CN106602052B - 一种锂离子电池负极材料及其制备方法 - Google Patents

一种锂离子电池负极材料及其制备方法 Download PDF

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CN106602052B
CN106602052B CN201611236059.6A CN201611236059A CN106602052B CN 106602052 B CN106602052 B CN 106602052B CN 201611236059 A CN201611236059 A CN 201611236059A CN 106602052 B CN106602052 B CN 106602052B
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孙陈
李星
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Abstract

本发明公开了一种锂离子电池负极材料及其制备方法，本发明将钠盐、钡盐、锶盐、锂盐、钛盐按一定比例混合，经球磨、烘干、研磨、烧结合成制备新的锂离子电池负极材料，其化学式Na0.5Ba0.25Sr0.5Li2Ti6O14，并研究了其电化学性能和储锂性能。电化学实验证明本方法制备的复合材料具有优异的物理化学性能，作为锂离子电池负极材料具有广阔的应用前景。在整个制备过程中，合成方法简单，易于操作，材料制备成本低，设备投资少，适合批量生产。

Description

一种锂离子电池负极材料及其制备方法
技术领域
本发明属于材料化学领域，具体涉及一种新型锂离子电池负极材料及其制备方法，特别是涉及对钛酸钠锂电池负极材料进行钡、锶离子的掺杂及其制备方法。
背景技术
锂离子电池由于其具有工作电压高，质量轻，比能量大，自放电小，循环寿命长，无记忆效应，无环境污染等突出优点，成为电子装置小型轻量化的理想电源，也是未来汽车高能动力电池的首选电源。负极材料是锂离子电池中的主要组成部分之一，负极性能的好坏直接影响到锂离子电池的性能。Na2Li2Ti6O14作为一种潜在的锂离子电池负极材料具有较低的放电电压平台、较好的离子电导率、较高的理论容量、充放电时不会形成SEI膜等优点，因此该材料与正极材料组装成电池可以获得高输出电压、安全、循环寿命长的锂离子电池，且有望满足电动汽车动力需求。但是Na2Li2Ti6O14负极材料的大倍率性能较差。
为使得电化学性能得以提高，研究者们提出了许多改进的措施，其中最普遍的做法是纳米化、可导电层包覆和离子掺杂。离子掺杂因其合成原料丰富、合成过程简便、无需进行后续处理等优点，成为众多研究者选择的改性措施。掺杂是目前提高负极材料导电性、减小极化程度，改善其倍率放电性能行之有效的方法之一。为解决Na2Li2Ti6O14负极材料倍率低的问题，本发明采用对Na2Li2Ti6O14进行钡、锶离子掺杂，通过掺杂合成新的物质Na0.5Ba0.25Sr0.5Li2Ti6O14去改善钛酸钠锂电池负极材料的电化学性能。
钛酸锂材料的合成方法主要有固相法，溶液化学法、均相沉淀法、溶胶-凝胶法和气相法等。固相反应法是制备钛酸锂盐的传统方法之一，并且固相法原理和工艺简单，易于实现工业化生产。本发明是将原料混合后经过球磨处理后再焙烧的方法制备。原料经过球磨处理后焙烧制备的样品为纯相的钛酸锂盐，表明球磨可以提高原料混合的均匀度，产物的粒径分布也更加均匀。
发明内容
本发明所要解决的技术问题是通过对钛酸钠锂电池负极材料Na2Li2Ti6O14进行钡、锶掺杂制备新的电池材料Na0.5Ba0.25Sr0.5Li2Ti6O14。
本发明为解决上述技术问题所采取的技术方案为：一种锂离子电池负极材料，该锂离子电池负极材料的化学式为Na0.5Ba0.25Sr0.5Li2Ti6O14。
在本发明中，该锂离子电池负极材料的首次放电比容量为160mAh g-1，嵌锂电位为1.390～1.420V。
进一步的，本发明还提供了所述的锂离子电池负极材料Na0.5Ba0.25Sr0.5Li2Ti6O14的制备方法，包括以下步骤：
(1)将钠盐、钡盐、锶盐、锂盐和钛盐按钠、钡、锶、锂、钛摩尔比Na:Ba:Sr:Li:Ti＝2:1:2:8:24用溶剂均匀混合，形成混合物A；
(2)将混合物A放入玛瑙罐中进行球磨混合5～15h，形成混合物B；
(3)将混合物B放在70～100℃的烘箱里烘干10～20h，形成物质C；
(4)将物质C放在玛瑙研钵将其研细，将研细后的材料放在马弗炉，以1～10℃/min的升温速度升温至500℃～800℃，恒温1～6h，经过充分反应后再以1℃～10℃/min的升温速度升温至800℃～1000℃，保温反应3～5h后冷却至室温，得到纯相得Na0.5Ba0.25Sr0.5Li2Ti6O14。
优选地，所述的溶剂为丙醇、乙醇、甲醇中的一种或者任意组合。
优选地，所述的钠盐为氯化钠、碳酸钠、三水醋酸钠中的一种或者任意组合。
优选地，所述的钡盐为氯化钡、碳酸钡、硝酸钡中的一种或者任意组合。
优选地，所述的锶盐为氯化锶、硝酸锶中的一种或者任意组合。
优选地，所述的锂盐为硝酸锂、碳酸锂、氯化锂中的一种或者任意组合。
优选地，所述的钛盐为锐钛矿、金红石、无定形钛矿的一种或者任意组合。
本发明通过对Na2Li2Ti6O14进行钡、锶离子掺杂的方法获得新的复合材料Na0.5Ba0.25Sr0.5Li2Ti6O14作为锂离子电池的负极材料并测其化学性能，充放电测试表明，此复合材料有比Na2Li2Ti6O14有更高首次放电比容量和较好的容量保持率，首次放电比容量为160mAh g-1，100次循环后，容量保持率不低于80％。
附图说明
图1是实施例1所制得的Na0.5Ba0.25Sr0.5Li2Ti6O14材料的XRD图；
图2是实施例1所制得的Na0.5Ba0.25Sr0.5Li2Ti6O14材料的SEM图；
图3是实施例1所制得的Na0.5Ba0.25Sr0.5Li2Ti6O14材料作为电极材料组装的锂离子电池的效率充放电比容量图。
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。
实施例1
称取氯化钠(1.4040g，0.024mol)，氯化钡(2.4987g，0.012mol)，氯化锶(3.8041g，0.024mol)，硝酸锂(6.6192g,0.096mol)，无定形二氧化钛(23.0014g，0.288mol)放在玛瑙球磨罐中，用甲醇做溶剂，球磨5h，将磨好的混合物放入70℃的烘箱里干燥20h，将干燥好的物质放在玛瑙研钵里充分研细，放在马弗炉以1℃/min的升温速度升温至500℃，保温反应6h后再以4℃/min的升温速度升温至1000℃，保温反应3h，反应结束后自然冷却至室温，得到复合材料；通过测定粉末衍射(XRD)确定其纯度，如图1所示；用扫描电镜(SEM)观察所述复合材料的形貌，如图2所示；在充满氩气的手套箱中组装模拟电池，测其电化学性能，如图3所示。
实施例2
称取三水醋酸钠(0.8165g，0.006mol)，硝酸钡(0.7507g，0.003mol)，硝酸锶(1.2698g，0.006mol)，碳酸锂(1.7734g，0.024mol)，锐钛矿型二氧化钛(1.4040g，0.072mol)放在玛瑙球磨罐中，用乙醇做溶剂，球磨10h，将磨好的混合物放入80℃的烘箱里干燥15h，将干燥好的物质放在玛瑙研钵里充分研细，放在马弗炉以5℃/min的升温速度升温至600℃，保温反应4h后再以10℃/min的升温速度升温至800℃，保温反应5h，反应结束后自然冷却至室温，得到所述复合材料；通过测定粉末衍射(XRD)确定其纯度；用扫描电镜(SEM)观察所述复合材料的形貌；在充满氩气的手套箱中组装模拟电池，测其电化学性能。
实施例3
称取碳酸钠(1.2720g，0.012mol)，碳酸钡(1.1820g，0.006mol)，硝酸锶(1.26982.5396g，0.012mol)，氯化锂(2.0754g，0.048mol)，金红石二氧化钛(11.5012g，0.144mol)放在玛瑙球磨罐中，用丙醇做溶剂，球磨15h，将磨好的混合物放入90℃的烘箱里干燥10h，将干燥好的物质放在玛瑙研钵里充分研细，放在马弗炉以10℃/min的升温速度升温至800℃，保温反应1h后再以1℃/min的升温速度升温至900℃，保温反应4h，反应结束后自然冷却至室温，得到所述复合材料；通过测定粉末衍射(XRD)确定其纯度；用扫描电镜(SEM)观察所述复合材料的形貌；在充满氩气的手套箱中组装模拟电池，测其电化学性能。
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改和改进等，均应包含在本发明的保护范围之内。

Claims (3)

1.一种锂离子电池负极材料，其特征在于，该锂离子电池负极材料的化学式为Na0.5Ba0.25Sr0.5Li2Ti6O14。
2.根据权利要求1所述的锂离子电池负极材料，其特征在于，该锂离子电池负极材料的首次放电比容量为160mAh g-1，嵌锂电位为1.390～1.420V。
3.一种如权利要求1或2所述的锂离子电池负极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将钠盐、钡盐、锶盐、锂盐和钛盐按钠、钡、锶、锂、钛摩尔比Na:Ba:Sr:Li:Ti＝2:1:2:8:24用溶剂均匀混合，形成混合物A；
(2)将混合物A放入玛瑙罐中进行球磨混合5～15h，形成混合物B；
(3)将混合物B放在70～100℃的烘箱里烘干10～20h，形成物质C；
(4)将物质C放在玛瑙研钵将其研细，将研细后的材料放在马弗炉，以1～10℃/min的升温速度升温至500℃～800℃，恒温1～6h，经过充分反应后再以1℃～10℃/min的升温速度升温至800℃～1000℃，保温反应3～5h后冷却至室温，得到纯相得Na0.5Ba0.25Sr0.5Li2Ti6O14；
所述的溶剂为丙醇、乙醇、甲醇中的一种或者任意组合；所述的钠盐为氯化钠、碳酸钠、三水醋酸钠中的一种或者任意组合；所述的钡盐为氯化钡、碳酸钡、硝酸钡中的一种或者任意组合；所述的锶盐为氯化锶、硝酸锶中的一种或者任意组合；所述的锂盐为硝酸锂、碳酸锂、氯化锂中的一种或者任意组合；所述的钛盐为锐钛矿、金红石、无定形钛矿的一种或者任意组合。
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