CN102918685A - 含有含氧锂过渡金属化合物的含碳复合材料 - Google Patents
含有含氧锂过渡金属化合物的含碳复合材料 Download PDFInfo
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- CN102918685A CN102918685A CN2011800206530A CN201180020653A CN102918685A CN 102918685 A CN102918685 A CN 102918685A CN 2011800206530 A CN2011800206530 A CN 2011800206530A CN 201180020653 A CN201180020653 A CN 201180020653A CN 102918685 A CN102918685 A CN 102918685A
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Abstract
本发明涉及一种涂覆两个含碳层的含氧锂过渡金属化合物的颗粒的含碳复合材料,并涉及其制备方法以及含有该复合材料的电极。
Description
本发明涉及一种含碳复合材料,所述含碳复合材料包含含氧的锂过渡金属化合物的颗粒,所述颗粒被具有两个含碳层的区域覆盖。本发明还涉及制备所述复合材料的方法以及包含所述复合材料作为活性材料的电极。
近来,掺杂和未掺杂的混合锂过渡金属化合物已经受到了关注,特别是在所谓(可充电的)“二次锂离子电池”中作为电极材料。
例如,从Goodenough等人的文献(US-A-5,910,382)开始,未掺杂或掺杂的混合锂过渡金属磷酸盐已经用作二次锂离子电池中的阴极材料。为了制备锂过渡金属磷酸盐,提出了固态合成以及所谓的从水溶液中的水热合成。同时,由现有技术已知,几乎所有的金属和过渡金属阳离子用作掺杂阳离子。
因此,WO 02/099913描述了一种制备LiMPO4的方法,其中,为了制备纯相的任选掺杂的LiMPO4,除了铁以外,M是元素周期表的第一过渡金属系列的一种或多种过渡金属阳离子。
EP 1195838A2描述了通过固相法制备锂过渡金属磷酸盐的方法,特别是LiFePO4,其中,典型的是磷酸锂和磷酸铁(II)混合并在约600℃的温度煅烧。
制备磷酸铁锂的其他方法例如在Journal ofPower Sources 119-121(2003)、247-251,JP2002-151082A以及DE 10353266中已经描述。
这样获得的掺杂或未掺杂的锂过渡金属磷酸盐通常补充添加导电剂,例如导电碳黑,并加工成阴极配料。因此,EP 1193784、EP 1193785以及EP 1193786描述了LiFePO4和无定形碳的所谓碳复合材料,在从硫酸铁、磷酸氢钠制备磷酸铁时,无定形碳也作为硫酸铁中残余的Fe3+残留物的还原剂以及防止Fe2+到Fe3+的氧化。碳的添加也用于增加阴极中磷酸铁锂活性材料的导电性。因此,特别是EP 1193 786表明,为了获得该材料的必需容量和相应的循环特性,在磷酸铁锂碳复合材料中必须含有不少于3重量%的碳。
EP 1049 182 B1提出通过用一层无定形碳涂覆磷酸铁锂来解决类似的问题。
另外,现有技术的锂过渡金属磷酸盐的一个缺点是不能抵抗水分以及所谓的“浸渍”,即电极活性材料的过渡金属溶解在二次锂离子电池的(液体)电解质中,从而降低其容量和电压。
一段时间以来,已经描述了在可充电锂离子电池中使用掺杂和未掺杂的钛酸锂,特别是钛酸锂Li4Ti5O12(钛酸锂尖晶石),作为阳极材料石墨的替代物。锂离子电池中的阳极材料的当前评述可以发现于例如Bruce等人的Angew.Chem.Int.Ed.2008,47,2930-2946页。
与石墨相比,Li4Ti5O12的优点特别是其更好的循环稳定性、其更好的热负载能力以及更高的运行可靠性。与锂相比,Li4Ti5O12具有1.55V的较恒定的电位差,并且获得若干个1000次充放电循环,且容量损失小于20%。钛酸锂因此显示出比石墨明显更正的电位。
但是,更高的电位也导致更小的电压差。与石墨的372mAh/g(理论值)相比,175mAh/g的较低容量,这导致比用石墨阳极的锂离子电池明显更低的能量密度。但是,Li4Ti5O12具有长寿命并且是无毒的,因此也不被分类为是对环境有威胁的。
详细地描述了钛酸锂Li4Ti5O12的制备的各个方面。通常,利用钛化合物和锂化合物之间在超过750℃的高温的固态反应获得(US-A-5,545,468),所述钛化合物通常是TiO2,所述锂化合物通常是Li2CO3。为了获得较纯的、令人满意的可结晶Li4Ti5O12,该高温煅烧步骤似乎是必要的,但是这带来的缺点在于获得过粗的一次颗粒并且发生材料的部分熔融。一般地,高温还常常产生副产品,如金红石或锐钛矿的残余物,其保留在产物中(EP 1 722 439 A1)。
还描述了制备Li4Ti5O12的溶胶-凝胶法(De 103 19 464 A1),和利用火焰喷涂热解的制备方法(Ernst,F.O.等人,Materials Chemistry and Physics 2007,101(2-3),372-378页),以及在无水介质中的所谓“水热法”(Kalbac,M.等,Journalof Solid State Electrochemistry 2003,8(1),2-6页)。
如上所述,掺杂和未掺杂LiFePO4最近已经用作锂离子电池中的阴极材料,结果是在Li4Ti5O12和LiFePO4的组合中,可以获得2V的电压差。
对于目前使用的可充电锂离子电池,特别是用于汽车中的,适用高要求,特别是与它们的放电循环及其容量相关的高要求。但是,到目前为止提出的用于阴极和用于阳极的电极活性材料的材料或材料混合物必须达到要求的电极密度,因为它们不能显示出必不可少的压实粉末密度。粉末密度可以近似地与电极密度或所谓电极活性材料的密度相关,并且同样与电池容量相关。电极活性材料的压实粉末密度越高,则电池的体积容量也越高。
到目前为止所用的许多电极材料的缺点,如上已经简单解释的,还在于它们对水分的敏感性以及它们在所用的电解质中的显著溶解度,所用的电解质中大多数常常含有锂氟化合物,例如LiPF6、LiBF4等。
因此,本发明的目的是提供一种用于二次锂离子电池的改进的电极活性材料,其与现有技术的材料相比,特别是具有改进的压实密度、提高的抗水性和在二次锂离子电池中的电解质中的低溶解度。
本发明的该目的通过一种含碳复合材料实现,所述含碳复合材料包含含氧的锂过渡金属化合物的颗粒,所述颗粒被具有两个含碳层的区域覆盖。
出乎意料地,根据本发明的复合材料,与现有技术的常用电极材料相比,具有改善至少5%的压实密度,在优选的实施方案中,与根据EP 1 049 182 B1的材料相比,具有改善大于10%的压实密度。
通过提高所述压实密度,在根据本发明的复合材料用作电极的活性材料时,因此还实现了更高的电极密度,结果是使用根据本发明的复合材料作为二次锂离子电池的阴极和/或阳极中的活性材料,与例如根据上述EP 1 049 182B1的材料相比,二次锂离子电池的体积容量也增大至少5%。
在本发明的一些实施方案中,所述复合材料仅由含氧锂过渡金属化合物的用两个含碳层覆盖的颗粒组成。
出乎意料地,含有根据本发明的复合材料的电极还具有比含有仅提供单一含碳层的锂过渡金属化合物作为活性材料的电极更高的导电性。与用碳涂覆一次或不用碳涂覆的锂过渡金属化合物相比,根据本发明的复合材料的BET表面积出乎意料地减小,因此在制备电极时需要更少的粘合剂。
由于所述复合材料的两个主要含碳的层,实现了提高的抗水性,特别是抗空气湿度性能,以及提高的抗“浸渍”性,“浸渍”是如上另外解释的,与仅有一个含碳层的材料(例如以上已经提及的EP 1 049 182 B1中所公开的)相比,所述性能明显提高。具体地,根据本发明的复合材料也是非常耐强酸的(见实验部分)。与涂覆一次或根本不涂覆的材料相比,过渡金属到二次电池所用的(液体)电解质中的放电(例如其溶解度)也明显减小。
根据上述专利EP 1 049 182 B1获得的“单一涂层”是多孔的,并且常常不能完全覆盖锂过渡金属化合物的颗粒,因此特别导致水分敏感的锂过渡金属磷酸盐部分分解并且增大过渡金属的溶解度,例如在酸或在液体电解质中的溶解度。
术语“含碳”在这里被理解为是指热解获得的碳材料,其通过合适的前驱体化合物的热分解形成。这种含碳材料也可以用术语“热解碳”同义地描述。
术语“热解碳”因此描述非结晶碳的优选无定形材料。如已经描述的,热解碳由合适的前驱体通过加热获得,即通过在低于1500℃,优选低于1200℃,更优选低于1000℃,最优选≤850℃,更优选≤800℃,并且优选≤750℃的温度热解获得。
在特别是>1000℃的更高温度下,由于所谓的“熔融”,优选的含氧锂过渡金属化合物的颗粒的团聚发生,这通常导致根据本发明的复合材料的载流量差。根据本发明,特别重要的是不形成结晶的、有序的合成石墨。
用于热解碳的典型前驱体化合物是例如碳水化合物,如乳糖、蔗糖、葡萄糖、淀粉、纤维素、乙二醇、聚乙二醇;聚合物例如聚苯乙烯-丁二烯嵌段共聚物、聚乙烯、聚丙烯;芳香族化合物如苯、蒽、甲苯、二萘嵌苯以及本领域技术人员已知的本质上适合于所述目的的所有其它化合物及其组合。特别合适的混合物是例如乳糖和纤维素、糖类(碳水化合物)相互之间的所有混合物。糖如乳糖、蔗糖、葡萄糖等与丙三醇的混合物也是优选的。
前驱体化合物可以分解的准确温度,以及前驱体化合物的选择,也取决于要涂覆的(含氧)锂过渡金属化合物,因为例如锂过渡金属磷酸盐常常在大约800℃已经分解成磷化物。
通过到与热解碳的前驱体化合物接触的颗粒上的直接原位分解,热解碳层可以沉积到含氧锂过渡金属化合物的颗粒上,或者含碳层通过气相间接沉积,因为部分前驱体化合物首先蒸发或升华,然后分解。根据本发明,利用这两种分解(热解)过程的组合的涂层也是可能的。
术语“两个含碳层”也覆盖以下可能性:在本发明的一些实施方案中,在两层之间没有分离的界面可以被限定,这也具体取决于用于热解碳的前驱体化合物的选择。但是,即使在“模糊的”界面的情况下,两个层的固态结构的不同仍然可以例如通过SEM或TEM法确定,不限于具体理论,这可能可以通过要涂覆的基质(“基底”)的结构不同来解释:第一层直接沉积在含氧锂过渡金属化合物的颗粒上,第二层沉积在第一层热解碳上。
两层热解碳的结构不同还可以例如通过各个起始化合物的选择、通过对每一层使用一种(或甚至若干种)不同的前驱体化合物进一步加强。因此,例如,第一层可以由乳糖获得,并且第二层可以由淀粉或纤维素获得,或者反过来。
当然,在本发明的一些实施方案中,也可能提供具有大于2个含碳层,例如3、4或者甚至更多层的根据本发明的复合材料。
含氧锂过渡金属化合物的根据本发明所用的概念在这里覆盖具有通式LiMPO4的化合物、具有通式LiMVO4的钒酸盐、相应的高铅酸盐、钼酸盐和铌酸盐,其中M通常表示至少一种过渡金属或其混合物。此外,“典型氧化物”,如通式LixMyO(0≤x,y≤1)的混合锂过渡金属氧化物,在该情况中也由该术语理解,其中M优选的是所谓“前过渡金属”,如Ti、zr或Sc,以及,尽管不是优选的,“后过渡金属”如Co、Ni、Mn、Fe、Cr,以及它们的混合物,即诸如LiCoO2、LiNiO2、LiMn2O4、LiNi1-xCoxO2、LiNi0.85Co0.1Al0.05O2等的化合物。
在本发明的优选的实施方案中,含氧锂过渡金属化合物是通式LiMPO4的锂过渡金属磷酸盐,其中,M具体表示Fe、Co、Ni、Mn或其混合物。
在本发明的框架中,术语“锂过渡金属磷酸盐”是指以掺杂和未掺杂形式存在的锂过渡金属磷酸盐。
“未掺杂”是指使用纯的,特别是纯相的锂过渡金属磷酸盐。如上已经说明的,过渡金属M优选选自Fe、Co、Mn或Ni,因此具有通式LiFePO4、LiCoPO4、LiMnPO4或LiNiPO4,或其混合物。LiFePO4是特别优选的。
掺杂的锂过渡金属磷酸盐是指式LiM’yM”xPO4的化合物,其中,优选M”=Fe、Co、Ni或Mn,M’与M”不同,表示选自Co、Ni、Mn、Fe、Nb、Ti、Ru、Zr、B、Al、Zn、Mg、Ca、Cu、Cr中的至少一种金属阳离子或其组合,但是优选表示Co、Ni、Mn、Fe、Ti、B、Al、Mg、Zn和Nb,x是<1且>0.01的数,y是>0.001且<0.99的数。典型的优选化合物是例如LiNbyFexPO4、LiMgyFexPO4、LiByFexPO4、LiMnyFexPO4、LiCoyFexPO4、LiMnzCoyFexPO4、LiMn0.80Fe0.10Zn0.10PO4、LiMn0.56Fe0.33Mg0.10PO4,其中0≤x,y,z≤1。
在本发明的仍然进一步优选的实施方案中,含氧锂过渡金属化合物是锂钛氧化物。与使用例如根据EP 1 796 189的用碳涂覆一次的锂钛氧化物作为阳极的现有技术的二次锂离子电池相比,在用作阳极时,根据本发明的涂覆两次的锂钛氧化物导致稳定性和循环稳定性增大约10%。
术语“锂钛氧化物”在这里是指空间群Fd3m的0≤x≤1/3的Li1+xTi2-xO4型的所有掺杂或未掺杂的锂钛尖晶石(所谓“钛酸锂”),并且一般也指通式LixTiyO(0≤x,y≤1)的所有混合锂钛氧化物。
如上所述,在本发明的一些实施方案中,锂钛氧化物用至少一种其它金属掺杂,与未掺杂材料相比,当掺杂的锂钛氧化物用作阳极时,这又导致稳定性和循环稳定性进一步增大约5%。具体地,这通过向晶格结构中引入附加的金属离子实现,所述金属离子优选的是Al、B、Mg、Ga、Fe、Co、Sc、Y、Mn、Ni、Cr、V、Sb、Bi或这些离子中的若干种。
掺杂的和未掺杂的锂钛尖晶石优选的是不含金红石。
在所有上述的含氧锂过渡金属化合物的情况下,相对于总化合物而言,掺杂的金属离子优选的存在量为0.05-3重量%,优选1-3重量%。掺杂金属阳离子占据过渡金属或锂的晶格位置。
对此例外的是混合的Fe、Co、Mn、Ni锂磷酸盐,其含有上述元素的至少两种,其中也可以存在更大量的掺杂金属阳离子,在极端情况下,最高达50重量%。
具有单模颗粒尺寸分布,根据本发明的复合材料的颗粒的D10值优选≤0.25,D50值优选≤0.75,D90值≤2.7μm。
如已经描述的,在二次锂离子电池中用作电极的活性材料时,根据本发明的复合材料的小颗粒尺寸导致更高的电流密度以及更好的循环稳定性。
所述复合材料的第一含碳层的厚度有利的是≤5nm,在本发明的优选的实施方案中约为2-3nm,第二层的厚度≤20nm,优选1-7nm。总之,两层的总厚度因此在3-25nm范围内,其中,所述的层厚可以通过前驱体材料的起始浓度、精确的温度选择和加热时间以定目标的方式具体设定。
在本发明的其他实施方案中,含氧锂过渡金属化合物的颗粒完全被包围在两层含碳材料中,因此对水分和酸的腐蚀和所谓“浸渍”的作用特别不敏感,所述“浸渍”即根据本发明的复合材料的过渡金属在电解质中的溶解。如已经描述的,“浸渍”导致包含根据本发明的复合材料的电极的容量和电容量的降低,并因此导致更短的寿命和更低的稳定性。
与现有技术的材料相比,根据本发明的复合材料在非水液体中具有非常低的溶解度,非水液体在二次锂离子电池中用作电解质,例如其中溶解锂氟盐如LiPF6或LiBF4的碳酸亚乙酯和碳酸二甲酯的混合物。对于含有1000ppm水的含锂氟盐的液体(例如碳酸亚乙酯和碳酸二甲酯的混合物),其中LiFePO4用作含氧锂过渡金属化合物的根据本发明的复合材料的铁溶解度是≤85mg/l,优选≤40mg/l,更优选≤30mg/l,通过以下解释的参比试验来测量。对于未涂覆的锂过渡金属化合物的值例如对于LiFePO4为约1750mg/l,对于根据EP 1 049182 B1获得的对比材料为约90mg/l。对于在此类化合物中的其它过渡金属,获得在上述极限内的类似值。
在相当特别优选的实施方案中,根据本发明的复合材料的BET表面积(根据DIN 66134确定)为≤16m2/g,特别优选≤14m2/g,最优选≤10m2/g。小的BET表面积的优点在于,提高了用根据本发明的复合材料作为活性材料的电极的压实密度以及电极密度,并因此也提高了电池的体积容量和寿命。另外,在电极配料中需要更少的粘合剂。
根据本发明的材料具有>2.3g/cm3的高压实密度,所述压实密度优选在2.3-3.3g/cm3范围内,仍然更优选在>2.3-2.7g/cm3范围内。与具有单层碳的复合材料相比(例如根据EP 1 049 182 B1获得的),这提高了约8%。
根据本发明获得的压实密度在含有根据本发明的复合材料作为活性材料的电极中比用现有技术的材料产生明显更高的电极密度,结果是在使用这样的电极时,二次锂离子电池的体积容量也提高了。
根据本发明的复合材料的粉末电阻(见下文)优选为<30Ω/cm,因此具有含有根据本发明的复合材料(即锂金属氧化物颗粒)的电极的二次锂离子电池特征还在于特别高的载流量。
相对于复合材料的总质量,根据本发明的复合材料的总碳含量(因此,第一和至少第二含碳层的热解碳的总和)优选<2重量%,更优选<1.6重量%。
在本发明的其它实施方案中,总碳含量约为1.4±0.2重量%。
通过制备根据本发明的复合材料的方法进一步实现了本发明的目的,所述方法包括以下步骤:
a)提供颗粒形式的含氧锂过渡金属化合物,
b)添加热解碳的前驱体化合物并制备两种成分的混合物,
c)通过加热使所述混合物反应,
d)向反应后的混合物中加入用于热解碳的新的前驱体化合物并制备第二混合物,
e)通过加热使第二混合物反应。
如上已经描述的,用于根据本发明的方法的含氧锂过渡金属化合物可以是掺杂的和未掺杂的。以上更详细描述的所有含氧锂过渡金属化合物都可以用在根据本发明的方法中。
根据本发明,在用于根据本发明的方法之前如何进行含氧锂过渡金属化合物的合成也不是重要的,即可以通过固态合成的方案获得,或者也可以通过所谓水热合成来获得,或者通过任何其他方法获得。
但是,已经表明,特别是使用通过水热途径获得的锂过渡金属磷酸盐或钛酸锂在根据本发明的方法中和在根据本发明的复合材料中是特别优选的,因为这常常比通过固态合成制备的含有更少的杂质。
如上已经提及的,在根据本发明的方法的反应条件下可以反应形成碳的几乎所有有机化合物都适合于作为热解碳的前驱体化合物。
在根据本发明的方法的框架内,特别优选使用碳水化合物如乳糖、蔗糖、葡萄糖、淀粉、胶质、纤维素、乙二醇、聚乙二醇或其混合物,特别优选的是乳糖和/或纤维素,此外可以使用聚合物例如聚苯乙烯-丁二烯嵌段共聚物、聚乙烯、聚丙烯,芳香族化合物如苯、蒽、甲苯、二萘嵌苯及其混合物以及本领域技术人员已知的本质上适合于该目的的所有其它化合物。
在使用碳水化合物时,特别是在本发明的具体实施方案中,它们以水溶液的形式使用,或者在本发明的特别有利的实施方案中,在将碳与含氧锂过渡金属化合物和/或元素碳混合后再加入水,结果是获得浆料,与其它方法变体相比,从制备过程和排放的观点来看,其进一步加工是特别优选的。
其它前驱体材料如苯、甲苯、萘、聚乙烯、聚丙烯等可以直接以纯物质形式使用或者在有机溶剂中使用。
典型地,在根据本发明的方法的框架内,形成浆料,该浆料最常见的是先在100-400℃的温度干燥。
任选将干燥后的混合物压实。干燥混合物本身的压实可以以机械压实方式进行,例如利用碾压机或压片机,但是也可以以辊压、聚集或湿法造粒的方式进行,或者利用对于本领域技术人员来说适合于该目的的任何其他技术方法进行。
在步骤b)的混合物的任选压实之后,特别是干燥后的混合物,所述混合物特别优选的是在≤850℃,有利的是在≤800℃,更优选在≤750℃煅烧,如上已经详细描述的,其中,所述煅烧优选在保护气氛下进行,例如在氮气、氩气等气氛下。在所选择的条件下,不会从热解碳的前驱体形成石墨,但是形成部分或完全覆盖含氧锂过渡金属化合物的颗粒的热解碳的连续层。
虽然在更高的煅烧温度在宽温度范围内仍然从前驱体化合物形成热解碳,但是所形成的产物的颗粒尺寸在焙烧过程中增大,这使其产生上述的缺点。
出于制备工程的原因,在煅烧或热解过程中使用氮气作为保护气体,但是也可以使用所有其它已知的保护气体,例如氩气等等以及它们的混合物。也可以使用具有低氧含量的工业级氮气。在加热后,所得的产物仍然可以细磨。
在涂覆第一层热解碳后,如此获得的材料的碳含量相对于其总重量来说通常为1-1.5重量%。
通过重复上述步骤涂覆第二层,其中,如在本发明的某些实施方案中已经描述的,对于热解碳,可以使用与第一层所用的前驱体化合物相同的起始化合物或者与其不同的前驱体化合物。
通过含有根据本发明的复合材料的活性材料的二次锂离子电池的电极,进一步实现了本发明的目的。在本发明的其它实施方案中,电极的活性材料由根据本发明的锂过渡金属氧化物组成。其它成分是例如导电碳黑或不涂覆碳或仅提供一个碳层的其它相应的含氧锂过渡金属化合物。可以理解,根据本发明当然也可以使用具有或没有碳涂层(一层、两层或多层)的若干不同的含氧锂过渡金属化合物的混合物。
与未涂覆或仅涂覆一次的含氧锂过渡金属化合物相比,通过提高根据本发明的复合材料的压实密度,也可以实现电极配料中的更高的电极活性材料密度。除了活性材料以外,根据本发明的电极的典型其它成分(或者在所谓的电极配料中)是导电碳黑以及粘合剂。但是,根据本发明,甚至可能获得含有根据本发明的复合材料或者由根据本发明的复合材料组成的活性材料而没有其它添加的导电剂(即例如导电碳黑)的可用的电极。
本领域技术人员本质上已知的任何粘合剂都可以用作粘合剂,例如聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)、聚偏二氟乙烯六氟丙烯共聚物(PVDF-HFP)、乙烯-丙烯-二烯三聚物(EPDM)、四氟乙烯六氟丙烯共聚物、聚环氧乙烷(PEO)、聚丙烯腈(PAN)、聚甲基丙烯酸甲酯(PMMA)、羧甲基纤维素(CMC)、及其衍生物和混合物。
在本发明的框架内,电极材料的各个成分的典型比例优选为90重量份活性材料,例如根据本发明的复合材料的活性材料,5重量份的导电碳和5重量份的粘合剂。在本发明的框架内同样有利的不同配方由90-96重量份活性材料和4-10重量份粘合剂组成。
根据本发明的复合材料由于其涂层已经含有碳,因此如果在电极配料中使用附加的导电剂如导电碳,则使导电剂含量与现有技术的电极相比明显减少成为可能,现有技术的电极使用未涂覆的含氧锂过渡金属化合物。这导致电极密度的增大并且因此导致根据本发明的电极的体积容量增大,因为导电剂如碳黑通常具有低密度。
根据本发明的电极通常具有>2.0g/cm3,优选>2.2g/cm3,特别优选>2.4g/cm3的压实密度。根据本发明的电极的比容量约为160mA/g,体积容量>352mAh/cm3,更优选>384mAh/cm3(相对于锂金属测量)。
根据本发明的电极的典型放电容量D/10在150-165mAh/g范围内,优选在160-165mAh/g范围内。
根据复合材料的含氧锂过渡金属化合物的性质,所述电极可以作为阳极(优选在掺杂或未掺杂锂钛氧化物的情况下,锂钛氧化物在较不优选的实施方案中取决于反电极的性质可以用作阴极)或者作为阴极(优选在掺杂或未掺杂的锂过渡金属磷酸盐的情况下)。
通过含有根据本发明的电极作为阴极和/或阳极,进一步实现了本发明的目的,结果是获得具有更高电极密度(或活性材料密度)的电池,其具有比用现有技术材料的电极的以前已知的二次锂离子电池更高的容量。这样的根据本发明的锂离子电池也可能因此具体使用在汽车中,同时具有更小的电极尺寸或更小的整体电池的尺寸。
在本发明的实施方案中,根据本发明的二次锂离子电池含有两个根据本发明的电极,其中之一包含根据本发明的复合材料或由根据本发明的复合材料组成作为阳极,所述复合材料包含掺杂或未掺杂的锂钛氧化物,另一个包含根据本发明的复合材料或由根据本发明的复合材料组成作为阴极,所述复合材料包含掺杂或未掺杂的锂过渡金属磷酸盐。特别优选的阴极/阳极对是LiFePO4//LixTiyO,单电池电压约为2.0V,其适合于替代铅酸电池或LiCozMnyFexPO4//LixTiyO(其中x,y和z是如上所定义的),并具有提高的电池电压和改善的能量密度。
下面借助附图和实施例更详细地解释本发明,所述实施例不应当理解为限制本发明的范围。
附图说明:
图1:含有根据EP 1 049 182 B1获得的对比材料的电极的放电循环的图(图1a)和含有根据本发明的CC-LiFePO4作为活性材料的电极(图1b)的放电循环的图,
图2:根据本发明的复合材料的TEM照片(CC-LiFePO4),
图3:图2的含碳层的细节的TEM照片,
图4a和b:根据本发明的复合材料(CC-LiFePO4)的细节的其它TEM照片。
1.测量方法
BET表面积根据DIN 66134测定。
颗粒尺寸分布根据DIN 66133利用具有Malvern Mastersizer 2000的激光粒度仪确定。
压实密度和粉末电阻用具有Loresta-GP MCP-T610电阻仪的MitsubishiMCP-PD51压片机同时进行,其安装在填充氮气的手套箱内以排除氧和水分的潜在破坏作用。所述压片机通过手动Enerpac PN80-APJ液压机(最大10,000psi/700bar)液压操作。
4克根据本发明的材料按照制造商推荐的设置进行测量(7.5kN)。
然后根据以下公式计算粉末电阻:
粉末电阻[Ω/cm]=电阻[Ω]×厚度[cm]×RCF
RCF值是设备依赖性的并且对于每个样品由设备给出。
压实密度根据以下公式计算:
r=样品压片的半径
习惯误差公差最大为3%。
在FEI-Titan 80-300上进行TEM研究,其中用超声波将0.1g样品分散在10ml乙醇中,将一滴该悬浮液涂敷在Quantifoil金属网格结构上并在空气中干燥,然后开始测量。
2.实验过程:
2.1电极制备
标准电极组合物含有90重量%的活性材料,5重量%的Super P碳黑和5重量%的PVDF(聚偏二氟乙烯)。
通过先制备具有导电添加剂(Super P碳黑)的在NMP(N-甲基吡咯烷酮)中的10重量%PVDF 21216溶液来制备浆料,然后进一步用NMP稀释,最后加入各自的活性材料。所得的粘性悬浮液利用刮刀沉积在铝箔上,在80℃真空干燥。从该铝箔上切下直径1.3cm的圆盘,称量并滚压到约25μm。然后测量电极的厚度和密度。然后在Büchi干燥器中在120℃真空干燥过夜。然后在氩气氛下在手套箱内组装相应的电池。
测量的电位范围是2.0V-4.1V(相对于Li+/Li)。具有1M的LiPF6的EC(碳酸亚乙酯)∶DMC(碳酸二甲酯)为1∶1(体积)被用作电解质。
2.2容量和载流量的测定。
用标准电极组合物测量容量和载流量。
在这些测量过程中,充电速率(C)对第一循环被设定为C/10,对于所有其它循环被设定为1C。
如果需要,放电速率(D)从D/10增大到20D。
3.具有单一涂层的LiFePO4的制备
根据EP 1 049 182 B1制备用一个含碳层覆盖的LiFePO4(中间产物),为了确定该中间产物中的最佳碳量,变化乳糖的量。对于所制备的中间产物的相应值表示在表1中:
表1:中间产物中碳量的变化
样品编号 | 1 | 2 | 3 | 4 |
C(重量%) | 2.05 | 1.70 | 1.44 | 1.14 |
BET(g/cm2) | 13.4 | 12.8 | 12.5 | 11.4 |
d10(μm) | 0.19 | 0.19 | 0.20 | 0.21 |
d50(μm) | 0.45 | 0.46 | 0.46 | 0.56 |
d90(μm) | 2.43 | 2.13 | 1.96 | 2.03 |
粉末电阻(Ω.cm) | 23 | 25 | 28 | 44 |
压实密度(g/cm3) | 2.05 | 2.05 | 2.21 | 2.25 |
具有较低碳含量(样品3和4)的样品的压实密度的值比碳含量为2重量%的样品高10%。而且,它们具有最小的BET表面积,如上所述,这也是一个重要的参数。
这些参数,以及活性材料的总碳含量在根据本发明的电极的性能数据方面起重要作用的事实,导致样品3和4作为中间产物是优选的。换言之,也选择乳糖量的值,因此选择碳前驱体材料的量,使得中间产物的碳含量优选在0.9-1.5重量%范围内,特别优选在1.1-1.5重量%范围内。
4.涂覆两次的根据本发明的LiFePO4的制备(CC-LiFePO4)
根据两种不同的方法变体进行所述中间产物用第二个含碳层的涂覆,所述中间产物的碳含量在1.1-1.5重量%的优选范围内。
这里,将中间产物与相应量的乳糖在干燥状态混合并且随后在氮气气氛下在750℃煅烧3小时。
在其他实施方案中,将乳糖溶解在水中,将中间产物浸渍在其中,然后在105℃真空干燥整夜,随后在750℃在氮气气氛下煅烧3小时。
结果表示于表2中:
表2:根据本发明的复合材料的物理数据
利用TEM研究样品(图2)。碳层详细表示在图3和4中,图3和4表示含碳层的不同层结构。
根据本发明的CC-LiFePO4的BET表面积在9.5m2/g至9.4m2/g范围内。粉末电阻的值低于对比样品。
压实密度的值都在2.37和2.41g/cm3之间的范围内,这表明与对比样品的2.25g/cm3的值相比,提高了15-20%。
对于根据本发明的所有样品1-4,在用作电极中的活性材料时,放电速率通常为在D/10约160mAh/g±2%,在10D为122mAh/g±10%(图1b)。
对比样品的结果为在D/10为160mAh/g,在10D为123mAh/g(图1a)。
5.电极中活性材料密度的测定
为了测定活性材料的材料密度,制备包含90%活性材料、5重量%导电碳黑和5重量%的粘合剂的电极。
为此,将2.0g 10%的PVDF的NMP(N-甲基吡咯烷酮)溶液、5.4g的NMP、0.20g的Super P锂导电碳黑(Timcal)、3.6g的根据本发明的磷酸铁锂颗粒(2.2重量%的总碳量),以及具有相同碳含量的对比材料(见第四节)1a作为对比称量到50ml的螺旋盖瓶子中并以600rpm混合5分钟,用Hielscher UP200S超声探头分散1分钟,然后在加入20个4毫米直径的玻璃珠并密封所述瓶子后,以10rpm的速度在滚动台上旋转至少15小时。为了涂覆电极,将这样获得的均匀悬浮液用实验室刮刀涂覆到铝载体箔上,间隙为150μm,喂料速度为20mm/sec。在真空干燥箱中在80℃干燥后,从所述箔上冲压出直径13mm的电极,并且利用实验室辊压机在室温下机械后压缩到25μm。为了测定密度,由毛重和载体箔的已知单位重量确定净电极重量,用螺旋千分尺减去载体箔的已知厚度确定净电极厚度。
电极中用g/cm3表示的活性材料密度由下式计算:
(电极配料中的活性材料部分(90%)×电极净重量(g)/(π×(0.65cm)2×净电极厚度(cm))
作为电极中活性材料密度的值,对LiFePO4(得自Süd-Chemie AG)发现为2.0g/cm3,对于对比样品为2.3g/cm3,对于根据本发明的复合材料例如为2.4g/cm3(见表2)。
6.耐酸性试验
对未涂覆的LiFePO4(根据WO 02/099913获得的“Leifo”)的样品、具有单层碳的样品(根据EP 1049 182 B1涂覆,“C-Leifo”)和根据本发明的复合材料(“CC-Leifo”)进行耐酸腐蚀的试验,各自具有如下所示的不同总碳含量:
将粉末形式的5g样品用1M HNO3溶液制备到95ml,在烧杯中用磁搅拌器搅拌5分钟,静置5分钟,然后在4000rpm离心20分钟。通过过滤去除上清液,并将残余物在真空干燥葙中在105℃干燥过夜。在第二天,称量所述残余物。
样品 | 称量的质量 | 产量 | 收率(%) | C含量(%) | HNO3 |
CC-Leifo 1 | 5g | 1.85g | 37.0 | 2.2 | 1M |
CC-Leifo 2 | 5g | 1.53g | 30.6 | 2.2 | 1M |
C-Leifo 1 | 5g | 1.32g | 26.4 | 2.05 | 1M |
C-Leifo 2 | 5g | 1.1g | 22.0 | 1.14 | 1M |
CC-Leifo 3 | 5g | 1.24g | 25.0 | 1.43 | 1M |
C-Leifo 3 | 5g | 0.83g | 20.0 | 1.1 | 1M |
Leifo | 5g | 0.40g | 8 | 0 | 1M |
从表中明显看出,未涂覆的LiFePO4几乎完全溶解,用一个含碳层覆盖的LiFePO4溶解的较少,根据本发明的复合材料是最好的,即最耐浓酸侵蚀。
7.溶解度试验
对涂覆一次的LiFePO4(C-leifo)、涂敷两次的LiFePO4(CC-Leifo)和未涂覆的LiFePO4(Leifo)进行溶解度试验(浸渍)如下:
使用铝复合箔A30(d:103μm)的方袋(内部尺寸4.0×10.0cm,三边密封),Article-No.34042,Nawrot AG。
首先,确定铝复合箔袋(外部尺寸11cm×6cm)的净重量(梁式分析天平),将0.8g的电极材料(90重量%活性材料、5%导电碳黑、5重量%PVDF粘合剂)与4ml电解质(LiPF6(1M)在碳酸乙酯(EC)/碳酸二甲酯(DMC)1∶1中,水含量:1000ppm)焊接到铝袋中(约10cm×6cm)(袋1)或者与4ml电解质(LiPF6(1M)在碳酸乙酯(EC)/碳酸二甲酯(DMC)1∶1中,(没有可检测到的痕量水))密封(袋2),然后在60℃储存12星期。在试验时间到期后,重新称量所述袋以确定电解质的任何损失。然后利用ICP-OES(SpectroflameModula S)分析0.2μl的电解质。
结果如下:
从表中可以清楚看出,在根据本发明的复合材料(CC-Leifo)的情况下,铁的溶解度明显小于未涂覆的LiFePO4(Leifo)或仅涂覆一次的LiFePO4的情况(C-Leifo)。
Claims (20)
1.含碳复合材料,其含有被两个含碳层覆盖的含氧锂过渡金属化合物的颗粒。
2.根据权利要求1的复合材料,其中,所述锂过渡金属化合物是掺杂或未掺杂的锂过渡金属磷酸盐,所述过渡金属选自Fe、Co、Mn或Ni或其混合物。
3.根据权利要求1的复合材料,其中,所述锂过渡金属化合物是掺杂或未掺杂的锂钛氧化物。
4.根据权利要求3的复合材料,其中,所述锂钛氧化物是钛酸锂Li4Ti5O12。
5.根据前述权利要求1-4的任一项的复合材料,其中,每个含碳层中的碳在固体中具有不同结构。
6.根据权利要求5的复合材料,其中,所述第一含碳层的厚度为≤5nm,所述第二含碳层的厚度为≤20nm。
7.根据权利要求6的复合材料,其BET表面积为≤16m2/g。
8.根据权利要求7的复合材料,其在含有锂氟盐的液体中的过渡金属溶解度为≤85mg/l。
9.根据权利要求8的复合材料,其压实密度为>2.3g/cm3。
10.根据权利要求9的复合材料,其粉末电阻为<35Ω/cm。
11.根据权利要求10的复合材料,其总碳含量为<1.6重量%。
12.一种用于生产根据前述权利要求的任一项的复合材料的方法,包含以下步骤:
a)提供颗粒形式的含氧锂过渡金属化合物,
b)加入热解碳的前驱体化合物并制备该两种组分的混合物,
c)通过加热使所述混合物反应,
d)向反应后的混合物中加入热解碳的新的前驱体化合物,并制备第二混合物,
e)通过加热使第二混合物反应。
13.根据权利要求12的方法,其中,掺杂或未掺杂的锂过渡金属磷酸盐或者掺杂或未掺杂的锂钛氧化物被用作含氧锂过渡金属化合物。
14.根据权利要求13的方法,其中,所述碳水化合物被用作热解碳的前驱体化合物。
15.根据权利要求14的方法,其中,在步骤b)中和/或步骤d)中,以含水混合物作为浆料的形式制备所述混合物。
16.根据前述权利要求12-15的任一项的方法,其中,在步骤c)和/或e)中的加热在≤850℃的温度进行。
17.通过根据权利要求12-16的任一项的方法可获得的用碳涂覆两次的含氧锂过渡金属化合物。
18.具有包含根据权利要求1-11或17的任一项的复合材料的活性材料的二次锂离子电池的电极。
19.根据权利要求18的电极,其不含添加的导电剂。
20.具有根据权利要求18或19的任一项的电极的二次锂离子电池。
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- 2011-04-14 EP EP11714974A patent/EP2561567A2/de not_active Withdrawn
- 2011-04-14 KR KR1020127029647A patent/KR20130045268A/ko not_active Application Discontinuation
- 2011-04-14 JP JP2013505413A patent/JP2013525964A/ja not_active Withdrawn
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Also Published As
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WO2011131553A3 (de) | 2011-12-29 |
WO2011131553A2 (de) | 2011-10-27 |
CA2797030A1 (en) | 2011-10-27 |
EP2561567A2 (de) | 2013-02-27 |
TW201205945A (en) | 2012-02-01 |
KR20130045268A (ko) | 2013-05-03 |
US20130095385A1 (en) | 2013-04-18 |
JP2013525964A (ja) | 2013-06-20 |
DE102010018041A1 (de) | 2011-10-27 |
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