锂离子电池正极材料LiMgxMn2-xO4的合成及性能

利用相转移法合成了LiMgxMn2-xO4前驱体,在电炉中于一定温度下烧结一定时间,得到锂离子电池正极材料粉体,并利用XRD、SEM、IR等对材料粉体进行结构形态表征.考察焙烧温度、焙烧时间、Mg的掺杂含量等对产物结构和电化学性能的影响.实验结果表明:当Mg的掺杂量x=0.06,于750℃焙烧15 h时所制备的样品材料结构稳定且呈尖晶石型,样品电极的充放电性能良好,首次放电比容量达125 mAh/g,放电平稳,样品电极可逆循环性能良好.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy(SEM) were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the c1 space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0μm. During the Li ion chemical intercalation, radical P2O4-O7 is disrupted into two PO3-4 ions in the presence of O2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

Structure and electrochemical properties of LiLaxMn2-xO4 cathode material by the ultrasonic-assisted sol-gel method

Powders of spinel LiLaxMn2_xO4 were successfully synthesized by the ultrasonic-assisted sol-gel (UASG) method.The structure and properties of LiLaxMn2_xO4 were examined by X-ray diffraction (XRD),Fourier transform infrared (FT-IR) spectros-copy,scanning electronic microscopy (SEM),galvanostatic charge-discharge test,and cyclic voltammetry (CV).XRD results showthat the La3+ can partially replace Mn3+ in the spinel and the doped materials with La3+ have a larger lattice constant compared with pristine LiMn2O4.FT-IR indicates that the absorption peak of Mn3+-O and Mn4+-O bonds has a red and blue shift with the increase of doping lanthanum in LiLaxMn2_xO4,respectively.The charge-discharge test exhibits that the initial discharge capacity of LiLaxMn2_xO4 drops off,and the capacity retention increases gradually at C/5 discharge rate with the increase of doping lanthanum,and LiLa0.01Mn1.99O4 has a higher discharge capacity and a better cycling performance at 1C discharge rate.CV reveals that the dop-ing La3+ is beneficial to the reversible extraction and intercalation of Li+ ions.     

Preparation and electrochemical performance of MWCNTs@MnO2 nanocomposite for lithium ion batteries

Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-discharge tests were used to characterize the structures and electrochemical performances of the as-prepared nanocomposite.The capacity reaches 1233.6 mA h g-1 at a current density of 100 mA g-1 for the first discharge,and it can still maintain a capacity of 633.1mA h g-1 after 100 charge-discharge cycles.The results show that MWCNTs with good electrical conductivity as anchors of MnO2 can provide fast electron transport channels for MnO2 in the electrochemical reactions,and the as-prepared MWCNTs@MnO2 nanocomposite is a potential anode material for lithium ion batteries.     

溶胶-凝胶法制备 Ni0.5Zn0.5Fe2O4纳米材料特性的研究

利用溶胶．凝聚法制备了Ni0.5Zn0.5Fe2O4粉末材料,烧结温度范围600℃-950℃。对材料的结构、红外、磁学和微波吸收特性进行了研究。材料的XRD图谱和原子力显微镜形貌观察表明,材料在纳米尺度范围之内。在500cm-1--600cm-1波数范围内,材料具有明显的红外吸收特性。材料的晶粒尺寸随着烧结温度的提高而增加,且较高温度烧结的材料具有相对低的矫顽力和饱和磁场。利用反射衰减实验研究材料在6GHz--10GHz波段范围的吸波特性,结果表明,0．33mm厚度的样品在常温下的反射衰减达到1．8dBm。     

Microwave Synthesis of Cathode Material LixMn2O4 for Lithium-ion Battery

LixMn2O4 was synthesized rapidly by microwa heaing,the product phases of the microwave synthesis and comventional solid-solid-state synthesis were comparatively inesitigated,The capacity of microwave synthesis product decreases relatively slow,The lithium ion can be inserted into and extracted from the spinel framework structure fluently after cycling .But the capacity of the conventional solid-state synthesis product is more remarkably lowered.The spinel framework structure was destroyed which hindered the lithium ion from inserting and extracting,Tehe influential factors of the process parameters are discussed such as heat preservation time,pre-heating at 400℃ for 24 h and coupled agent.     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi0. 5 Mn1. 5 O4 was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi0. 5 Mn1. 5 O4 synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electro chemical test shows that the LiNi0. 5 Mn1.5 O4 calcined at 700 ℃ for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles.     

MgO和ZrO2包覆对正极材料结构和电性能的影响

通过共沉淀法制备了前驱体Ni1/3Co1/3-xMn1/3（OH）2,然后与LiOH·H2O、不同金属氧化物（MgO、ZrO2）分别混合制备锂离子电池正极材料LiNi1/3Co1/3-xMn1/3MxO2（M=Mg,Zr）.通过X射线衍射（XRD）、扫描电镜（SEM）、高精度电池测试系统、交流阻抗对材料结构和电化学性能进行了表征。实验结果表明,包覆MgO后,材料的结构发生变化,而包覆ZrO2没有改变正极材料的结构。与无包覆的正极材料相比较,包覆ZrO2材料的首次放电量为119.07 mAhg-1,20次循环后容量保持率为92.64%,放电量仍达到110.31 mAhg-1。     

Synthesis and characterization of triclinic structural LiVPO4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi0. 45 Co0. 10 Mn0. 4sO2 was synthesized from Li2CO3 and a triple oxide of nickel, cobalt and manganese at 950 ℃ in air. The structures and characteristics of LiNi0. 45 Co0.10 Mn0. 45 O2, LiCoO2 and LiMn2 O4 were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi0.4s Co0.10 Mn0. 45 O2 has a layered structure with hexagonal lattice. The commercial LicoO2 has sphere-like appearance and smooth surfaces, while the LiMn2 O4 and LiNi0.45 Co0. 10 Mn0. 45 O2 consist of cornered and uneven particles. LiNi0. 45 Co0.10 Mn0. 45 O2 has a large disLiMn2 O4 and LiCoO2, respectively. LiCoO2 and LiMn2 O4 have higher discharge voltage and better rate-capability than LiNi0. 45Co0.10 Mn0. 45 O2. All the three cathodes have excellent cycling performance with capacity retention of above 89.3 % at the 250th cycle. Batteries with LiMn2 O4 or LiNi0.45 Co0.10 Mn0. 45 O2 cathodes show better safety performance under abusive conditions than those with LiCoO2 cathodes.     

Co_(0.5)Zn_(0.5)Fe_2O_4/C复合物的制备及电磁性能研究

采用水热法制备出不同比的Co0.5Zn0.5Fe2O4/C复合物,通过X射线衍射分析仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)、振动样品磁强计(VSM)、网络分析仪对该复合物的形貌、电磁性能进行表征与分析。结果表明:Co0.5Zn0.5Fe2O4被碳包裹程度随碳相对含量的增加而增加;在频率为3~18 GHz范围内,Co0.5Zn0.5Fe2O4/C复合物的介电常数虚部和介电损耗随Co0.5Zn0.5Fe2O4的相对含量增加而增加;与Co0.5Zn0.5Fe2O4相比,Co0.5Zn0.5Fe2O4/C复合物的最大吸收峰有明显提高,且当0.5 g Co0.5Zn0.5Fe2O4与2 g葡萄糖混合时,制备的样品最大吸收峰在频率16 GHz左右可达到7 d B。     

水解法制备掺氟硅酸亚铁锂正极材料

采用水解法制得纯相掺氟硅酸亚铁锂正极材料.通过XRD衍射、充放电实验、交流阻抗谱、红外光谱、热重等现代手段,研究了所制备的样品的电化学性能.研究表明,通过400、600℃两步烧结可制得具有单斜结构(空间群P21/n)的Li2.05FeSiO4F0.02/C.制备的扣式电池在55℃下,分别以0.3C、1C、2C倍率电流连续充放电30循环时,第1循环的容量分别为116.8、106.5、99.2 mAh.g-1.掺氟改善了硅酸亚铁锂的电化学性能.     

空气中合成锂离子电池正极材料LiNi1-xTixO2

以N i(OH)2、TiO2和LiOH.H2O为原料,采用固相反应法在空气中合成了LiN i1-xTixO2(x=0.025、0.050、0.100),用XRD研究了合成材料的物相和结构,用SEM研究了合成材料的形貌,用电池性能测试仪研究了合成材料的电化学性能.结果表明,原料中的n(Ti)/n(N i Ti)值对合成材料的结构和电化学性能影响很大.少量的钛可以进入LiN iO2的晶格形成LiN i1-xTixO2固溶体,而钛含量过大则会出现杂相.n(Ti)/n(N i Ti)值为0.050的样品结构有序度最高,充放电容量最大.     

Electrochemical performance of LiFePO4/（C＋Fe2P） composite cathode material synthesized by sol-gel method

A LiFePO4/(C+Fe2P) composite cathode material was prepared by a sol-gel method using Fe(NO3)3·9H2O,LiAc·H2O,NH4H2PO4 and citric acid as raw materials,and the physical properties and electrochemical performance of the composite cathode material were investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM) and electrochemical tests.The Fe2P content,morphology and electrochemical performance of LiFePO4/(C+Fe2P) composite depend on the calcination tempera...     

Synthesis and electrochemical characterization of LiNi0.78Co2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78Co2Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.78Co2Al0.02O2 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry (3.0-4.2 V) illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared ma-terial was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles (0.2C,3.0-4.2 V, vs. Li /Li) with the capacity retention ratio of 97.7%.     

Structure and electrochemical properties of La, F dual-doped LiLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa0.01Mn1.99O3.99F0.01 and LiLa0.01Mn1.99O4 samples have smaller lattice parameters and unit cell volume than LiMn2O4. SEM indicates that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 129.9, 122.8, and 126.4 mAh·g-1, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn2O4.     

Synthesis and electrochemical characterization of LiNi0.78Co0.2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78 Co0.2 Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.rsCoo.2AI~0202 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry （3.0- 4. 2 V） illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared material was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles （0. 2C, 3.0 - 4. 2 V, vs. Li^＋/Li） with the capacity retention ratio of 97.7%.     

均相沉淀法制备Zn Fe2 O4负极材料及其储锂性能

采用均相沉淀法制备了ZnFe2 O4前驱体,探索了烧结温度对ZnFe2 O4结构和电化学性能的影响。用X射线衍射（XRD）和场发射扫描电子显微镜（FESEM）表征了材料的微观结构和形貌;采用循环伏安（CV）、电化学交流阻抗谱（EIS）和充放电测试了ZnFe2 O4作为锂离子电池负极材料的储锂性能。结果表明：随着烧结温度的升高,样品粒径增大;当烧结温度达到900℃时可以得到纯相尖晶石型ZnFe2 O4,其中在900℃下烧结的ZnFe2 O4样品具有最高的嵌锂活性、最好的电化学反应可逆性、最低的电化学反应阻抗和优良的倍率性能。