CN102239583B - 制造由硅或硅基材料构成的结构化粒子的方法及其在锂可充电电池中的用途 - Google Patents
制造由硅或硅基材料构成的结构化粒子的方法及其在锂可充电电池中的用途 Download PDFInfo
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- CN102239583B CN102239583B CN200980148870.0A CN200980148870A CN102239583B CN 102239583 B CN102239583 B CN 102239583B CN 200980148870 A CN200980148870 A CN 200980148870A CN 102239583 B CN102239583 B CN 102239583B
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Classifications
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明了提供蚀刻硅以形成柱体的方法,所述柱体尤其用作Li离子电池中的活性阳极材料,该方法在工业规模下的运行简单,因为其使用仅含少量需要控制浓度的成分的蚀刻浴,并且其在运行上比之前的方法廉价。该蚀刻溶液包含:5至10M、例如6至8M?HF,0.01至0.1M?Ag+离子,0.02至0.2M?NO3 -离子,和任选地,SiF6 2-离子,碱金属或铵离子,和附带的添加物和杂质。在蚀刻过程中追加NO3 -离子,例如以碱金属或铵的硝酸盐形式添加,以使硝酸根离子浓度保持在上述范围内。
Description
技术领域
本发明涉及制造具有蚀刻在其表面上的柱体的硅(例如硅粒子)的方法,涉及通过将柱体与下方硅分离来制造硅纤维的方法,涉及含有此类粒子或纤维作为其活性材料的电极、电化电池和锂可充电电池阳极。
背景技术
近来便携电子器件(例如移动电话和笔记本电脑)的应用增加和在混合动力电动汽车中使用可充电电池的新兴趋势导致需要更小、更轻、更持久的可充电电池,为上述和其它电池供电器件提供动力。在90年代,锂可充电电池、尤其是锂离子电池变得普遍,就出售数量而言,如今占据便携电子器件市场并开始用于新的成本敏感的用途。但是,随着在上述器件中加入功耗越来越大的功能(例如移动电话上的照相机),需要每单位质量和每单位体积储存更多能量的改进的和更低成本的电池。
图1显示了包括石墨基阳极的常规锂离子可充电电池组电池的基本组成。该电池组电池包括单电池,但也可以包括多于一个电池。
电池组电池通常包含铜集电极作为阳极10和铝集电极作为阴极12,它们可适当外连接至负荷或连接至充电源。石墨基复合阳极层14覆盖集电极10,含锂的金属氧化物基复合阴极层16覆盖集电极12。在石墨基复合阳极层14和含锂的金属氧化物基复合阴极层16之间提供多孔塑料隔片或隔板20;液体电解质材料分散在多孔塑料隔片或隔板20、复合阳极层14和复合阴极层16内。在一些情况下,可以将多孔塑料隔片或隔板20换成聚合物电解质材料,在这样的情况下,在复合阳极层14和复合阴极层16内都存在聚合物电解质材料。
当电池组电池完全充电时,锂已从含锂的金属氧化物经由电解质传输至石墨基的层,在此其与石墨反应产生化合物LiC6。作为复合阳极层中的电化学活性材料的石墨具有372mAh/g的最大容量。要指出,术语“阳极”和“阴极”在该电池组接在负荷两端的意义上使用。
已知的是,可以使用硅作为可充电锂离子电化学电池组电池的活性阳极材料(参见例如InsertionElectrodeMaterialsforRechargeableLithiumBatteries,M.Winter,J.O.Besenhard,M.E.Spahr,和P.NovakinAdv.Mater.1998,10,No.10)。通常相信,在用作锂离子可充电电池中的活性阳极材料时,硅可提供明显高于目前使用的石墨的容量。硅在通过与电化电池中的锂反应来转化成化合物Li21Si5时具有4,200mAh/g的最大容量,明显高于石墨的最大容量。因此,如果可以将锂可充电电池中的石墨换成硅,可以实现每单位质量和每单位体积储存能量的所需提高。
但是,在锂离子电化电池中使用硅或硅基活性阳极材料的许多现有方法无法在所需的充放电周期数内表现出不变容量,因此在商业上不可行。
业内公开的一种方法使用具有直径10微米的粒子的粉末形式的硅,其在一些情况下被制成含或不含电子添加剂并含有适当的粘合剂(例如聚偏二氟乙烯)的复合材料;将这种阳极材料涂布到铜集电极上。但是,这种电极***在经受反复充放电周期时无法表现出不变容量。据信,这种容量损失是由于硅粉物质的部分机械分离,这种分离与锂嵌入基质硅/从基质硅中脱出相关的体积膨胀/收缩造成的。这又造成硅粒子与铜集电极和硅粒子相互之间的电分离。此外,体积膨胀/收缩造成单粒子破碎,以造成球形单元本身内的电接触损失。
业内已知的用于解决连续周期过程中大的体积变化问题的另一方法是使构成硅粉的硅粒子的尺寸非常小,即在1至10纳米的范围内。这种策略不防止在硅粉经受与锂嵌入/脱出相关的体积膨胀/收缩时球形单元与铜基电极之间和球形单元本身之间的电分离。重要的是,纳米级单元的大表面积可导致产生含锂的表面膜,其将大的不可逆容量引入锂离子电池组电池。此外,大量的小硅粒子在规定的硅质量下产生大量的粒子间接触,并且它们各自具有接触阻力并因此可能造成该硅料的电阻太高。
因此,上述问题阻碍了硅粒子在锂可充电电池(具体而言,锂离子电池)中成为商业上可行的石墨替代品。
在Ohara等人在JournalofPowerSources136(2004)303-306中描述的另一方法中,硅以薄膜形式蒸发到镍箔集电极上,这种结构然后用于形成锂离子电池的阳极。但是,尽管这种方法产生良好的容量保持率,但这仅是非常薄的膜(即~50纳米)的情况,因此这些电极结构未产生可用的每单位面积容量。
Kasavajjula等人(J.PowerSources(2006),doi:10.1016/jpowsour.2006.09.84)已提供了用于锂离子二次电池的纳米硅基和块状硅基嵌入阳极的综述,其经此引用并入本文。
英国专利申请GB2395059A中描述的另一方法使用一种硅电极,其包含在硅基底上制成的硅柱的规则或不规则阵列。这些结构化硅电极在经受反复充放电周期时表现出良好的容量保持率,本发明人认为这种良好的容量保持率是由于硅柱在该柱不破碎或破坏的情况下从基质硅中吸收与锂嵌入/脱出相关的体积膨胀/收缩的能力。但是,上述出版物中所述的结构化硅电极是使用高纯单晶硅片制成的,因此该电极昂贵。
从US-7033936中获知硅基材料的选择性蚀刻以制造这样的硅柱。根据该文献,通过如下制造掩模来制造柱体:在硅基底表面上沉积半球形氯化铯岛,用薄膜覆盖包括这些岛在内的基底表面,并从该表面上除去半球形结构(包括覆盖它们的薄膜)以形成具有暴露区域的掩模,所述暴露区域原为半球所在之处。然后使用反应性离子蚀刻在该暴露区域中蚀刻基底,并除去抗蚀剂(例如通过物理溅射),以在未蚀刻区域中、即在半球位置之间的区域中留下硅柱阵列。
在PengK-Q,Yan,Y-J,GaoS-P和ZhuJ.,Adv.Materials,14(2002),1164-1167,Adv.FunctionalMaterials,(2003),13,No2,2月,127-132和Adv.Materials,16(2004),73-76中描述了另一化学方法。Peng等人展示了通过化学方法在硅上制造纳米柱的方式。根据这种方法,使用下述溶液在50℃蚀刻硅片,该硅片可以是n型或p型的且{111}面暴露于溶液:5MHF和20mMAgNO3。这些论文中假定的机制是,在初始阶段(成核)中,分立的银纳米簇无电沉积在硅表面上。在第二(蚀刻)阶段中,银纳米簇和它们周围的硅区域充当局部电极,它们造成银纳米簇周围区域中的硅电解氧化,形成SiF6阳离子,其从蚀刻点扩散开,从而以柱形式留下银纳米簇下方的硅。
K.Peng等人,Angew.Chem.Int.Ed.,44(2005),2737-2742;和K.Peng等人,Adv.Funct.Mater.,16(2006),387-394涉及蚀刻硅片的方法,其类似于Peng等人之前的论文中描述的方法,但成核/银纳米粒子沉积步骤和蚀刻步骤在不同的溶液中进行。在第一(成核)步骤中,将硅片在4.6MHF和0.01MAgNO3的溶液中放置1分钟。然后第二(蚀刻)步骤在不同的溶液中,即在4.6MHF和0.135MFe(NO3)3中进行30或50分钟。这两个步骤都在50℃进行。在这些论文中,为蚀刻步骤提出与之前的论文不同的机制,即除去银(Ag)纳米粒子下方的硅,且纳米粒子逐渐沉到块状硅中,从而在并非直接在银纳米粒子下方的区域中留下硅柱。
为了提高在硅片上生长的柱体的均匀性和密度以及生长速度,在WO2007/083152中已提出在醇的存在下进行该方法。
WO2009/010758公开了硅粉而非硅片的蚀刻,以制造用在锂离子电池中的硅材料。所得蚀刻粒子(其实例显示在图2中)在其表面上含有柱体,且整个所得粒子可用在电池的阳极材料中;或者,柱体可以从粒子上脱离以形成硅纤维,且只使用该硅纤维制造阳极。所用的蚀刻方法与WO2007/083152中公开的相同。
发明内容
本发明的第一方面提供蚀刻硅以形成柱体的方法;该方法在工业规模下的运行简单,因为该方法能使硅在单个浴中成核和蚀刻,即,该方法不要求将硅从浴移到另一浴,该方法使用仅含少量需要控制浓度的成分的蚀刻浴,并且该方法在运行上比之前的方法成本低。
在本发明方法中形成的柱体具有良好品质;当蚀刻的硅为颗粒形式时,该方法的产物可以是“带柱粒子”,即,具有在其表面上形成的柱体的粒子,或当蚀刻的硅为块状或颗粒形式时,该方法的产物可以是纤维,即,已与该粒子或块状硅的下方硅分离的柱体。带柱粒子和纤维的最重要用途是形成用于锂离子电池的阳极材料,且该方法提供了优异的阳极材料。
本发明的方法包括:
用溶液处理硅,该溶液包含:
5至10MHF、例如6至8MHF
0.01至0.1MAg+离子
0.02至0.2MNO3 -离子,和
追加NO3 -离子,例如以碱金属硝酸盐或硝酸铵形式,以使硝酸根离子的浓度保持在上述范围内;和
将被蚀刻的硅与溶液分离。
附图描述
图1是显示电池组电池的部件的示意图;
图2是带柱粒子的电子显微图。
优选实施方案的具体描述
在下列描述中,参考蚀刻粒状硅以形成被蚀刻的硅粒子来描述本发明。但是,相同的情况也适用于块状材料形式的硅,例如硅片。
蚀刻硅颗粒的方法在两个阶段中进行——成核和蚀刻。在成核中,银岛根据下述反应无电沉积在硅颗粒上:
4Ag++4e-→4Ag(金属)
成核通常花费最多大约1分钟。
蚀刻优先沿某些晶体面发生,并将硅蚀刻成柱。根据下述公式蚀刻硅:
Si+6F-→SiF6 2-+4e-半反应(1)
通过半反应(1)生成的电子经硅传导至沉积的银,在此发生逆反应,其中溶液中的银离子被还原成单质银:
4Ag++4e-→4Ag(金属)半反应(2)
沉积的单质银形成从最初沉积的银岛延伸出的枝状物。这些枝状物与相同粒子上和其它粒子上的枝状物连结,并因此形成网垫。枝状物的互连加速了电解过程,因为存在更多可发生还原半反应(2)的位点,并可使电荷离域。在该过程中释放一些气体,这使该网垫浮起。
尽管该过程可以被搅动,但不需要这样做,且如果搅动弄碎网垫,则这样做是不利的。
粒状硅原材料可包括未掺杂的硅、p型或n型掺杂硅或混合物,例如硅-铝掺杂硅。优选地,硅具有一定的掺杂,因为这提高了硅在蚀刻过程中的电导率。我们已经发现,具有1019至1020个载流子/cc的p掺杂硅表现良好。通过研磨被掺杂的硅,例如来自IC工业的硅,并然后筛分磨碎材料以获得所需尺寸的颗粒,可以获得这种材料。
或者,所述颗粒可以是相对低纯度的冶金级硅,它可以购得;由于缺陷的密度相对较高(与半导体工业中所用的硅片相比),冶金级硅特别合适。这造成低的电阻,并因此造成高的电导率,当带柱粒子或纤维用作可充电电池中的阳极材料时,这是有利的。可以如上所述将这种硅研磨和分级。这种硅的一个实例是来自挪威Elkem的“Silgrain”,如果必要,可以将其研磨和筛分,以产生在是带柱粒子的情况下平均粒径为5至500微米、例如15至500微米、优选15至40微米的粒子,在制造纤维的情况下平均粒径为50至500微米的粒子。该颗粒的横截面可以是规则的或不规则的。
当制造硅纤维时,可以将除去纤维后留下的颗粒再循环。
所述颗粒可具有90.00质量%或更大、优选99.0%至99.99%的硅纯度。该硅可以被任何材料掺杂,例如被锗、磷、铝、银、硼和/或锌掺杂。
用于蚀刻的颗粒可以是结晶的,例如微晶尺寸等于或大于所需柱高的单晶或多晶。多晶粒子可包含任何数量的晶体,例如两个或更多个。
该方法可以在0℃至70℃的温度进行,但在室温下进行是最容易的,因为只有非常昂贵的容器才能在趋向于上述范围顶端的温度耐受高腐蚀性HF。由于该原因,温度通常不超过40℃。如果必要,在该方法的过程中可能必须冷却反应混合物,因为该方法是放热的。
反应容器的优选材料是聚丙烯,但也可以使用其它耐HF的材料。
在硅已被充分蚀刻以提供高度为1至100微米、例如3至100微米、更优选5至40微米的轮廓清晰的柱体时,应终止该方法。带柱粒子的柱高通常为5至15微米,在制造纤维时更大,例如10至50微米。该方法的最佳持续时间取决于溶液中的材料浓度、硅的电导率、温度和与被蚀刻的颗粒硅的量相比所用蚀刻溶液的量。
柱体通常从其底部(即它们与下方硅接合之处)开始逐渐变细,柱体在其底部的直径通常为大约0.08至0.70微米,例如0.1至0.5微米,例如0.2至0.4微米,例如0.3微米。柱体因此通常具有大于10∶1的纵横比。柱体可以是基本圆形横截面的,但它们不需要如此。
柱体表面密度可用于规定粒子表面上的柱体密度。在本文中,这被定义为F=P/[R+P],其中:F是柱体表面密度;P是粒子被柱体占据的总表面积;R是粒子未被柱体占据的总表面积。
柱体表面密度越大,硅粒子电极每单位面积的锂容量越大,且可用于制造纤维的可收取的柱体量越大。
例如,使用来自挪威Elken的具有400微米蚀刻前平均粒径的上述硅粉,在整个表面上产生柱高为大约10至50微米、直径为大约0.2至0.5微米、且柱体表面密度F为10至50%、更通常30%的柱体。在另一实例中,蚀刻前平均粒径为大约63至80微米的颗粒被发现产生了高度为大约10至15微米、覆盖率为大约30%、且直径为大约0.2至0.5微米的柱体。
成核阶段和枝状物生长要求溶液中存在银,但一旦完成这些阶段,蚀刻仅要求溶液中存在可被还原的离子。这可以是银(半反应2),但同样不需要如此,因为银是昂贵的,优选使用一些其它逆反应。在WO2007/083152中,本申请人建议添加硝酸铁以提供三价铁离子,其可以在逆反应中被还原成亚铁离子。但是,我们已经发现,将三价铁离子添加到反应混合物中增加了该方法的复杂性和成本。
WO2007/083152还提议使用氢离子提供逆反应,但氢和氟离子浓缩在溶液中,降低了氢离子用于此用途的可供性。
我们已经发现,最佳逆反应是溶液中硝酸根离子的还原。选择硝酸根离子是因为既然以硝酸银形式添加银,其已存在于该溶液中,且因为其它阴离子可能使银沉淀。尽管WO2007/083152建议在蚀刻步骤过程中添加硝酸根离子,但这是硝酸银或硝酸铁形式。前者昂贵,而在后者中,三价铁离子也被还原并具有上述缺点。我们因此以碱金属硝酸盐或硝酸铵、特别是硝酸钠或硝酸铵形式将硝酸根添加到蚀刻溶液中,因为这些材料具有高的溶解度,但也比硝酸铁廉价,并具有在该溶液中无害的惰性阳离子(Na+和NH4 +)。
相应地,溶液基本不含铁离子(三价铁或亚铁)。“基本不含”是指不足以对该方法产生实质影响的浓度,通常应小于0.05重量%和小于5mM,例如小于2mM。
WO2007/083152的一个特征在于,醇应存在于成核阶段,并且应以1至40%的量存在。WO2007/083152的方法在芯片或晶片上进行,我们已经发现,在硅颗粒上进行的本方法中,醇的存在是不必要的,且其存在使该方法复杂化,因为其是在控制该溶液中的浓度时必须考虑的另一成分。相应地,根据本发明的一个实施方案,本发明中所用的溶液基本不含醇,这意味着任何醇的量小于对该方法具有实质影响的浓度,并且可小于0.5体积%。
本发明中最初使用的溶液具有5至10M、例如6至8M、例如6.5M至7.5M、和通常大约7M或7.5M的HF浓度。在该方法的过程中不需要追加HF,但如果与溶液体积相比蚀刻大量的材料,则这是可以的。
为了沉积银岛和枝状物,Ag+的浓度可以为0.01M至0.1M,例如0.02M至0.06M,通常大约0.03M。优选地,Ag+离子的量不足以参与该方法中所有硅的蚀刻,而是应限于仅足以形成岛和枝状物的量。然后由硝酸根离子的还原提供与蚀刻半反应相反的半反应。优选地,在蚀刻反应开始后不向溶液中加入银。
如前所示,NO3 -可提供硅蚀刻(半反应(1))的逆反应,并可以以0.02M至0.2M、例如0.04M至0.08M、例如大约0.06M的浓度存在。银通常以其硝酸盐形式添加到蚀刻溶液中,因为其它盐通常不可溶。这将提供所需的一些硝酸根离子,任何余量可通过在该方法过程中添加碱金属或铵的硝酸盐(例如钠、钾或铵的硝酸盐)来补偿。
一旦开始蚀刻,将在该溶液中存在SiF6 2-。
溶液的组成可以通过添加碱(优选NaOH或NH4OH)来调节,因为它们相对廉价且这些离子高度可溶,或者可以用硝酸酸化。
除水之外,所述溶液根据本发明的一个实施方案可不含其它成分。这种溶液在该方法开始时基本由下述物质构成:
5至10、例如6至8MHF
0.01至0.1MAg+离子
0.02至0.2MNO3 -离子
水、氢和羟基离子
和任选地,
SiF6 2-离子
碱金属或铵离子,和
附带的添加物和杂质。
相对于硅颗粒量,所用蚀刻溶液的量应足以蚀刻所需柱体。我们已经发现,对于20克硅颗粒,3升蚀刻溶液提供了良好结果,但在按比例上调或下调量时,可能需要调节相对比例。
本发明的另一些方面提供通过本发明方法制成的带柱粒子或纤维,和含有这种粒子或纤维以及集电极的复合电极,尤其是阳极,所述集电极可任选地由铜制成。所述复合电极可如下制造:制备含有由上述方法制成的带柱粒子或纤维的溶剂基浆料,将该浆料涂布到集电极上,并蒸发溶剂以制造复合膜。
本发明进一步提供一种电化电池,例如可充电电池,其含有如上定义的电极和阴极,该阴极包含能够释放和再吸收锂离子的含锂化合物作为其活性材料,尤其是锂基金属氧化物或磷酸盐,LiCoO2或LiMnxNixCo1-2xO2或LiFePO4,尤其是二氧化钴锂。
硅纤维可以如下制造:通过刮削、搅动(尤其是通过超声振动)或化学蚀刻中的一项或多项,从第一方面的粒子上分离柱体。
本发明的结构化粒子和纤维提供可充电电池中硅与锂的良好可逆反应。特别地,通过将粒子或纤维布置在复合结构(即粒子或纤维、聚合物粘合剂和导电添加剂的混合物)中,或通过将粒子或纤维粘合在集电极上,该充放电过程变得可逆和可重复,并实现了良好的容量保持率。本发明人认为,这种良好的可逆性是由于构成结构化硅粒子的一部分的硅柱和硅纤维在该柱体不破碎或破坏的情况下从基质硅中吸收与锂嵌入/脱出相关的体积膨胀/收缩的能力。
重要的是,本发明中所述的方法可以使用低纯度的冶金级硅作为原料硅颗粒,因此与使用硅片作为原料的现有技术相比,降低了制造用在可充电电池的电极中的硅粒子和纤维的成本。如上所述,硅颗粒可以主要是n型或p型的,并可以在任何暴露的晶面上蚀刻。由于该蚀刻沿晶面进行,因此所得柱体是单晶。由于这种结构特征,这些柱体基本直立,有助于大于10∶1的长径比。
总而言之,本发明提供了本发明人认为是蚀刻带柱硅粒子或硅纤维(尤其是可用在可充电锂离子电池中的那些)的最佳条件。
现在参照一个或多个下述非限制性实施例举例说明本发明:
实施例1-为了获得带柱粒子
反应在8升体积的聚乙烯容器中进行。提供具有孔的盖子,该孔用于引入成分和搅动器。使用下述反应物:
反应在室温(10至25℃)进行。在反应室中将35毫升AgNO3/HNO3溶液与3升7MHF溶液混合,然后加入溶解在30毫升水中的5.1克NaOH。所得溶液含有0.0299MAgNO3。
借助漏斗经由容器盖中的孔加入20克筛过的Si粉(<40微米),然后经盖中的孔使用棒温和手工搅动物料1分钟。
使该反应混合物静置40分钟。在前1至2分钟内在蚀刻溶液表面上形成硅+银的“网垫”。
在40分钟后,加入15克NaNO3(或13克NH4NO3)。将NaNO3或NH4NO3溶解在50毫升水中,然后经漏斗加入。然后在已完成NaNO3或NH4NO3添加后将该溶液搅动大约1分钟。使该混合物再静置50分钟。然后在该方法开始后90分钟,在蚀刻几乎完全时,开始将用过的蚀刻溶液泵入储存室,这花费大约4至5分钟,因此总蚀刻时间为大约95分钟。
现在用3至4升水洗涤该网垫3次。前两次洗涤使得水接触5分钟,而第三次洗涤为1分钟洗涤。硅和银的湿网垫应立即用硝酸处理,以除去银。将被蚀刻的硅进一步洗涤并湿储存。洗涤水含有银,并可被搁置以回收银内容物。
实施例2-为了获得纤维
反应容器和反应物与实施例1中相同。该反应仍在室温进行,因为反应混合物不会变得非常热。
在反应室中将40毫升AgNO3/HNO3溶液与3升7MHF溶液混合,然后加入溶解在30毫升水中的5.9克NaOH。最终溶液含有0.033MAgNO3。
在容器顶部经漏斗加入20克Si粉(J272.1),经盖中的孔使用棒温和手工搅动该物料1分钟。使该反应混合物静置40分钟。在前1至2分钟内在蚀刻溶液表面上形成硅+银的“网垫”。
在40分钟的最后,加入14克NaNO3(或12克NH4NO3)。将NaNO3或NH4NO3溶解在50毫升水中,然后在顶部经漏斗加入。在加料后搅动该溶液大约1分钟。使该混合物再静置50分钟。然后在该方法开始后90分钟,在蚀刻几乎完全时,开始将用过的蚀刻溶液泵入储存室,这花费大约4至5分钟,因此总蚀刻时间为大约95分钟。现在用3至4升水洗涤该网垫3至4次。前两次洗涤使得水接触5分钟,而第三次洗涤为1分钟洗涤。
由硅和银构成的湿网垫应立即用硝酸处理5至10分钟,以除去银。将硅进一步洗涤并湿储存。洗涤水含有银,并可被搁置以回收银内容物。
将粒子置于烧杯或任何适当的容器中,用惰性液体(例如乙醇或水)覆盖粒子,并对它们施以超声搅动,由此可以通过超声振动从附有柱体的所得粒子上收取纤维。据发现,在几分钟内,液体看起来浑浊,通过电子显微镜检查可以看出,在该阶段,已从粒子上除去柱体。
可以在两阶段法中从粒子上除去柱体。在第一阶段,将粒子在水中洗涤数次,如果必要,在低真空***中干燥以除去水。在第二阶段,在超声浴中搅动粒子以分离柱体。将它们悬浮在水中,然后使用离心机分离以收集硅纤维。
实施例3-制造阳极
使用带柱粒子或纤维作为锂离子电化电池的复合阳极中的活性材料。为了制造复合阳极,将带柱粒子或纤维与聚偏二氟乙烯混合,并用流延溶剂(例如正甲基吡咯烷酮)制浆。然后将该浆料施用或涂布到金属板或金属箔或其它导电基底上,例如用刮刀或以任何其它适当方式物理地施用或涂布,以产生具有所需厚度的涂膜,然后使用可利用50℃至140℃的升高温度的适当干燥***从该薄膜中蒸发流延溶剂,以留下不含或基本不含流延溶剂的复合膜。所得复合膜具有多孔结构,其中硅基带柱粒子或纤维的质量通常为70%至95%。该复合膜具有10至30%、优选大约20%的孔体积百分比。
此后可以以任何适当的方式进行锂离子电池组电池的制造,例如遵循图1中所示的一般结构,但使用含硅的活性阳极材料而非石墨活性阳极材料。例如,用多孔隔板18覆盖硅粒子基复合阳极层,在最终结构中加入电解质以充满所有可用的孔体积。电解质的添加是在将电极置于适当的外壳中后进行的,并可以包括阳极的真空填充,以确保孔隙体积被液体电解质充满。
容量保持率得到提高,因为硅带柱粒子或纤维的柱状结构能够顺应与锂的嵌入/脱出(充电和放电)相关的体积膨胀。
可以制造大片硅基阳极,然后卷绕,或如锂离子电池组电池的石墨基阳极的当前情况那样压印,这意味着可以用现有制造能力改造本文所述的方法。
Claims (18)
1.蚀刻颗粒形式的硅以形成带柱粒子的方法,其中所述颗粒形式的硅具有5至500微米的平均粒径,该方法包括:
用蚀刻溶液处理硅,所述蚀刻溶液包含:
5至10MHF
0.01至0.1MAg+离子
0.02至0.2MNO3 -离子,和
以碱金属或铵的硝酸盐形式或以硝酸的形式追加NO3 -离子,以使硝酸根离子的浓度保持在上述范围内;和
将被蚀刻的硅与溶液分离,
其中在蚀刻反应开始后不向溶液中加入银。
2.权利要求1的方法,其中所述追加的NO3 -离子以碱金属硝酸盐或硝酸铵的形式添加。
3.权利要求1的方法,其中所述颗粒形式的硅具有15至500微米的平均粒径。
4.权利要求1的方法,其中所述颗粒形式的硅具有15至40微米的平均粒径。
5.权利要求1至4任一项的方法,其中所述溶液基本不含三价铁或亚铁离子,即三价铁或亚铁离子的浓度小于0.05重量%。
6.权利要求1至4任一项的方法,其中所述溶液基本不含醇,即任何醇的量小于0.5体积%。
7.权利要求1至4任一项的方法,其中所述溶液基本由下述物质构成:
5至10MHF
0.01至0.1MAg+离子
0.02至0.2MNO3 -离子
水、氢和羟基离子。
8.权利要求1至4任一项的方法,其在单浴中进行。
9.权利要求1至4任一项的方法,其中最初使用的溶液具有6.5至9M的HF浓度。
10.权利要求1至4任一项的方法,其包括下述步骤:通过添加碱或硝酸来调节组成。
11.权利要求1至4任一项的方法,其中所述硅具有90.00质量%或更高的纯度。
12.权利要求1至4任一项的方法,其中所述柱体具有1至100微米的高度。
13.权利要求1至4任一项的方法,其中所述柱体在其底部具有0.08至0.70微米的直径。
14.权利要求10的方法,其中所述碱选自NaOH或NH4OH。
15.权利要求1至4任一项的方法,其中所述溶液基本由下述物质构成:
5至10MHF
0.01至0.1MAg+离子
0.02至0.2MNO3 -离子
水、氢和羟基离子
SiF6 2-离子
碱金属或铵离子,和
附带的添加物和杂质。
16.电极,含有通过如权利要求1至15任一项所述的方法制成的带柱粒子作为其活性材料之一。
17.如权利要求16所述的电极,其中所述带柱粒子被合并到集电极上的复合膜中。
18.电化电池,含有阴极以及如权利要求16或17所述的电极作为阳极,该阴极包含能够释放和再吸收锂离子的含锂化合物作为其活性材料。
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US20110269019A1 (en) | 2011-11-03 |
TW201027829A (en) | 2010-07-16 |
EP2335307A1 (en) | 2011-06-22 |
GB2464158A (en) | 2010-04-14 |
KR101419280B1 (ko) | 2014-07-15 |
TWI460908B (zh) | 2014-11-11 |
GB0818645D0 (en) | 2008-11-19 |
KR20110082171A (ko) | 2011-07-18 |
JP2012505505A (ja) | 2012-03-01 |
CN102239583A (zh) | 2011-11-09 |
US9184438B2 (en) | 2015-11-10 |
WO2010040985A1 (en) | 2010-04-15 |
JP5535222B2 (ja) | 2014-07-02 |
GB2464158B (en) | 2011-04-20 |
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