Si Lan Ligao Yang Qi Liu Department of Physics City University of Hong KongHong Kong 999077China Argonne National Laboratory X-Ray Science DivisionArgonneIL 60439USA School of Material Science and Engineering Nanjing University of Science and TechnologyNanjing 210094JiangsuChina Shenzhen Research Institute City University of Hong KongShenzhen 518057GuangdongChina Changsha University of Science&Technology Changsha 410000HunanChina

Iron-and manganese-based layered metal oxides,as cathodes for sodium ion batteries,have received widespread attention because of the low cost and high specific ***,the jahn-teller effect of Mn^(3+)ions and the resulted unstable structure usually lead to continuously capacity ***,Titanium(Ti)has been successfully doped into Na_(2/3)Fe_(2/3)Mn_(2/3)O_(2)to suppress the jahn-teller distortion and improve both cycling and rate performance of sodium ion *** situ high-energy synchrotron X-ray diffraction study shows that Ti-doped compound(Na_(2/3)Fe_(1/3)Mn_(0.57)Ti_(0.1)O_(2))can maintain the single P2 phase without any phase transition during the whole charging/discharging *** electrochemical characterizations are also applied to explore the better kinetics of sodium ions transfer in the Na_(2/3)Fe_(1/3)Mn_(0.5)7 Ti_(0.1)O_(2).This work provides a comprehensive insight into the Ti-doping effects on the performance from both structural and electro kinetic perspectives.

关键词： Layered transition metal oxides jahn-teller effect In situ synchrotron X-ray diffraction Phase transition

High-excited-state splitting and multimode vibrational coupling in Mn^(4+)-activated fluoride phosphor

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Science China(Physics,Mechanics & Astronomy) 2024年第3期67卷 95-101页

作者： Debao Zhang Wanggui Ye Xuguang Cao Ji Zhou Fei Tang Changcheng Zheng Jiqiang Ning Shijie Xu Department of Optical Science and Engineering School of Information Science and TechnologyFudan University Shanghai 200438China Jiangsu Key Laboratory of Advanced Laser Materials and Devices Schoolof Physics and Electronic Engineering Jiangsu Normal UniversityXuzhou 221116China Division of Natural and Applied Sciences Duke Kunshan UniversityKunshan 215316China

Excited-states play a crucial role in the optical absorption and luminescence of solids and hence their accurate information is highly desired. Herein, we attempt to seize the excited-states information of Mn^(4+)ions in K_(2)SiF_(6) microcrystals via measuring and calculating their variable-temperature photoluminescence excitation(PLE) spectra. At cryogenic temperatures, an unpredicted splitting of the high-excited-state is observed. Moreover, the two-split high-excited-state levels are further revealed to primarily couple with the two hyperfine split modes of quasi-localized ν2 vibration in the distorted Mn-F_(6) octahedral configuration,whereas the coupling strengths are found to be substantially different from each other. The slightly split vibrational mode is firmly supported by the low-temperature Raman spectra. jahn-teller lattice distortion is believed to be responsible for the observed splitting of the electronic high-excited-state and the quasi-localized vibrational mode.

关键词： splitting of excited-state photoluminescence excitation spectrum electron-phonon coupling jahn-teller effect

Discovering Cathodic Biocompatibility for Aqueous Zn–MnO_(2) Battery:An Integrating Biomass Carbon Strategy

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Nano-Micro Letters 2024年第6期16卷 111-126页

作者： Wei Lv Zilei Shen Xudong Li Jingwen Meng Weijie Yang Fang Ding Xing Ju Feng Ye Yiming Li Xuefeng Lyu Miaomiao Wang Yonglan Tian Chao Xu Institute of Energy Power Innovation North China Electric Power UniversityBeijing 102206People’s Republic of China Department of Power Engineering School of EnergyPower and Mechanical EngineeringNorth China Electric Power UniversityBaoding 071003People’s Republic of China Key Laboratory of RNA Biology Institute of BiophysicsChinese Academy of SciencesBeijing 100101People’s Republic of China Collaborative Innovation Center of Integrated Exploitation of Bayan Obo Multi‑Metal Resources Inner Mongolia University of Science and TechnologyBaotou 014010People’s Republic of China

Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable ***,γ-MnO_(2) uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work,and particularly the composite cathode with carbon carrier quality percentage of 20 wt%delivers the specific capacity of 391.2 mAh g^(−1)at 0.1 A g^(−1),outstanding cyclic stability of 92.17%after 3000 cycles at 5 A g^(−1),and remarkable energy density of 553.12 Wh kg^(−1) together with superior coulombic efficiency of~100%.Additionally,the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments,which verifies its tremendous potential in the application of clinical ***,Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of jahn–teller effect and Mn domains distribution combined with theoretical analysis and experimental ***,a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed.

关键词： Aqueous Zn-ion batteries Biocompatibility jahn-teller effect Mn domains γ-MnO_(2)

Solvothermal Synthesis and Crystal Structures of Two Manganese Complexes [Mn（Ⅱ）（acac-）2（4,4＇-bipy）]n （bipy-4,4＇-bipyridine） and [Mn（Ⅲ）（acac-）3].4CO（NH2）2

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Chinese Journal of Chemistry 2012年第5期30卷 1063-1068页

作者：程一峰夏寺丰冯骏杜世振安澜鲁晓明 Department of Chemistry Capital Normal UniversityBeijing 100048China

Two special manganese complexes [Mn（II）（acac ）2（4,4＇-bipy）]n （bipy=4,4＇-bipyridine）（complex 1） and [Mn（II1）（acac-）3].4CO（NH2）2 （acacH=acetylacetone）（complex 2） were synthesized in the same strategy by sol- vothermal method. Single crystal X-ray diffraction revealed the complex 1 consists of one-dimensional infinite coordination chain, with the manganese centers bridged by 4,4＇-bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14-membered carbamide ring and a zig-zag plane. Both enantiomers of Mn（III）（acac ）3 exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig-zag planes are linked with hydrogen bonds to form an unique spatial network.

关键词： bipyridine enantiomer manganese complex one-dimensional infinite chain jahn-teller effect

Roles of Electron Hopping on Orbital Ordering for Vanadium Spinels

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Communications in Theoretical Physics 2012年第9期58卷 441-444页

作者：黄元杰张裕恒 High Magnetic Field Laboratory Chinese Academy of Sciences and University of Science and Technology of China

We investigate the orbitM ordering quantitatively for the spinel systems RV204 （R=Mg, Zn, Cd） in the viewpoint of single-ion physics through the method of diagonalization. Through the quantitative calculation, it is found that the spin-orbit （SO）coupling and the jahn-teller （JT） effect enable the orbital ordering under the conditions of negligible electron hopping among different V3＋ sites. For the systems RV204, the electron hopping is implied to be observable from the energy gap in conductivity, so the orbital ordering of RV2 04 cannot be induced by the SO coupling and JT effect at definite temperature, which is on contrary to the conclusions in [Phys. Rev. Lett. 93 （2004） 157206].

关键词： orbital ordering jahn-teller effect orbital-spin coupling