CN101918317B - 用于锂离子电池的负极材料 - Google Patents
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- 229910001416 lithium ion Inorganic materials 0.000 title description 6
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Abstract
本发明涉及锂电池、二次电池或蓄电池,更具体地,涉及用于可充电电池负极的活性材料。更具体地,本发明涉及包含通式Li2+v-4cCcTi3-wFexMyM′zO7-α的相的材料,其中M和M′为在氧八面体环境中离子半径为0.5~0.8
Description
本发明涉及锂电池、二次电池(accumulator)或蓄电池(battery),更具体地,涉及用于可充电电池负极的活性材料。
为了满足需求,设计锂离子型电池用于需要更高的功率和能量的新用途(便携式电子仪器、无线工具、混合动力车辆)。所述锂离子型电池在其循环同时的使用寿命期间及在长时间内应当是稳定的。最后,它们应当满足与安全性和环境保护相关的社会要求。
通常将石墨用作锂离子蓄电池的负极。然而,认为因为锂钛酸盐氧化物(斜方锰矿(ramsdellite),Li2Ti3O7)的电化学性能以及其低的制造成本和其无毒性,所以它是一种有前途的材料。这种负极材料在比碳的电压高的电压(>1V)下起作用,从而以此方式确保了更好的功能安全性。而且,其比石墨较少发生极化(即充放电之间的电位差),因而导致其自身用于需要高功率的用途。然而,这种材料的容量相对低,在低模式(C/15)时达到约130Ah/kg,在高模式(1C)时达到100Ah/kg,但其具有在快速模式循环期间具有优异可逆性的优点。
首先,通过由Fe3+取代Ti4+的一部分,从而提高了这种Li2Ti3O7的容量和电流密度。然后,按照EP-1623473的教导,通过利用如下元素中的一种或多种进行补充取代,在低模式下的可逆容量现在可以达到140Ah/kg:Ti3+、Co2+、Co3+、Ni2+、Ni3+、Cu2+、Mg2+、Al3+、In3+、Sn4+、Sb3+、Sb5+。这些取代还使得可以降低合成温度,从而降低制造成本。
首先,本发明提出了改进取代的斜方锰矿,从而得到提高的比容量,同时保持了现有多取代产物的其它性能。
本发明更精确地涉及满足前述要求的负极材料。
本发明涉及用于锂电池电极的活性材料,所述活性材料包含具有通式Li2+v-4cCcTi3-wFexMyM′zO7-α的相,其中M和M′为在八面体氧环境中离子半径为0.5~0.8的2~15族金属离子,v、w、x、y、z和α通过保证电中性的如下关系关联:2α=-v+4w-3x-ny-n′z,其中n和n′为M和M′各自形式氧化度;-0.5≤v≤+0.5;y+z>0;x+y+z=w;0<w≤0.3;其特征在于,按照关系0<c≤(2+v)/4,至少一部分锂被碳取代。
M和M′离子可以选自Ti3+、Co2+、Co3+、Ni2+、Ni3+、Cu2+、Mg2+、Al3+、In3+、Sn4+、Sb3+和Sb5+。M优选为Ni2+,M′优选为Al3+。
在x≤0.1、y≤0.2以及z≤0.1时获得最佳结果。而且,在1∶3.9~4.1∶0.90~1.10的范围内选择x∶y∶z之比是有用的。更主张满足c≥0.1,优选c≥0.2。
本发明的另一个目的涉及一种合成上述活性材料的方法,其包括如下步骤:
-对含有元素Li、Ti、Fe、C、O、M和M′的前体化合物进行反应性混合和研磨;
-通过在950~1050℃的温度下在惰性气氛中对所述混合物进行加热来合成陶瓷相;
-将所述陶瓷相快速冷却。
不言而喻,本领域技术人员能够确定各种反应物的合适量,从而使合成的产物对应于如上所述期望相的通式。
在该方法期间,从合成温度以至少100℃/分钟进行陶瓷相的冷却直至不超过400℃是有用的。
本发明还涉及上述活性材料用于制造锂电池、二次电池或蓄电池的用途。
最后,本发明涉及含有上述活性材料的锂电池、二次电池或蓄电池。
本发明的材料具有可以达到190Ah/kg或602Ah/m3的质量容量和体积容量,也就是说比现有技术的质量容量和体积容量大,同时保持了先前获得的优点,特别是:
-2~10Ah/kg的小的第一循环容量损失;
-优异的循环性能;
-在C/15模式下30~70mV的低极化。
所述斜方锰矿结构由网络构成,所述网络包含八面体氧环境中的Ti和Li离子以及被四面体环境中的Li原子部分占据的通道。这种排列在通道内留下了大量空的四面体位点,且Li/空位分布可以随着合成条件而变化。取代金属占据网络的八面体位点。
此处证明,可以用碳部分或全部地取代锂,从而形成锂低的改性的斜方锰矿。由常规符号□2+w-v-(x+y+z)+3c表示的特定数量的插入位点与通式Li2+v-4cCcTi3-wFexMyM′zO7-α相对应。这种改性有利于占据这些位点,因此提高了原始材料的容量。然而,不排除作为复合材料、特别是参数c的值高的复合材料的合成材料。因此,合成材料包含Li低的含碳的斜方锰矿相,且视情况也可以为富集Li的不含碳的斜方锰矿。
应当注意,四面体锂被碳取代,所述碳构成CO3 2-基团,同时布置在3个氧的平面内,空位数目于是取决于上面通式中v、x、y、z和c的值。为了限制用C取代Li的值,所述相没有结构锂。应当注意,任何过量的碳优选在晶界处析出并可能提高材料的导电性。
本发明方法的第一步骤包含化合物的反应性混合物。
选择细粉末形式的固体前体并进行混合。这种混合物优选包含Ti和Fe的氧化物,以及金属M和M′的氧化物。其它前体同样是合适的,这些物质可以为能够通过缩合或水解/缩合而形成Me-O-Me键(其中Me为金属)的有机和/或无机化合物。例如,可以提及氧化物、碳酸盐、乙酸盐、氢氧化物、氯化物(如AlCl3)、硝酸盐、Me-氧醇盐,这并不是穷举,本领域技术人员会清楚如何完成它。关于锂,可以由另一种前体如氧化物、氢氧化物或氯化物提供。然而,优选Li2CO3。
所述混合物还包括碳或碳的前体,所述碳的前体为最简单的含碳水化合物的相如糖类或糖类的衍生物,例如葡萄糖、果糖、蔗糖、抗坏血酸,和与糖类的缩合物相对应的多糖如淀粉、纤维素和糖原。
前体混合物中各种金属的比例与所研究材料的化学计量比相对应,从而形成复合材料。考虑因氧化而造成CO和CO2的损失来计算碳的比例。如果期望在晶界处有过量碳,则可以增大该比例。
本发明方法的第二步骤包含热处理。
根据本发明,在受控气氛(例如N2、Ar)中进行热处理。在可能为980℃~1050℃的温度下,优选在1小时30分钟~2小时内进行热处理,从而获得良好的结晶性以及受限的粒度。可以以单一的快速步骤进行达到反应平台的升温,因为其使得可以最小化二次反应和不期望的钛酸盐的形成。
最后的步骤由对所述材料进行快速冷却构成。
所述制造方法在整体上是快速的且运行成本降低。
附图说明
图1:在不含碳(a)以及相对于每摩尔合成材料各种碳含量为0.14(b)摩尔、0.27(c)摩尔和0.68(d)摩尔的条件下,用Fe、Ni和Al取代的材料Li2Ti3O7的扫描电子显微照片。
图2:在不含碳(a)以及相对于每摩尔合成材料各种碳含量为0.14(b)摩尔、0.27(c)摩尔和0.68(d)摩尔的条件下合成的用Fe、Ni和Al取代的各种材料之间红外光谱带的比较。
图3:在不含碳(a)以及相对于每摩尔合成材料碳含量为0.27(b)摩尔的条件下,用Fe、Ni、Al取代的材料Li2Ti3O7在C/15模式下的充电/放电恒电流曲线。
图4:在C/15和1C模式下,活性材料以Ah/kg计的比容量作为以相对于每摩尔合成材料的摩尔数计的碳量的函数。
比较例1
实施例1涉及按照通式Li2+v-4cCcTi3-wFexNiyAlzO7-α、被三种元素Fe、Ni、Al取代而未被碳取代的斜方锰矿Li2Ti3O7,其中c=0,v=-0.14,w=0.15,x=0.025,y=0.1,z=0.025。在7中利用玛瑙球对化合物Li2CO3(0.7235g)、纳米尺寸的锐钛矿TiO2(1.2028g)、Fe2O3(0.021g)、NiO(0.0393g)和最后的Al2O3(0.0134g)进行反应性研磨(持续15分钟;速度8),球的重量/产物的重量之比等于10。在Ar中于舟皿内以单一步骤进行热处理。施加7℃/分钟的升温直至合成温度980℃,将该温度保持1小时30分钟。在氩气中进行快速冷却,从而确定高温结构。
实施例2~4
实施例2~4涉及按照通式Li2+v-4cCcTi3-wFexNiyAlzO7-α,被三种元素Fe、Ni、Al并且被碳取代的斜方锰矿Li2Ti3O7,其中v=-0.14,w=0.15,x=0.025,y=0.1,z=0.025,0.1≤c≤0.465。添加蔗糖作为碳前体,按合成之前称量的总重量计为5、10和15wt%。参考表1的各种碳含量。在7中利用玛瑙球对化学计量的量的化合物Li2CO3、纳米尺寸的锐钛矿TiO2、Fe2O3、NiO、Al2O3进行反应性研磨(持续15分钟;速度8),球的重量/产物的重量之比等于10。按实施例1中进行热处理。
表1实施例1~4中碳含量的总结
蔗糖(%)合成之前 | C的总量(%)合成之后 | C的总量(摩尔/摩尔)合成之后 | 取代的C(参数c)合成之后 | |
实施例1(*) | 0 | 0 | 0 | 0 |
实施例2 | 5 | 0.63 | 0.14 | 0.14 |
实施例3 | 10 | 1.25 | 0.27 | 0.27 |
实施例4 | 15 | 2.95 | 0.68 | 0.465 |
(*)比较例
图1显示了各种合成例的扫描电子显微照片。实施例1不含碳的基材显示了(a)具有多孔织构的直径为10~20μm的聚集体。通过用实施例2~4的各种碳含量来取代斜方锰矿相,观察到了形态和织构的变化(b~d),从而产生了粒子和细丝的附聚物。根据实施例4,碳为0.68摩尔,在晶界处出现了碳的剩余物(d),从而导致在合成期间这种元素过量。事实上应当注意,能够插入v=-0.14的斜方锰矿结构中的最多碳为0.465摩尔/摩尔,即参数c的值为0.465。
图2的IR谱图(b~d)显示,对于根据实施例2~4制备的产物,在1430~1500cm-1之间存在振动带,这是基团CO3 2-的特征。这确认了在斜方锰矿结构中碳的取代。根据实施例4制备的产物(d)也显示了接近1650cm-1的振动带。这些与属于表面碳的共轭C-C带相对应。
在两个电极中的负极为金属锂垫圈的半电池进行电化学试验。正极包含85wt%的活性材料、5wt%的炭黑和10wt%的PTFE粘合剂的混合物。使用的电解质为在碳酸亚乙酯、碳酸二甲酯和碳酸亚丙酯(1∶3∶1)中的LiPF6(1M)。在C/15和1C模式下,在相对于Li/Li+为1~2.5V之间,于25℃下以恒电流模式进行循环。
图3(a)显示了根据实施例1制备的不含碳的材料的充放电曲线(相对于Li)。图3(b)对应于实施例3含有碳的材料。在C/15模式下,在相对于Li/Li+为1~2.5V之间,以恒流模式进行这些测量。所观察到的不含碳的材料的容量为130Ah/kg。在图3(b)中,所述曲线在1.4~2.4V之间显示了肩状部分。由于碳,提高了可逆容量值,本文中达到了180Ah/kg,其中具有8Ah/kg的低不可逆容量和67mV的低极化。
在图4中,将根据实施例1和4制备的产物的比容量值显示为在斜方锰矿相中测得的碳量的函数。在两种模式C/15和C下,所述比容量随着碳的存在而增大。在超过饱和点(c=0.465)的情况下,容量不再提高,超过所述饱和点在材料表面上发现了过量的碳。
Claims (11)
1.一种用于锂电池电极的活性材料,其包含具有通式Li2+v-4cCcTi3-wFexMyM′zO7-α的相,其中M和M′为在氧八面体环境中离子半径为的元素周期表中的2~15族金属离子,v、w、x、y、z和α通过如下关系式关联:
2α=-v+4w-3x-ny-n′z,其中n和n′为M和M′各自的形式氧化度;
-0.5≤v≤+0.5;
y+z>0;
x+y+z=w;且0<w≤0.3;
其特征在于,按照关系式0<c≤(2+v)/4,至少一部分锂被碳取代。
2.如权利要求1所述的活性材料,其特征在于,M和M′选自:Ti3+、Co2+、Co3+、Ni2+、Ni3+、Cu2+、Mg2+、Al3+、In3+、Sn4+、Sb3+和Sb5+。
3.如权利要求1或2所述的活性材料,其特征在于,M为Ni2+,M′为Al3+。
4.如权利要求1所述的活性材料,其特征在于,
x≤0.1;
y≤0.2;以及
z≤0.1。
5.如权利要求1所述的活性材料,其特征在于,x∶y∶z之比在1∶3.9~4.1∶0.90~1.10的范围内。
6.如权利要求1所述的活性材料,其特征在于,c≥0.1。
7.如权利要求1所述的活性材料,其特征在于,存在由碳构成的相。
8.一种合成权利要求1~7中任一项的活性材料的方法,所述方法包括如下步骤:
-对含有元素Li、Ti、Fe、C、O、M和M′的前体化合物进行反应性混合和研磨;
-通过在950~1050℃的温度下在惰性气氛中对所述混合物进行加热来合成陶瓷相;
-将所述陶瓷相快速冷却。
9.如权利要求8所述的合成活性材料的方法,其特征在于,从合成温度以至少100℃/分钟进行所述陶瓷相的冷却,直至不超过400℃。
10.权利要求1~7中任一项的活性材料用于制造锂电池或蓄电池的用途。
11.一种锂电池或蓄电池,其含有权利要求1~7中任一项的活性材料。
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