CN104377344A - 一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法及应用 - Google Patents

一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法及应用 Download PDF

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CN104377344A
CN104377344A CN201410522387.7A CN201410522387A CN104377344A CN 104377344 A CN104377344 A CN 104377344A CN 201410522387 A CN201410522387 A CN 201410522387A CN 104377344 A CN104377344 A CN 104377344A
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李宏斌
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Li Hongbin
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Abstract

本发明公开了一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法及应用，所述钛酸锂LiTi2O4和石墨烯复合材料的制备方法为：首先采用溶胶凝胶法制备钛酸锂LiTi2O4和石墨烯复合材料前驱体，再在保护气体氛围中煅烧，还原制备得到钛酸锂LiTi2O4和石墨烯复合材料。本发明的制备方法简单，设备和反应条件要求低，产率和纯度高，制备得到的钛酸锂LiTi2O4和石墨烯复合材料粒径小，分布均匀，具有高克容量，适合在锂离子二次电池上的应用。

Description

一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法及应用
技术领域
本发明属于纳米材料技术领域，具体涉及一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法及其在锂离子二次电池中的应用。
背景技术
新能源动力和储能对锂离子二次电池性能提出了更高的要求。具有尖晶石结构钛酸锂(Li4Ti5O12)具有长寿命、高倍率、耐低温高安全性等特点在快速充电公交系统和储能上受到越来越多的应用。但是钛酸锂(Li4Ti5O12)的导电率低，只有10-13S/cm，属于绝缘体，作为锂电池负极材料时，需要加入导电剂增加导电性能。
钛酸锂(LiTi2O4)是钛酸锂(Li4Ti5O12)的同系化合物，具有和钛酸锂(Li4Ti5O12)相似的晶体结构和物理化学性能。
LiTi2O4具有两个同属面心立方晶系的同质异相体，即尖晶石结构(spinel)和斜方锰矿结构(ramsdellite)，两种结构都具有开放性间隙通道，适合锂离子嵌入嵌出。LiTi2O4的结构形态由制备温度决定。当温度低875℃时，LiTi2O4呈尖晶石结构，空间群为Fd3m。当温度高于925℃时，LiTi2O4呈斜方锰矿结构，空间群为Pbnm。
相比Li4Ti5O12，LiTi2O4具有很高的电子导电率。常温下LiTi2O4粉末压片的电阻率约1.8mΩ·cm。LiTi2O4在临界温度[超过10K(Tc＝13.8K)]时具有超导性。其晶体呈深蓝色，常温下为半导体。
因此，LiTi2O4作为锂离子二次电池负极材料时不需加更多导电剂，比Li4Ti5O12具有更高应用价值。
目前为止，合成LiTi2O4的报道不多。主要有固相合成法(Preparation andcharacterization of LiTi2O4anode material synthesized by one-step solid-statereaction,Jianwen Yang,Jiang Zhao,Yongzhen Chen,Yanwei Li,Ionics,2010,16,425–429)采用碳酸锂、二氧化钛和炭黑高温还原下得到；或者采用锂钛氧化合物(Li2TiO3)、二氧化钛和金属钛在高温下还原制备得到(Structural evolutionof ramsdellite-type LixTi2O4upon electrochemical lithium insertion–deinsertion(0≤x≤2),A.Kuhn,C.Baehtz,F.García-Alvarado,Journal of Power Sources,2007,174,421–427)。电解法(电解法制备纳米粉体，朱传高，周幸福，褚道葆，精细化工，20，4,244-246)，采用金属钛和锂，在有机电解液中阳极氧化制得。电化学熔融盐法(Electrochemical Synthesis of LiTiO2and LiTi2O4inMolten LiCl Molten LiCl,Kai Jiang,Xiaohong Hu,Huijiao Sun,Dihua Wang,Xianbo Jin,Yaoyao Ren,and George Z.Chen,Chem.Mater.2004,16,4324-4329)，采用二氧化钛在氯化钾700℃熔融盐体系中，正极氧化电解法制得。溶胶凝胶法(LiTi2O4用作锂离子电池负极的研究进展，杨建文，赵江，陈永珍，钟晖，化学通报)，采用四氯化钛和维生素C在盐酸和氢氧化锂溶液中一步反应制备得到。
上述方法中，高温固相法反应在高温下进行，反应条件相对较高；电化学熔融盐法和电解法设备相对比较复杂，在电化学电解合成过程中，容易引进杂质；溶胶凝胶法制备较难得到纯度较高产物。
石墨烯具有很高的比表面积、导电率和反应活性。在溶液中，离子可以均匀的分散在石墨烯表面，在石墨烯表面高反应活性位点催化条件下，化学反应更易进行，可以制备得到成分粒径均一的纳米颗粒和石墨烯的复合材料。
本发明提出了一种采用溶胶凝胶法制备钛酸锂(LiTi2O4)前驱体和石墨烯复合材料，然后将钛酸锂(LiTi2O4)前驱体和石墨烯复合材料在真空或保护气氛中煅烧制备得到钛酸锂(LiTi2O4)和石墨烯复合材料的方法。
发明内容
为了解决现有的LiTi2O4合成方法存在反应条件复杂、产物纯度低的技术问题，本发明的目的在于提出了一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法。
本发明的另一目的在于提供制备的钛酸锂LiTi2O4和石墨烯复合材料在锂离子二次电池中的应用。
针对现有技术中的不足，本发明采用如下技术方案：
一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特殊之处在于，包括以下步骤：
1)制备石墨烯；
2)将锂源、钛源和石墨烯均加入有机溶剂和水的混合溶液中，得到悬浊液；在悬浊液中加入碳源，混合均匀，制备得到凝胶溶液；
3)将凝胶溶液在真空或保护气体氛围中煅烧，制备得到钛酸锂LiTi2O4和石墨烯复合材料。
步骤2)中所述的锂源包括碳酸锂和醋酸锂中的一种或两种。
步骤2)中所述的钛源包括四氯化钛和钛酸四丁酯的一种或两种。
步骤2)中所述的有机溶剂包括乙醇、丙醇、异丙醇、丁醇、异丁醇、丙酮、二乙醇胺、三乙醇胺中的一种或多种。
步骤2)中所述的碳源包括天然石墨、人造石墨和碳黑导电剂的一种或多种。
步骤2)中所述的碳源中的碳元素和钛源中的钛元素的摩尔比M，满足0.5≤M<2。
步骤3)中所述的煅烧条件为：在真空或保护气体氛围中，以2～10℃/分钟的速度升温到350～950℃，并在此温度下保持2～30小时，反应结束后在真空或保护气体氛围中自然冷却至室温。
上述保护气体为氮气、氦气和氩气的一种或多种。
上述方法所制备的钛酸锂LiTi2O4和石墨烯复合材料在锂离子二次电池中的应用。
本发明的有益效果是：
1、本发明采用溶胶凝胶法把锂离子和四价钛离子吸附在石墨烯层状表面，然后加入还原碳，再在真空或保护气体氛围下煅烧还原钛元素制备钛酸锂LiTi2O4和石墨烯复合材料，四价钛离子在石墨烯表面和还原碳反应更易进行，生成的钛酸锂LiTi2O4和石墨烯结合紧密，工艺实现简单。
2、本发明制备得到的产物钛酸锂LiTi2O4和石墨烯复合材料，粒径小，分布均匀。
附图说明
图1是实施例1生成的钛酸锂LiTi2O4和石墨烯复合材料的XRD谱图；
图2是实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末的SEM图像；
图3是实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末的X射线能量散射EDS光谱；
图4是实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末元素面分布图；
图5是实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯复合材料粉末的SEM图像；
图6是实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯粉末的X射线能量散射EDS光谱；
图7是实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯复合材料的粉末元素面分布图；
图8是实施例1生成的钛酸锂LiTi2O4和石墨烯复合材料的电化学循环伏安图；
图9是实施例1生成的钛酸锂LiTi2O4和石墨烯复合材料的0.1C充放电循环曲线。
具体实施方式
下面结合具体的实施例对本发明作进一步的说明，但并不局限于此。
所有药品均为分析纯，含量≥99.9％。
实施例1
步骤1)采用改进Hummers方法制备石墨烯。
步骤2)称0.65克碳酸锂，加入20毫升水和20毫升无水乙醇的混合液中，混合搅拌均匀，得到溶液1；将0.1克石墨烯在搅拌情况下加入溶液1，制成悬浊液；称10.2克钛酸四丁酯，溶于100毫升无水乙醇中，得淡黄色溶液2；在搅拌情况下缓慢将溶液2加入溶液1中，混合后溶液呈黑色浑浊，再加入0.3克炭黑导电剂SP，超声波处理4小时，得到黑色凝胶；将黑色凝胶放入烘箱中于70℃干燥1天，得到黑色粉末。
步骤3)将黑色粉末置于上海久工电器有限公司JQF1400-30高温气氛电炉，抽真空，通99.9％氩气保护气，然后以5℃/分钟的速度升温到700℃，并在此温度下保持15小时，自然冷却后，得到蓝灰色粉末产物。
实施例2
步骤1)采用改进Hummers方法制备石墨烯。
步骤2)称6.80克钛酸四丁酯，溶于20毫升无水乙醇中，搅拌均匀；加入1.1克二水醋酸锂，搅拌溶解后，再加0.1克石墨烯、1.70克三乙醇胺和2.0克纯水。混合溶液搅拌3小时，加入0.132克炭黑导电剂SP，再搅拌4小时，得到黑色凝胶。
将黑色凝胶放入烘箱中50℃密封陈化10小时，再在70℃下干燥6小时，得黑色固体。
步骤3)将黑色固体置于上海久工电器有限公司JQF1400-30高温气氛电炉，抽真空，通99.9％氩气保护气，然后以5℃/分钟的速度升温到900℃，并在此温度下保持15小时，自然冷却后，得到黑色粉末。
材料性能表征
1)晶体结构测试在日本理学公司D/max 2500VL/PC型XRD衍射仪上进行，采用铜靶，测试精度±0.02°，扫描范围从5～90°。
实施例1生成的钛酸锂LiTi2O4和石墨烯粉末的XRD谱图见图1。
2)材料表面形貌在德国蔡司公司EV018型扫描电子显微镜SEM上进行，X射线能量散射EDS光谱和元素面分布图在牛津X-MAX20型能谱仪上进行。
实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末的SEM图像见图2。
实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末的X射线能量散射EDS光谱见图3。
实施例1步骤2)生成的钛酸锂LiTi2O4和石墨烯复合材料前驱体粉末的元素面分布图见图4。
实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯复合材料粉末的SEM图像见图5。
实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯复合材料粉末的X射线能量散射EDS光谱见图6。
实施例1步骤3)生成的钛酸锂LiTi2O4和石墨烯复合材料粉末的元素面分布图见图7。
电化学性能测试
按质量比85：10：5称取钛酸锂LiTi2O4和石墨烯复合材料、导电剂Super P和粘结剂PVDF(HSV900)，加入适量N-甲基吡咯烷酮作为溶剂，在自制手套箱中氩气保护下，用磁力搅拌器搅拌10小时，制备得到扣电所需浆料。涂布机为深圳科晶智达科技有限公司MSK-AFA-Ⅲ自动涂膜烘干机，涂布间隙25微米，速度5厘米/分钟，浆料均匀涂覆在梅县金象铜箔有限公司生产的9微米厚，纯度99.8％光面铜箔上，120℃下真空干燥12小时，然后在深圳科晶MSK-T06纽扣电池冲片机冲压成直径约为16毫米左右的电极薄片。CR2032扣式电池组装在德国布劳恩(Mbraun,Unilab)手套箱中进行，充满99.9％高纯氩气。采用深圳科晶MSK-110小型液压纽扣电池封装机。负极是纯度99.99％直径15.8毫米的高纯锂片，隔膜为厚度16微米美国ENTEKLP16型PE隔膜，电解液为EC：DMC：EMC(30:30:40，质量百分比)，加入电解液EC、DMC和EMC质量总量1％VC，1.3MLiPF6。扣式电池电化学循环伏安测试在上海晨华仪器有限公司CHI604E型恒电位上进行，电压扫速是0.1mV/s，扫描范围0～2V，对电极和参比电极是锂片。扣式电池循环和倍率测试在武汉蓝电电子有限公司的CT2001A测试仪上进行。
实施例1生成的钛酸锂LiTi2O4和石墨烯复合材料的电化学循环伏安图见图8。
实施例1成的钛酸锂LiTi2O4和石墨烯复合材料的0.1C充放电循环曲线见图9。首次放电容量可以达到168.7mAh/g，具有较高克容量。

Claims (9)

1.一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于，包括以下步骤：
1)制备石墨烯；
2)将锂源、钛源和石墨烯均加入有机溶剂和水的混合溶液中，得到悬浊液；在悬浊液中加入碳源，混合均匀，制备得到凝胶溶液；
3)将凝胶溶液在真空或保护气体氛围中煅烧，制备得到钛酸锂LiTi2O4和石墨烯复合材料。
2.根据权利要求1所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤2)中所述的锂源包括碳酸锂和醋酸锂中的一种或两种。
3.根据权利要求1所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤2)中所述的钛源包括四氯化钛和钛酸四丁酯的一种或两种。
4.根据权利要求1所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤2)中所述的有机溶剂包括乙醇、丙醇、异丙醇、丁醇、异丁醇、丙酮、二乙醇胺、三乙醇胺中的一种或多种。
5.根据权利要求1所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤2)中所述的碳源包括天然石墨、人造石墨和碳黑导电剂SP的一种或多种。
6.根据权利要求1-5之任一所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤2)中所述的碳源中的碳元素和钛源中的钛元素的摩尔比M，满足0.5≤M<2。
7.根据权利要求6所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：步骤3)中所述的煅烧条件为：在真空或保护气体氛围中，以2～10℃/分钟的速度升温到350～950℃，并在此温度下保持2～30小时，反应结束后在真空或保护气体氛围中自然冷却至室温。
8.根据权利要求7所述的一种钛酸锂LiTi2O4和石墨烯复合材料的制备方法，其特征在于：所述保护气体为氮气、氦气和氩气的一种或多种。
9.权利要求1-8之任一项所制备的钛酸锂LiTi2O4和石墨烯复合材料在锂离子二次电池中的应用。
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