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CN102282110B - 通过从高挥发物焦炭中萃取沥青而生产涂覆的石墨阳极粉末和原位涂覆它 - Google Patents

通过从高挥发物焦炭中萃取沥青而生产涂覆的石墨阳极粉末和原位涂覆它 Download PDF

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CN102282110B
CN102282110B CN2010800047027A CN201080004702A CN102282110B CN 102282110 B CN102282110 B CN 102282110B CN 2010800047027 A CN2010800047027 A CN 2010800047027A CN 201080004702 A CN201080004702 A CN 201080004702A CN 102282110 B CN102282110 B CN 102282110B
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M·W·卡雷尔
E·J·纳尼
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Abstract

本发明涉及一种制备用于包括可充电锂离子电池组的电池组中的碳涂覆的石墨阳极粉末的方法，其中该方法包括用作其它产物中的前体，更优选地作为其它粉末或颗粒产品的涂覆材料的副产物各向同性沥青。该方法包括从高挥发物生焦炭粉末中溶剂萃取挥发物的步骤。当所需量的挥发物被萃取时，改变溶剂浓度以使一些挥发物沉淀在粉末颗粒上以涂覆它。然后将涂覆且溶剂萃取的颗粒与溶剂分离并氧化稳定化，然后碳化并优选石墨化。保留在溶剂中的挥发物是有价值的，且被回收用于其它过程和其它产品中。

Description

通过从高挥发物焦炭中萃取沥青而生产涂覆的石墨阳极粉末和原位涂覆它
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关于由联邦政府资助的研究或开发的声明
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发明领域
本发明涉及用于锂离子电池组的负极中的材料和这种材料的制备方法。
发明背景
由于它的轻重量、高电压、高电化学等效性和良好传导性，可再充电的锂离子电池组技术是便携式电力系统中有吸引力的较广泛采用的技术。随着电池组电源在汽车推进系统中的广泛使用的发展，无论混杂或插入或其它技术，已做出许多努力改善锂离子电池组以满足预期的市场需求和获得尽可能多的可能来自广泛执行的基本效益和价值。商业锂离子电池组中可采用的一个发展是用于锂离子电池组的阳极或负极上的碳涂覆的石墨粉末。石墨提供有效的锂离子插层和脱插层，同时，碳涂层提高导电性和保护来自电池组中电介质的下面的石墨。在阳极中用这种材料能更好地赋予高的第一循环效率和长循环寿命。
然而，和几乎任何事情一样，改善的性能或改善的特征如较轻的重量总是理想的，总是驱使以较低的费用提供高性能。对于目前制备碳涂覆的石墨颗粒的方法，起始原料由石油焦得到。可在涂覆以前将焦炭煅烧或可在将它涂覆以后煅烧。涂层通过选择性沉淀方法施加，其中形成碳残余物的材料，优选高分子量石油沥青溶于溶剂中。将焦炭颗粒加入沥青溶液中并通过加入更多溶剂或其它液体改变溶剂浓度以导致沥青中较高分子量的品种沉淀在颗粒上。然后将涂覆的焦炭颗粒从涂覆过程中除去并在升高的温度下在氧气的存在下稳定化，并在高于稳定化温度的温度下在惰性环境中石墨化。该方法通常描述于通常拥有的2008年1月29日提交的美国专利No.7,323,120中。
非常理想的是制备确实小粒度的石墨材料，并能调整粒度分布使得可赋予电池组生产商每生产商规格具有预定平均值的粒度预定范围。能够在快速且便宜的方法中用低成本前体生产这种材料甚至是更理想的。
附图简述
可通过参考以下描述连同附图最佳地理解本发明及其其它优点，其中：
图1为说明本发明基本步骤的工艺流程图；
图2为说明本发明方法的可选择实施方案的工艺流程图；
图3为已溶剂萃取挥发物的高挥发物焦炭颗粒的扫描电子显微镜图像；和
图4为通过本发明方法制备的颗粒的扫描电子显微镜图像，具体显示已涂覆有已从焦炭颗粒中原位萃取，然后选择性涂于其上的挥发物的高挥发物焦炭颗粒。
发明详述
当涉及电池组的各个参数和品质时，将通过陈述几个定义协助本发明的说明书、讨论和理解。如本文所用，术语意欲具有它们在本领域中的通常含义，但为了清晰，提供具体定义以避免混淆和有助于清楚地理解。
“电池”为用于储存和释放电能的基本电化学单元。
“电池组”为以适当的串联/并联布置电互连以提供所需工作电压和电流水平的两个或更多个电化学电池。在一般的使用中，术语“电池组”也适用于单电池装置。
“阳极”为电池的负极。
“阴极”为电池的正极。
“比电容”为每单位重量充电的电池中可得到的电能，以单位mAh/g或mAh/cc给出。
“库仑效率(％)”为从电极材料中放出的电荷量与将电极充电至放电前状态所用的电荷量之比。
“电极电势”为在所关心的电极和另一电极(参比电极)之间的电压。
“功率”指每单位时间释放的能量。
“稳定化”是这样一个过程，该过程使得形成碳残留物的材料(CRFM)的颗粒不熔，使得只要随后的热处理温度不超过稳定化的CRFM的瞬时熔点，CRFM颗粒的表面在随后的热处理期间就不软化或熔化并熔合至相邻的CRFM颗粒上。
“碳化”是将含碳化合物转化成特征在于“基本上为碳”的材料的热过程。本文所用“基本上为碳”表示所述材料的至少95重量％为碳。
“石墨化”是将含碳化合物转化成特征在于为至少99重量％碳的材料的热过程，包括石墨片的形成和片在彼此预部上的排序或堆叠。
“形成碳残留物的材料”(CRFM)指任何这样的材料：当在惰性气氛中在600℃的碳化温度或达约1600℃的甚至更高的温度下热分解时，其形成基本上为碳的残留物。沥青为形成碳残留物的材料。
据先前理解，本发明涉及一种制备用于电池组的阳极中，尤其是用于可再充电锂离子电池组的阳极中的碳涂覆的石墨粉末的方法。该方法特别包括涂覆其中具有高挥发物的生焦(green coke)的原位方法。认为约10-30％的挥发物含量为高的。挥发物相当于沥青，为形成碳残留物的材料。萃取生焦中的至少一部分挥发物并用于涂覆颗粒。本发明的部分是从生焦中回收挥发物，而不是使其作为涂层保留在其它颗粒上，使得它可用于制备用于电池组和其它技术中的其它材料。
如图1所示，方法基本开始于将挥发物含量为10-30％的研磨生焦与芳族溶剂如苯、甲苯或二甲苯以0.5∶1-5∶1的溶剂/焦炭比在50℃以上，更优选200℃以上的温度，和环境或以上的压力下混合。在将至少一部分挥发性物质通过溶剂从生焦中萃取以后，将抗溶剂加入悬浮液中以使挥发性物质沉淀。焦炭颗粒用作使挥发性物质沉淀的成核点，因此将挥发性物质分布在表面上以涂覆颗粒。
通常，溶剂处理/萃取在密闭容器或高压釜中进行。取决于溶剂和温度，在升高压力下的溶剂悬浮液可在密闭容器中自发地产生至多200psi的压力。产生焦炭的精炼厂的生焦加工条件确定可得到的可溶性沥青和油的分子量范围。选择用于萃取挥发物的溶剂的量和类型以调整萃取油的分子量范围。用于使挥发物沉淀在颗粒上的抗溶剂的量和类型确定涂层的厚度和软化点。
方法的下一步骤是从溶剂中除去现在溶剂处理和涂覆的生焦。这优选通过过滤进行，但适于将颗粒固体与液体分离的任何其它合适方法可以是令人满意的。其它潜在技术可包括离心分离、倾析和蒸发分离。优选将溶剂处理的生焦用低溶剂浓度的溶剂，例如溶剂与抗溶剂的混合物洗涤以除去可能保留的不想要可溶性油。然后将溶剂处理的生焦颗粒在空气中或在其它温和条件下干燥以从涂层中消除溶剂。较高碳数的烃通常首先从挥发性组分中沉淀，且在大气条件下没有溶剂地基本不溶。
优选将涂层通过在升高的温度下在氧气的存在下稳定化而进一步加工。随着稳定化处理的温度提高，通常以约1℃/分钟起始于约室温直至约350℃，并在约350℃下保持约2小时，沥青涂层发生氧化并变得不熔，尽管温度提高。如果温度太快地升高或氧化没有随温度提高充分地进行，则沥青涂层将变粘，颗粒可能熔合在一起。颗粒的熔合由于以下几个原因是不希望的：1)它产生具有不可控的颗粒分布和大于所需的颗粒比例的产物，2)大于所需的颗粒使得颗粒加工至电池组中困难，和3)研磨熔合离子以分离各个颗粒可能产生表面积高且可能使电池组中所用电解质催化分解的参差不齐的表面。更重要的是，电解质分解使电池组的性能劣化。由于电解质分解是非常不希望的，具有光滑表面、圆形和低表面积的石墨阳极材料是理想的。因此，优选控制温度陡升使得适当地进行氧化稳定化。
一旦颗粒在约325-350℃下稳定化，就将颗粒在600-1600℃的温度下在惰性环境中碳化。在该过程期间，涂层和下面焦炭颗粒中的非碳组分被还原至碳占颗粒重量的至少约95％的点。
最后，将颗粒通过在惰性环境中加热到至少2200℃，优选至少2500℃，更优选至少2800℃而石墨化。通常，石墨化温度不高于3200℃。石墨化产生碳晶体的密集片或板，其在其间容纳锂离子。颗粒涂层中的石墨形成接近片或板末端的片，基本防止电解质参与与下面颗粒的长片或板的破坏性副反应。这被认为是通过氧化稳定化期间碳的固定导致的，使得在石墨化期间，涂层被固定，不能跟随或沿着下面颗粒的板或片模板传递。此外，石墨涂层提供导电性以使电子从锂离子移至阳极箔并通过电池组外部的电路，而不需要其它添加剂增强导电性。
作为本发明的任选方面，可向生焦提供用于电池组阳极中的其它材料如天然石墨、硅、锡或钛酸锂。生焦中的挥发物可用于涂覆焦炭颗粒和溶剂悬浮液中的所有辅助基质。如果使用辅助基质如硅或锡，则取消石墨化，这是由于它会熔融和分解硅、锡或钛酸锂颗粒。
在第二实施方案中，不是加入抗溶剂，而是将另外量的溶剂加入悬浮液中以提高溶剂/焦炭比，使得该比为至少2∶1且至多约20∶1。图2阐述突出提高溶剂比的第二实施方案。尽管常识建议将更多溶剂加入溶剂悬浮液中会导致更多挥发物从焦炭颗粒中萃取出，但实际上较高的浓度降低溶剂的溶剂浓度，导致挥发物沉淀，由此以类似于通过初级方法涂覆的方式涂覆颗粒。
在两个实施方案中，将具有溶于其中的任何材料的液体溶剂材料与固体分离，使得可回收沥青材料并用于在其它方法中涂覆其它颗粒。用于涂覆用于电池组中的粉末的沥青材料的来源是有限的，不存在宽范围的供应商。因而，低成本沥青的供应对可使用沥青涂覆它们的材料的那些而言是个问题。在同时制备有用阳极电池组粉末的方法中从生焦中萃取沥青提供可选择的沥青来源，且为双赢局面，因为在收集其它产物的前体的方法中制得有价值产物。
可通过已知方法如蒸馏、刮膜蒸发或其它技术将沥青与溶剂流体或溶剂/抗溶剂混合流体分离。此外，可将可回收的挥发性物质处理或热加工以改变各向同性沥青以提高介晶(mesogen)含量。
提供用于公开本发明的实施例。第一实施例为未涂覆最终产物焦炭颗粒的对照。第二实施例的最终产物为沥青涂覆的焦炭颗粒。
实施例1
在不锈钢Parr高压釜中将量为20g来自Rodeo Refinery、平均直径为16.6μm的微粉化生阳极级高挥发物焦炭与20ml甲苯(1∶1溶剂/沥青比)结合。将焦炭-甲苯浆料用氮气洗涤15分钟，作为密闭系统在自生压力下加热至280℃，同时搅拌，并在压力下在280℃下搅拌15分钟。
在反应器冷却至140℃以后，将120ml甲苯“抗溶剂”加入容器中并将混合物在125℃下搅拌另外15分钟。使容器冷却至24℃并减轻容器中的压力。将焦炭-甲苯浆料通过0.45μm烧结过滤器过滤。然后将焦炭滤饼用～100ml二甲苯洗涤并使其在真空下在60℃下干燥。回收量为18.5g的干焦炭。图3中提供了干焦炭的扫描电子显微镜照片(SEM)。在显微镜照片中证明颗粒表面上缺乏沥青涂层。颗粒具有尖锐的清晰边缘，这通常是未涂覆的研磨的颗粒。然后将未涂覆的颗粒在1000℃下碳化1小时并在3000℃下石墨化45分钟。将滤液旋转蒸发以除去甲苯并回收甲苯可溶的沥青油。得到量为2g的甲苯可溶性沥青。在校正沥青油中甲苯的量以后，甲苯可溶性沥青的收率为～9.95％。通过用18％沸程为大于1328°F的组分模拟蒸馏发现沥青的沸程为大于389°F。
实施例2
在不锈钢Parr高压釜中将量为30g来自Rodeo Refinery、平均直径为6.13μm的微粉化生阳极级高挥发物焦炭与90ml甲苯(3∶1溶剂/沥青比)结合。将焦炭-甲苯浆料用氮气洗涤15分钟，作为密闭系统在自生压力下加热至280℃，同时搅拌，并在压力下在260℃下搅拌15分钟。在反应器冷却至100℃以后，将100ml的50/50庚烷/甲苯加入容器中并将混合物在160℃下搅拌另外15分钟。在该方法中庚烷为甲苯的抗溶剂。使容器冷却至30℃并减轻容器中的压力，并将焦炭-甲苯浆料通过0.45μm烧结过滤器过滤。然后将焦炭滤饼用～100ml的50/50庚烷/甲苯混合溶剂洗涤并使其在真空下在60℃下干燥。回收量为26.7g的干焦炭。下图2说明干焦炭的扫描电子显微镜照片(SEM)。在显微镜照片中证明颗粒表面上的沥青涂层。不像图3中的颗粒，图4中的颗粒由于板状颗粒的涂层而具有更圆的不定边缘。然后将涂覆颗粒在1000℃下碳化1小时并在3000℃下石墨化45分钟。发现溶剂具有可回收的各向同性沥青。将石墨化的颗粒涂覆在铜片基质上，石墨涂覆的铜用作锂离子纽扣电池(2025)中的阳极，其中锂箔用作该电池的阴极材料。测试纽扣电池的第一循环放电容量和第一循环库仑效率。发现第一循环放电容量为304mA-h/g；第一循环库仑效率为90％。
最后，本发明的保护范围不受上述说明书限制，而仅受以下权利要求书限制。本发明的范围意欲包括权利要求主题的所有等价物。将各个和每个权利要求作为本发明的实施方案并入说明书中。因此，权利要求书为说明书的部分，为另外的描述，且本发明的优选实施方案除外。任何参考文献的讨论不是承认其对于本发明为现有技术，尤其是其出版日期可在本申请的优先权日期之后的任何参考文献。

Claims (5)

1.一种制备用于电池组中的碳涂覆的石墨阳极粉末的方法，其中所述方法包括：
a)提供具有至少10重量%挥发物的高挥发物的生焦；
b)将高挥发物生焦与液体溶剂以选择的溶剂/碳比混合，以形成溶剂悬浮液和从生焦中萃取挥发物，其中所述溶剂选自甲苯、苯和二甲苯；
c)改变溶剂悬浮液的溶剂浓度，并使已从生焦中萃取的挥发物沉淀在焦炭颗粒上并在其上形成涂层，其中所述改变溶剂浓度包括将抗溶剂加入溶剂悬浮液中，且抗溶剂选自戊烷、己烷、庚烷、辛烷和壬烷；
d)将具有残余溶解的挥发性物质的溶剂与涂覆的生焦颗粒分离；
e)通过氧化稳定化，同时在含氧环境中加热到至少200℃的温度而使涂覆的生焦颗粒稳定化；
f)将稳定化的涂覆的生焦颗粒在惰性环境中碳化到至少600℃的温度；和
g)将涂覆的碳化焦炭颗粒石墨化到至少2200℃的温度。
2.根据权利要求1的制备碳涂覆的石墨阳极粉末的方法，其还包括从来自步骤d)的分离的溶剂液体中回收溶解的挥发物的步骤。
3.根据权利要求1的制备碳涂覆的石墨阳极粉末的方法，其中进行所述氧化稳定化步骤使得温度逐渐上升，以使涂层在稳定化过程中保持不熔直至在预定期间达到所需温度。
4.根据权利要求1的制备碳涂覆的石墨阳极粉末的方法，其中所述石墨化温度为2500-3200℃。
5.根据权利要求1的制备碳涂覆的石墨阳极粉末的方法，其中所述碳化温度为600-1600℃。
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