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.

Effects of sodium substitution on properties of LiMn_2O_4 cathode for lithium ion batteries

Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge measurements. The results show that all the samples exhibit the same cubic spinel phase structure without impurity.The lattice constant and unit cell volume decrease with increasing the sodium dopant amount.As the molar ratio of sodium to manganese(x=n(Na)/n(Mn))increases from 0 to 0.03,the initial discharge capacity of the Li1.05Mn2O4 cathodes decreases from 119.2 to 107.9 mA·h/g,and the discharge capability at large current rate and the storage performance decline dramatically,while cycling performance at room temperature and 55℃are improved.The CV and EIS studies indicate that reversibility of Li1.05Mn2O4 cathodes decreases and the electrochemical impedance increases with increasing the sodium dopant amount.

Surface modification and characterization of F-Co doped spinel LiMn_2O_4

Spinel LiCo0.09Mn1.91O3.92F0.08 as cathode material was modified with LiCoO2 by the sol-gel method, and the crystal structure, morphology and electrochemical performance were characterized with XRD, SEM, EDS, AAS and charge-discharge test in this paper. The results show that a good clad coated on parent material can be synthesized by the sol-gel method, and the materials with modification have perfect spinel structure. LiCo0.09Mn1.91O3.92F0.08 materials coated by LiCoO2 improve the stability of crystal structure and decrease the dissolution of Mn into electrolyte. With the LiCoO2 content increasing, the specific capacity and cycle performance of samples are improved. The capacity loss is also suppressed distinctly even at 55 ℃.

Co^3+-modified Surface of LiMn2O4 Spinel for its Improvement of Electrochemical Properties

Cobalt was used to modify the surface of spinel LiMn2O4 by a solution technique to produce Co3+-modified surface material (COMSM). Cobalt was only doped into the surface of LiMn2O4 spinel. XPS(X-ray photoelectron spectroscopy) analysis confirms the valence state of Co3+. COMSM has stable spinel structure and can prevent active materials from the corrosion of electrolyte. The ICP(inductively coupled plasma) determination of the spinel dissolution in electrolyte showed the content of Mn dissolved from COMSM was smaller than that from the pure spinel. AC impedance patterns show that the charge-transfer resistance (Ret) for COMSM is smaller than that for pure spinel. The particles of COMSM are bigger in size than those of pure spinel according to the micrographs of SEM(scanning electron microscopy). The determinations of the electrochemical characterization show that COMSM has both good cycling performance and high initial capacity of 124.1 mA/h at an average capacity loss of 0.19 mAh/g per cycle.

Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn_2O_4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide （LiMn2O4） by supercritical hydrothermal （SH） accelerated solid state reaction （SSR） route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn2O4 materials were studied. The experimental results show that after 15 min reaction in SH route at 400 ℃ and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 ℃, compared with the conventional solid state reaction method. The prepared LiMn2O4 material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA.h/g at a rate of 0.1C （1C=148 mA/g） and a good rate capability at high rates, even up to 50C.

Synthesis and Characterization of LiCo_xMn_(2-x)O_4 Cathode Materials

LiCoxMn2.04 cathode materials for lithium ion batteries were synthesized by mechanical activation-solid state reaction at 750 ℃ for 24 h in air atmosphere, and their crystal structure, morphology, element composition and electrochemical performance were characterized with XRD, SEM, ICP-AES and charge-discharge test. The experimental results show that all samples have a single spinel structure, well formed crystal shape and uniformly particle size distribution. The lattice parameters of LiCo Mn2-xO4 decrease and the average oxidation states of manganese ions increase with an increase in Co content. Compared with pure LiMn2O4, the LiCo Mn2xO4 （x=0.03-0.12） samples show a lower special capacity, but their cycling life are improved. The capacity loss of LiCo009Mn191O4 and LiCo0.1Mn1.88O4 is only 1.85% and 0.95%, respectively, after the 20th cycle. The improvement of the cycle performance is attributed to the substitution of Co at the Mn sites in the spinel structure, which suppresses the Jahn-Teller distortion and improves the structural stability.

Structure characteristics and electrochemical properties of LiMn_2O_4 modified by LiCoO_2

In order to improve the cycle performance of LiMn2O4, the modified LiMn,O4 was prepared by solid-state reactions using LiMn2O4 and LiCoO2 as precursors. XRD and EDS were used to study the structure properties of the modified LiMn2O4. The electrochemical properties of the modified LiMn2O4 were also investigated. The results show that Li and Co atoms could insert into the LiMn2O4crystal lattice and a newly formed spinel phase, modified LiMn2O4 was obtained. The modified LiMn2O4 exhibits excellent cycle ability at room and elevated temperatures compared to pure LiMn2O4. The improved electrochemical stability of the modified LiMn2O4 attributes to the entrance of Li and Co ions inserted into the spinel crystal structure.

LiCoO_2对LiMn_2O_4改性过程的研究

Modified lithium manganese oxides were prepared by using LiMn 2 O 4 and LiCoO 2 as precursors by solid state reaction.A study has been carried out by TG - DSC,XRD and FTIR to analyze the reaction process and structural characterization of products.The results showed that the LiMn 2 O 4 reacted chemically with LiCoO 2 at high temper - ature.Li and Co atom could insert into the LiMn 2 O 4 crystal lattice and obtained the Cobalt - Doped spinel com - pound.The results of constant - current cyclic test showed that the cyclic stability of the products are increased with the amount of doped LiCoO 2 ,while their initial capacity is decreased.

Electrochemical Performance of LiMn2O4/LiFePO4 Blend Cathodes for Lithium Ion Batteries

A series of LiMn2O4/LiFePO4 blend cathodes was prepared by hand milling and ball milling in order to compensate the disadvantage of spinel LiMnaO4 and olivine LiFePO4. The morphologies of the blends were studied by scanning electron microscopy, and their electrochemical properties were studied by charge-discharge cycling, cyclic voltarnmetry and electrochemical impedance spectroscopy. It is easy to obtain uniform LiMn2Oa/LiFePO4 blends by the hand milling technique, while significant particle agglomeration is caused by the ball milling technique. When the LiMn2O4：LiFePO4 mass ratio is 1：1, the nano-sized LiFePO4 powders not only uniformly cover the micron-sized LiMn2O4 particles but also effectively fill in the cavities of the LiMn2O4 space. Such morphology offers a good electrical contact and a high tap density, which leads to a high discharge capacity and good cycle stability.

Synthesis of LiMn2O4 Nano-wires via Flux Method and Their Usage as Cathode Material for Lithium Ion Batteries

LiMn2O4 nano-wires with ideal size distribution were readily synthesized by flux method. Samples prepared conventionally were used as the comparison references to investigate the effect of flux. The structural, morphological and electrochemical properties of nano-sized materials were examined by powder X-ray diffraction（XRD） analysis, scanning electron microscopy（SEM） and charge-discharge cycling analysis. Results from galvanostatic charge-discharge analysis show that the samples prepared at 700 ℃ via flux method（FM-700） afford the highest initial discharge capacity of 125.5 mA·h/g between 3.0 to 4.3 V at a rate of 0.2 C. After 50 cycles, a cycling retention of 89.6% is evident. Overall, the LiMn2O4 nano-wires developed in this work seem to be promising cathode materials for lithium ion batteries suitable to different energy-saving settings.

超高镍LiNi_(0.91)Co_(0.06)Al_(0.03)O_(2)@Ca_(3)(PO_(4))_(2)正极材料的储锂稳定性的提升机制

超高镍正极材料具有高比能、高电压和低成本等特点,在新一代锂离子电池中备受关注,但在电池的长循环过程中会出现微裂纹、机械粉化和不可逆相变,导致差的循环性能。本研究采用简便的湿化学法制备了一系列Ca_(3)(PO_(4))_(2)包覆的超高镍LiNi_(0.91)Co_(0.06)Al_(0.03)O_(2)材料(NCA@n CP)。其中,NCA@1CP在1C (1C=200 m A/g)、2.7~4.3 V下可获得204.8 m Ah/g的放电比容量,100圈循环后容量保持率为91.5%,甚至在2C的倍率下循环300圈后仍保留153.4 mAh/g的放电比容量。表征结果证实该包覆层可抑制材料的Li/Ni混排、不可逆相变和机械粉化,从而大幅提升了循环稳定性。本研究表明Ca_(3)(PO_(4))_(2)包覆策略在提升超高镍正极材料储锂稳定性方面具有较大的应用潜力。

Synthesis and electrochemical properties of LiMn_2O_4/Li_4Ti_5O_(12) composite

LiMn2O4/Li4Ti5O12 composite was synthesized by in-situ composite technique using LiMn2O4,lithium acetate,tetrabutyl titanate as starting materials and characterized by various electrochemical methods in combination with X-ray diffractometry(XRD), infrared(IR)spectroscopy and scanning electron microscopy(SEM).The results show that Li4Ti5O12 is coated on the surface of crystalline LiMn2O4 to form LiMn2O4/Li4Ti5O12 composite.The structure of LiMn2O4 does not change due to the introduction of Li4Ti5O12.By being coated with Li4Ti5O12,the rate capability and high temperature cyclability of LiMn2O4 is improved greatly.At room temperature,the discharge capacity of LiMn2O4/Li4Ti5O12 composite is more than 108.4 mA·h/g and the capacity loss per cycle is only 0.053%after 20 cycles at 2.0C.While at 55℃,the discharge capacity of LiMn2O4/Li4Ti5O12 composite is more than 109.9 mA·h/g and the capacity loss per cycle is only 0.036%after 60 cycles at 1.0C.

Performances of lithium manganese oxide prepared by hydrothermal process

A simple hydrothermal process followed by heat treatment was applied to the preparation of spinel Li1.05Mn1.95O4. In this process, electrolytic manganese dioxide(EMD) and LiOH·H2O were used as starting materials. The physiochemical properties of the synthesized samples were investigated by thermogravimetry-differential scanning calorimetry(TG-DSC), X-ray diffractometry(XRD), and scanning electronic microscopy(SEM). The results show that the hydrothermally synthesized precursor is an essential amorphous. The precursor can be easily transferred to spinel powders with a homogeneous structure and a regularly-shaped morphology by heat treatment. Li1.05Mn1.95O4 powder obtained by heat treating the precursor at 430 °C for 12 h and then calcining at 800 °C for 12 h shows an excellent cycling performance with an initial charge capacity of 118.2 mA·h·g-1 obtained at 0.5C rate and 93.8% of its original value retained after 100 cycles.

Nanoarchitectured LiMn_2O_4/Graphene/ZnO Composites as Electrodes for Lithium Ion Batteries

LiMn2O4 nanoparticles are facilely synthesized using a sol-gel processing method. Graphene is added to LiMn2O4 electrode aiming at increasing specific capacity and improving rate capability. In order to further improve cycling stability of LiMn2O4/graphene electrode, atomic layer deposition （ALD） is used to deposit ultrathin ZnO coating composed of six ZnO ALD layers and modify the surface of either LiMn2O4/graphene electrode or individual LiMn2O4 particles to form nanoarchitectured LiMn2O4/graphene/ZnO electrodes. Both ZnO-ALD-modified LiMn2O4/graphene electrodes demonstrate enhanced cycling performance at 1C, retaining the final discharge capacity above 122 mA h g 1 after 100 electrochemical cycles, which is higher than 115 mA h g-1 of pristine LiMn2O4/graphene electrode and 109 mA h g-1 of bare LiMn2O4 electrode. The improved electrochemical performance of nanoarchitectured LiMn2O4/graphene/ZnO electrodes can be attributed to the cooperative effects from high electronic conductivity of graphene sheets to facilitate electron transportation and effective protection of ZnO ALD coating to restrict Mn dissolution and electrolyte decomposition.

Mg2+掺杂锰酸锂的第一性原理研究

利用基于密度泛函理论的第一性原理平面波超软赝势法对Mg^2+掺杂锰酸锂的晶格常数与能带结构、态密度、键布居进行计算和分析,计算结果表明:掺杂Mg^2+后将会促使Mn、O原子的电荷重新分布且其相互作用加强,能带带隙减小,费米能级附近的带数增加,费米能由-1.29 eV增加到-1.02 eV,Mn、O、Mg在总态密度中贡献比较大,锂离子贡献比较小且峰型尖锐局域化严重,提高了Li^+的扩散效率,Mn—O键变短,共价性增强,形成的共价键较稳定,其相互作用形成的骨架较稳定不易坍塌.从而提高了材料的循环充放电性能和电池使用寿命.

锂离子电池的正极材料

综述了国外锂离子蓄电池正极材料的进展，着重叙述了ＬｉＣｏＯ２、ＬｉＮｉＯ２和ＬｉＭｎ２Ｏ４的合成方法。Ｌｉ－ＣｏＯ２主要用Ｌｉ２ＣＯ３和ＣｏＣＯ３为原料，在９００℃温度下合成。最近通过Ｌｉ２ＣＯ３和ＣｏＣＯ３在４００℃下反应制成了“低温”ＬｉＣｏＯ２（ＬＴ－ＬｉＣｏＯ２），（ＬＴ－ＬｉＣｏＯ２）的电化学性质不同于高温合成的ＬｉＣｏＯ２。制取化学计量的ＬｉＮｉＯ２比较困难，采用ＬｉＮＯ３和Ｎｉ（ＯＨ）２为原料在７００℃～８００℃温度下进行反应制得了Ｌｉ０．９６Ｎｉ１．０４Ｏ２材料。采用ＭｎＯ２和Ｌｉ２ＣＯ３或ＬｉＮＯ３为原料，在７５０℃温度下合成了Ｌｉ０．９３Ｍｎ２Ｏ４。在４００℃低温下采用Ｌｉ２ＣＯ３和ＭｎＣＯ３为原料，在Ｌｉ／Ｍｎ＝２／３和Ｌｉ／Ｍｎ＝４／５情况下分别合成了Ｌｉ２Ｍｎ４Ｏ９和Ｌｉ４Ｍｎ５Ｏ１２。

Structure and electrochemical properties of La, F dual-doped LiLa_(0.01)Mn_(1.99)O_(3.99)F_(0.01) 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 LiLao.olMnl.9904 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.