CN102186775B - 涂覆碳的锂钛尖晶石 - Google Patents

涂覆碳的锂钛尖晶石 Download PDF

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CN102186775B
CN102186775B CN200980139531.6A CN200980139531A CN102186775B CN 102186775 B CN102186775 B CN 102186775B CN 200980139531 A CN200980139531 A CN 200980139531A CN 102186775 B CN102186775 B CN 102186775B
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oxide
carbon
particle
lithium
carbon coating
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CN102186775A (zh
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J·多林格
A·波尔纳
M·霍尔茨阿普费尔
N·陈
N·施尔
M·埃斯格鲁伯
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EV Metals UK Ltd
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Abstract

本发明公开了一种含碳锂钛氧化物，包含直径为1-80μm的球形粒子聚集体，所述聚集体包括涂覆碳的锂钛氧化物主要粒子。本发明还公开了用于生产前述含碳锂钛氧化物的方法、包含前述含碳锂钛氧化物的电极、活性材料、及包含前述电极的锂离子副电池。

Description

涂覆碳的锂钛尖晶石
本发明涉及覆碳的钛酸锂Li4Ti5O12及其生产方法。
钛酸锂Li4Ti5O12或简称锂钛尖晶石用作可再充电锂离子电池的阳极材料尤其用作石墨的替代物已在不久前提出。
前述电池中的阳极材料的最近概述可在下述文献中找到：Bruceetal.，Angew.Chem.Int.Ed.2008，47，2930-2946。
Li4Ti5O12相较于石墨的优点特别在于其更好的循环稳定性、更好的热负荷容量及更高的工作可靠性。相较于锂，Li4Ti5O12具有相当恒定的为1.55V的电势差并实现几千次充电和放电循环，而容量损失＜20％。
因此，钛酸锂相较于以前通常用作可再充电锂离子电池的阳极的石墨具有明显更正的电势。
然而，更高的电势也导致电压差更低。连同相较于石墨的372mAh/g(理论值)减少的175mAh/g容量，这导致相较于具有石墨阳极的锂离子电池明显更低的能量密度。
然而，Li4Ti5O12寿命长且无毒，因而也未被分类为对环境造成威胁的材料。
最近，LiFePO4已被用作锂离子电池中的阴极材料，结果是在Li4Ti5O12和LiFePO4组合的情形下可实现2V的电压差。
生产钛酸锂Li4Ti5O12的各个方面已有详细描述。通常，Li4Ti5O12通过钛化合物和锂化合物之间在超过750℃的高温下的固态反应获得，其中钛化合物通常为TiO2，及锂化合物通常为Li2CO3，如US5,545,468或EP1057783A1中所述。
用于生产Li4Ti5O12的溶胶凝胶方法也有描述(DE10319464A1)。此外，提出了借助于喷火高温分解的生产方法(Ernst，F.O.etal.MaterialsChemistryandPhysics2007，101(2-3，pp.372-378)及所谓的无水介质中的“热水方法”(Kalbac，M.etal.，JournalofSolidStateElectrochemistry2003，8(1)pp.2-6)。
由于作为电极的钛酸锂通常压到具有碳的电极上，尤其是石墨或炭黑，EP1796189A2提出了提供离位复合锂过渡金属氧化物，即在它们与含碳涂层完全合成之后。然而，该方法的缺点在于所含产品的大粒子尺寸，尤其是辅助粒子尺寸。此外，该方法中的碳涂层位于辅助粒子上而不是主要粒子上，这导致差的电化学性质，尤其是容量特性。
因此，需要提供另一锂钛氧化物，具体为钛酸锂Li4Ti5O12，其具有特别小的粒子及改善的电化学性质。
根据本发明，该目标由包含直径为1-80μm的球形(辅助)粒子集料的含碳锂钛氧化物实现，其包括涂覆碳的锂钛氧化物主要粒子。
德语“粒子”和“颗粒”在此均同义地意为粒子。
在下面，锂钛氧化物意为钛酸锂，根据本发明其包括Li1+xTi2-xO4类型的所有锂钛尖晶石，0≤x≤空间群Fd3m的1/3，通常也包括一般分子式LixTiyO的所有混合锂钛氧化物(0＜x，y＜1)。
如上所述，根据本发明的涂覆碳的锂钛氧化物包括由涂覆碳的主要粒子形成的辅助粒子。辅助粒子为球形形状。
根据本发明的辅助粒子的粒子大小导致包含根据本发明的覆碳锂钛氧化物材料的电极中的电流密度特别高，且其相较于目前技术水平的材料(具体在EP1796189A2中描述)具有高循环稳定性。
令人惊奇的是，还发现根据本发明的含碳锂钛氧化物具有1-10m2/g的BET表面积(根据DIN66134测量)，优选＜10m2/g，＜8m2/g更好，最好＜5m2/g。在最佳实施例中，典型值在3-5m2/g的范围中。
涂覆碳的主要粒子通常具有＜1μm的大小。根据本发明，主要粒子小且至少部分涂覆碳很重要，这导致包含根据本发明的锂钛氧化物的电极相较于未涂覆碳的材料或未被均匀涂覆的材料或相较于其中只有辅助粒子被涂覆的材料具有特别高的载流容量和循环稳定性。
在本发明的优选实施例中，根据本发明的锂钛氧化物的碳含量为0.05-2wt.-％，在特别首选的实施例中为0.05-0.5wt.-％。
令人惊奇的是，已发现相当低的碳含量因而相当薄的主要粒子碳涂层足以在包含根据本发明的材料的电极中致使上面提及的有利效果。
在锂钛氧化物中，首选Li4Ti5O12，因为其特别适合用作电极材料。
本发明的目标进一步由用于生产含碳锂钛氧化物的方法实现，该方法包括步骤：
(a)在溶剂中混合锂盐、氧化钛和含碳化合物；
(b)使来自步骤(a)的混合物干燥；
(c)煅烧所干燥的混合物。
根据锂盐和氧化钛的比，可获得已经在上面描述的空间群Fd3m的锂钛尖晶石Li1+xTi2-xO4或一般分子式LixTiyO的混合锂钛氧化物。
根据本发明的锂钛氧化物的最终碳含量也可在混合期间设置。
术语“溶剂”在此定义成使得起始物质的至少一成分可至少部分溶解在溶剂中，即具有至少0.5的溶度积L。该溶剂优选为水。在特别首选的实施例中，起始物质的一成分容易溶解在水中，即其具有至少10的溶度积L。
特别首选地，Li和Ti的原子比为4∶5，这导致可获得具有碳涂层的尤其纯相的Li4Ti5O12。纯相在此意为，在通常的测量准确度的限制内，通过XRD测量在金红石相中检测不到TiO2。
优选地，用于执行根据本发明的方法的锂盐选自下组：LiOH、LiNO3、Li2CO3、Li2O、LiHCO3、和乙酸锂，因为其它起始化合物可添加到其中的水溶液可特别容易地从这些起始化合物制造。
优选地，使用锐钛矿形式或非晶形形式的TiO2，其在根据本发明的方法中有利地不变为金红石。
适合执行根据本发明的方法的含碳化合物例如选自：碳氢化合物，例如多环芳烃及其化合物、二萘嵌苯及其化合物、聚合物和共聚物，如聚烯烃、粉末形式的聚丙烯共聚物、苯乙烯-聚丁二烯嵌段共聚物、糖及其衍生物。特别首选的聚合物为聚烯烃、聚丁二烯、聚乙烯醇、来自酚的浓缩产品、源自糠基的聚合物、苯乙烯衍生物、二乙烯基苯衍生物、萘酚二萘嵌苯、丙烯腈和乙酸乙烯、白明胶、纤维素、淀粉及其酯和醚及其混合物。
选择糖已证明对于执行根据本发明的方法尤其首选，因为这些糖特别好地溶解在水中。在糖中，首选乳糖、砂糖、蔗糖，尤其首选乳糖。
干燥步骤(b)通常以所谓的喷雾干燥形式进行，其中所获得的混合物通过喷嘴进行微细喷雾并沉淀为预聚物的形式。然而，也可使用其中起始化合物均匀混合然后引入气流中进行干燥的任何其它方法。除了喷雾干燥之外，例如这些方法还可以是流化床干燥、滚动选粒及干燥或制冷干燥或其组合。首选喷雾干燥及其通常在从90到300℃的温度梯度下进行。
在获得步骤(a)的含水混合物的干燥产品之后，其还有利地避免了目前技术水平的其它方法的溶剂间题，所获得的喷雾干燥的预聚物在从700到1000℃的温度进行煅烧，优选在保护气氛下进行，以避免在煅烧期间出现可导致不希望的结果的可能辅助反应，例如碳涂层的氧化。适当的保护性气体例如为氮、氩等或其混合。
本发明还涉及可通过根据本发明的方法获得的锂钛氧化物，其特征在于特别小的BET表面积、主要粒子的粒子尺寸小、及由主要粒子形成的辅助粒子的粒子尺寸小，这些特征已在上面描述。
本发明的问题进一步由包含根据本发明的涂覆碳的锂钛氧化物的电极解决。优选地，该电极为阳极。具体地，在此已发现前述电极在1C和4C之间具有＞85％的容量比及在锂离子副电池中在C/10具有至少165mAh/g的放电容量。
本发明在下面结合实施例和附图进行详细描述，然而，这些实施例和附图并不视为限制。
在附图中：
图1为根据本发明的涂覆碳的Li4Ti5O12的SEM显微图。
图2为包含根据本发明的(原位)覆碳钛酸锂的电极的充电和放电容量图。
图3为用作比较的、离位涂覆的钛酸锂的充电和放电容量。
图4为随后(离位)覆碳的Li4Ti5O12的SEM显微图。
图5为无涂层的Li4Ti5O12的SEM显微图。
图6为无涂层的Li4Ti5O12的充电和放电容量；在充电期间和放电期间电流一样。
实施例
1、概述
LiOH·H2O及锐钛矿形式的TiO2在下面用作起始产品。在商用(来自Merck)的情形下，水含量在批次之间不同并在合成前确定。
LiOH/TiO2/乳糖的悬浮液在30-35℃下产生，其通过首先将LiOH·H2O溶解在水中然后在搅拌的同时添加锐钛矿形式的TiO2及乳糖进行。
例1
生产根据本发明的钛酸锂(Li4Ti5O12)
9.2kgLiOH·H2O溶解在45l水中，然后添加20.8kgTiO2。之后添加不同数量的乳糖。乳糖的数量有更多的变化，为改变根据本发明的钛酸锂中的碳数量，执行30g乳糖/kgLiOH+TiO2、60g乳糖/kgLiOH+TiO2、90g乳糖/kgLiOH+TiO2等批次。
令人惊奇的是，发现乳糖对降低初始悬浮液的粘性有作用，这导致相较不添加乳糖的情形，在生产相应悬浮液时少用25％的水。之后，该混合物在Nubilosa喷雾干燥器中进行喷雾干燥，起始温度为约300℃，及结束温度为100℃。
首先形成几微米级的多孔球形聚集体。
然后，按这种方式获得的产品在氮气氛下在800℃煅烧一小时。获得聚集的主要粒子(主要粒子的粒子大小＜1μm)的大(1-80μm)聚集体。
图1示出了根据本发明的涂覆碳的钛酸锂，具有0.2wt.％的总碳含量(60g乳糖/kgLiOH+TiO2)，而图5示出了也借助于喷雾干燥获得的无涂层的钛酸锂。在根据本发明的方法的起始产品中含碳化合物用作烧结孵化器并导致明显更小的粒子。
比较例子
无涂层的钛酸锂根据例1的方法产生，即不添加乳糖。
因此，所获得的及所煅烧的钛酸锂进而浸入乳糖溶液3小时并在750℃加热3小时(参见EP1796198A2)。该产品的SEM显微图如图4中所示并示出了相较于根据本发明的图1的产品更粗的粒子，这些更粗的粒子不是由大小＜1μm的主要粒子组成，而是烧结在一起的更大的主要粒子。此外，比较例子的辅助粒子具有“模糊”涂层。碳含量同样约为0.2wt.％。
之后，对根据本发明的材料和对比较例子的材料执行充电/放电循环，即对随后涂覆钛酸锂(根据EP1796198A2)及对无涂层的钛酸锂进行，二者均通过同样的方法获得。
每一情形下的阳极包括85％的活性材料、10％的超P炭黑和5％的PVDF21256粘合剂。测量针对根据本发明的材料或比较材料作为半电池中的阳极进行，与金属锂相比较。电极的有效质量含量为2.2mg/cm2。循环中覆盖的范围为1.0-2.0伏特。图2示出了根据本发明的涂覆碳的钛酸锂的充电/放电曲线，其中1C和4C之间的容量比为87.5％；在充电期间和放电期间电流一样。
相较于无涂层的钛酸锂，根据图6，可观察到明显的稳定性，其具有82％的相应容量性能。
同样，相较于离位涂覆的钛酸锂(图3)，其中在4C时测量到仅75％的容量，可见根据本发明的材料更好。电流在充电期间和放电期间一样。
因此，结果表明根据本发明的原位涂覆碳的钛酸锂相较于随后施加碳涂层或无涂层的钛酸锂在容量比方面具有重要优点。

Claims (4)

1.用于生产含碳锂钛氧化物的方法，所述含碳锂钛氧化物包含直径为1-80μm的球形粒子聚集体，所述聚集体包括涂覆碳的锂钛氧化物主要粒子，所述方法包括步骤：
(a)在水中混合锂盐、氧化钛和含碳化合物，其中所述锂盐选自下组：LiOH、Li2O、LiNO3、LiHCO3、LiCH3COO；
(b)对来自步骤(a)的混合物进行喷雾干燥；
(c)在保护气氛下在从700到1000℃的温度下煅烧步骤(b)中获得的干燥后的混合物；
其中所述含碳化合物选自下组的糖类：乳糖和蔗糖。
2.根据权利要求1的方法，其中Li/Ti的原子比设为4:5。
3.根据权利要求2的方法，其中使用锐钛矿形式或非晶形形式的TiO2。
4.根据权利要求1或3的方法，其中所述喷雾干燥在从90到350℃的温度梯度下进行。
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US20110217593A1 (en) 2011-09-08
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TW201024222A (en) 2010-07-01
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US20140175687A1 (en) 2014-06-26
CA2738853A1 (en) 2010-04-15
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JP2012505137A (ja) 2012-03-01
EP2349931B1 (de) 2018-12-05
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