CN101790806A - 用于锂离子应用的稳定锂金属粉末、组合物和制备方法 - Google Patents
用于锂离子应用的稳定锂金属粉末、组合物和制备方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 112
- 239000000843 powder Substances 0.000 title claims abstract description 34
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- 229910001416 lithium ion Inorganic materials 0.000 title description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 61
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- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims 1
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- 239000010703 silicon Substances 0.000 claims 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了由基本连续的聚合物层保护的锂金属粉末。这种基本连续的聚合物层提供了改进的保护,例如与典型的CO2钝化处理相比。
Description
相关申请的交叉引用
本申请要求以下美国临时申请的优先权,并通过引用将其整体结合此处:2007年8月31日提交的美国临时申请第60/969,267号。
发明领域和背景
本发明涉及具有改进的空气和溶剂稳定性且具有较长的储存寿命的稳定锂金属粉末(“SLMP”)。这种改进的SLMP能够用于广泛的应用中,包括有机金属和聚合物合成、一次锂电池组、可再次充电的锂电池组和可再次充电的锂离子电池组。
最近发现了锂和锂离子二次或可再次充电电池组在某些应用(例如便携式电话、摄像放像机和膝上型计算机)中的应用,甚至更近以来发现了其在更大功率应用(例如在电动车和混合电动车)中的应用。在这些应用中优选该二次电池组具有可能的最高比容量但仍提供安全的操作条件和良好的可循环性,以使得在随后的再次充电和放电循环中保持高比容量。
尽管二次电池组有多种构造,但各种构造都包括正极(或阴极)、负极(或阳极)、分隔该阴极和阳极的隔板、和与该阴极和阳极电化学连通的电解质。对于二次锂电池组,当该二次电池组放电(即用于其特定应用)时,锂离子从阳极通过电解质传送到阴极。在该工艺过程中,从阳极收集电子并将其通过外部电路传送到阴极。当该二次电池组充电或再充电时,锂离子从阴极通过电解质传送到阳极。
传统上,二次锂电池组是使用具有高比容量的非锂化化合物(例如TiS2、MoS2、MnO2和V2O5)作为阴极活性材料而制备的。这些阴极活性材料通常与锂金属阳极相结合。当该二次电池组放电时,锂离子从该锂金属阳极通过电解质传送到阴极。不幸的是,一旦循环使用,该锂金属发展为树枝状晶体,其最终会在该电池组中造成不安全的情况。因此,在二十世纪九十年代早期停止这种类型的二次电池组的制造而转向锂离子电池组。
锂离子电池组典型地使用锂金属氧化物(例如LiCoO2和LiNiO2)作为与碳基阳极相结合的阴极活性材料。在这些电池组中,避免了在阳极上形成锂树枝状晶体,从而使该电池组更安全。然而,该锂全部是从阴极供应的,锂的量决定了该电池组的容量。这样限制了阴极活性材料的选择,因为该活性材料必须包含可除去的锂。而且,在充电中形成的对应于LiCoO2和LiNiO2的脱锂产物(例如LixCoO2和LixNiO2,其中0.4<x<1.0)和在过充电过程中形成的对应于LiCoO2和LiNiO2的脱锂产物(例如LixCoO2和LixNiO2,其中x<0.4)是不稳定的。特别地,这些脱锂产物容易与电解质反应而放热,这提高了对安全的关注。
另一种选择是锂金属。然而,锂金属(特别是锂金属粉末)由于其具有高的表面积,能够由于其自燃性质而妨碍其用于广泛的应用中。已知通过用CO2钝化该金属粉末表面来稳定锂金属粉末,例如美国专利第5,567,474、5,776,369和5,976,403号中所述,其内容通过引用整体结合进来。然而,由于锂金属与空气的反应,该CO2钝化的锂金属粉末仅能够在该锂金属的含量减少之前用于具有低水分含量的空气中有限的时间。
因此,仍存在对具有改进的稳定性和储存寿命的稳定锂金属粉末的需求。
发明内容
本发明提供了被基本连续(substantially continuous)的聚合物层保护的锂金属粉末。这种基本连续的聚合物层比如与典型的CO2钝化相比提供了改进的保护。所得到的锂金属粉末具有改进的空气和溶剂稳定性和改进的储存寿命。而且,该聚合物保护的锂金属粉末表现出在N-甲基-2-吡咯烷酮(NMP)中显著更好的稳定性,所述N-甲基-2-吡咯烷酮(NMP)通常用作电极制造工艺中的浆料溶剂并与未保护的锂反应。通过参照附图描述本发明的各种实施方案,本发明的目的和优点将变得更显而易见。
附图说明
图1是用NMP原样(<100ppm水分)和掺杂0.6%水的NMP对涂覆有CO2的SLMP(对比例2)的ARSST稳定性测试。
图2是用掺杂0.6%水的NMP对涂覆有PEO的SLMP(实施例2)的ARSST稳定性测试。
图3是实施例10的用掺杂0.6%水的NMP对涂覆有EVA的SLMP的ARSST稳定性测试。
图4是实施例7的用掺杂0.6%水的NMP对涂覆有SBR的SLMP的ARSST稳定性测试。
图5是实施例3的用掺杂0.6%水的NMP对涂覆有BYK P 104(低分子量聚羧酸聚合物)的SLMP的ARSST稳定性测试。
图6证明了涂覆有聚合物的锂对电化学性能的影响。
图7是涂覆有CO2的SLMP和实施例11的ARSST稳定性测试。
图8A、8B和8C是使用不同工艺参数制备的样品的SEM图像。
图9A是在无水NMP中的金属锂浓度作为时间的函数的比较。
图9B是在掺杂0.6%水的NMP中的金属锂浓度作为时间的函数的比较。
具体实施方式
在附图和以下详述中,详细描述了多种实施方案以使能够实施本发明。尽管参照这些特别实施方案对本发明进行了描述,但将认识到本发明并不限定于这些实施方案。而相反,本发明包括考虑到以下详述和附图将变得显而易见的多种替代方式、改进和等价物。
此处所用的术语仅用于描述特定的实施方案,并不意于限制本发明。此处所用的术语“和/或”包括一个或多个相关所列项目的任意和所有组合。除非上下文有明确的另外表示,此处所用的单数形式“a”、“an”和“the”也意于包括复数形式。将进一步认识到术语“包括”和/或“comprising”当用于本说明书中时表示所指特征、整数、步骤、操作、元素和/或部件的存在,但并不排除存在或添加一种或多种其他特征、整数、步骤、操作、元素、部件和/或其组。此外,此处所用的术语“约”当涉及可测量的数值(例如本发明的化合物或试剂的量、剂量、时间、温度等)时,表示包括所指量的20%、10%、5%、1%、0.5%或甚至0.1%的变化。
除非另外定义,此处所用的所有术语(包括技术和科学术语)都具有与本发明所属领域技术人员通常理解相同的含义。将进一步认识到术语(例如常用词典中定义的那些)应当解释为具有与其在相关现有技术中的含义相一致的含义,并不以理想或过于刻板的含义解释,除非此处如此清楚定义。
此处提及的所有公开内容、专利申请、专利和其他参考文献都整体通过引用结合进来。然而,此处参考文献的引用不应当解释为认可该参考文献是此处所述的本发明的现有技术。
依照本发明,通过以下制备锂分散体:将该锂金属粉末在烃油中加热到高于其熔点的温度,经受足以使该熔融锂分散的条件,剧烈搅动或搅拌,并将该锂金属粉末与聚合物在该温度和等于或大于锂的熔点之间的温度下接触以提供该聚合物的基本连续层。该聚合物的基本连续层具有25~200nm的厚度,通常具有80~120nm的厚度。依照本发明能够涂覆其他碱金属,例如钠和钾。
适合的聚合物能够是防水的且是锂离子传导性的或非锂离子传导性的(例如如果其可溶于通常的电解质溶剂)的聚合物。该聚合物可以与锂反应或者不与锂反应。以下仅是该聚合物化合物的实例,包括:聚氨酯、聚四氟乙烯、聚氟乙烯、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、聚甲醛(Delrin)、苯乙烯-丁二烯-苯乙烯嵌段聚合物、乙烯-乙酸乙酯、乙烯-丙烯酸共聚物、聚氧化乙烯、聚酰亚胺、聚噻吩、聚(对-亚苯基)、聚苯胺、聚(对-亚苯基亚乙烯基)、二氧化硅二氧化钛共聚物、不饱和聚羧酸聚合物和聚硅氧烷共聚物等。
能够在分散过程中,或在该锂分散体冷却之后在较低的温度下,使该聚合物与锂液滴接触。认识到能够使用具有不同化学组成、分子量、熔点和硬度的不同类型的聚合物的组合来实现用于特定应用的特定涂料特征。例如,在需要一定程度粘度的情况下,能够控制粘度的水平以能够使用“迁移释放纸”概念来引入SLMP。还认识到该单体能够用于在该锂颗粒的表面上产生原位聚合物涂层。
进一步,将聚合物或聚合物混合物与一些无机涂料(例如Li2CO3、LiF、Li3PO4、SiO2、Li4SiO4、LiAlO2、Li2TiO3、LiNbO3、Al2O3、SiO2、SnO2、ZrO2等)相结合以改进空气稳定性和极性溶剂稳定性是有利的,这样会允许更安全地操作且可以使用溶解通常使用的聚合物粘结剂的通常使用的极性溶剂。认识到大多数聚合物在升高的温度下可溶于非极性溶剂中,且在室温下的溶解度能够是显著的(参见表2),用于从该颗粒上去除油的洗涤溶剂应当适当选择。有时,能够将干的非稳定或稳定粉末转移到与锂相容的非极性溶剂中,且能够使用例如rotovap技术沉积聚合物涂层,因此避免了溶解性问题。
上述适合的聚合物能够在锂颗粒上产生两种类型的涂层:第一种代表物理或粘附类型,第二种代表化学键合涂层,在其中使用具有官能团的聚合物。例如,聚乙烯(PE)、聚丙烯(PP)和聚苯乙烯(PS)包含不与Li反应的碳-氢基团。这种类型的聚合物作为用于锂颗粒的涂料试剂是有价值的,因为物理范德华相互作用允许碳-氢分子粘附到锂颗粒的表面上。另一方面,聚合物(例如聚丙烯酸和乙烯-乙酸乙烯酯)不与锂反应,因为其包含酸官能团,因此形成化学键合涂层。
通过改变该工艺和工艺参数和该试剂在涂覆有聚合物的锂颗粒中的添加顺序能够产生独特的表面性质。不同的工艺参数能够导致具有不同表面性质的样品(参见图7)。能够在其他分散剂(例如蜡)和涂料试剂添加之前或之后在锂的熔点之上引入聚合物或聚合物混合物,以通过改变反应界面而提高保护层的化学键合和均匀性。该冷却曲线(即,在分散过程中聚合物引入时的温度)能够用来控制结晶度并获得具有预定粘度的样品。
以下实施例仅是对本发明的举例说明,并不对其限制。
实施例
对比例1
将电池组等级的锂金属(405g)切割成2×2英寸片,并在室温下在干氩气恒流中添加到具有装备有与固定高速搅拌电机连接的搅拌轴的4”盖的3升不锈钢瓶状反应器中。该反应器装备有顶部和底部加热罩。然后组装该反应器并添加1041.4g PenetekTM油(Penreco,Division of thePenzoil Products Company)。然后将该反应器加热到约200℃,并保持在250rpm~800rpm范围内的轻柔搅拌以确保所有金属熔融,在整个该加热步骤中保持氩气流。然后将该混合物在高速下(高达10000rpm)搅拌2分钟。将8.1g油酸添加到该反应器中,继续高速搅拌另外3分钟,然后添加5.1g CO2。然后停止该高速搅拌,去除加热罩,将分散体冷却到约50℃,并转移到储存瓶中。此外,在氩气流下,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤1次,以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
对比例2
将PenetekTM矿物油(4449g)和1724g电池组等级的锂金属在室温下在氩气气氛下添加到15升加套分散反应器中。然后通过将热的传热流体泵送通过该套而将该反应器从室温加热到200℃。在加热过程中,将该分散搅拌器保持在低速以便于传热。一旦反应器内部的温度达到200℃,将该分散搅拌器速度提高到5000rpm。在高速搅拌3.5分钟之后,将36g油酸添加到该反应器中,继续高速搅拌另外4.5分钟,然后添加22g CO2气体。在再高速搅拌4分钟之后,停止该高速搅拌器,并将反应器内容物降低到室温。在该冷却过程中,使用低速搅拌将该分散体保持悬浮。在氩气压力下将该锂分散体转移到间歇式过滤器中。将该矿物油排出。用己烷将该过滤器中的分散体洗涤4次;然后将干氩气吹动通过该过滤器以除去任何残余的挥发性有机物。将涂覆有该干稳定聚合物的锂分散体从该过滤器中去除作为最终产品。
实施例1
将包含13.01g具有45微米中值粒度的锂的、用CO2气体钝化过的在油中的锂分散体(47.30g)(27.5%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy(哈斯特洛伊)罐中。还在该罐中添加1.3gPEO(Polyox WSR N80)干粉末。将该溶液以5℃/min的速率从环境温度加热到75℃并保持10分钟。进一步将该样品以5℃/min从75℃加热到175℃并保持1小时。在该加热阶段过程中将该混合物以200rpm连续搅拌。将样品冷却到室温,并转移到该储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例2
将包含12.37g中值粒度45微米的锂的、用CO2气体钝化过的在油中的锂分散体(45.00g)(27.5%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。还在该罐中添加1.2g PEO(Polyox WSRN80)干粉末。将该溶液以5℃/min的速率从环境温度加热到75℃并保持10分钟。进一步将该样品以5℃/min从75℃加热到175℃并保持1小时。最后将该样品以20℃/min从175℃加热到200℃。在该加热阶段过程中将该混合物以200rpm连续搅拌。将样品冷却到室温,并转移到该储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例3
将包含12.10g中值粒度45微米的锂的、用CO2气体钝化过的在油中的锂分散体(44.00g)(27.5%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。将该溶液加热到75℃,并在该锂分散体中添加1.2ml BYK-P 104 S(BYK Chemie)。将该混合物以200rpm连续搅拌1小时。将样品冷却到室温并转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例4
将包含6.20g中值粒度58微米的锂的、在油中的稳定锂分散体(54.99g)(11.275%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。在环境温度下,将以在对-二甲苯(Aldrich)中的10%溶液形式的0.62g SBR添加到该锂分散体中。将该混合物以200rpm连续搅拌19小时。将样品转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例5
将包含6.17g中值粒度58微米的锂的、在油中的稳定锂分散体(54.68g)(11.275%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。在环境温度下,将以预溶解在对-二甲苯(Aldrich)中的5%溶液形式的0.62g EVA(Aldrich)添加到该锂分散体中。将该混合物以200rpm连续搅拌2.5小时。将样品转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例6
将包含6.09g中值粒度58微米的锂的、在油中的稳定锂分散体(54.00g)(11.275%)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。在环境温度下,将0.5ml丁二烯(Aldrich)和0.5ml苯乙烯(Aldrich)添加到该锂分散体中。将该混合物以200rpm连续搅拌1小时。将样品转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例7
称取10.0g SLMP(稳定锂金属粉末)到1升圆底烧瓶中。将32.1g p-二甲苯(Aldrich)和以预溶解在对-二甲苯(Aldrich)中的10%溶液的形式的0.28g SBR添加到该烧瓶中。将包含该混合物的烧瓶放在rotavap真空提取器上,并在转动中加热到70℃。在将该温度在70℃保持15分钟之后,施加真空以提取溶剂。然后将该样品转移到储存瓶中。
实施例8
将4.0g中值粒度58微米的非稳定锂粉末和36g对-二甲苯(Aldrich)添加到装备有1”的涂覆有Teflon的搅拌棒的120ml hastelloy罐中。在以200rpm混合的同时将该混合物加热到40℃。在40℃,在该锂、对-二甲苯混合物中添加以预溶解在对-二甲苯(Aldrich)中的10%溶液的形式的0.40g EVA。将该混合物以200rpm连续搅拌20小时。将样品转移到200ml圆底烧瓶中。此外,通过将干氩气在该样品上通过而将对-二甲苯蒸发掉。将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例9
将包含236.5g中值粒度58微米的锂的、在油中的稳定锂分散体(2149.8g)(11.0%)添加到装备有推进器型可变速混合器的3升圆底烧瓶中。在环境温度下,将以在对-二甲苯(Aldrich)中的10%溶液的形式的23.8g EVA(Aldrich)添加到该锂分散体中。将该混合物以500rpm连续搅拌4小时。将样品转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例10
将包含126.6g中值粒度63微米的锂的、在油中的稳定锂分散体(1127.0g)(11.2%)添加到装备有推进器型可变速混合器的5升圆底烧瓶中。将温度升高到41.3℃,将以在对-二甲苯(Aldrich)中的5%溶液形式的12.5g EVA(Aldrich)添加到该锂分散体中。将该混合物在40℃以500rpm连续搅拌大约6小时,然后在环境温度下再搅拌~18小时。将样品转移到储存瓶中。此外,将锂分散体在封闭的烧结玻璃过滤漏斗中过滤并用己烷洗涤3次并用正戊烷洗涤2次以去除烃油介质。用热风器加热该漏斗以除去痕量的溶剂,将得到的自由流动粉末转移到紧盖的储存瓶中。
实施例11
将15390g PenetekTM矿物油和4415g电池组等级的锂金属在室温下在氩气气氛下添加到57升加套分散反应器中。然后通过将热的传热流体泵送通过该套而将该反应器从室温加热到190℃。在加热过程中,将该分散搅拌器保持在低速以便于传热到反应器内容物。一旦反应器内部的温度达到190℃,将该分散搅拌器速度提高到4800rpm。在高速搅拌3分钟之后,将90g油酸添加到该反应器中,继续高速搅拌另外4分钟,然后添加56g CO2气体。在再高速搅拌6分钟之后,将154g聚氧化乙烯(PEO)颗粒添加到反应器中,继续再高速搅拌3分钟。然后停止该高速搅拌器,并将反应器内容物降低到室温。在该冷却过程中,使用低速搅拌将该分散体保持悬浮。在氩气压力下将该锂分散体转移到间歇式过滤器中,在氩气压力下将该矿物油排出。用己烷将该分散体洗涤4次;然后将干氩气吹动通过该过滤器以除去任何残余的挥发性有机物。将涂覆有干稳定聚合物的锂分散体从该过滤器中去除作为最终产品。
下图1~5和7证明了该涂覆有聚合物的样品在可再充电锂离子电池组工业中的电极制备过程中广泛用作溶剂的NMP中的稳定性。使用以下程序进行该测试:将SLMP和溶剂在氩气下填充到测试电池中,然后将该测试电池提高到25℃,继续等温保持72小时,然后将温度逐渐上升至55℃,并继续等温保持48小时,将该混合物连续搅拌。一旦完成该测试就测定该样品的金属锂含量:该含量越高,该涂层的保护性质就越好。如下表1中能够看到的那样,对于呈现的实施例中的样品,锂浓度为17.3%及更高。没有观察到聚合物添加到石墨电极的电化学性质的不利影响。(参见图6)图8A、8B和8C显示出由于工艺参数的改变造成的实施例5、8和9的不同表面性质。进行单独测试以确定使用掺杂水的NMP时锂含量作为时间的函数,观察到显著的改进。(参见图9A和9B)
表1.使用标准ARSST测试用掺杂0.6%水的NMP测定的残余金属锂浓度的实施例
涂覆剂 | 实施例 | 残余金属锂浓度 |
EVA | 实施例10(785-106) | 24.3% |
SBR | 实施例7(767-200) | 17.3% |
PEO | 实施例1(PEOR043007) | 38.2% |
PEO | 实施例2(PEOR050807) | 30.9% |
表2.聚合物在选定溶剂中的溶解度的实施例
LuWax A | SBR | EVA | PEO | |
己烷 | 0.46% | 3.92% | 1.21% | 0.03% |
戊烷 | 0.48% | 4.1% | 0.46% | 0.03% |
二甲苯 | 0.81% | >10% | >10% | >10% |
由此描述了本发明的特定实施方案,但应当认识到后附权利要求限定的本发明并不限定于上述说明书中提出的特别细节,因为在不脱离后文要求保护的其精神和范围的情况下可以对其进行很多显而易见的变型。提供以下权利要求以确保本申请满足作为优先权申请在所有权限中的所有法定要求,且不应当理解为提出本发明的完整范围。
Claims (9)
1.涂覆有基本连续的聚合物层的稳定锂金属粉末,该聚合物选自由以下构成的组:聚氨酯、聚四氟乙烯、聚氟乙烯、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、聚甲醛、苯乙烯-丁二烯-苯乙烯嵌段聚合物、乙烯-乙酸乙酯、乙烯-丙烯酸共聚物、聚氧化乙烯、聚酰亚胺、聚噻吩、聚(对-亚苯基)、聚苯胺、聚(对-亚苯基亚乙烯基)、二氧化硅二氧化钛基共聚物、不饱和聚羧酸和聚硅氧烷。
2.权利要求1的稳定锂金属粉末,其中该基本连续的聚合物层具有25~200nm的厚度。
3.权利要求2的稳定锂金属粉末,进一步包括无机涂层。
4.阳极,包括能够在电化学系统中吸收或解吸锂的主体材料,其中在该主体材料中分散有权利要求3的涂覆有聚合物的稳定锂金属粉末。
5.权利要求4的阳极,其中所述主体材料包括选自由以下构成的组的至少一种材料:碳质材料、硅、锡、锡氧化物、复合锡合金、过渡金属氧化物、锂金属氮化物、石墨、炭黑和锂金属氧化物。
6.权利要求5的阳极,其中该基本连续的聚合物层具有25~200nm的厚度。
7.稳定锂金属粉末,涂覆有厚度为25~200nm的基本连续的聚合物层。
8.阳极,包括能够在电化学系统中吸收或解吸锂的主体材料,其中在该主体材料中分散有权利要求7的涂覆有聚合物的稳定锂金属粉末。
9.形成锂分散体的方法,包括以下步骤:
a)将锂金属与烃油接触;
b)将该锂金属和烃油加热到高于该锂金属的熔点的温度;
c)将该经加热的锂金属和烃油经受足以将该锂金属分散到该油中的条件;和
d)在该锂金属的熔点与该聚合物的熔点之间的温度,将该锂金属与选自由以下构成的组的聚合物接触:聚氨酯、聚四氟乙烯、聚氟乙烯、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、(聚甲醛)、苯乙烯-丁二烯-苯乙烯嵌段聚合物、乙烯-乙酸乙酯、乙烯-丙烯酸共聚物、聚氧化乙烯、聚酰亚胺、聚噻吩、聚(对-亚苯基)、聚苯胺、聚(对-亚苯基亚乙烯基)、二氧化硅二氧化钛基共聚物、不饱和聚羧酸和聚硅氧烷,以在该锂金属上提供基本连续的聚合物层。
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2008
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2014
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2017
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JP5548126B2 (ja) | 2014-07-16 |
DE112008002212T5 (de) | 2010-07-08 |
JP2014167936A (ja) | 2014-09-11 |
RU2010112410A (ru) | 2011-10-10 |
EP2186151B1 (en) | 2013-12-04 |
GB2490433A (en) | 2012-10-31 |
WO2009029270A1 (en) | 2009-03-05 |
CA2696771A1 (en) | 2009-03-05 |
CA2696771C (en) | 2016-05-24 |
GB2463217B (en) | 2013-02-13 |
GB201211010D0 (en) | 2012-08-01 |
EP2186151A1 (en) | 2010-05-19 |
US20170149052A1 (en) | 2017-05-25 |
EP2463940B1 (en) | 2014-07-02 |
CN105618735A (zh) | 2016-06-01 |
EP2463940A1 (en) | 2012-06-13 |
US11171323B2 (en) | 2021-11-09 |
JP6001596B2 (ja) | 2016-10-05 |
US20090061321A1 (en) | 2009-03-05 |
JP2010538424A (ja) | 2010-12-09 |
GB2463217A (en) | 2010-03-10 |
GB201000554D0 (en) | 2010-03-03 |
GB2490433B (en) | 2013-02-27 |
KR20100081304A (ko) | 2010-07-14 |
US20180261829A1 (en) | 2018-09-13 |
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