CN1286714C - 制造电极的方法和由此制备的电极 - Google Patents

制造电极的方法和由此制备的电极 Download PDF

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CN1286714C
CN1286714C CNB2004100077067A CN200410007706A CN1286714C CN 1286714 C CN1286714 C CN 1286714C CN B2004100077067 A CNB2004100077067 A CN B2004100077067A CN 200410007706 A CN200410007706 A CN 200410007706A CN 1286714 C CN1286714 C CN 1286714C
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O·Z·周
B·高
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Abstract

一种含有碳的同素异形体，如单壁碳纳米管的碳基材料，其能够接纳掺入的碱金属。该材料呈现的可逆容量在约650mAh/g-1000mAh/g之间。该材料的高容量使其对许多应用，如电池的电极材料(50)具有吸引力。一种生产单壁碳纳米管的方法，包括提纯回收的纳米管材料和将提纯的材料沉积在一种导电基体(42)上。将该有涂层的基体(42)装入一种电化学电池中，并且测量其接纳掺入的材料，如一种碱金属(例如锂)的能力。

Description

制造电极的方法和由此制备的电极
本申请是基于申请日为2000年2月24日申请号为00806392.3的申请所提交的分案申请。
        有关联邦政府资助的研究或开发的声明
本发明的至少一些方面是在合同号为N00014-98-1-0597的政府资助下进行的。政府对本发明可以有一定的权利。
                      技术领域
在下面的叙述中参考了某些化合物、装置和一些方法。在实际应用的法规规定下，不必将这些参考解释为承认这样的化合物、装置及其方法为现有技术。
                       背景技术
在1990年证明了称之为“富勒烯”碳的第三种方式的存在，其触发了旨在使这种“新”材料发挥最大潜力的研究和开发的巨大浪潮。
“富勒烯”一词通常用于表示具有笼形中空晶格结构的一族碳分子。这些“笼”可以是不同的形状，如球状(“跳格球”)、或管状(“纳米管”)。例如见：Robert F.Curl和Richard E.Smalley所著，Fullerenes(富勒烯)，Scientific American，October 1991.
随着电池广泛应用的重要性增加，从携便式电子设备到航天飞机的供电装置，长期以来都需要具有更高能量密度的新材料。通过测量能够与材料进行可逆反应的供电子原子的数量可以定量材料的能量密度。一种获得这样测量值的方法是通过建立一种电化学电池。该电池包括：一个容纳电解质的容器；一个由供电子材料(例如一种碱金属)制成的电极；由容量待测的材料(例如一种碳基材料)制成另一个电极；和连接电极的电路。供电子物质的原子经过氧化反应形成供电子物质的离子和自由电子。这些离子被相反电极吸引并且自由电子通过电路运动。由于供电子物质的每一个原子“给出”电子的数量是已知的，所以测量通过电路移动的电子数量，就可以确定移动到待研究物质的离子的数量。这个数量就是材料的比容量，并且可以表达为毫安-小时/克材料。例如，有报道石墨接纳锂的最大比容量(可逆的)大约372mAh/g。因为因为对于每一个释放的电子，都有一个锂离子移动到石墨电极上，其比容量可以根据电极材料的化学当量来表示。对于石墨，电极材料可以表征为LiC6。例如见：J.R.Dahn等人所著的，Mechanisms for Lithium Insertion in Carbonaceous Materials，Science，卷270，1995年10月27日。
锂掺入石墨和其它含碳材料被商业用作高级锂离子电池的电极。例如见：M.S.Whittingham，editor， Recent Advances in rechargeable  Batteries，Solid State Ionics，卷3和4，number69，1994；和D.W.Murphy等人，editors， Materials for Advanced Batteries，Plenum Press，New York，1980。这些传统电池材料的能量容量部分地被石墨中的LiC6饱和Li浓度所限制(等于372mAh/g)。
碳纳米管用作潜在的电极材料已经引起注意。碳纳米管通常是以紧密的同心多层壳或多壁纳米管(MWNT)存在。纳米管也可以以单壁纳米管(SWNT)形成。该单壁纳米管(SWNT)形成束，这些束具有紧密堆叠的2-D三角晶格结构。
多壁纳米管(MWNT)和单壁纳米管(SWNT)都已经生产出来了，并且通过蒸汽传输反应测出了这些材料的比容量。例如见：O.Zhou等人所著， Defects in Carbon Nanotubes，Science：263，pgs.1744-47，1994；R.S.Lee等人所著， Conductivity Enhancement in Single- Walled Nanotube Bundles Doped with K and Br，Nature：388，页257-59，1997；A.M.Rao等人所著， Raman Scattering Study of Charge Transfer in Doped Carbon Nanotube Bundles，Nature：388，页257-59，1997；和C.Bower等人所著， Synthesis and Structure of Pristine and Cesium Intercalated Single-Walled Carbon Nanotubes，Applied Physics：A67，页47-52，spring 1998。报道称这些纳米管材料的最高碱金属的饱和度为MC8(M=K、Rb、Cs)。这些数值表明并不显著优于现存的普遍商用的材料，如石墨。
因此长期以来，一直需要具有改善性能的材料，但是这一需要至今未能得到满足。对具有能使其用于电池和其它高能量应用的改善性能的材料存在着需求。特别是，需要比目前正用于这些应用的那些材料具有更高能量密度的材料。
                        发明内容
根据本发明的原理可以实现这些和其它目的。
本发明的一个方面包括一种具有掺入了碱金属的碳同素异形体的碳基材料。该材料具有的可逆容量高于900mAh/g。
本发明的另一个方面包括一种具有单壁碳纳米管并掺入了锂金属的材料。该材料具有的可逆容量高于550mAh/g。
在本发明的另一个方面，一种制造的部件，其包括表面上置有一层薄膜的导电基体。该薄膜含有单壁碳纳米管和掺入的锂金属。该部件具有的可逆容量高于550mAh/g。
还有在本发明的另一个方面，一种制造方法，其包括：通过将至少含有大约80％的单壁纳米管的一种碳基材料加入到一种溶剂中而产生一种混合物，将基体浸渍在该混合物中，并将溶剂蒸发，从而在所述基体的至少一个表面上留下碳基材料的薄膜。
还有在本发明的另一个方面，通过产生一种混合物生产具有可逆容量高于550mAh/g的一种电极材料。通过将至少含有大约80％的单壁纳米管的一种碳基材料加入到一种溶剂中产生该混合物，将基体浸渍在该混合物中，并将溶剂蒸发，从而在所述基体的至少一个表面上留下碳基材料的薄膜。
具体地说，本发明涉及以下方面：
1.一种制造电极的方法，其包括：
通过将一种含有至少约80体积％的单壁纳米管的碳基材料加入到一种溶剂中而制备混合物；
将基体浸渍在该混合物中；和
将所述溶剂挥发，从而使所述碳基材料薄膜留在所述基体至少一个表面上。
2.第1项的方法，其还包括：
使用高能激光束轰击靶材，从而产生含有至少50体积％单壁纳米管的融化材料；
通过将所速融化材料加入到一种悬浮介质中而制备悬浮液，并引入超声波能，从而在所述悬浮介质中悬浮所述纳米管；和
使所述悬浮液通过过滤膜并回收含有至少80体积％碳纳米管的所述碳基材料。
3.第2项的方法，其中所述悬浮介质包括乙醇。
4.第2项的方法，其中所述超声波能是通过一种工作在约60W和20kHz的超声波辐射器产生的。
5.第1项的方法，其还包括将所述含有至少80体积％单壁纳米管的碳基材料进行球磨的步骤。
6.第5项的方法，其中所述球磨进行的时间至少为1分钟。
7.第6项的方法，其中所述时间为20分钟或更少。
8.第7项的方法，其中所述时间是约5-10分钟。
9.第1项的方法，其中所述基体包括一种导电材料。
10.第9项的方法，其中所述导电材料包括铜或镍中的一种。
11.第1项的方法，其中所述薄膜基本上不含粘结剂。
12.一种电极，其至少有一部分是通过第1项的方法制成的，该电极具有的可逆容量高于550mAh/g。
13.一种电极，其至少有一部分是通过第6项的方法制成的，该电极具有的可逆容量高于650mAh/g。
14.一种电极，其至少有一部分是通过第8项的方法制成的，该电极具有的可逆容量高于约900mAh/g。
15.一种电极，其至少有一部分是通过第8项的方法制成的，该电极具有的可逆容量高于约1000mAh/g。
16.一种电极，其至少有一部分是通过第1项的方法制成的，其中所述薄膜基本上不含有粘结剂。
                    附图说明
图1是用于生产含有单壁纳米管的一种碳基材料的激光熔化系统的示意说明图；
图2是一种球磨设备的示意说明图；
图3A是本发明的成膜技术的示意说明图；
图3B是本发明的涂敷有纳米管的基体剖视图；
图4是根据本发明形成的纳米管薄膜的扫描电子显微镜(SEM)显微照片；
图5是引入了本发明的电极材料的电化学电池的示意图；
图6是根据本发明原理形成的提纯纳米管材料的充电-放电特征曲线；和
图7是纳米管材料经过球磨处理后的充电-放电特征曲线。
                    具体实施方式
通过许多技术如碳靶的激光熔化、碳氢化合物分解和在两个石墨电极之间形成弧光，可以形成一种含有单壁纳米管(SWNT)的碳基材料。
例如，在C.Bower等人所著， Synthesis and Structure of Pristine and Cesium Intercalated Single-Walled Carbon Nanotubes，Applied Physics：A67，页47-52，spring 1998.文献中叙述了一种用于生产SWNT束的合适技术，将其公开的全部内容在此引入作为参考。
如图1所示，根据该技术将合适的靶2放置在石英管4之中。优选靶2是由石墨制成，并含有Ni/Co催化剂的。在一优选实施方案中，该靶材是由混合有0.6原子％的Ni和0.6原子％的Co的石墨粉和石墨粘结剂形成的。
通过合适的连接器8连接在管4的一端的真空泵6对管4抽真空。通过合适的气源，如罐10向管4通入惰性气流G，如氩气。各种装置如流量控制器和/或压力表可以接入该系统中，用于控制和监测流入管4的情性气体G的气流。将惰性气体的压力保持在合适的水平，如大约800托。适用于收集流出管4的情性气体的收集装置16，如装着水的瓶子可以通过连接器8连接在管4的端部。
通过管式加热器5，优选有程度控制器的，将管4内的靶材加热到约1150℃。
能量源18，如一种Nd:YAG脉冲激光用于在高温下熔化靶材2。优选使用第一和/或第二谐振激光束(即分别为1064nm和532nm)来熔化靶材。合适的装置如水平扫描器20和垂直扫描器22可以与能源相连接。通过合适的透镜部件24使激光束B聚焦在靶材2上。
在管的一端可以用透明窗26如石英窗密封，以便于激光束透过和监控激光熔化过程。在这一端可以使用合适的监控装置。例如，CCD装置可以定向通过窗口26，并且输出量传入监控装置30中，其能够观察和记录熔化过程。
在靶材熔化时，含有纳米管的材料通过情性气流的下流传输并在管4的内壁上形成沉积物D。将这些沉积物移出以回收含有纳米管的材料。
根据上述技术形成的碳基材料，在回收后对其进行分析，发现其含有50-70体积％的SWNT(单壁纳米管)，其单个管的直径为1.3-1.6nm(纳米)并且管束直径为10-40nm。该管束是随机取向的。杂质相包括不定形碳的纳米颗粒和金属催化剂，构成总靶材1原子％。
根据本发明，通过合适的提纯方法对回收的材料进行提纯。在一个优选实施方案中，将纳米管材料放置在一种合适的液体介质如乙醇中。使用高能超声波辐射器使纳米管材料在液体介质中悬浮几个小时，然后使悬浮液通过微孔隔膜。任选地，在将其放置在悬浮液中之前，可以用酸对回收的材料进行冲洗。
超声波能量的上述应用也可能在纳米管中造成损害或产生缺陷。正如下面将要进一步详细叙述的，这也许实际上有利于用于增加其容纳掺入材料的能力。
透射和扫描电子显微镜检测表明提纯的材料含有80体积％以上的单壁纳米管(SWNT)束。
任选地，提纯的材料可以用球磨进一步加工。该加工通常如图2所示。将提纯的单壁纳米管试样32和球磨介质36一起放置在合适容器34的里面。密封该容器并将其放在球磨机合适的固定器38上。根据本发明，试样的球磨时间是可变的。例如，试样球磨的时间可以在约1-20分钟之间。
本发明的纳米管材料的一个优点是它们可以相当容易地以薄膜形式沉积在基体材料上。例如，提纯和任选球磨的纳米管材料的试样可以以溶液形式沉积在合适的基体上。这样的方法通常如图3A所示。将合适的基体42放置在容器44的底部。在一优选实施方案中，基体是一种导电材料，如铜或镍。基体42可以形成为平的铜极片。虽然极片的尺寸可以改变，但可以使用面积为1cm×1cm的极片。通过使用超声波能量，单壁纳米管材料和合适的溶剂如乙醇的混合物可以被放入悬浮液46。然后将该悬浮液46放置在容器44中。然后将基体42浸渍在混合物46中。通过被动蒸发或主动去除将溶剂挥发，致使单壁纳米管材料的薄膜48至少涂敷在基体42的上表面上，如图3B所示。然后将有涂层的基体进行适当的热处理以去除任何残留的溶剂并提高薄膜48对基体42的附着力。例如，在真空下将有涂层的基体加热到约130-150℃并保温几个小时或足以去除溶剂的时间。
根据上述技术形成的单壁纳米管薄膜和传统碳基材料薄膜相比，具有许多的优点。例如，石墨通常用作电极材料。但是，很难形成由石墨构成的薄膜。因此必需在石墨中加入粘结剂材料以便促进成膜。但是加入粘结剂材料对电极材料的电性能有负面影响。通过本发明的上述技术，能够不必使用这样的粘结剂材料而将单壁纳米管材料的薄膜沉积在基体上，从而避免了上述的有关缺点。
另外，典型地，将导电剂如炭黑加入到石墨材料中以便增加材料的导电性。炭黑的加入增加了形成产品的成本。但是，本发明的单壁纳米管材料具有很好的导电性，并且不需要加入昂贵的导电剂如炭黑。
在扫描电子显微镜(SEM)下分析了根据本发明形成的薄膜。图4是显示单壁纳米管薄膜的纯度和形态的显微照片。
根据上述原理生产的单壁纳米管材料具有意想不到的能量密度性能，其超过了其它碳基材料所拥有的那些性能。
通过形成类似于上述背景技术部分中所叙述的电化学电池，可以测量本发明的单壁纳米管材料的能量密度或能够接纳掺入金属如碱金属的能力。图5示意说明了一种引入了本发明的单壁纳米管材料的电化学电池。
一种电池是由锂箔电极50和用作第二电极的具有如上述形成的单壁纳米管薄膜48的铜基极片42而构成的。将浸透有电解液的聚丙烯过滤膜52放置在这两个电极之间。在一个优选实施方案中，使用1M(1摩尔)的LiClO4和体积比为1∶1的EC(碳酸亚乙酯)和DMC(碳酸二甲酯)的溶液作为电解液。测得的该液体电解液的离子导电性为10-3S/cm。电接触件是由两个不锈钢活柱54、56压靠在电极上而构成的。电源58连接在该活柱上。使用静电方式在0.0-3.0V之间和以50mAh/g的速率对该电池进行放电和充电。如上述背景技术中所述，从使用的时间和电流可以计算出Li的比容量(单位碳掺入Li的数量)。
与传统的材料相比，本发明提纯的单壁纳米管具有明显更高的容量。本发明的提纯的单壁纳米管材料所展现的可逆容量要高于550mAh/g，并且特别是其容量大约650mAh/g(等于Li1.7C6)。通过上述的球磨工序，可逆容量可以进一步增加到900-1000mAh/g(Li2.4+C6)的水平。
如图6所示的电压-容量的曲线，完全掺入锂的提纯的单壁纳米管试样所显示的总容量大约2000mAh/g(Li5.4C6)。可逆部分定义为在第二次放电后所显示的容量，其大约600mAh/g。这相当于Li1.6C6，比石墨的理论值还高60％。再进行循环仅导致Li容量的少量下降。在同样的条件下对不同批次的几个试样进行了测量，显示其可逆容量在550-650mAh/g之间。当使用不同的电解液时，不可逆容量(定义为在第一次和第二次放电之间的容量差)的大小只有微小的变化。
如图7所示，单壁纳米管的机械球磨导致了其可逆容量的明显增加，并大大降低了其不可逆容量。测量并分析了球磨1-20分钟的单壁纳米管的放电-充电特性。X-光衍射和TEM(透射电子显微镜)的数据表明球磨诱发了无序并且将单壁纳米管束切割得更短并成为开口的片断。也观察到了其形态的变化。球磨后降低了单壁纳米管材料的多孔性。
球磨了5分钟的单壁纳米管试样所显示的可逆容量为830mAh/g，并且其不可逆容量为400mAh/g。
球磨了10分钟的单壁纳米管试样所显示的可逆容量增加到了超过900mAh/g(Li2.4C6)的水平，并且更特别是到了约1000mAh/g。其不可逆容量降低到600mAh/g。再进行循环时观察到其可逆容量几乎没有下降。与没有球磨的提纯单壁纳米管一样，该试样对充电显示出大的滞后。
另一个重要的性能参数是充电和放电速率对材料容量有何影响。有些应用，如电动车辆要求电极材料在高速充电和放电条件下工作。一般地说，材料的容量随着速率的增加而降低。当在50mAh/g速率时测量上述球磨了10分钟的单壁纳米管试样，其呈现的可逆容量为1000mAh/g。50mAh/g是通常的测试速率。当以500mAh/g的速率对同样试样进行测试时，其保持了非常高的容量600mAh/g。
球磨工艺对可逆容量的影响可以进行如下的解释。正常情况下，单壁纳米管的内部核心区是不能接纳掺入的材料，因为它们具有封闭结构，并且在本实验条件下，锂离子是不能通过形成单壁纳米管晶格的碳五边形和六边形而扩散的。因此，这样的掺入的材料通常容纳在形成管束的单壁纳米管之间的空间里。机械球磨增加了缺损密度和降低了单壁纳米管的长度，并因此便于Li+扩散进入纳米管中。例如，可以打破纳米管的端部，从而形成纳米管上的开口。通过这些开口端和也许通过其它缺损位置，相当数量的Li+离子可以容易地扩散进入这些结构受损的单壁纳米管，提高了容量。正如上面所指出的，提纯时将超声波能施加在单壁纳米管上，也能引入这样的缺损，因此其对单壁纳米管材料的容量也有类似的作用。
球磨超过10分钟的试样开始显示其可逆容量下降。这认为是纳米管的晶格结构被过度破坏，其对材料的导电性有负面影响，并且纳米管被转变成石墨片和非晶碳，从而造成了这种下降。
为了说明本发明优异的和意想不到的性能，根据上述技术收集了多壁纳米管(MWNT)薄膜的电压-容量的数据。在第一次放电时获得的总容量为500mAh/g。测量其可逆部分(定义为在第二次放电时所呈现的容量)为250mAh/g，这甚至小于石墨的理论值372mAh/g(LiC6)。再进行循环时其容量仅仅有微量的下降。其它的文献报道多壁纳米管材料的容量在100-400mAh/g之间。例如见：E.Frackowiak等人所著，“ Electrochemical Storage of Lithium Multiwalled Carbon Nanotubes”，Pergamon，Carbon 37(1999)，61-69。
根据上述方法也收集了亚稳碳微束(MCMB)薄膜的电压-容量的数据。该试样所显示的可逆容量为300mAh/g。
本发明的单壁纳米管材料的优异的容量，并结合有极好的机械和电性能，以及容易成膜，这些使其应用于高能量密度的电极材料，如锂离子电池，很具有吸引力。
尽管通过参考特别的实施方案说明了本发明，但本发明决不受此限制。相反，对于那些本领域技术人员，下面权利要求中的改进和变化都是显而易见的。

Claims (16)

1.一种制造电极的方法，其包括：
通过将一种含有至少约80体积％的单壁纳米管的碳基材料加入到一种溶剂中而制备混合物；
将基体浸渍在该混合物中；和
将所述溶剂挥发，从而使所述碳基材料薄膜留在所述基体至少一个表面上。
2.权利要求1的方法，其还包括：
使用高能激光束轰击靶材，从而产生含有至少50体积％单壁纳米管的融化材料；
通过将所述融化材料加入到一种悬浮介质中而制备悬浮液，并引入超声波能，从而在所述悬浮介质中悬浮所述纳米管；和
使所述悬浮液通过过滤膜并回收含有至少80体积％碳纳米管的所述碳基材料。
3.权利要求2的方法，其中所述悬浮介质包括乙醇。
4.权利要求2的方法，其中所述超声波能是通过一种工作在约60W和20kHz的超声波辐射器产生的。
5.权利要求1的方法，其还包括将所述含有至少80体积％单壁纳米管的碳基材料进行球磨的步骤。
6.权利要求5的方法，其中所述球磨进行的时间至少为1分钟。
7.权利要求6的方法，其中所述时间为20分钟或更少。
8.权利要求7的方法，其中所述时间是约5-10分钟。
9.权利要求1的方法，其中所述基体包括一种导电材料。
10.权利要求9的方法，其中所述导电材料包括铜或镍中的一种。
11.权利要求1的方法，其中所述薄膜基本上不含粘结剂。
12.一种电极，其至少有一部分是通过权利要求1的方法制成的，该电极具有的可逆容量高于550mAh/g。
13.一种电极，其至少有一部分是通过权利要求6的方法制成的，该电极具有的可逆容量高于650mAh/g。
14.一种电极，其至少有一部分是通过权利要求8的方法制成的，该电极具有的可逆容量高于约900mAh/g。
15.一种电极，其至少有一部分是通过权利要求8的方法制成的，该电极具有的可逆容量高于约1000mAh/g。
16.一种电极，其至少有一部分是通过权利要求1的方法制成的，其中所述薄膜基本上不含有粘结剂。
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