锂离子电池正极材料Li_2MnSiO_4固体核磁共振谱研究

应用水热-溶胶凝胶法合成了Li2MnSiO4正极材料.由XRD、FTIR、固体NMR及恒流充放电等方法表征、分析样品的相组成、晶体结构和电化学性能.结果表明,合成的样品主相为Li2MnSiO4,同时存在少量Li2CO3杂质.该材料的首次放电容量可达190mAh·g-1,但在充放电循环过程中由于结构坍塌、分解导致其容量衰退明显.     

微波合成法制备锂离子电池正极材料Li2FeSiO4

研究了一种制备锂离子电池正极材料Li2FeSiO4的新方法. 采用机械球磨结合微波热处理合成了Li2FeSiO4正极材料. 通过XRD、SEM和恒流充放电测试, 对样品结构、形貌和电化学性能进行了表征和分析. 与传统固相法合成的材料在晶体结构、微观形貌以及充放电性能方面进行了比较. 结果表明, 微波合成法可以快速制备具有正交结构的Li2FeSiO4材料; 在650 ℃时处理12 min, 获得了纯度高、晶粒细小均匀的产物, 该产物具有较高的放电比容量和良好的循环性能. 在60 ℃下以C/20倍率(电流密度, 1C=160 mA·g-1)进行充放电, 首次放电容量为119.5 mAh·g-1, 10次循环后放电容量为116.2 mAh·g-1. 与传统高温固相法相比, 微波合成法制备的材料具有较高的纯度、均匀的形貌和较好的电化学性能.     

球磨微波法制备Li3V2（PO4）3/C及其电化学性能表征

本文采用球磨微波法合成锂离子电池正极材料Li3V2(PO4)3/C,并研究了微波辐射时间对样品电化学性能的影响.结果表明,640 W微波辐射18 min合成的材料,结晶度高,粒径小而均匀.该电极5C倍率下首次放电比容量达101.3 mAh·g-1,300周期循环,其放电比容量仍保持100.8 mAh·g-1,展示出良好的应用前景.     

钒酸盐化合物NaV_2O_5的水热合成及电化学性质

应用水热合成法制备NaV2O5晶体,XRD、SEM、拉曼光谱和XPS分析测试及电化学表明,该材料属正交晶系,空间群为Pmmn,呈纯相的棒状结构,长度约有20μm,宽度大约200 nm.该材料的V离子均价为+4.5价.首次放电容量达到120 mAh/g,放电平台为2.0 V.经过20个循环,容量保持率98 mAh/g,表现了良好的循环性能.     

固相烧结法制备锂离子电池正极材料Li2FeP2O7及其电化学性能研究

介绍了一种先冷冻干燥后固相烧结制备正极材料Li₂FeP₂O₇的方法. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)和傅里叶变换红外光谱(FTIR)对材料的组成和形态进行表征, 并通过循环伏安曲线(CV)和电化学阻抗谱(EIS)研究了Li₂FeP₂O₇材料的电化学性能. 研究发现, 合成Li₂FeP₂O₇的最佳温度为590 ℃, 此温度下反应较完全且产物杂质较少, 1.6C倍率下的放电比容量达到55 mA·h·g^?1, 明显高于其它温度下合成样品的放电比容量. 该温度下合成的Li₂FeP₂O₇还具有低阻抗和较大的交换电流密度, 说明这种合成方式有利于提高锂离子在Li₂FeP₂O₇中的扩散.     

草酸盐共沉淀法制备锂离子电池正极材料LiNi0.5Mn0.5O2及其电化学性能

使用草酸盐共沉淀法合成了LiNi0.5Mn0.5O2, 并研究了共沉淀时的pH条件对终产物的结构、形貌及电化学性能的影响. 采用X射线衍射(XRD)和扫描电镜(SEM)表征了在pH值为4.0、5.5、7.0和8.5时得到的共沉淀和终产物LiNi0.5Mn0.5O2的结构和形貌. 使用充放电实验研究了不同pH条件下得到的LiNi0.5Mn0.5O2的电化学性能. 结果表明, pH为7.0时, 合成的材料颗粒更小、分布最均匀, 材料具有良好的层状特征, 且材料中锂镍的混排程度最小. 电化学测试结果印证了pH为7.0时合成的材料具有更好的电化学性能, 在0.1C的倍率下, 材料的首次放电比容量达到了185 mAh·g-1, 在循环20周后, 放电比容量仍然保持在160 mAh·g-1. X射线光电子能谱(XPS)测试结果表明, pH为7.0时合成的LiNi0.5Mn0.5O2中Ni为+2价, Mn为+4价.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的低温燃烧合成

以LiNO3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、CO(NH2)2为原料,通过低温燃烧法在空气中合成了锂离子正极材料LiNi1/3Mn1/3Co1/3O2.采用XRD研究了合成产物的物相与结构,用SEM研究了合成产物的形貌,考察了点火温度、回火温度,回火时间以及锂过量对合成产物电化学性能的影响.研究结果表明,合成产物与层状LiNiO2的结构相同,属α-NaFeO2型层状结构,合成产物的粒度较小且比较均匀,并具有良好的电化学性能.采用低温燃烧法在空气中合成LiNi1/3Mn1/3Co1/3O2的最佳条件为:500℃点火,850℃回火20h,锂过量为15mol%.在此条件下得到的合成产物首次放电比容量达到158.9mAh/g.     

锂离子电池正极材料LiNi_(0.85)Co_(0.10)(TiMg)_(0.025)O_2合成及表征

以LiOH·H2O、Ni2O3、Co2O3、TiO2和Mg(OH)2为原料,应用固相反应法合成Co Ti Mg共掺杂的LiNiO2化合物LiNi0. 85Co0. 10 (TiMg)0. 025O2;TG DTA、XRD、SEM和电化学测试表明,该材料首次放电容量达182. 7mAh/g(3. 0~4. 3V, 18mA/g), 10次循环之后,容量还有 175. 5mAh/g,容量保持率为 96. 2%;与未掺杂的LiNiO2相比,该材料显示出良好的循环性能,是一种很有应用前景的锂电池正极材料.     

熔融法合成2-芳氧甲基苯并咪唑化合物

以邻苯二胺和芳氧基乙酸为原料, 采用熔融法合成出了10种2-芳氧甲基苯并咪唑化合物, 并利用IR和1H NMR对其结构进行了表征. 在熔融法的合成中, 两种原料物质的量之比为n(邻苯二胺)∶n (芳氧乙酸)＝1∶1.1, 反应温度为(180±5) ℃. 该合成方法具有操作简便、反应时间短、后处理容易、副产物少、产率较高、绿色环保等优点.     

柠檬酸络合法合成H_2SrTa_2O_7材料及其光催化还原CO_2活性（英文）

利用柠檬酸络合法及离子交换合成质子化钙钛矿H_2SrTa_2O_7(HST)光催化材料. HST的比表面积和结晶度由焙烧温度控制调节.结果表明,当焙烧温度为1000℃时, HST同时具有较高的结晶度和大的比表面积从而具有最高的活性, CO的最大生产速率为0.25μmol·g~(-1)·h~(-1).另外,相对于H_2的析出, CO的产生更依赖于大的比表面积.该工作对制备高活性的还原CO_2光催化剂材料具有一定的指导意义.     

纳米纤维素/MnO2自支撑锌离子电池正极的制备及其电化学性能研究

以羟基纳米纤维素为原料,利用其表面丰富的羟基还原KMnO 4,在纳米纤维表面原位生成MnO₂纳米颗粒,并与Super P混合,通过简单抽滤的方式获得CNF@MnO₂/Super P自支撑正极。结果表明:无粘结剂的CNF@MnO₂/Super P自支撑正极具有较高的循环稳定性,在0.5 A·g^-1的电流密度下,循环800圈后,容量仍能达到247 mAh·g^-1;均匀分布的纳米MnO₂与Super P能够有效缩短离子和电子扩散路径,大大降低材料的电阻,使正极具有良好的倍率性能,在2 A·g^-1的电流密度下,循环300圈之后,电池容量仍保持在175 mAh·g^-1,库仑效率~99%;利用该正极良好的延展性,制备了软包电池,并表现出了较高的循环稳定性和容量保持率,该工作为柔性无粘结剂的水系Zn-MnO₂二次电池的设计开发提供了新的研究思路。     

纳米MgO掺杂改善LiNi1/3Co1/3Mn1/3O2正极材料

将氢氧化物共沉淀法制备的(Ni_1/3Co_1/3Mn_1/3)（OH）₂在500℃热处理5 h得到具有尖晶石结构、纳米尺寸的氧化物M₃O₄(M=Ni_1/3Co_1/3Mn_1/3).将其与LiOH及不同量的纳米MgO混合均匀,并在850℃热处理24 h制备了Li(Ni_1/3Co_1/3Mn_1/3)_1/xMg_xO₂（x=0,0.01,0.02,0.03,0.04,0.05）正极村料.随着Mg掺杂量的增大,正极材料的晶胞参数增大;少量的Mg掺杂增大了锂离子的扩散系数,而过度掺杂却使锂离子扩散系数有所降低,其中Li(Ni_1/3Co_1/3Mn_1/3)_0.98Mg_0.02O₂的锂离子扩散系数最大,其脱出和嵌入扩散系数分别为D_Li-dein=29.20×10^-11cm²·S^-1和D_Li-in=4.760×10^-11cm²·s^-1;其以3C倍率充放电的平均放电比容量为139.3 mAh·g^-1,比未掺杂的原粉约高9.5 mAh·g^-1;另外其循环性能也得到了大幅度改善.     

表面活性剂对氧化铝修饰富锂锰基正极材料的影响

采用氧化铝修饰改性富锂锰基正极材料,探讨了表面活性剂在修饰改性中的作用。利用扫描电子显微镜、X射线衍射仪、透射电子显微镜和电化学性能测试等方法对材料结构和电化学性能进行分析。实验结果表明,十二烷基三甲基溴化铵(DTAB)能使Al_2O_3纳米颗粒均匀包覆在富锂锰基正极材料表面,有效增强了复合材料结构的稳定性。在600 mA·g~(-1)电流密度下,该复合材料的初始放电容量为186mAh·g~(-1)。经过500次循环后,其可逆放电比容量仍高于132 mAh·g~(-1),初始容量保持率高达71%。此外,电压衰退也被有效抑制,复合材料表现出优异的综合电化学性能。     

LiFePO4包覆的Li1.2Mn0.54Ni0.13Co0.13O2锂离子电池正极材料:增强的库伦效率和循环性能

In this work, we present a new design for a surface protective layer formed by a facile aqueous solution process in which a nano-architectured layer of LiFePO₄ is grown on a Li-rich cathode material, Li_1.2Mn_0.54Ni_0.13Co_0.13O₂. The coated samples are then calcined at 400 or 500℃ for 5 h. The sample after calcination at 400℃ demonstrates a high initial columbic efficiency of 91.9%, a large reversible capacity of 295.0 mAh·g^-1 at 0.1 C (1 C=300 mA·g^-1), and excellent cyclability with a capacity of 206.7 mAh·g^-1after 100 cycles at 1 C. Meanwhile, voltage fading of the coated sample is effectively suppressed by protection offered by a LiFePO₄ coating layer. These superior electrochemical performances are attributed to the coating layer, which not only protects the Li-rich cathode material from side reaction with the electrolyte and maintains the stability of the interface structure, but also provides excess reversible capacity.     

Fabrication of Nb2O5/C nanocomposites as a high performance anode for lithium ion battery

Nb₂O₅/C nanosheets are successfully prepared through a mixing process and followed by heating treatment.Such Nb₂O₅/C based electrode exhibits high rate performance and remarkable cycling ability, showing a high and stable specific capacity of ~380 mAh g^-1 at the current density of 50 mA g^-1(much higher than the theoretical capacity of Nb₂O₅).Further more,at a current density of 500 mA g^-1,the nanocomposites electrode still exhibits a specific capacity of above 150 mAh g^-1 after 100 cycles.These results suggest the Nb₂O₅/C nanocomposite is a high performance anode material for lithium-ion batteries.     

不同生物炭材料的制备及其在Li-S电池中的应用

Biochar derived from reproducible massive biomasses presents the advantages of low cost and renewable resources. In this work aiming to solve the existing problems of the lithium-sulfur battery, sulfur@biochar (S@biochar) composite cathode materials with high capacity and good cycle performance were developed. Specifically, four kinds of biochar prepared from rice husk, miscanthus, fir, and pomelo peel were used as host matrices for the Li-S battery. Among them, the S@biochar derived from rice husk delivered the highest specific capacity and the best cycle stability according to electrochemical tests. To further optimize its performance, we prepared a highly porous rice husk derived biochar (HPRH-biochar) using silica gel as the template. The S@HPRH-biochar composite (60% (w, mass fraction) S) enables the homogeneous dispersion of amorphous sulfur in the carbon matrix and its porous structure could effectively suppress the dissolution of the polysulfide. As a result, its electrochemical performance improved, achieving a high initial charge capacity of 1534.1 mAh·g^-1 and maintaining a high capacity of 738.7 mAh·g^-1 after 100 cycles at 0.2C (1C corresponds to a current density of 1675 mA·g^-1). It also gives a capacity of 485.3 mAh·g^-1 at 2.0C in the rate capacity test.     

类石墨烯类活性炭材料的简易合成及其在锂硫电池中的应用研究

锂硫电池由于具有较高的理论容量被视为一种最具发展潜力的储能装置. 然而,硫的利用率较低及循环寿命短等问题限制着其商业化进程. 本文通过一种简单易行的方法将三聚氰胺（C₃H₆N₆）和L半胱氨酸(C₃H₇NO₂S)碳化,制备出一种氮掺杂类石墨烯活性炭材料（NGC）. 该材料的类石墨烯结构能够有效抑制锂硫电池在充放电过程中产生的体积效应,以此提升其循环性能. 不仅如此,材料中含有的含氮官能团还可以促进离子转移,抑制多硫化物的溶解,进而提升硫的利用率. 其中,制备出的NGC-8/PS复合电极用于锂硫电池时在0.2 C的电流密度下初始容量为1164.1 mAh·g^-1,在经过400圈的充放电循环之后依然具有909.4 mAh·g^-1的比容量,每圈容量衰减仅为0.05%,甚至在2C的电流密度下也能达到820 mAh·g^-1的高比容量.     

锂硫电池用高度环化硫化聚丙烯腈的制备

硫化聚丙烯腈因其不溶解机制和有效缓解锂硫电池中多硫化物“穿梭效应”,被认为是具有吸引力的锂硫电池正极候选材料。硫化聚丙烯腈的导电聚合物骨架具有优异的电子导电性,同时共轭主链能有效解决充放电过程中硫正极体积变化引起的正极结构坍塌问题。因硫化聚丙烯腈的固-固反应机理,有效克服了传统硫正极在醚类电解液中多硫化物溶解及穿梭效应的问题,具有高正极活性物质利用率、出色的循环稳定性和结构稳定性等优势。有许多研究工作致力于通过硫化促进剂来提高硫化聚丙烯腈的硫含量,进而提高材料的能量密度。其中,硫化聚丙烯腈主链的环化度与循环稳定性的关系引起了我们的关注。在该研究工作中,通过在硫化过程中引入无水硫酸铜和正乙基正苯基二硫代氨基甲酸锌(ZDB)合成了SPAN-C-V复合材料。无水硫酸铜和ZDB的共同引入降低了聚丙烯腈环化反应的起始温度,同时提高了产物SPAN-C-V内碳碳双键的含量,在提高了材料硫含量的同时提高了其环化度。以SPAN-C-V为正极活性物质所组装的锂硫电池展现出良好的循环稳定性和倍率性能：在0.2 C (1 C = 600 mAh·kg^-1)下循环100次后的可逆容量为601 mAh·kg^-1,容量保持率为93%。该工作对于硫化聚丙烯腈材料的发展提供了参考。     

碳布负载的缺氧型Na2Ti3O7纳米带阵列作为高性能柔性钠离子电池负极材料

作为锂离子电池的理想替代品,钠离子电池因具有能源储备丰富、成本低廉等优点而受到人们的广泛关注。柔性便携式电子产品的发展亟需柔性储能器件的研制。因此,发展一种廉价、高性能的柔性钠离子电池负极材料成了科研工作者的共同目标。在此项工作中,我们通过简单的水热合成和热还原法发展了一种以柔性碳布为基底,与缺氧型的Na₂Ti₃O₇纳米带(NTO)构成三维阵列结构的新型柔性钠离子电池负极材料。复合材料(R-NTO/CC)的导电性和活性位点得到提高,电化学性能也大幅提升,在200 mA·cm^-2的电流密度下,实现100 mAh·cm^-2的面积比容量,且经过200次循环后仍保留最初电容值的80%。此外,这种电极还具有优良的倍率性能,当电流密度提高到400 mA·cm^-2时,仍保持69.7 mAh·cm^-2的面积比容量,是未引入氧空位材料的三倍之多。这种三维缺氧的电极材料可有效提高载流子浓度,缩短离子传输通道,从而大幅提升电极的电化学性能。此工作为设计合成高储钠性能的新型的负极材料提供了一种实用有效的策略。     

NaTiSi2O6/C复合材料用于锂离子电池负极材料

The development of human society and the continuously emerging environmental problems call for cleaner energy resources. Lithium-ion batteries, since their commercialization in the early 1990s, have been an important power source of mobile phones, laptops as well as other portable electronic devices. Their advantages include environment-friendliness, light weight, and no memory effect compared with lead-acid or nickel-cadmium batteries. Electrode materials play an important role in the performance of lithium-ion batteries. The traditional commercial anode material, graphite, has a theoretical specific capacity of 372 mAh·g^-1 and working potential close to 0 V (vs Li⁺/Li), making it prone to the formation of lithium dendrite, which may cause short circuit especially when large current is applied. Another commercial anode material Li₄Ti₅O₁₂, which also undergoes an intercalation reaction during lithiation process, has a theoretical specific capacity of 175 mAh·g^-1 along with three lithium-ion intercalations per formula unit. This is relatively small, and it has a relatively high working potential of 1.55 V (vs Li⁺/Li), which reduces its output voltage and specific energy when assembled in full battery. To overcome the shortcomings mentioned above, it is essential to search for new anode materials that are low-cost, environment-friendly, and easy to synthesize. Silicate materials have gained widespread attention owing to their low cost and facile synthesis. Herein, we report for the first time a novel titanosilicate, NaTiSi₂O₆, synthesized by sol-gel and solid sintering. It is isostructural to pyroxene jadeite NaAlSi₂O₆, belonging to monoclinic crystal system with a space group of C2/c. By in situ pyrolysis and carbonization of glucose, nanosized NaTiSi₂O₆ mixed with carbon was successfully obtained with a specific surface area of 132 m²·g^-1, calculated according to the Brunauer–Emmett–Teller formula. The specific charge/discharge capacity in the first cycle at current density of 0.1 A·g^-1 is 266.6 mAh·g^-1 and 542.9 mAh·g^-1, respectively, with an initial coulombic efficiency of 49.1%. After 100 cycles, it retains a specific charge capacity of 224.1 mAh·g^-1, corresponding to a capacity retention rate of 84.1%. The average working potential of NaTiSi₂O₆ is 1.2–1.3 V (vs Li⁺/Li), slightly lower than that of Li₄Ti₅O₁₂. The reaction mechanism while charging and discharging was determined by in situ X-ray diffraction test as well as selected area electron diffraction. The results showed that NaTiSi₂O₆ undergoes an intercalation reaction during lithiation process, with two lithium-ion intercalations per formula unit. This makes NaTiSi₂O₆ a new member of the silicate anode material family, and may provide insights into the development of new silicate electrode materials in the future.