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Suppressed Internal Intrinsic Stress Engineering in High-Performance Ni-Rich Cathode Via Multi layered In Situ Coating Structure

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Energy & Environmental Materials 2024年第2期7卷 58-66页

作者： Jiachao Yang Yunjiao Li Xiaoming Xi Junchao Zheng Jian Yu zhenjiang he School of Metallurgy and Environment Central South UniversityChangsha 410083China Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083China Changsha Research Institute of Mining and Metallurgy Changsha 410083China Ningbo Ronbay New Energy Technol Co Ltd Tanjialing East Rd 39Ningbo 315400China

LiNi_(x)Co_(y)Al_(z)O_(2)(NCA)cathode materials are drawing widespread attention,but the huge gap between the ideal and present cyclic stability still hinders their further commercial application,especially for the Ni-rich LiNi_(x)Co_(y)Al_(z)O_(2)(x>0.8,x+y+z=1)cathode material,which is owing to the structural degradation and particles'intrinsic *** tackle the problems,Li_(0.5)La_(2)Al_(0.5)O_(4)in situ coated and Mn compensating doped multilayer LiNi_(0.82)Co_(0.14)Al_(0.04)O_(2)was *** refinement indicates that La-Mn co-modifying could realize appropriate Li/Ni disorder *** results and in situ XRD patterns reveal that the LLAO coating layer could effectively restrain crack in secondary particles benefited from the suppressed internal *** further improves as NCA-LM2 has superior mechanical *** SEM,TEM,XPS tests indicate that the cycled cathode with LLAO-Mn modification displays a more complete morphology and less side reaction with *** was used to further investigate cathode-electrolyte interface which was reflected by gas ***-LM2 releases less CO_(2)than NCA-P indexing on a more stable *** modified material presents outstanding capacity retention of 96.2%after 100 cycles in the voltage range of 3.0-4.4 V at 1C,13%higher than that of the pristine and 80.8%at 1 C after 300 *** excellent electrochemical performance could be attributed to the fact that the high chemically stable coating layer of Li_(0.5)La_(2)Al_(0.5)O_(4)(LLAO)could enhance the interface and the Mn doping layer could suppress the influence of the lattice mismatch and *** believe that it can be a useful strategy for the modification of Ni-rich cathode material and other advanced functional material.

关键词： compensating doped in situ coating multilayer material Ni-rich cathode materials suppressed internal strain

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The Multiple Modification Road of Li-Rich Manganese-Based Cathode Materials

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Chinese Journal of Structural Chemistry 2022年第9期41卷 45-55页

作者： Yuming Liu Jingyi Li Feixiang Wu Yunjao Li Junchao Zheng zhenjiang he Schoolof Metallurgy and Environment Central South UniversityChangsha 410083China National Engineering Laboratory for High Efficiency Recovery of Refractory Nonferrous Metals Central South UniversityChangsha 410083China Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083China

Li-rich manganese-based cathode materials(LR) are considered as excellent cathode materials for a new generation of lithium-ion batteries causes their outstanding electrochemical performance, friendly price, and environmental friendliness. But defects such as rapid voltage decay and loss of lattice oxygen limit their applications. The electrochemical performance of LR has to be improved by means of modification. The previous single modification methods like element doping, surface coating, structure design, etc. can only optimize the electrochemical performance of LR from one aspect. Recently, multiple modifications,which can combine the advantages of multiple modifications, have been favored by researchers. here, we comprehensively review the recent progress of multiple modification of LR based on the combination of different modification means. The review and summary of the multiple modification of LR will play a guiding role in its development in the future.

关键词： lithium-ion batteries Li-rich manganese-based high energy density multiple modification

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Suppress voltage decay of lithium-rich materials by coating layers with different crystalline states

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Journal of Energy Chemistry 2021年第9期30卷 591-598页

作者： Zhiwei Zhou Ziyan Luo zhenjiang he Junchao Zheng Yunjiao Li Cheng Yan Jing Mao School of Metallurgy and Environment Central South UniversityChangsha 410083HunanChina National Engineering Laboratory for High Efficiency Recovery of Refractory Nonferrous Metals Central South UniversityChangsha 410083HunanChina Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083HunanChina School of Mechanical Medical and Process EngineeringScience and Engineering FacultyQueensland University of Technology(QUT)BrisbaneQueensland4001Australia School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001HenanChina

Li-rich oxides are considered as the most commercial potential cathode materials due to the high theoretical specific discharge capacity. here, ZrO_(2) in different crystalline states are applied as the coating layers to enhance the electrochemical performance of hollow Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_(2) ***, a series of characterizations(XRD, SEM, TEM, EDX etc.) are conducted to compare the effects of ZrO_(2) coating layer with different crystalline states on the host material. The results elucidate that the Li-rich Mn-based material with the polycrystal ZrO_(2) coating layer has a slight advantage in rate performance, while the host material with the single crystal ZrO_(2)-coating layer has a better cycling performance and effectively suppresses voltage decay with the effect of excellently inhibiting layered to spinel-like phase transition and metal dissolution during charging and discharging process.

关键词： Lithium-ion battery Cathode material Surface modification Electrochemical performance Voltage decay

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One-time sintering process to modify xLi2MnO3(1-x)LiMO2 hollow architecture and studying their enhanced electrochemical performances

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Journal of Energy Chemistry 2020年第11期29卷 271-279页

作者： Renheng Wang Yiling Sun Kaishuai Yang Junchao Zheng Yan Li Zhengfang Qian zhenjiang he Shengkui Zhong College of Physics and Optoelectronic Engineering Shenzhen UniversityShenzhen 518060GuangdongChina School of Metallurgy and Environment Central South UniversityChangsha 410083HunanChina School of Marine Science and Technology Hainan Tropical Ocean UniversitySanya 572000HainanChina College of Environmental Science and Engineering Donghua UniversityShanghai 201620China

To solve the critical problems of lithium rich cathode materials, e.g., structure instability and short cycle life, we have successfully prepared a ZrO2-coated and Zr-doping xLi2MnO3·(1–x)LiMO2 hollow architecture via one-time sintering process. The modified structural materials as lithium-ion cathodes present good structural stability and superior cycle performance in LIBs. The discharge capacity of the ZrO2-coated and Zr-doped hollow pristine is 220 mAh g-1 at the 20th cycle at 0.2 C(discharge capacity loss, 2.7%)and 150 m Ah g-1 at the 100 th cycle at 1 C(discharge capacity loss, 17.7%), respectively. However, hollow pristine electrode only delivers 203 m Ah g-1 at the 20 th cycle at 0.2 C and 124 mAh g-1 at the 100 th cycle at 1 C, respectively, and the corresponding to capacity retention is 92.2% and 72.8%, *** coefficients of modified hollow pristine electrode are much higher than that of hollow pristine electrode after 100 cycles(approach to 1.4 times). In addition, we simulate the adsorption reaction of HF on the surface of ZrO2-coated layer by the first-principles theory. The calculations prove that the adsorption energy of HF on the surface of ZrO2-coated layer is about-1.699 e V, and the ZrO2-coated layer could protect the hollow spherical xLi2MnO3·(1–x)LiMO2 from erosion by HF. Our results would be applicable for systematic amelioration of high-performance lithium rich material for anode with the respect of practical application.

关键词： Lithium rich cathode materials One-time sintering process Coated and doped Electrochemical performances First-principles calculations

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Structural self-reconstruction strategy empowering Ni-rich layered cathodes with low-strain for superior cyclabilities

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Nano Research 2023年第4期16卷 4950-4960页

作者： Zhouliang Tan Yunjiao Li Xiaoming Xi Shijie Jiang Xiaohui Li Xingjie Shen Panpan Zhang zhenjiang he School of Metallurgy and Environment Central South UniversityChangsha 410083China Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083China Changsha Research Institute of Mining and Metallurgy Changsha 410083China Office of Laboratory and Equipment Management Xinjiang UniversityUrumqi 830000China

The key to hindering the commercial application of Ni-rich layered cathode is its severe structural and interface degradation during the undesired phase transition(hexagonal to hexagonal(H2→H3)),degenerating from the build-up of mechanical strain and undesired parasitic ***,a perovskite Li_(0.35)La_(0.55)TiO_(3)(LLTO)layer is built onto Ni-rich cathodes crystal to induce layered@spinel@perovskite heterostructure to solve the root cause of capacity *** exploration based on structure characterizations,in situ X-ray diffraction techniques,and first-principles calculations demonstrate that such a unique heterostructure not only can improve the ability of the host structure to withstand the mechanical strain but also provides fast diffusion channels for lithium ions as well as provides a protective barrier against electrolyte ***,the LLTO modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)cathode manifests an unexpected cyclability with an extremely high-capacity retention of≈94.6%after 100 cycles,which is superior to the pristine LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(79.8%).Furthermore,this modified electrode also shows significantly enhanced cycling stability even withstanding a high cut-off voltage of 4.6 *** surface self-reconstruction strategy provides deep insight into the structure/interface engineering to synergistically stabilize structure stability and regulate the physicochemical properties of Ni-rich cathodes,which will also unlock a new perspective of surface interface engineering for layered cathode materials.

关键词： Ni-rich layered oxides cathode structural self-reconstruction phase transition mechanical strain first-principal calculation

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External-to-internal synergistic strategy to enable multi-scale stabilization of LiCoO_(2)at high-voltage

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Journal of Energy Chemistry 2023年第1期76卷 516-527,I0013页

作者： Shuaipeng Hao Yunjiao Li Jiachao Yang Shan Wang Zhouliang Tan Xiaoming Xi zhenjiang he Panpan Zhang School of Metallurgy and Environment Central South UniversityChangsha 410083HunanChina Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083HunanChina Changsha Research Institute of Mining and Metallurgy Changsha 410083HunanChina Office of Laboratory and Equipment Management Xinjiang UniversityUrumqi 830000XinjiangChina

High-voltage LiCoO_(2)(LCO)offers a prelude to breaking the bottleneck of the energy density of lithium-ion batteries,however,LiCoO_(2)is subject to serious structural and interfacial degradation above voltages>4.55 V(***/Li^(+)).herein,an in-situ Li_(6.25)La_(3)Zr_(2)A_(l0.25)O_(12)(LLZAO)layer is constructed on the LCO surface to achieve operating voltage at 4.6 *** detailed characterizations(ex-situ XRD,ex-situ Raman,DFT,etc.)reveal that the LLZAO layer greatly enhances Li+conductivity attributed to the ionconducting layer on the surface/interface,and closely combines with LiCoO_(2)particle to ensure stable cathode/electrolyte interface,thus suppressing the highly reactive Co^(4+)and O^(-)triggered surface side reactions at ***,the introduction of La^(3+)/Zr^(4+)/Al^(3+)with a larger ionic radius(La^(3+)/Zr^(4+)are larger than Co^(3+))and weaker electronegativity(La/Zr/Al are weaker than Co)into Co^(3+)sites readjusts the electron cloud density between Co–O–Li,which reinforces the Co–O bond and widens the band-center gap of Co 3d and O 2p,thus restraining the detrimental phase transition(from H3 to H1-3 phase)and the formation of Co_(3)O_(4)spinel phase(attributed to lattice oxygen release),subsequently alleviating the particle cracking and structural collapse during repeated Li^(+)de/***,after 100 cycles at 3.0–4.6 V,LCO@1.0LLZAO exhibits a superior discharge capacity of 188.5 m A h g^(-1),with a capacity retention of 85.1%.The above research has brought about meaningful guidance for the evolution of cathode materials with high voltage.

关键词： LLZAO layer High-voltage LiCoO_(2) Irreversible phase transition Band-center gap Lattice oxygen release

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FORM AND EFFECT OF Zr IN CuCoBeZr ALLOY

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Acta Metallurgica Sinica(English Letters) 1993年第3期6卷 153-156页

作者： LIU hefa SUN Naizhen DAI Xueli REN he zhenjiang Shipbuilding Institute,zhenjiang,Jiangsu,ChinaLI Lijun Shanghai,Electrical Machinery Plant.Shanghai.China professor.Institute of Metallic Materials Research,zhenjiang Shipbuilding Institute,zhenjiang,Jiangsu 212003,China zhenjiang Shipbuilding Inst Zhenjiang China

Precipitation form of Zr in CuCoBeZr alloy during *** and final aging,as well as its effect on the high temperature properties have been studied and *** show that during solidificotion and *** precipitates as fine ***_3Zr,which pre- vents X-Cu grains from growing and provides more nuclei for CoBe and hence leads to finer primary *** Cu_3Zr partrticles also precipitate during aging. Because Co_3Zr is difficult to coalesce at high temperatures,the recrystallization temper- uture increases and the high temperature mechanical properties improve.

关键词： CuCoBeZr alloy Zr

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Defect engineering of high-loading single-atom catalysts for electrochemical carbon dioxide reduction

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Materials Reports(Energy) 2023年第2期3卷 124-141,I0003页

作者： Yang Li zhenjiang he Feixiang Wu Shuangyin Wang Yi Cheng Sanping Jiang Hunan Provincial Key Laboratory of Nonferrous Value-added Metallurgy Central South UniversityChangsha410083China Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha410083China State Key Laboratory of Chem/Bio-Sensing and Chemometrics Provincial Hunan Key Laboratory for Graphene Materials and DevicesCollege of Chemistry and Chemical EngineeringHunan UniversityChangsha410082China WA School of Mines:Minerals Energy and Chemical EngineeringCurtin UniversityPerthWA 6102Australia Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory Xianhu Hydrogen ValleyFoshan528216China

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added ***,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction ***-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high *** appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be *** construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are *** key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal *** this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site ***,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.

关键词： Single-atom catalysts High loading Electrocatalysis Carbon dioxide reduction(CO_(2)RR) Transition metals

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A novelty strategy induced pinning effect and defect structure in Ni-rich layered cathodes towards boosting its electrochemical performance

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Journal of Energy Chemistry 2022年第9期31卷 570-580,I0016页

作者： Zhouliang Tan Yunjiao Li Xiaoming Xi Shijie Jiang Xiaohui Li Xingjie Shen Panpan Zhang zhenjiang he Junchao Zheng School of Metallurgy and Environment Central South UniversityChangsha 410083HunanChina Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083HunanChina Changsha Research Institute of Mining and Metallurgy Changsha 410083HunanChina Office of Laboratory and Equipment Management Xinjiang UniversityUrumqi 830000XinjiangChina

Layered Ni-rich transition metal oxide is treated as the most promising alternative cathode due to their high-capacity and flexible ***,the severe lattice strain and slow Li-ion migration kinetics severely restrict their practical ***,a novelty strategy induced pinning effect and defect structure in layered Ni-rich transition metal oxide cathodes is proposed via a facile cation(iron ion)/anion(polyanion)co-doping ***,the effects of pinning effect and defect structure on element valence state,crystal structure,morphology,lattice strain,and electrochemical performance during lithiation/delithiation are systematically *** detailed characterizations(soft X-ray absorption spectroscopy(sXAS),in-situ X-ray diffraction(XRD),etc.)and density functional theory(DFT)calculation demonstrate that the pinning effects built-in LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)materials by the dual-site occupation of iron ions on lithium and transition metal sites effectively alleviate the abrupt lattice strain caused by an unfavorable phase transition and the subsequent induction of defect structures in the Li layer can greatly reduce the lithium-ion diffusion ***,the modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)exhibits a high-capacity of 206.5 mAh g^(-1)and remarkably enhanced capacity retention of 93.9%after 100 cycles,far superior to~14.1%of the pristine ***,an excellent discharge capacity of 180.1 mAh g^(-1)at 10 C rate is maintained,illustrating its remarkable rate *** work reports a pinning effect and defect engineering method to suppress the lattice strain and alleviate lithium-ion kinetic barriers in the Ni-rich layered cathodes,providing a roadmap for understanding the fundamental mechanism of an intrinsic activity modulation and structural design of layered cathode materials.

关键词： Ni-rich layered cathode Pinning effect Defect structure Lattice strain Lithium-ion kinetic

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基于紫外荧光法的大气SO_2气体浓度分析仪

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仪器仪表学报 2008年第1期29卷 174-178页

作者：邱健杨冠玲何振江黄林海华南师范大学物理与电信工程学院广州510006

本文详细介绍了紫外荧光法测量二氧化硫（SO2）浓度的原理和分析仪的电路系统设计。阐述了该分析仪硬件电路结构和软件系统结构与流程。分别实现了高温与制冷等温控电路对反应室、转换室和光电倍增管的温度控制；采用基于复杂可编程逻... 详细信息

本文详细介绍了紫外荧光法测量二氧化硫（SO2）浓度的原理和分析仪的电路系统设计。阐述了该分析仪硬件电路结构和软件系统结构与流程。分别实现了高温与制冷等温控电路对反应室、转换室和光电倍增管的温度控制；采用基于复杂可编程逻辑器件实现了对紫外荧光信号的信号拾取电路；实现了串行口与USB桥接电路；实现了并行口对GPIB接口电路模拟通信。在性能实验中，表明该分析仪样机能对浓度为0～143mg／m^3的SO2保持线性的和稳定的检测。与国外同类仪器的48h连续工作对比情况表明，该分析仪具有检测灵敏度高、实时检测以及稳定性好等特点，达到了实际应用的水平。

关键词： SO2监测紫外荧光法光子计数仪器电路设计性能测试

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