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Advances of high-performance LiNi_(1-x-y)co_(x)M_(y)O_(2) cathode materials and their precursor particles via co-precipitation process

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Particuology 2024年第3期86卷 67-85页

作者： Wenbiao Liang Yin Zhao Liyi Shi Zhuyi Wang Yi Wang Meihong Zhang Shuai Yuan School of Materials Science and Engineering Shanghai UniversityShanghai200444China Research Center of Nanoscience and Nanotechnology Shanghai UniversityShanghai200444China Emerging Industries Institute Shanghai UniversityJiaxingZhejiang314006China

Layered LiNi_(1-x-y)co_(x)M_(y)O_(2)(M=Mn or Al)is a promising cathode material for lithium-ion batteries due to its high specific capacity and acceptable manufacturing cost.However,the polycrystalline LiNi_(1-x-y)co_(x)M_(y)O_(2) cathode material suffers from disordered orientation of primary particles and poor geometric symmetry of secondary particles,which severely hampers the migration of Lit ions.Furthermore,the resulting anisotropy accelerates the disintegration of the secondary particle structure,significantly affecting the electrochemical performance of the polycrystalline cathode.In spite of less grain boundary,the single-crystal LiNi_(1-x-y)co_(x)M_(y)O_(2) cathodes still suffer from severe microcracks generated by repeated planar gliding during cycling,which poses a great challenge to the cycling stability of single-crystal materials.It's worth noting that the microstructure of the cathode material is mainly inherited from its precursor.Therefore,it is necessary to deeply understand the influence of the microstructure of Ni_(1-x-y)co_(x)M_(y)(OH)2 on the electrochemical properties of LiNi_(1-x-y)co_(x)M_(y)O_(2) cathode materials,so as to optimize the production process of preparing high-performance cathode precursors.In this review,we summarize recent advances in the research and development of Ni-rich cathode precursor materials.Firstly,the challenges faced by the Ni-rich hydroxide precursor materials are presented,including the effect of primary particle morphology and arrangement on the electrochemical performance of cathode materials,the influence of secondary particle morphology on lithium insertion reactions in cathode,and the effect of particle size on the microcracking of single-crystal particles.Secondly,the presentation of the conventional co-precipitation reactor,the mechanism of precursor particle growth,and the influence of coprecipitation parameters are described in detail.Finally,the strategies are systematically discussed to solve the challenges of hydroxide precursors,such as the inno

关键词： Lithium-ion batteries Cathode materials co-precipitation Ni-rich layered oxides Single crystal Precursor particles

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Thermodynamic equilibrium theory-guided design and synthesis of Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4)/C cathode for lithium-ion batteries

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Journal of Energy Chemistry 2024年第4期91卷 619-627页

作者： Wei Lyu Wenlong Cai Tuan Wang Xiaobo Sun Enhao Xu Jinxuan Chen Kaipeng Wu Yun Zhang college of Materials Science and Engineering Sichuan UniversityChengdu 610064SichuanChina

Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.

关键词： (Fe_(0.4)Mn_(0.6))_(1-x)MgxC_(2)0_(4) precursors Thermodynami cequilibrium co-precipitation Mg doping Lithium-ion batteries

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Effect of precipitants on Ni-CeO_2 catalysts prepared by a co-precipitation method for the reverse water-gas shift reaction

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Journal of Rare Earths 2013年第10期31卷 969-974页

作者：王路辉刘辉刘源陈英杨淑清 Department of Chemical Engineering School of Petrochemical Technology and Energy Engineering Zhejiang Ocean University School of Food and Pharmaceutical Zhejiang Ocean University Department of Catalysis Sciences and Technology School of Chemical Engineering Tianjin University

A series of Ni-CeO2 catalysts were prepared by co-precipitation method with Na2co3, NaOH, and mixed precipitant （Na2co3：NaOH; 1：1 ratio） as precipitant, respectively. The effect of the precipitants on the catalytic performance, physical and chemical properties of Ni-CeO2 catalysts was investigated with the aid of X-ray diffraction （XRD）, Bmmaner-Emmett-Teller method （BET）, Fou- rier-transform infrared spectroscopy （FT-IR）, thermogravimetry （TG）, and H2-TPR characterizations. The Ni-CeO2 catalysts were exam- ined with respect to their catalytic performance for the reverse water-gas shift reaction, and their catalytic activities were ranked as： Ni-CeO2-CP （Na2co3：NaOH=I：I）〉Ni-CeO2-CP（Na2co3）〉Ni-CeO2-CP（NaOH）- correlating to the characteristic results, it was found that the catalyst prepared by co-precipitation with mixed precipitant （Na2co3：NaOH; 1：1 ratio） as precipitant hadthe most amount of oxygen vacancies accompanied with highly dispersed Ni particles, which made the corresponding Ni-CeO2-CP（Na2co3：NaOH=I： 1） catalyst exhibit the highest catalytic activity. While the precipitant of Na2co3 or NaOH resulted in less or no oxygen vacancies in Ni-CeO2 catalysts. As a result, Ni-CeO2-CP（Na2co3） and Ni-CeO2-CP（NaOH） catalysts presented poor catalytic performance.

关键词： reverse water-gas shift reaction Ni-CeO2 catalyst co-precipitation oxygen vacancy precipitant rare earths

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In situ X-ray diffraction and thermal analysis of LiNi0.8co0.15Al0.05O2 synthesized via co-precipitation method

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Journal of Energy Chemistry 2018年第6期27卷 1655-1660页

作者： Na Zhang Xiaoyu Zhang Erbo Shi Shiyong Zhao Kezhu Jiang Di Wang Pengfei Wang Shaohua Guo Ping He Haoshen Zhou Center of Energy Storage Materials & Technology College of Engineering and Applied Sciences National Laboratory of Solid State Microstructures and Collaborative Innovation Center of Advanced Microstructure Nanjing University Nanjing 210093 Jiangsu China National Institute of Advanced Industrial Science and Technology (AISF) Umezono 1-1-1 Tsukuba 305-8568 Japan Zhangjiagang Guotoi Huarong New Chemical Material co. Ltd Suzhou 215634 Jiangsu China

LiNi0.9co0.15Al0.05O2 （NCA） material is successfully synthesized with a modified co-precipitation method,in which NH3,H2O and EDTA are used as two chelating agents. The obtained LiNi0.9co0.15Al0.05O2 materialhas well-defined layered structure and uniform element distribution, which reveals an enhanced electro-chemical performance with a capacity retention of 97.9% after 100 cycles at 0.2 C, and reduced thermalrunaway from the isothermal calorimetry test. In situ X-ray diffraction （XRD） was employed to capturethe structural changes during the charge-discharge process. The reversible evolutions of lattice parame-ters （a, b, c, and V） further verify the structural stability.

关键词： LiNi0.9co0.15Al0.05O2 co-precipitation Isothermal calorimetry Insitu X-ray diffraction

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Synthesis of luminescent KY_3F_(10) nanopowder multi-doped with lanthanide ions by a co-precipitation method

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Journal of Rare Earths 2016年第8期34卷 808-813页

作者： Szymon Goderski Marcin Runowski Stefan Lis Department of Rare Earths Faculty of Chemistry Adam Mickiewicz University

A series of KY3F10 nanophosphors doped with Gd3＋, Ce3＋ and Eu3＋ ions were obtained with the use of a co-precipitation method. The resulting products were white precipitates, consisting of spherical particles with diameter about 150-200 nm, which was confirmed using transmission electron microscopy （TEM） technique. Powder X-ray diffraction （XRD） and energy dispersive X-ray analysis （EDX） measurements confirmed appropriate structures of the nanoparticles obtained. Spectroscopic properties of the prod- ucts were examined on the basis of the measured excitation/emission spectra and luminescence decay curves. The synthesized sam- ples showed orange-red luminescence, characteristic for Eu3＋ ions. The reaction process was performed in required alkaline pH ad- justed with the use of ethylenediaminetetraacetic acid （EDTA） and potassium hydroxide. The samples containing large amounts of Gd3＋ dooant ions exhibited a tendencv to form nroducts with different momhologies.

关键词：： fluorides co-precipitation nanophosphors luminescence nanopowders Ce3＋/Gd3＋/Eu3＋ doping rare earths

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Photoluminescence properties of YAG:Ce3+,pr3+nano-sized phosphors synthesized by a modified co-precipitation method

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Journal of Rare Earths 2017年第4期35卷 341-346页

作者：戴鹏吉成沈丽明钱祺郭国标张晓艳暴宁钟 State Key Laboratory of Materials-Oriented Chemical Engineering Nanjing Technology UniversityNanjing 210009China Jiangnan Graphene Research Institute Changzhou 213149China

Abstract： Monophasic Ce3＋ and Pr3＋ co-doped yttrium aluminum garnet （YAG：Ce3＋,pr3＋） nanoparticles with good dispersity and uniform grain sizes in the range of 50-80 nm were prepared by a two-step route, which consisted of a modified co-precipitation preparation of mixed metal hydroxide hydrate intermediates at low temperature of about 40℃ and a subsequent calcination conversion of the synthesized intermediates to crystalline nanoparticle products at about 1000℃. The influences of both the lanthanide ion （Ce3＋ and Pr3＋） doping concentration and different doping （Ce3＋/pr3＋） ratio on the photoluminescence intensity were systematically investigated. The synthesized （Ce0.6Pr0.4）0.04Y2.96Al5O12 nanoparticles were near spherical nanoclusters with good dispersity and uniform sizes in the range of 50-80 nm for about 85% of the particles. The strongest photoluminescence intensity was observed for the （Ce0.6Pr0.4）0.04Y2.96Al5O12 nanoparticle products.

关键词： YAG：Ce3＋,pr3＋ phosphor nanoparticles co-precipitation photoluminescence rare earths

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Synthesis and electrochemical properties of LiNi_(0.8)Al_(0.2-x)Ti_xO_2 cathode materials by an ultrasonic-assisted co-precipitation method

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International Journal of Minerals,Metallurgy and Materials 2009年第4期16卷 452-457页

作者： Meng Chen Wen-le Ao Chang-song Dai Tao Tao Jun Yang college of Materials Science and Chemical Engineering Harbin Engineering University Harbin 150001 China Department of Applied Chemistry Harbin Institute of Technology Harbin 15001 China

A new co-precipitation route was proposed to synthesize LiNi0.8A10.2-xTixO2 （x=0.0-0.20） cathode materials for lithium ion batteries, with Ni（NO3）2, Al（NO3）3, LiOH·H2O, and TiO2 as the starting materials. Ultrasonic vibration was used during preparing the precursors, and the precursors were protected by absolute ethanol before calcination in the air. The influences of doped-Ti content, calcination temperature and time, additional Li content, and ultrasonic vibration on the structure and properties of LiNi0.8A10.2-xTixO2 were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and charge-discharge tests, respectively. The results show that the optimal molar fraction of Ti, calcination temperature and time, and additional molar fraction of Li for LiNi0.8A10.2-xTixO2 cathode materials are 0.1,700℃, 20 h, and 0.05, respectively. Ti doping facilitates the formation of the α-NaFeO2 layered structure, and ultrasonic vibration improves the electrochemical performance of LiNi0.8A10.2-xTixO2.

关键词： lithium ion batteries cathode materials ultrasonic vibration co-precipitation electrochemical properties

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Influence of pH value on properties of YPO_4:Tb^(3+) phosphor by co-precipitation method

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Journal of Rare Earths 2015年第4期33卷 346-349页

作者：李旭王皓岩关丽付跃举郭镇袁坤生铁利成杨志平滕枫 Hebei Key Laboratory of Optic-electronic Information and Materials College of Physics Science and Technology Hebei University Key Laboratory of Luminescence and Optical Information Ministry of Education School of Science Beijing Jiao Tong University

A series of Y1_xPO4：xTb3＋（x=0.005-0.1） phosphors were successfully fabricated by using co-precipitation method with NHzH2PO4 as phosphorus source. The structure and morphology characterization of the luminescent material was investigated with X-ray powder diffraction （XRD） and field emission scanning electron microscopy （FESEM）. The XRD patterns indicated that the samples belonged to tetragonal phase. Luminescence properties were discussed by measuring the excitation and emission spectra. The phosphor could be excited by UV light （340-390 nm） and emitted green light, with the emission peaks located at 491 （5Da→7F6）, 550 （SD4→7Fs）, 589 （5D4→7F4） and 624 nm （SD4→TF3）. In addition, the pH value and activator concentration had great effects on the emission intensity. The results illuminated that this phosphor could be used for UV based white light emitting diodes and co-precipitation method could be used to prepare better appearance phosphor.

关键词： luminescence phosphor co-precipitation pH value rare earths

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Synthesis of Yb:Lu_3Al_5O_(12) nano powders with the reverse strike co-precipitation method:influence of decomposition of NH_4Hco_3

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Journal of Rare Earths 2016年第9期34卷 901-907页

作者：陈思圆范金太潘良杰姜本学毛小建李日红袁新强姜雄伟张龙 Shanghai Institute of Optics and Fine Mechanics Chinese Academy of Sciences School of Materials Science and Engineering Shanghai University

Yb：Lu3Al5O12 （Yb：LuAG） nano powders were synthesized with the co-precipitation method from cation （Lu3＋, Yb3＋, Al3＋） solution of different concentrations using NH4Hco3 as the precipitant. The influence of cation concentration on the morphology and purity of the calcined powders was studied. contrary to the conventional suggestion that recommends thin solution to obtain loosely agglomerated nano powders, results showed that thin cation （Lu＋Yb＋Al） concentration ≤0.08 mol/L led to formation of Al2O3 and LuAP impurities in the obtained nano powders. By means of Tg/（DTA）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, the cause was revealed to be re-dissolution of Lu at high pH value that resulted from the decomposition of NH4Hco3.（Lu＋Yb＋Al） concentration of ~0.24 mol/L was recommended to achieve pure Yb：LuAG nano powders. Transparent Yb：LuAG ceramics were fabricated with the prepared Yb：LuAG nano powders. The transmittance around 800 nm was 77.5%.

关键词： Yb：LuAG transparent ceramics co-precipitation rare earths

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Oxidative coupling of methane over LaAlO3 perovskite catalysts prepared by a co-precipitation method: Effect of co-precipitation pH value

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Journal of Energy Chemistry 2019年第8期28卷 1-8,I0001页

作者： Yujin Sim Jihoon Yoo Jeong-Myeong Ha Ji Chul Jung Department of Chemical Engineering Myongji UniversityYongin 17058 Republic of Korea Clean Energy Research Center Korea Institute of Science and TechnologySeoul 02792 Republic of Korea

Oxidative coupling of methane(OCM) was conducted over LaAlO3X catalysts that were prepared by a coprecipitation method using different co-precipitation pH values(X = 6–10). The aim is to investigate the effect of p H values on the catalytic activity of La AlO3 catalysts in this reaction. The results showed that the co-precipitation pH value affected greatly on the formation of chemical species of precipitate precursors in the co-precipitation step, leading to different phases of the finally obtained LaAlO3 catalysts.When the co-precipitation pH value increased up to 8, the lanthanum-related phases such as La2 O3 and La(OH)3 were gradually formed as by-products, preventing the formation of LaAlO3 perovskite crystalline structure and facilitating the formation of oxygen vacancies on catalyst surface. However, at pH value of9 or higher, the lanthanum content in the precipitate precursor was increased greatly. Not LaAlO3 perovskite but lanthanum-related phases were developed as main phases, reducing their catalytic activities in this reaction. Among LaAlO3 catalysts, the one prepared at pH = 8 showed the highest C2 yield due to its well-developed oxygen vacancies and electrophilic lattice oxygen. Therefore, the co-precipitation pH value strongly affected the LaAlO3 catalyst activity in OCM reaction. A precious pH control should be required to prepare various perovskite catalysts for the OCM.

关键词： LaAlO3 Perovskite Oxidative coupling of methane co-precipitation pH value

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