pH值对共沉淀制备的LiCo1／3Ni1／3Mn1／3Oz结构与电化学性能的影响

用在不同PH值下制备的共沉淀前驱体合成了LiCo1/3Ni1／3Mn1/3O2材料。用XRD、IR、ESEM、交流阻抗、充放电测试仪测试了PH值对材料结构和电化学性能的影响。结果表明在pH=11条件下合成的材料的层状结构特征和结晶度较好；pH值对材料颗粒的大小没有显著的影响，所有材料的粒径均在0．3～0.7μm范围内；pH=11时合成的材料的放电比容量最高（达163．48mAh／g），循环性能最好，可能是由于此条件下合成的材料在电池充放电过程中电荷传递速率较快所致。     

锂离子电池正极材料LiCo1/3Ni1/3Mn1/3O2的研究进展

综述了近几年锂离子电池正极材料层状三元过渡金属氧化物LiCoxNiyMn1-x-yO2的研究进展，重点讨论了综合性能优异的LiCo1/3Ni1/3Mn1/3O2的电化学性能、结构、制备方法以及存在的不足，LiCo1/3Ni1/3Mn1/3O2与其它商业化正极材料相比具有高容量、热稳定性好、高倍率放电等诸多优异的性能，若能解决循环、存放等问题，将有望成为新一代锂离子电池正极材料。     

合成方法对LiNi1/3Co1/3Mn1/3O2电化学性能的影响

采用碳酸盐共沉淀法、草酸盐共沉淀法、溶胶-凝胶法、高温固相法、氢氧化物共沉淀法(pH=10、11、12)制得LiNi1/3Co1/3Mn1/3O2正极材料,通过X射线衍射(XRD)、扫描电镜(SEM)和电化学性能测试对样品的结构和性能进行了表征.结果表明,溶胶-凝胶法合成的样品层状结构较完整,阳离子混排程度低,粒径相对较小,颗粒分布均匀;该样品首次放电比容量较高为151 mAh·g-1,循环30次后容量保持率达到93.31％.     

前驱体热处理温度对LiNi1/3Co1/3Mn1/3O2材料的影响

以NaCO3为沉淀剂,NH3·H2O为缓冲溶液,将NiSO4、CoSO4和MnSO4混合溶液共沉淀制备（Ni1/3Co1/3Mn1/3）CO3前驱体,将其在400-900℃热处理5h制备得（Ni1/3Co1/3Mn1/3）Ox氧化物。EDTA络合滴定、BET、XRD及SEM研究表明,随着热处理温度的升高,（Ni1/3Co1/3Mn1/3）Ox中过渡金属含量及结晶度随着增加,而比表面积却减小。（Ni1/3Co1/3Mn1/3）Ox与LiOH混合后在850℃热处理24h制备出LiNi1/3Co1/3Mn1/3O2材料,其结构、形貌及电性能的测试结果表明,前驱体在600℃条件下热处理制备的正极材料电化学性能最佳,其首次放电比容量为189.7mAh·g^-1,不同倍率循环60周后,循环保持率为92.4%。     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的合成及性能研究

以氢氧化钠为沉淀剂,采用共沉淀法合成了Ni1/3Co1/3Mn1/3(OH)2前驱体,前驱体和LiOH·H2O充分混合高温烧结制备了锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2.采用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学性能测试对LiNi1/3Co1/3Mn1/3O2正极材料的结构、微观形貌及电化学性能进行了表征.XRD结果表明,所合成的LiNi1/3Co1/3Mn1/3O2物相单一无杂相,具有标准的α-NaFeO2型层状结构.SEM测试显示,颗粒粒度均一,粒径大约在0.5μm,粒径分布窄.以20mA/g电流密度放电,充放电电压在2.8～4.4 V之间,首次放电比容量达到181mAh/g,80次循环之后放电比容量仍然保持在172mAh/g;循环伏安测试显示,LiNi1/3Co1/3Mn1/3O2反应中主要是Ni2 /Ni4 、Co3 /Co4 2个电对在起作用,锰的价态保持不变,起到支撑结构的作用.     

层状锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的共沉淀法合成

以Ni(NO3)2·6H2O,Co(NO3)2·6H2O,Mn(CH3COO)2·4H2O,LiOH·H2O为原料,采用NaOH-Na2CO3共沉淀的方法,在空气中合成了三元层状锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2.采用XRD研究了所合成材料的结构.考查了不同烧结温度对材料电化学性能的影响.结果表明,所合成的材料具有典型的α-NaFeO2层状结构特征,900℃下合成的材料具有最优的循环性能,初始放电容量为169.4mAh/g,初次库仑效率为83.2%,且20次循环后,容量保持率达到96.3%.     

合成方法对LiNil/3Co1/3Mn1/3O2电化学性能的影响

采用碳酸盐共沉淀法、草酸盐共沉淀法、溶胶-凝胶法、高温固相法、氢氧化物共沉淀法(pH=10、11、12)制得LiNil/3Co1/3Mn1/3O2正极材料,通过X射线衍射(XRD)、扫描电镜(SEM)和电化学性能测试对样品的结构和性能进行了表征。结果表明,溶胶-凝胶法合成的样品层状结构较完整,阳离子混排程度低,粒径相对较小,颗粒分布均匀;该样品首次放电比容量较高为151mAh·g-1,循环30次后容量保持率达到93.31%。     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的合成及性能

采用氢氧化物共沉淀法合成了LiNi1/3Co1/3Mn1/3(OH)2前驱体,然后以Ni1/3Co1/3Mn1/3(OH)2和LiOH·H2O为原料,合成出了层状锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2.通过XRD、SEM和电化学测试对LiNi1/3-Co1/3Mn1/3O2材料的结构、形貌及电化学性能进行了测试和表征.结果表明,800℃烧结12h所合成的样品粒度大小分布比较均匀,该材料以0.2C充放电,其首次放电容量为150mAh·g-1,循环30次后容量为137mAh·g-1.     

共沉淀法合成球形正极材料xLi2MnO3·(1-x)Li(Ni1/3Co1/3Mn1/3)O2(x=0.2、0.4、0.6)及其性能研究

以氨水作为络合剂,采用氢氧化物共沉淀法合成了球形富锂锰基正极材料xLi2MnO3·(1-x)Li(Ni1/3Co1/3Mn1/3)O2(x=0.2、0.4和0.6),并对合成的不同组分样品材料的化学成分、结构、形貌和电化学性能进行了表征。结果表明,样品材料的化学组分与其理论含量相同,随着x 的增大,材料的粒度变小,在电压范围为2.5~4.6V条件下进行充放电性能测试时,材料的首次充放电容量随着x 值减小而增加,且当x=0.2时,材料在不同倍率条件下具有最大的放电容量。     

Synthesis and electrochemical behavior of a new layered cathode material LiCo1/2Mn1/3Ni1/6O2

A new layered type lithium nickel manganese cobalt oxide with the composition of LiCo_1/2Mn_1/3Ni_1/6O₂ was synthesized by using a layered double hydroxides (LDHs) as precursor and solid state reaction method. Phase-pure LiCo_1/2Mn_1/3Ni_1/6O₂ was obtained when the mixed precursors of NiMnCo–LDHs and LiOH·H₂O were calcined at 750 °C for 12 h. It showed discharge capacity of 180 and 148 mAh/g in the first cycle, corresponding to the discharge voltage ranges of 2.5–4.5 and 2.5–4.2 V, respectively, and still delivered 173 and 140 mAh/g after 60 cycles at room temperature, which represented favorable capacity retention upon cycling. This material was expected as a potential alternative of cathode material to be used for Li-ion secondary battery because of its good electrochemical performance and lower synthesis cost.     

草酸盐共沉淀法制备Li(Ni1/3Co1/3Mn1/3)O2-xFx正极材料及电化学性能

采用草酸盐共沉淀法合成了锂离子电池用Li(Ni1/3Co1/3Mn1/3)O2-xFx(x=0,0.03,0.05,0.1)粉末材料,考察了掺杂氟对Li(Ni1/3Co1/3Mn1/3)O2结构与性能的影响。采用XRD、SEM和电池充放电循环测试方法等表征了Li(Ni1/3Co1/3Mn1/3)O2-xFx材料的结构与性能。结构表明,950℃焙烧10h制备的Li(Ni1/3Co1/3Mn1/3)O1.97F0.03材料具有较好的层状结构与综合电化学性能,阳离子混合度小、六角晶格有序性高,颗粒的平均粒径为2～3μm。I003/I104为1.29,R值为0.42,首次放电容量为141.7mA·h/g(2.8～4.2V,0.2C倍率),首次充放电容量效率为82.4%,0.2C倍率循环30次后的放电容量为首次放电容量的95.6%。     

草酸盐共沉淀法合成LiNi0.8Co0.1Mn0.1O2及电化学性能

采用草酸盐共沉淀法合成前驱体,然后经过氧化气氛高温焙烧制备了锂离子电池正极材料LiNi0.8Co0.1Mn0.1O2.用X射线衍射(XRD)、扫描电镜(SEM)和恒电流充放电技术研究了pH值、焙烧温度、焙烧时间和锂用量对材料结构、微观形貌及电化学性能的影响.草酸盐共沉淀-氧化焙烧合成LiNi0.8 Co0.1Mn0.1O2的工艺条件为:pH值为5.5,焙烧温度为800℃,焙烧时间为12h,Li/M摩尔比为1.05.所制备的LiNi0.8 Co0.1 Mn0.1 O2在0.5C倍率下的首次充放电比容量达到174.5mAh·g-1,循环20周容量保持率为88.5％.     

Spray-drying synthesis of P2-Na2/3Fe1/2Mn1/2O2 with improved electrochemical properties

Owing to its high theoretical capacity, P2-type Na_2/3Fe_1/2Mn_1/2O₂ has been considered as a kind of promising cathode material. However, the practical application is limited due to excessively high calcining temperature during traditional preparation processes. Here, we report the synthesis of P2-Na_2/3Fe_1/2Mn_1/2O₂ by using a facile spray-drying method followed by calcining at low temperature. Under the optimal conditions, the well-crystallized P2-Na_2/3Fe_1/2Mn_1/2O₂ material with excellent rate capability and cycle ability is obtained. And the sample exhibits the initial discharge capacities of 217.9, 171.3 and 117.4 mAh g⁻¹ at 0.1 C, 0.5 C and 2 C rate, respectively. The developed Na_2/3Fe_1/2Mn_1/2O₂ material, synthesized by a new spray drying-calcining procedure, may potentially be used as a suitable cathode in sodium ion batteries.     

Synthesis, structure, and some properties of LiNi1/3Co1/3Mn1/3O2

Crystalline LiNi_1/3Co_1/3Mn_1/3O₂ powders have been synthesized by two different procedures, using carbonate coprecipitation from sulfate and nitrate solutions, followed by two-step heat treatment of a mixture of the resultant Ni_1/3Co_1/3Mn_1/3CO₃ precursor and Li₂CO₃ at 500 and 900°C. The powders have been characterized by X-ray diffraction, scanning electron microscopy, and dynamic light scattering. The results demonstrate that the synthesized compounds have a hexagonally ordered, layered structure of the α-NaFeO₂ type. The primary-particle (crystallite) size in the powders is 50 nm and the aggregate size is 150–250 nm. The average size of larger structures (agglomerates) is 11 and 18 μm in the powders prepared via the sulfate and nitrate routes, respectively. The chemical stability of the synthesized powders is shown to depend on the ambient medium. Prolonged storage in air leads to the formation of new, lithium-deficient phases, especially in the case of the powders prepared from nitrate solutions.     

Submicron size Li(Ni1/3Co1/3Mn1/3)O2 particles prepared by spray pyrolysis from polymeric precursor solution

Submicron-sized Li(Ni_1/3Co_1/3Mn_1/3)O₂ particles were prepared by spray pyrolysis. A polymeric precursor solution containing citric acid and ethylene glycol enabled the formation of submicron-sized Li(Ni_1/3Co_1/3Mn_1/3)O₂ spherical particles with narrow-sized distribution and non-aggregation characteristics in the spray pyrolysis. The mean sizes of the particles post-treated at temperatures of 800 and 900^∘C were 380 and 770 nm. On the other hand, the Li(Ni_1/3Co_1/3Mn_1/3)O₂ particles obtained from the aqueous solution had irregular morphology and broad-sized distribution. The discharge capacity of the particles prepared from polymeric precursor solution decreased from 88 mAh/g to 135 mAh/g after 50 cycles. The particles prepared from polymeric precursor solution had high discharge capacity and good cyclic properties than those of the particles prepared from the aqueous solution.     

Synthesis and electrochemical properties of modification LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery

The layered LiNi1/3CO1/3Mn1/3-xMg(x)O2 (x = 0, 0.01, 0.03, 0.05) cathode materials were prepared by solid state reaction, then copper oxide was coated on the product. The structures, morphologies and electrochemical properties of the LiNi1/3Co1/3Mn1/3-xMg(x)O2 and CuO-coated LiNi1/3Co1/3Mn1/3-xMg(x)O2 were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and electrochemical tests. The results showed that the electrochemistry properties and cycle performance of magnesium doped LiNi1/3Co1/3Mn1/3O2 and CuO-coated LiNi1/3Co1/3Mn1/3-xMg(x)O2 materials were improved. The optimal doping content of Mg was x = 0.03 in the LiNi1/3Co1/3Mn1/3-xMg(x)O2 samples to achieve high discharge capacity and good cyclic stability, and the first discharge special capacity was 158.5 mAh/g at 0.2 C in the voltage of 2.5-4.3 V, then CuO-coated LiNi1/3Co1/3Mn1/3-0.03Mg0.03O2 was investigated. The electrode reaction reversibility and electronic conductivity were enhanced through Mg-doped and CuO-coated.