CN101542787A - 用于锂离子电池的阳离子取代的尖晶石氧化物和氟氧化物阴极 - Google Patents
用于锂离子电池的阳离子取代的尖晶石氧化物和氟氧化物阴极 Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
本发明包括阳离子取代的、氟取代的尖晶石阴极组合物及其制备方法，所述制备方法包括将LiMn2－y－zLiyMzO4氧化物与NH4HF2在大约300－700℃的低温下烧制2－8小时，其中η大于0且小于大约0.50，将由尖晶石阴极和层状氧化物阴极组成的两相混合物混合，并将它们与未经改性或经表面改性的石墨阳极在锂离子电池中结合。
Description
发明的技术领域
本发明一般地涉及锂离子阴极材料领域，更具体地，涉及具有氟化物离子取代氧化物离子的阳离子取代的尖晶石氧化物阴极。
背景技术
不限制本发明的范围，描述与锂离子电池相关的背景。
通常，锂离子电池将锂离子在阳极与阴极间运输，且同时对主体电极分别进行氧化或还原。本领域中普通的阴极材料包括含有锂的过渡金属氧化物如层状氧化钴锂(LiCoO2)、尖晶石氧化锰锂(LiMn2O4)和橄榄石磷酸铁锂(LiFePO4)。例如，锂离子电池利用层状氧化钴锂阴极；然而，由于其钴含量，这些材料昂贵且对环境不利。因此，正在开发具有期望的放电容量和放电电压的供选择材料作为电极，所述放电容量与可以可逆萃取(extract)的锂的量有关，所述放电电压取决于过渡金属离子和晶体结构。
例如，通常的电极材料包括分别包含Mn和Fe的尖晶石LiMn2O4和橄榄石LiFeO4，且因此便宜且对环境有利。然而，尖晶石LiMn2O4阴极在高温下受严重的容量衰减影响1-7。尖晶石电极在电池环境中不稳定，并且当在高于室温的温度下运行时尤其不稳定。
容量衰减通常被认为是由于锰从晶格中溶解至电解质溶液中并随后进入碳阳极中。已经研究了通过阳离子取代来实现的供选择的尖晶石组合物，但是它们不能完全克服容量衰减问题。
此外，合成尖晶石结构的方法和化学取代会导致局部缺陷和微观结构差异，这会影响包括容量保持(capacity retention)、倍率(功率)性能和储存特性的电化学性能因素。
例如，于1997年10月7日授予Amatucci等人的标题为“LithiumManganese Oxy-Fluorides for Li-Ion Rechargeable Battery Eletrodes”的第5,674,645号美国专利(‘645专利)。‘645专利公开了利用具有通式Li1+xMyMn2-x-yO4-zFz的氟氧化锰锂电极组分嵌入材料来改进Li离子可充电电池的容量和循环稳定性，所述通式中M为过渡金属，例如Co、Cr或Fe。
相似地，授权给Sugiyama等人的标题为“Positive Electrode Material forSecondary Lithium Battery”的第6,087,042号美国专利公开了高温循环特性优异的用于二次锂电池的正电极材料，其为具有尖晶石结构的氟氧化锰锂，其中氟氧化物具有由组合物通式Li1+xMn2-xO4-yFz表示的组合物，其中x表示0.0133-0.3333的数字；y表示0-0.2的数字(不包括0)，而z表示0.01-0.2的数字(不包括0.01)，条件是：(y-z)大于0但不大于0.07。用于二次锂电池的正电极材料据说不仅显示了充电/放电的高循环耐久性，而且还显示了充电/放电起始容量的最小下降以提供高能量密度。
发明内容
本发明人认识到，制备氟取代的氟氧化物组合物的现有方法是不足的，因为它们没有教导本发明的组合物，且不能用于掺入期望的氟含量以制备本发明的组合物。
本发明人认识到，可以通过适当的阳离子取代，减小在循环期间形成的两个立方相间的晶格参数差Δa来显著改进高温下的循环能力、倍率性能和储存特性8-11。然而，阳离子取代通常导致可逆容量值的降低，这会使得阳离子取代的尖晶石组合物对于实际应用而言没有吸引力。
本发明人认识到，在阳离子取代的尖晶石氧化物阴极中用氟化物离子取代氧化物离子，由于降低了Mn的氧化态而提高了可逆容量。此外，本发明人认识到，可以通过适当的阳离子取代，减小在循环期间形成的两个立方相间的晶格参数差Δa来显著改进高温下的循环能力、倍率性能和储存特性。
本发明人认识到，在保持其它电化学性能特征的同时，需要提高可逆容量。本发明人在阳离子取代的尖晶石氧化物中用氟化物离子部分取代氧化物离子，以获得相应的尖晶石氟氧化物阴极。为了使尖晶石晶格中的氟含量最大化，本发明人开发了一种低温工序，包括将已经合成的阳离子取代的尖晶石氧化物LiMn2-y-zLiyMzO4与氢氟化铵(NH4HF2)在450℃的低温下进行短时间烧制。
本发明提供了通过将LiMn2-y-zLiyMzO4氧化物与NH4HF2在大约200-700℃的温度范围下烧制2-8小时以形成阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石氧化物结构来制备氟取代的氟氧化物组合物的方法。通常，M可以为Mg、Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn或其组合。掺入阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石结构的尖晶石晶格中的氟在大约η＝0到η＝0.30之间。具有阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石结构的组合物的一些具体的非限定性实例包括LiMn1.8Li0.2O3.88F0.12、LiMn1.8Li0.2O3.79F0.21、LiMn1.8Li0.1Ti0.1O3.9F0.1、LiMn1.8Li0.1Cu0.1O3.9F0.1、LiMn1.8Li0.1O3.9F0.1、或LiMn1.8Li0.1Ni0.1O3.8F0.2。
本发明还提供了具有尖晶石晶体结构的阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物的锂阴极组合物。M可以为Mg、Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn或其组合。
此外，本发明提供了通过将LiMn2-y-zLiyMzO4-ηFη组合物与导电稀释剂和粘合剂混合以形成阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物来制备尖晶石阴极的方法。然后可以将该阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物成形为阴极形状，例如，通常为圆柱形或通常为圆盘形。
尖晶石阴极的一个实例包括阴极混合物重量的大约1-10％的粉末状聚四氟乙烯粘合剂，阴极混合物重量的大约5-25％的乙炔黑导电稀释剂，以及阴极混合物重量的大约70-95％重量的LiMn2-y-zLiyMzO4-ηFη粉末组合物。
本发明还提供了由尖晶石和层状氧化物组成的混合阴极。该阴极包括阳离子取代的尖晶石氧化物材料和层状氧化物材料的混合物。在一些情况下，阳离子取代的尖晶石氧化物材料还为氟取代的，例如LiMn2-y-zLiyMzO4- ηFη，其中y在大约0-大约0.3的范围内，z在大约0-大约1.0的范围内，而η在大约0-大约0.5的范围内。该混合物可以含有大约20重量％-95重量％的阳离子取代的尖晶石氧化物或氟氧化物和大约80重量％-大约5重量％的层状氧化物材料(例如，大约70重量％-大约80重量％的LiMn1.85Li0.075Ni0.04Al0.035O4和大约20重量％-大约30重量％的LiCoO2，或大约70重量％-80重量％的LiMn1.8Li0.1Ni0.1O3.8F0.2和大约20重量％-大约30重量％的LiCoO2)。
本发明还提供了具有与碳阳极表面相接触的尖晶石Li4Ti5O12或TiO2涂层的碳阳极表面改性。Li4Ti5O12和TiO2均提供有助于阳极容量的优点。本领域技术人员会认识到，也可以使用会或不会有助于容量的其它氧化物或导电聚合物，例如Mg、Al、Si、V、Cr、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Cd、In、Sn、Sb、La、Ce、Hf、Ta、W、Bi的氧化物，及其组合，以及聚苯胺、聚吡咯、聚噻吩、多酚、聚乙炔、聚亚苯基，及其组合。
还提供了一种制备尖晶石和层状氧化物阴极的方法。所述阴极由阳离子取代的尖晶石氧化物材料和层状氧化物材料的混合物形成。在一些情况下，阳离子取代的尖晶石氧化物材料也是被氟取代的，并且具有组成LiMn2-y-zLiyMzO4-ηFη，其中y在大约0-大约0.3的范围内，z在大约0-大约1.0的范围内，而η在大约0-大约0.5的范围内。所述混合物可以含有大约60重量％-大约90重量％的阳离子取代的尖晶石氧化物和大约40重量％-大约10重量％的层状氧化物材料(例如，大约70重量％-大约80重量％的LiMn1.85Li0.075Ni0.04Al0.035O4和大约20重量％-30重量％的LiCoO2，或大约70重量％-大约80重量％的LiMn1.8Li0.1Ni0.1O3.8F0.2和大约20重量％-30重量％的LiC0O2)。
附图描述
为了更完整地理解本发明的特征和优点，现参照本发明的详述和附图，且其中：
图1为选择的母体LiMn2-y-zLiyMzO4-ηFη和化学脱锂的Li1-xMn2-y-zLiyMzO4-ηFη尖晶石阴极的X射线衍射图形；
图2A和图2B为在不同温度下电化学循环性能的对比图；
图3为在不同C速率下放电曲线的对比图；
图4A和图4B为说明容量衰减对锰溶解度(4A)和在充电-放电过程中形成的两个立方相间晶格参数差Δa(4B)的相关性的图；
图5为以LiMn2O4、LiMn1.8Li0.2O4、LiMn1.8Li0.2O3.79F0.21和LiMn1.8Li0.1Ni0.1O3.8F0.2的不同放电深度进行储存后，容量保持百分率的对比图；
图6为具有不同比率的尖晶石和层状氧化物混合物阴极以及商品碳阳极的锂离子电池的循环性能的对比图；和
图7为具有不同比率的尖晶石和层状氧化物混合物阴极以及商品碳阳极的锂离子电池的循环性能的图。
发明详述
尽管以下详细地讨论了本发明各种实施方案的制备和应用，但应当理解的是，本发明提供了许多可适用的发明构思，这些发明构思可以体现在各种各样的具体上下文中。本文所讨论的具体实施方案仅仅说明制备和应用本发明的具体方式，而不限定本发明的范围。
本发明人认识到，需要Li1+xMyMn2-x-yO4-zFz(且具体地，LiMn1.8Li0.1Ni0.1O4-ηFη)组合物，利用该组合物的方法(电池，电池组等)以及制备该组合物的方法。现有的参考文献没有教导Li1+xMyMn2-x-yO4-zFz(且具体地，LiMn1.8Li0.1Ni0.1O4-ηFη)组合物，制备或使用的方法。尽管‘645专利陈述了可以制备Li1+xMyMn2-x-yO4-zFz的组合物，其中M为过渡金属，但是，本发明人也认识到，‘645专利没有教导或使能够制备本发明的组合物。
例如，本发明人认识到，‘645专利要求保护具有通式Li1+xMyMn2-x-yO4-zFz的氟氧化锰锂化合物，其中x≤0.4，y≤0.3且0.05≤z≤1.0。‘645专利要求保护M为过渡金属并进一步限定了该过渡金属为Co、Cr或Fe。然而，本发明人认识到，‘645专利的方法没有教导本发明的组合物，且‘645专利不能用于制备本发明。
本发明人已试图通过第5,674,645号美国专利(‘645专利)所述的方法合成LiMn1.8Li0.1Ni0.1O4-ηFη。该合成是通过如‘645专利所述，在空气中将对于各种标称氟含量的所需量的Li2CO3、LiF、MnO2和NiO在800℃下加热来进行的。然后通过X射线衍射来对样品进行表征，用原子吸收光谱分析锂含量，以及通过氧化还原滴定进行氧化态分析。合成样品中的氟含量是基于锂含量和锰/镍的氧化态的实验值来计算的，利用电中性原理并假设阴离子(O+F)总含量会为4.0。表1将基于这些化学分析得到的实验组合物与标称组合物进行比较。可见，通过‘645专利所述的合成方法难以将任何氟掺入到LiMn1.8Li0.1Ni0.1O4-ηFη。这是因为在‘645专利所用的800℃的较高合成温度下，LiF易挥发。为了克服该问题并使氟含量最大化，本发明人采用了一种低温方法，其中首先通过在800℃下烧制合成LiMn1.8Li0.1Ni0.1O4氧化物，然后在450℃的中等温度下用NH4HF2对该氧化物进行热处理。本发明人采用的低温方法有助于提高LiMn1.8Li0.1Ni0.1O4-ηFη中的氟含量。
表1还给出了对于LiMn1.8Li0.1Ni0.1O4-ηFη中的不同标称氟含量的实验测定的晶格参数。所述晶格参数随标称氟含量的增加而增大，这一般与‘645专利所报道的相似。尽管可以认为观察到的随标称氟含量增加的晶格参数的增大可能是由于一价F-取代二价O2-和随后的较小Mn4+离子还原成较大的Mn3+离子，但是，原子吸收光谱数据表明，由‘645专利的方法制备的LiMn1.8Li0.1Ni0.1O4-ηFη样品中的锂含量的实验值低于标称期望的锂含量值(表1)。这是因为在‘645专利所用的800℃的高合成温度下LiF自身的挥发。随标称氟含量增加的锂含量的降低导致了锰氧化态的降低以及随后的晶格参数的增大。因此，观察到的随标称氟含量增加的晶格参数的增大不是由于将氟掺入尖晶石晶格，而是由于LiF的挥发。相反，我们的方法包括将已合成的LiMn1.8Li0.1Ni0.1O4氧化物在450℃的中等温度下烧制，避免了这样的锂挥发并且有助于使LiMn1.8Li0.1Ni0.1O4-ηFη中的氟含量最大化。
相比于‘645专利，本发明通过利用低温方法来克服这些问题且使氟含量最大化，在所述低温方法中，首先在大约800℃下烧制来合成LiMn1.8Li0.1Ni0.1O4氧化物，然后在450℃的中等温度下用NH4HF2对该氧化物进行热处理。本发明所使用的低温方法有助于LiMn1.8Li0.1Ni0.1O4-ηFη中氟含量的增加。
因此，要理解的是，‘645专利没有教导本发明的组合物或本文公开的制备或使用这些组合物的方法。
为了有助于理解本发明，以下定义了许多术语。本文所定义的术语具有本发明相关领域的普通技术人员通常所理解的含义。术语如“一个”、“一种”、“该”不意在仅指一个单数的实体，而是包括可以用于阐释具体例子的一般类型。本文的术语用于描述本发明的具体实施方案，但它们的用法并不限制本发明，除了如在权利要求中所概括的。
本文所使用的术语“安培-小时(Ah)”指的是用于说明电池储存容量的单位。例如，1Ah容量的电池可以提供1小时1A的电流或2小时0.5A的电流等。1安培-小时(Ah)相当于3600库仑的电荷。
本文所使用的术语“C速率”是指电池或电池组的充电或放电速率，用其总储存容量以Ah或mAh来表示。例如，1C的速率意思是在1小时内利用所有储能；0.1C意思是在1小时内利用10％的能量和在10小时内利用全部能量，而5C意思是在12分钟内利用全部能量。
本文所使用的术语金属氧化物包括金属氧化物的前体如硝酸盐、碳酸盐和乙酸盐，它们可以通过热处理转化成它们的相应金属氧化物。
在阳离子取代的尖晶石氧化物阴极中用氟化物离子取代氧化物离子，由于降低了Mn氧化态而增加了可逆容量。阳离子取代的尖晶石氟氧化物阴极如LiMn1.8Li0.1Ni0.1O3.79F0.21相比于其它尖晶石组合物如LiMn2O4、LiMn2O4-ηFη、LiMn1.8Li0.2O4和LiMn1.8Li0.2O4-ηFη显示出在60℃下优异的容量保持和出色的倍率性能。在LiMn2-y-zLiyMzO4-ηFη中氟化物离子的掺入，η可以在大于大约0.0-大约0.5的范围内；然而，该范围可以为大约0.05-大约0.27，大约0.1-大约0.25，大约0.1-大约0.21，或大约0.1-大约0.1。在LiMn2-y-zLiyMzO4-ηFη中y的值可以在大约0.0-大约0.3之间，然而，该范围可以为大约0.05-大约0.27，大约0.1-大约0.25，大约0.1-大约0.2，或大约0.1-0.15。相似地，在LiMn2-y-zLiyMzO4-ηFη中的z可以在大约0.0-大约1之间；然而，该范围可以为大约0.1-大约0.9，大约0.2-大约0.8，大约0.3-大约0.7，大约0.4-大约0.6，大约0.5-大约0.6，或大约0.01-大约0.5。
目前锂离子电池使用层状LiCoO2阴极，但是Co的高成本和毒性促使特别是用于电动车辆和混合动力电动车辆应用的可选择阴极的发展。在这方面，尖晶石LiMn2O4和橄榄石LiFePO4均由于Mn和Fe便宜且对环境友好而具有吸引力。然而，LiMn2O4尖晶石阴极在高温下受严重的容量衰减的影响。已经提出了若干机理来解释容量衰减，如Jahn-Teller畸变(distortion)1，锰溶解于电解质溶液中2-5，在充电-放电过程期间形成两个立方相6，7，由于在循环期间形成的两个立方相间晶格参数差Δa所造成的微应变的形成8-11。
本发明人认识到，可以通过适当的阳离子取代，减小在循环期间形成的在两个立方相间的晶格参数差Δa来显著改进高温下的循环能力、倍率性能和储存特性9-11。例如，双取代的尖晶石组合物如LiMn1.85Li0.075Ni0.075O4相比于未取代的LiMn2O4显示出优异的电化学性能。
然而，在LiMn2-2yLiyNiyO4中较低价态阳离子如Li+和Ni2+取代Mn3+/4+，增加了Mn的平均氧化态并将可逆容量降低至＜大约100mAh/g。本发明人在阳离子取代的尖晶石氧化物中利用氟化物离子部分取代氧化物离子以获得相应的尖晶石氟氧化物阴极。在这方面，Amatucci等人12-14已研究了通过利用LiF在800℃下合成来对Li1+xMn2-xO4-ηFη和LiMn2-yAlyO4-ηFη进行F-对O2-的取代，并且发现氟取代的阴极显示出比LiMn2O4高的放电容量和好的循环能力。最近，Kang等人15也发现用在850℃下利用LiF合成的Li1.05Mn1.85Al0.1O4-ηFη来改进其循环能力；然而，由于在高温下氟的挥发，烧制温度和时间强烈地影响掺入晶格中的氟的量。为了使尖晶石晶格中的氟含量最大化，本发明人开发了一种低温工序，包括将已经合成的阳离子取代的尖晶石氧化物LiMn2-y-zLiyMzO4与氟源(优选为氟化氢铵NH4HF2)在450℃下烧制短短的5小时。呈现了氟氧化物阴极LiMn2-y-zLiyMzO4-ηFη(M＝Mg、Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn、或其组合，且0≤η≤0.2)的循环能力和倍率性能与相应的氧化物阴极的循环能力和倍率性能的比较，和电化学性能与在循环期间形成的两个立方相间晶格参数差Δa和锰溶解程度的相关性，。
在一些实施方案中，将已经合成的阳离子取代的尖晶石氧化物LiMn2-y-zLiyMzO4与氟化物源一起烧制的温度为200-649℃、300-600℃、350-550℃、400-500℃、或425-475℃。相似地，将已经合成的阳离子取代的尖晶石氧化物LiMn2-y-zLiyMzO4与氟化物源一起烧制的时间可以在2-8小时、2-6小时、2-5小时、2-4小时、3-5小时、或4-5小时间变化。
通过将所需量的Li2CO3和Mn2O3与TiO2、NiO或CuO在空气中在800℃下烧制48小时来合成阳离子取代的LiMn2-y-zLiyMzO4尖晶石氧化物(M＝Mg、Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn、或其组合)。通过将LiMn2-y-zLiyMzO4氧化物与所需量的二氟化氢铵(NH4HF2)在空气中在450℃下烧制5小时来制备氟取代的LiMn2-y-zLiyMzO4-ηFη氟氧化物。本领域技术人员会认识到，具有类似特性的其它类似化合物可以取代二氟化氢铵，例如氟化铵NH4F。通过在氩气氛下将LiMn2-y-zLiyMzO4-ηFη粉末与氧化剂NO2BF4的乙腈溶液一起搅拌2天，随后用乙腈洗涤产物来进行锂的化学萃取(extraction)16。产物中的锂含量通过原子吸收光谱(AAS)来测定，而锰的平均氧化态由涉及草酸钠和高锰酸钾的氧化还原滴定来测定。初始样品的晶格参数以及在化学脱锂期间形成的两个立方相由X射线衍射(XRD)数据的Rietveld分析来测定17。锰溶解的程度是通过下述方法来评估的：将母体样品粉末在55℃下浸泡于含有在1∶1碳酸亚乙酯(EC)和碳酸二乙酯(DEC)中的1M LiPF6的电解质中7天，并且利用AAS来测定电解质中锰的量。
用CR2032钮扣电池(coin cell)来评价电化学性能，所述CR2032钮扣电池是用金属锂阳极、在1∶1碳酸亚乙酯(EC)和碳酸二乙酯(DEC)中的1M LiPF6电解质、Celgard聚乙烯隔板和阴极制造的。所述阴极是通过将LiMn2-y-zLiyMzO4-ηFη粉末与大约20重量％的导电碳和5重量％的聚四氟乙烯(PTFE)粘合剂混合，将混合物滚压成薄片，并切割成0.64cm2面积的圆形电极来制备的。本领域技术人员会认识到，电极可以是除圆形外的任何形状(例如，多边形、长方形、卵形、正方形等)，且电极面积可以在任意范围。
在大约3.5-4.3伏之间、在室温和大约60℃的两者温度下，在C/10-4C的不同速率下收集电化学数据。下表2给出了通过氧化还原滴定测定的尖晶石氟氧化锰的化学、结构和电化学表征数据和过渡金属离子的平均氧化态值。
表2
a通过假定Li+、Ti4+、Ni2+、Cu2+和F-来计算的
b基于样品重量的溶解％
对于给定的阳离子组合物，由于二价O2-离子被一价F-离子取代，氧化态随氟的取代而降低。在合成样品中的氟含量是基于分别从AAS和氧化还原滴定数据中获得的锂含量和过渡金属离子的平均氧化态值、利用电中性原理和假定阴离子(O+F)总含量会为4.0来计算的。基于分析数据，已将大量的氟(0≤η≤0.21)掺入尖晶石晶格中。将已合成的氧化物粉末与NH4HF2在大约450℃的低温下烧制，比传统的使用LiF作为氟源的高温(大约800℃)合成LiMn2O4-ηFη相比，有助于将挥发问题最小化并使得样品中的氟含量最大化12-14；NH4HF2在大约220℃以上的温度下分解，并作为易得到的氟源起作用。
图1为选择的母体LiMn2-y-zLiyMzO4-ηFη和化学脱锂的Li1-xMn2-y-zLiyMzO4-ηFη尖晶石阴极的X射线衍射图形的图像。在右侧示出了在大约27-33°和大约63-67°的小2θ区域的图形的放大，以分别说明脱锂组合物的Mn5O8杂质相的存在和两个立方相的形成。用*标记的反射是指Mn5O8杂质。
图1比较了一些尖晶石氧化物和氟氧化物组合物的XRD图形。阳离子取代的氟氧化物如LiMn1.8Li0.2O3.79F0.21和LiMn1.8Li0.1Ni0.1O3.8F0.2显示了相似于没有任何杂质相的母体阳离子取代的氧化物的XRD图形的图形。试图将多于大约0.2的氟掺入至阳离子取代的尖晶石氧化物中，导致作为杂质相的Mn5O8的形成。相反，在不存在阳离子取代的情况下，甚至在大约0.08的低氟含量下(例如，LiMn2O3.92F0.08)发现痕量的Mn5O8杂质相，并且对应于Mn5O8杂质的反射的强度随LiMn2O4-ηFη中氟含量的增加而增大。这可能是由于在LiMn2O4-ηFη的情况下(没有任何对Mn的阳离子取代)，难以将Mn的氧化态显著降低至大约3.5+以下。表1给出了LiMn2-y-zLiyMzO4-ηFη样品的晶格参数值。对于给定的阳离子组合物，由于将较小的Mn4+离子还原成较大的Mn3+离子，晶格参数随氟含量的增加而增大，证实了在整体尖晶石晶格中F-对O2-的取代。这种对晶格参数增大的观察与以前在Li1+xMn2-x-yAlyO4-ηFη体系中观察到的相一致14，15。
图2比较了LiMn2O4-ηFη、LiMn1.8Li0.2O4-ηFη和LiMn1.8Li0.1Ni0.1O4-ηFη阴极以C/5的速率，在室温和大约60℃下的循环性能。图2A比较了在大约25℃下阴极的电化学循环性能。图2B比较了LiMn2-y-zLiyMzO4-ηFη在大约60℃下阴极的电化学循环性能：(●)LiMn2O4、(○)LiMn2O3.92F0.08、(▲)LiMn1.8Li0.2O4、(△)LiMn1.8Li0.2O3.88F0.12、
LiMn1.8Li0.2O3.79F0.21、(■)LiMn1.8Li0.1Ni0.1O4、(口)LiMn1.8Li0.1Ni0.1O3.9F0.1和(◇)LiMn1.8Li0.1Ni0.1O3.8F0.2。上表1中总结了初始容量值以及在大约25℃和大约60℃下经50次循环后的容量损失百分比。氟氧化物尖晶石组合物由于降低了锰的氧化态而显示出比相应氧化物对应物高达最高至大约20mAh/g的容量。例如，LiMn1.8Li0.1Ni0.1O4、LiMn1.8Li0.1Ni0.1O3.9F0.1和LiMn1.8Li0.1Ni0.1O3.8F0.2在室温下显示出82、90和104mAh/g的初始容量和在大约50次循环中分别仅1.1、0.9和0.9％的容量衰减。LiMn1.8Li0.1Ni0.1O4、LiMn1.8Li0.1Ni0.1O3.9F0.1和LiMn1.8Li0.1Ni0.1O3.8F0.2相比于LiMn2O4的大约50％的衰减，在大约60℃下在50次循环中分别显示出2.6、2.1和1.9％的容量衰减。LiMn2O3.92F0.08相比于以前已发现的LiMn2O4，也显示出在容量保持上的改进12-14，但没有任何初始容量的增加，可能是由于电化学不活泼性杂质相Mn5O8的存在13，18。尽管以前在文献中已知氟取代如在Li1+xMn2-xO4-ηFη，12-14LiMn2-yAlyO4-ηFη，12-14和Li1.05Mn1.85Al0.1O4-ηFη，15的情况下改进了循环能力，但是在某些优化的阳离子取代的组合物如LiMn1.8Li0.1Ni0.1O3.8F0.2中氟的取代提供了在不显著牺牲容量值(＞100mAh/g)的情况下的高温下非常优异的容量保持。此外，在尖晶石中用氟取代的改进容量保持也与近来Kang等人19，20和Kim等人21用层状氧化物作出的相似观察相一致。
图3为在不同C速率下的放电曲线的对比图，说明了在以C/10速率充电至最高达大约4.3V后，LiMn2O4，LiMn1.8Li0.2O4-ηFη和LiMn1.8Li0.1Ni0.1O4-ηFη在不同速率下(C/10-4C)的倍率性能。阳离子取代的氧化物样品LiMn1.8Li0.2O4和LiMn1.8Li0.1Ni0.1O4在C/10-4C的速率下分别保持它们95％和98％的容量，但是在4C倍率下具有大约75和大约81mAh/g的低容量值。相比之下，阳离子取代的氟氧化物样品LiMn1.8Li0.2O3.79F0.21和LiMn1.8Li0.1Ni0.1O3.8F0.2在4C速率下分别保持它们C/10容量的92％和96％，但是在4C速率下仍然具有大约92和大约100mAh/g的合理容量。因此，阳离子取代的氟氧化物在不显著牺牲倍率性能的情况下显示出极好的循环能力和可接受容量值的结合。
检测到在尖晶石阴极充电-放电过程期间在大约(1-x)≈0.3-0.5出现的立方相到立方相转变以及两相区域的形成。所研究的尖晶石氧化物阴极已揭示了电化学性能对在形成的两立方相间晶格参数差Δa的相关性9，10。图1比较了通过用NO2BF4的乙腈溶液进行化学脱锂而获得的Li1-xMn2O4-ηFη，Li1-xMn1.8Li0.2O4-ηFη和Li1-xMn1.8Li0.1Ni0.1O4-ηFη(0.35≤(1-x)≤0.4)样品的XRD图形。尽管Li0.37Mn2O4在大约2θ≈65°下显示出两个不同的峰，对应于具有较大晶格参数差Δa的两个立方相，但是氟取代的Li1-xMn2O3.92F0.08(没有阳离子取代)显示出在两峰间减小的分离。另一方面，Li0.37Mn1.8Li0.2O3.79F0.21和Li0.34Mn1.8Li0.1Ni0.1O3.8F0.2(没有阳离子取代)两者，由于两立方相间小很多的晶格参数差Δa而仅显示出宽峰。但是，宽反射可以通过Rietveld分析来解析以获得两立方相的晶格参数。
图4A显示了在大约60℃下，大约50次循环中的容量衰减与锰溶解程度的相关性，而图4B显示了在60℃下，大约50次循环中的容量衰减与在充电-放电过程期间形成的两立方相间的晶格参数差Δa的相关性的图。实心的正方形和空心的三角形分别指的是氧化物和氟氧化物阴极。数字指的是表2中的样品编号。图4B使得容量衰减和晶格参数差Δa相关联。阳离子取代和氟取代均降低了Δa，而容量衰减随Δa的减小而降低。Δa值随锂含量而略有变化，且图4中所使用的Δa值为在(1-x)≈0.35-0.40的两相区域中的最大值。图4A还比较了锰溶解程度，且使容量衰减与锰溶解相关联。容量衰减随锰溶解程度降低而降低，证实了已经被文献广泛认可的锰溶解为容量衰减的原因。锰溶解的程度随一些阳离子取代而显著降低，例如相比于Li和Ti对Mn的共取代的Li和Ni对Mn的共取代。更重要的是，对于给定的阳离子取代，用氟的阴离子取代导致了锰溶解程度的进一步降低。通过氟化物离子的表现钝化，以及相比于Mn-O键更具有离子性的Mn-F键可以导致对锰溶解的抑制。由图4可见，锰溶解显示出与晶格参数差Δa的关系，并且容量衰减随Δa和锰溶解的减小而降低。因此，由于在两相区域中较小的Δa以及被抑制的锰溶解而降低的界面晶格应变导致了改进的容量保持。
发现容量为104mAh/g的LiMn1.8Li0.1Ni0.1O3.79F0.21的优异电化学性能，是由于在充电-放电过程期间形成的两立方相间小很多的晶格参数差所造成的被显著抑制的锰溶解。研究表明，在基于锰的尖晶石阴极中适当的阳离子和阴离子取代会提供可行的策略以开发它们用于EV和HEV应用。图5为以不同深度放电(DOD)的在60℃下储存7天后的容量保持百分比的对比图：(●)LiMn2O4，、(▲)LiMn1.8Li0.2O4、
LiMn1.8Li0.2O3.79F0.21、和(◇)LiMn1.8Li0.1Ni0.1O3.8F0.2。通过使钮扣电池在室温下在4.3-3.5V间经受一次充电放电循环，随后在第二次循环中放电至不同放电深度(DOD)来评价储存性能。然后将样品以不同的DOD在60℃下储存7天。
在冷却到环境温度后完成第二次放电循环。在室温下评价第三次循环中的全放电容量。以第三次放电容量与第一次放电容量的比率得到容量保持百分比。尽管LiMn2O4在储存后损失了大量的容量(20-40％)，但是阳离子取代的氟氧化物保持了其初始容量的＞95％，说明了极好的储存特性。因此，氟氧化物阴极提供了极好的循环能力和储存特性的结合。
尖晶石阴极的主要问题是在高温下严重的容量衰减，其主要被认为是锰从晶格中溶解至电解质中，然后其迁移到碳阳极并与碳阳极相互作用。锰溶解是由于在由LiPF6产生的痕量质子(酸性HF)和电解质中存在的痕量水的存在下Mn3+离子岐化为Mn4+和Mn2+离子。阳离子和阴离子(氟)取代有助于显著降低锰溶解和在充电放电过程期间形成的两个立方相间的晶格参数差Δa，这导致了良好的电化学性能。供选择地，在充电-放电过程的开始阶段，产生的质子可以被捕获在另一种材料中以降低锰溶解。
利用乙腈介质中的氧化剂NO2BF4的化学脱锂研究已经表明，层状氧化物阴极组合物如Li1-xCoO2和Li1-xMn0.5Ni0.5O2以及Li1-xMn1/3Ni1/3Co1/3O2，由于在深度锂萃取时的Li+与H+的离子交换而将质子掺入至晶格中22。抑制来自尖晶石阴极的锰溶解的一种方法是利用由主要是尖晶石和少量层状氧化物组成的混合阴极，最初将混合物充电至足够高的电压(例如，大约4.7V)以使得层状氧化物过度充电(深度锂萃取)并将质子捕捉在过度充电的层状氧化物中。然后可以在大约3.5-大约4.3伏的正常操作电压区域下将混合物循环。本发明包括优化的阳离子和阴离子取代的尖晶石阴极和层状氧化物阴极如LiCoO2和LiMn0.5Ni0.5O2的混合物。
图6为具有尖晶石LiMn2O4、尖晶石LiMn1.85Li0.075Ni0.04Al0.035O4和层状LiCoO2的混合物、以及尖晶石LiMn1.8Li0.1Ni0.1O3.8F0.2和层状LiCoO2的阴极混合物、以及商品碳阳极的锂离子电池在60℃下以C/5的速率的循环性能图。通过在第一次循环中首先充电至最高达4.7伏并然后在60℃下在4.3-3.5伏间循环来进行研究：(●)LiMn2O4，、(▲)LiMn1.85Li0.075Ni0.04Al0.035O4(△)80重量％LiMn1.85Li0.075Ni0.04Al0.035O4和20重量％LiCoO2，
70重量％LiMn1.85Li0.075Ni0.04Al0.035O4和30重量％LiCoO2，(■)LiMn1.8Li0.1Ni0.1O3.8F0.2，和(□)70重量％LiMn1.8Li0.1Ni0.1O3.8F0.2和30重量％LiCoO2。将各个锂离子电池在第一次循环中充电至最高达4.7伏，并且使其在开路状态下(无负载施加)静置2小时。然后将锂离子电池在3.5-4.3伏之间循环。尽管LiMn2O4在30次循环后显示出33％的严重容量衰减以及容量的持续下降，但是阳离子取代的LiMn1.85Li0.075Ni0.004Al0.035O4显示出更好的循环性能，以及在7次循环后容量值变得更稳定。
尖晶石和层状氧化物阴极的混合物不但提供好得多的循环能力，而且还有容量的显著增加。例如，LiMn1.85Li0.075Ni0.04Al0.035O4，80重量％LiMn1.85Li0.075Ni0.04Al0.035O4和20重量％LiCoO2的混合物，以及70重量％LiMn1.85Li0.075Ni0.04Al0.035O4和30重量％LiCoO2的混合物在30次循环中分别显示出87、91和103mAh/g的初始容量和仅仅21.9、13.8和14.4％的容量衰减。此外，102mAh/g的初始容量是利用70重量％LiMn1.8Li0.1Ni0.1O3.8F0.2和30重量％LiCoO2的阴极混合物的11.2％的容量衰减来实现的。
在用尖晶石和层状LiNi0.5Mn0.5O2氧化物阴极的混合物制造的锂离子电池中也看出在循环能力上的相似改进。图7为具有不同比率的尖晶石和层状氧化物混合物阴极和商品碳阳极的锂离子电池的循环性能的图。通过首先在第一次循环中充电至最高达4.7伏，然后在60℃下在4.3-3.5伏间循环进行研究：(▲)LiMn1.85Li0.075Ni0.04Al0.035O4和(△)80重量％LiMn1.85Li0.075Ni0.04Al0.035O4和20重量％LiNi0.5Mn0.5O2。如图7所示，80重量％LiMn1.85Li0.075Ni0.04Al0.035O4和20重量％LiNi0.5Mn0.5O2的混合物显示出并相应单独的尖晶石阴极更好的循环能力。该方案进一步的工作在进行中。
对用尖晶石和层状氧化物阴极的混合物制造的锂离子电池(钮扣电池)中的锰溶解也进行了研究。所述混合物确实比相应单独的尖晶石阴极显示出较低的锰溶解，证明了层状氧化物阴极可以有助于电池在最初受到＞4.3伏的过度充电时捕捉质子。
此外，碳阳极表面可以用氧化物阳极如尖晶石Li4Ti5O12或TiO2改性或涂覆。这样的表面改性会有助于避免溶解的锰与碳阳极之间的相互作用以及随后的在电化学性能上的降级。有利的是，尖晶石Li4Ti5O12或TiO2会有助于阳极容量。这些材料可以通过基于溶液的技术，随后在300-900℃的中等温度下在惰性气氛中烧制而在石墨表面上产生。碳阳极的这种表面改性也可以采用其它会或不会有助于容量的氧化物，如Mg、Al、Si、V、Cr、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Cd、In、Sn、Sb、La、Ce、Hf、Ta、W和Bi的氧化物。表面改性也可以用导电聚合物进行，例如聚苯胺和聚吡咯。表面改性材料的量可以为1重量％-10重量％。用其它物种进行碳表面改性可以消除来自阳离子取代的尖晶石氧化物或氟氧化物阴极的任何溶解锰的直接相互作用，并且从而为锂离子电池提供了长期的稳定性和良好的循环能力。
此外，掺杂剂可以掺入本发明中。本文所用的掺杂剂为选择以证明构思的元素或化合物。掺杂剂用于替代过渡金属M，而不用于替代锂金属氧化物中的锂离子。例如，用于本发明的掺杂剂包括金属和非金属如Mg、Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn、Si、B及其组合。
尽管本发明设想了本领域技术人员已知的许多氟源(例如，NH4HF2)，但是也可以使用其它氟源。例如，可以将尖晶石氧化物粉末分散在稀氢氟酸溶液中，蒸发，并在较低温度(200-500℃)下烧制以获得氟氧化物组合物。可以将氟化氢铵或氟化铵溶解在溶剂(例如甲醇或乙醇)中并且可以将尖晶石氧化物粉末分散在其中，蒸发，并在较低的温度(例如200-500℃)下烧制以获得氟氧化物组合物。可以将氟化氢铵溶解在溶剂(例如，甲醇或乙醇)中，并且将尖晶石氧化物粉末分散在其中，回流、过滤，并在较低的温度(例如200-500℃)下烧制以获得氟氧化物组合物。可以将氟化氢铵溶解在如乙醇、异丙醇或水的溶剂中，并将尖晶石氧化物粉末分散在其中。可将混合物在水热或溶剂热(solvothermal)条件下，在80-250℃下保持在高压釜中，过滤，并在较低的温度(例如200-500℃)下烧制以获得氟氧化物组合物。还有，可以将尖晶石氧化物粉末与氟化氢铵固体混合、研磨、制粒，并在大约300-500℃下烧制。
预期的是，本说明书中所讨论的任何实施方案可以由关于本发明的任何方法、试剂盒、试剂或组合物来实施，反之亦然。此外，本发明的组合物可以用于实现本发明的方法。
要理解的是，本文所述的具体实施方案是通过阐释而不是限制本发明的方式来展示的。本发明的主要特征可以在不脱离本发明范围的情况下体现在各种实施方案中。本领域技术人员将认识到，或者仅仅利用例行的实验能够确定，本文所述具体步骤的许多等同物。这样的等同物被认为是在本发明的范围内，且被权利要求所涵盖。
本说明书中提到的所有出版物和专利申请指示了本发明所涉及领域的技术人员的水平。所有的出版物和专利申请均引入本文作为参考，其引入的程度如同各个独立的出版物或专利申请具体并独立地被指明引入作为参考。
词语“一个”或“一种”当与权利要求和/或说明书中的术语“包含”结合使用时，可以指“一种”，但其也与“一种或多种”、“至少一种”和“一种或多于一种”的意思相一致。在权利要求中所使用的术语“或者”是指“和/或”，除非明确指明仅仅是指供选择物，或供选择物为相互排斥的，尽管公开内容支持仅仅指供选择物及“和/或”的定义。在整个本申请中，术语“大约”用来说明这样的值，其包括装置和用来测定所述值的方法的误差的固有变化，或者研究受试者之间存在的变化。
如在本说明书和权利要求书中所使用的，词语“包含”(以及任何形式的“包含”)，“具有”(以及任何形式的“具有”)，“包括”(以及任何形式的“包括”)或“含有”(以及任何形式的“含有”)是包括的或开放式的，且不排除额外的，未述及的元素或方法步骤。
本文所使用的术语“或其组合”是指在该术语之前所列举项目的全部排列和组合。例如，“A、B、C或其组合”意在包括A、B、C、AB、AC、BC或ABC中的至少一种，并且如果在特定的上下文中顺序是重要的，那么还包括BA、CA、CB、CBA、BCA、ACB、BAC或CAB。继续这个例子，明显包括的是包含一种或多种项目或术语重复的组合，如BB、AAA、AB、BBC、AAABCCCC、CBBAAA、CABABB等等。本领域技术人员将理解的是，通常对任何组合中的项目或术语的数目没有限制，除非从上下文中另外是明显的。
根据本发明的公开内容，在没有不适当的实验下可以制备和实施本文所公开和要求保护的全部组合物和/或方法。尽管已就优选的实施方案描述了本发明的组合物和方法，但是对于本领域技术人员来说明显的是，在不脱离本发明的概念、精神和范围的情况下，可以改变本文所述的组合物和/或方法以及方法的步骤或方法的步骤的顺序。所有这样类似的对本领域技术人员而言明显的取代和修饰被认为是在附加的权利要求所限定的本发明的精神、范围和概念内。
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Claims (29)
1.一种制备氟氧化物组合物的方法，该方法包括以下步骤：
将具有式LiMn2-y-zLiyMzO4的组合物在氟源的存在下，在大约200-700℃的温度下加热2-8小时以形成阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石氧化物结构，其中y在大约0-大约0.3的范围内，其中z在大约0-大约1.0的范围内，而其中η大于0且小于大约0.50。
2.根据权利要求1所述的方法，其中M选自Mg、Al、V、Cr、Fe、Co、Zn、Zr、Nb、Mo、Ga、Sn及其组合。
3.根据权利要求1所述的方法，其中所述氟源包括NH4HF2。
4.根据权利要求1所述的方法，其中y在大约0-大约0.3的范围内，z在大约0-大约1.0的范围内，而η在大约0.05-大约0.25的范围内。
5.根据权利要求1所述的方法，其中η在大约0.1-0.20的范围内。
6.根据权利要求1所述的方法，其中将所述组合物加热至大约300-600℃的温度。
7.根据权利要求1所述的方法，其中将所述组合物加热至大约425-500℃的温度。
8.根据权利要求1所述的方法，其中所述阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石氧化物结构，当被掺入锂离子电池时，具有大于大约80mAh/g的容量。
9.一种包含将氟掺入尖晶石晶格的阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη尖晶石氧化物结构的组合物，其中η大于0且小于大约0.50。
10.根据权利要求9所述的组合物，其中η在大约0.1-0.2的范围内。
11.一种制备阴极的方法，该方法包括以下步骤：
将LiMn2-y-zLiyMzO4-ηFη组合物与导电稀释剂和粘合剂混合以形成阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物；和
将阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物成形为阴极。
12.根据权利要求11所述的方法，其中所述阴极基本上为圆柱形或基本上为圆盘形。
13.根据权利要求11所述的方法，其中所述粘合剂包括粉末状的聚四氟乙烯或或聚偏1，1二氟乙烯，而其中所述导电稀释剂包括乙炔黑、炭黑、石墨、镍粉末、铝粉末、钛粉末或不锈钢粉末。
14.根据权利要求11所述的方法，其中所述M选自Mg、Al、V、Cr、Fe、Co、Zn、Zr、Nb、Mo、Ga、Sn及其组合。
15.根据权利要求11所述的方法，其中将所述组合物加热至大约300-600℃的温度。
16.根据权利要求11所述的方法，其中将所述LiMn2-y-zLiyMzO4-ηFη组合物在空气中在大约400-500℃的温度下加热。
17.根据权利要求11所述的方法，其中将所述LiMn2-y-zLiyMzO4-ηFη组合物在空气中在温度下加热2-8小时。
18.根据权利要求11所述的方法，其中将所述LiMn2-y-zLiyMzO4-ηFη组合物在空气中在温度下加热3-5小时。
19.根据权利要求11所述的方法，该方法还包括将阳离子取代的、氟取代的LiMn2-y-zLiyMzO4-ηFη组合物切割成具有大约0.30cm2-0.90cm2的面积的圆形电极。
20.一种阴极，其包括：
LiMn2-y-zLiyMzO4-ηFη阳离子取代的尖晶石氧化物材料，其中y为大约0-0.3，z为大约0-1.0，而η为大于0且小于大约0.5，所述LiMn2-y-zLiyMzO4-ηFη阳离子取代的尖晶石氧化物材料与包含Li[Ni，Mn，Co，Li]O2或其组合的层状氧化物材料相接触。
21.根据权利要求20所述的阴极，其中M选自Mg、Al、V、Cr、Fe、Co、Zn、Zr、Nb、Mo、Ga、Sn及其组合。
22.根据权利要求20所述的阴极，其中所述阳离子取代的尖晶石氧化物材料为大约20重量％-95重量％，而所述层状氧化物材料为大约80重量％-5重量％。
23.根据权利要求20所述的阴极，其中所述LiMn2-y-zLiyMzO4-ηFη阳离子取代的尖晶石氧化物材料包含大约70重量％-大约80重量％的LiMn1.85Li0.075Ni0.04Al0.035O4、LiMn1.8Li0.1Ni0.1O3.8F0.2、LiMn1.8Li0.1Ni0.1O3.8F0.2或其组合，而其中所述层状氧化物材料包含大约20重量％-大约30重量％的LiCoO2、LiNi0.5Mn0.5O2或其组合。
24.根据权利要求20所述的阴极，其还包括TiO2或尖晶石Li4Ti5O12或涂层。
25.一种制备尖晶石及层状氧化物阴极的方法，包括：
由阳离子取代的尖晶石氧化物材料和层状氧化物材料的混合物形成阴极。
26.根据权利要求25所述的方法，其中所述阳离子取代的尖晶石氧化物材料包含LiCoO2。
27.根据权利要求25所述的方法，其中所述阳离子取代的尖晶石氧化物材料包含LiMn2-y-zLiyMzO4-ηFη。
28.根据权利要求25所述的方法，其中M选自Mg、Al、V、Cr、Fe、Ti、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ga、Sn及其组合。
29.根据权利要求25所述的方法，其中所述阴极包括大约60重量％-大约90重量％的阳离子取代的尖晶石氧化物材料的混合物，和大约40重量％-大约10重量％的层状氧化物材料。
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2008039808A2 (en) | 2008-04-03 |
| EP2067198A2 (en) | 2009-06-10 |
| WO2008039808A3 (en) | 2008-07-03 |
| US20080157027A1 (en) | 2008-07-03 |
| US20100183925A1 (en) | 2010-07-22 |
| US8722246B2 (en) | 2014-05-13 |
| US7718319B2 (en) | 2010-05-18 |
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