CN101213039A - 应用于锂离子的经稳定的金属锂粉的制备方法 - Google Patents
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Abstract
提供了使金属锂粉稳定化的方法。所述方法包括以下步骤:将金属锂加热到超过其熔点的温度,搅动所述熔融金属锂和使所述金属锂与氟化剂接触以提供经稳定的金属锂粉。
Description
相关申请的交叉引用
本申请要求2005年7月5日提交的美国临时申请60/695,565的优先权,所述临时申请的公开内容通过全文引用结合于本文中。
发明领域与背景
本发明涉及具有更好稳定性和较长储存寿命的经稳定的金属锂粉(“SLMP”)。如此改进的SLMP可用于各种各样的应用,包括有机-金属和聚合物合成、可再充电锂电池和可再充电锂离子电池。引人注意的一个领域是可再充电锂和锂离子电池在电子应用如手机、可携式摄像机和膝上型电脑等中和甚至最近在较大动力应用如电动汽车和混合动力汽车中的用途。在这些应用中,希望二次电池具有可能的最高比容量但仍提供安全运行条件和良好循环性能,从而在随后再充电和放电循环中保持所述高比容量。
尽管可再充电锂电池有多种结构,各结构包括正极(或阴极)、负极(或阳极)、分开阴极和阳极的隔板以及与阴极和阳极电化学相连的电解质。就二次锂电池而言,当所述二次电池放电时,即用于其特定应用时,锂离子通过电解质从阳极转移到阴极。在此过程中,来自阳极的离子汇集并通过外部电路到达阴极。当对二次电池进行充电或再充电时,锂离子通过电解质从阴极转移到阳极。
过去采用具有高比容量的非锂化化合物如TiS2、MoS2、MnO2和V2O5作为阴极活性材料制备二次锂电池。这些阴极活性材料与金属锂阳极耦合。当所述二次电池放电时,锂离子通过电解质从金属锂阳极转移到阴极。遗憾的是,循环时,金属锂形成枝状晶体,所述枝状晶体最终在电池中导致不安全状况。结果,这类二次电池的生产在20世纪90年代早期因为有了锂离子电池而停止。
已知如何使锂粉稳定,特别是为了将其用于二次电池。例如,如美国专利5,567,474、5,776,369和5,976,403中所述可通过用CO2将金属粉表面钝化来使锂粉稳定,所述专利的公开内容可通过全文引用结合于本文中。然而,CO2钝化的金属锂粉仅可在低湿度水平的空气中使用有限的一段时间,此后由于金属锂与空气反应金属锂含量衰变。因此仍然需要储存寿命提高的经稳定的金属锂。
发明概述
为了这个目标,提供了更稳定的锂粉。所述金属锂粉被氟或含氟化合物钝化。与CO2相比,由于LiF的溶解度(即25℃下0.133g溶解于100gH2O中)比Li2CO3的溶解度(即25℃下1.29g溶解于100gH2O中)低约1个数量级,这种薄而密的连续LiF层提供了更好的钝化。LiF钝化层相当光滑,这在表面上提供更连续和密集的保护性钝化。所得金属锂粉具有改进的稳定性和提高的储存寿命。
考虑以下详细描述和附图后,本发明的这些和其他特征和优点对本领域技术人员而言将变得更显而易见,所述详细描述和附图对本发明优选实施方案和替代实施方案进行了描述。
附图简述
图1是实施例1和经CO2稳定的金属锂粉的衰变率对比(试验A)。
图2是实施例1和经CO2稳定的金属锂粉的衰变率对比(试验B)。
图3是实施例3和经CO2稳定的金属锂粉的平均衰变率对比。
图4是实施例1和实施例3的平均衰变率对比。
图5是实施例1和3及经CO2稳定的金属锂粉在-34℃露点(D.P.)下金属锂含量损失对比(试验C)。
附图和以下详述对优选实施方案进行了详细描述以能实施本发明。尽管参考这些具体的优选实施方案对本发明进行描述,应该理解本发明不局限于这些优选实施方案。相反,本发明包括许多供选项、改进和等同内容,这些通过考虑以下详细描述和附图将变得显而易见。
发明详述
根据本发明如下制备锂分散体:在烃油中将金属锂加热到超过其熔点的温度,搅动(如剧烈搅拌)所述熔融锂,并使锂与氟化剂接触。已认识到其他碱金属如钠和钾可按照本发明氟化。合适的氟化剂可为氟或含氟化合物且可包括氟气、HF、SiF4、SnF4、SF6等;全氟烃化合物如全氟戊胺、全氟己烷、全氟-1,3-二甲基环己烷;含氟无机化合物如三氟化硼叔丁基甲基醚合物或氟硼酸/乙醚。可在分散过程中或在锂分散体冷却后较低温度下将氟化剂引入来接触锂滴。
各种各样的烃油可用于本发明中。本文中所用术语“烃油”包括主要或全部由烃混合物组成的各种油状液体并包括矿物油即具有公认为油的粘度极限的矿物原料的液体产物,因此包括但不局限于石油、页岩油、石蜡油等。示例性的烃油为白油(高度精炼的),诸如烃油如Pennzoil Products Inc.的Penreco分公司生产的Peneteck(其在100的粘度为43-59帕斯卡·秒,闪点为265),产自Pennzoil Products的Penreco分公司的Parol 100(其在100的粘度为213-236帕斯卡·秒,闪点为360),产自Witco的Sonneborn分公司的Carnation白油(在100的粘度=133-165帕斯卡·秒)。可使用在包括金属锂或钠熔点的范围内沸腾的纯化烃类溶剂,如Unocal 140溶剂。此外,还可使用未精炼的油,如Unocal 460溶剂和烃类密封油和Exxon的Telura 401和Telura 407。烃油的选择在本领域技术人员的技能之内。
本方法制备金属粒径为10-500微米的锂分散体。公认本领域技术人员将能够根据锂分散体的预期用途选择合适的粒径。冷却后,容易将所得锂分散体过滤以除去大部分分散剂烃油且可用溶剂如己烷洗涤金属以除去残余油,之后,可将金属粉干燥。烃油滤出液是澄清、无色的且可回收至金属分散过程,而无需进一步处理,与在再使用之前需要用粘土柱将油纯化的现有技术方法形成对比。干燥的金属粉在环境气氛下出人意料地稳定,使之能在这种环境下从一个容器中安全转移到另一容器中。
用于本发明各实施方案的金属锂可以锂粉提供。所述锂粉可经过处理或经过调适以在运输过程中保持稳定。例如,如通常所知可在二氧化碳存在下制备干锂粉。其可在惰性气氛如氩中包装。锂粉可在悬浮液中制备,如在矿物油溶液或其他溶剂的悬浮液中。在溶剂悬浮液中制备锂粉可促进较小锂粉颗粒的形成。本发明某些实施方案中,锂粉可在溶剂中制备,所述溶剂可用于本发明各实施方案。在所述溶剂中制备的金属锂粉可在所述溶剂中运输。此外,所述金属锂粉和溶剂混合物可用于本发明实施方案中,所述实施方案可免除电极制备过程的混合步骤,因为所述溶剂和金属锂粉作为单一组分提供。此外,这可能降低生产成本并使得较小或较细金属锂粉粒子用于本发明实施方案中。
通常金属锂粉的中值粒径为10-500微米。
或者,经稳定的金属锂粉可通过将熔融金属从雾化器喷嘴喷出来制备,氟化步骤可在小滴在氟化气体和氩气的混合物中飞行过程中或粉末被收集后进行。
经稳定的金属锂粉可单独使用或可与分散剂如油酸组合使用。其他合适的分散剂包括亚油酸、油酸钠、油酸锂、亚麻子油、CO2、N2、NH3、Teluraoil、硬脂酸、草酸、单宁酸(tanic acid)和CO。
经稳定的金属锂粉可用于二次电池,如美国专利6,706,447 B2中所述,所述专利的公开内容通过全文引用结合于本文中。典型的二次电池包括正极或阴极、负极或阳极、分隔所述正极和负极的隔板及与所述正极和负极电化学相连的电解质。二次电池还包括与所述阴极电接触的集流器及与所述阳极电接触的集流器。所述集流器通过外部电路相互电接触。二次电池可具有本领域中已知的任何结构如“果冻卷(jelly roll)”或堆栈结构。
所述阴极由活性材料制成,所述活性材料通常与碳质材料和粘合剂聚合物组合。用于阴极的活性材料优选为可在有用电压(如对锂而言2.0-5.0V)下锂化的材料。优选非锂化材料如MnO2、V2O5或MoS2或其混合物可用作活性材料,且更优选采用MnO2。然而还可使用可进一步锂化的锂化材料如LiMn2O4。优选非锂化活性材料,因为它们通常比此结构中的锂化活性材料具有更高比容量、较低成本和更广选择,且因此可比包含锂化活性材料的二次电池提供更高的功率。此外,因为如下所讨论的,阳极包括锂,因此阴极不必包括锂化材料来使所述二次电池工作。阴极中活性材料的量优选足够接受阳极中的可移动金属锂。
阳极由能吸收和解吸电化学体系中的锂的基质材料组成,经稳定的金属锂粉分布于所述基质材料中。例如,在电池(且尤其阳极)再充电时阳极中的锂可插入基质材料、与基质材料形成合金或被基质材料吸收。所述基质材料包括能吸收和解吸电化学体系中的锂的材料如碳质材料;包含硅、锡(Sn)、锡(tin)和硅氧化物或复合锡和/或硅合金的材料;过渡金属氧化物如CoO;金属锂氮化物如Li3-xCoxN(其中0<x<0.5)和金属锂氧化物如Li4Ti5O12。
经稳定的金属锂粉的一个供选用途是以良好产率制备有机锂产品。认为薄LiF层不会减慢反应活性但确实保护金属不与环境气氛反应。
以下实施例仅用于对本发明进行说明,而非限定。
实施例
采用两类经稳定的金属锂粉进行稳定性试验。按照US5,567,474、5,776,369和5,976,403中公开的方法制备表面积为0.06M2/g(根据粒径分布计算)的I型(TypeI)粉或经CO2稳定的金属锂粉。
实施例1
将电池级金属锂(440克)切成2×2英寸小块并在室温、恒流的干燥氩气流下放入3升不锈钢烧瓶反应器,所述反应器的4英寸顶口装有连接到固定的高速搅拌电机的搅拌轴。所述反应器装有顶部和底部加热套。装配反应器并加入1215g PeneteckTM油(Penreco,Penzoil Products Company的分公司)。接下来,将反应器加热到约200℃并以250rpm-800rpm保持缓慢搅拌以确保所有金属熔融。然后,将混合物高速(最高达10,000rpm)搅拌2分钟。将8.78g油酸加入反应器并继续再高速搅拌3分钟。然后停止高速搅拌,除去加热套并使分散体冷却到约100℃。接下来,将32.5g氟化剂FC70(全氟戊胺)装入反应器,同时以约800rpm搅拌直到所得混合物冷却到约45℃。然后将分散体转移到储存瓶。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密加盖的储存瓶。
对该材料进行的自燃测试(Method 1050 of DOT regulations forthe transport of spontaneously combustible material(自燃物质运输的DOT规则的方法1050),美国联邦法规173部分,附录E)表明它是非自燃的。将该材料的物理和化学性能示于下表1中。
按照实施例1中所述制备表面积为0.29m2/g(根据粒径分布计算)的II型(Type II)粉或经全氟戊胺稳定的金属锂粉。
按照如下进行两个稳定性试验并对衰变速率或金属锂百分含量的减少进行分析:
试验A:在相对湿度为40%的环境中将样品暴露于空气中。
试验B:在相对湿度为20%、恒定空气流的环境室(environmentalchamber)中将样品暴露于空气中。
试验C:在-34℃露点和恒定空气流的环境室中将样品暴露于空气中。
从图1和图2可见,表面积为0.29m2/g的经全氟戊胺稳定的金属锂粉的衰变速率比表面积为0.06m2/g的经CO2稳定的金属锂粉小,尽管其表面积几乎高五倍。
此外,II型粉没有观察到颜色变化,且随着暴露时间变化增加氮含量保持在约0.5%,这显示了类LiF涂层的良好钝化性能。观察到经CO2稳定的样品(I型)形成黑色层,这表明在湿气存在下与空气中的氮反应。在试验A条件下氮含量从0.04%稳定提高到1.4%而在试验B条件下氮含量从0.04%稳定提高到0.7%。
实施例2
将电池级金属锂(439克)切成2×2英寸小块并在室温、恒流的干燥氩气流下放入3升不锈钢烧瓶反应器,所述反应器的4英寸顶口装有连接到固定的高速搅拌电机的搅拌轴。所述反应器装有顶部和底部加热套。装配反应器并加入1215g PeneteckTM油。将反应器加热到约200℃并以250rpm-800rpm保持缓慢搅拌以确保所有金属熔融。然后,将混合物高速(最高达10,000rpm)搅拌2分钟。将8.78g油酸加入反应器并继续再高速搅拌3分钟。然后停止高速搅拌,除去加热套并使分散体冷却到约100℃。接下来,将16.24g全氟戊胺装入反应器,同时以约800rpm搅拌直到所得混合物冷却到约45℃。然后将分散体转移到储存瓶。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密加盖的储存瓶。将该材料的物理和化学性能示于下表1中。
实施例3
将电池级金属锂(444克)切成2×2英寸小块并在室温、恒流的干燥氩气流下放入3升不锈钢烧瓶反应器,所述反应器的4英寸顶口装有连接到固定的高速搅拌电机的搅拌轴。所述反应器装有顶部和底部加热套。装配反应器并加入1218.6g PeneteckTM油。接下来,将反应器加热到约200℃并以250rpm-800rpm保持缓慢搅拌以确保所有金属熔融。然后,将混合物高速(最高达10,000rpm)搅拌2分钟。将4.44g油酸加入反应器并继续再高速搅拌3分钟。然后停止高速搅拌,除去加热套并使分散体冷却到约100℃。接下来,将16.43g全氟戊胺装入反应器,同时以约800rpm搅拌直到所得混合物冷却到约45℃。然后将分散体转移到储存瓶。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密加盖的储存瓶。将该材料的物理和化学性能示于下表1中。
表1
实施例1 | 实施例2 | 实施例3 | |
D50,微米 | 22.3 | 22.7 | 31.4 |
SA,m2/g(计算值) | 0.29 | 0.29 | 0.21 |
金属锂,% | 93.3 | 96.9 | 95.8 |
F,% | 3.74 | 1.80 | 1.92 |
从图3中看出,实施例3样品比经CO2稳定的金属锂粉更稳定。从图4中看出,两个样品都显示稳定性。参考图5,在-34℃露点下实施例1和3及对比实施例的金属锂含量损失相当。
实施例4
将12.7g 27%未经稳定的锂在油中的分散体放入装有磁力搅拌器的120ml hastelloy合金罐。在搅拌下将8.845g三氟化硼叔丁基甲基醚合物作为在甲基叔丁基醚中的23.9%溶液一次加入且温度升高为约278℃。使样品冷却并转移到储存瓶中。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密封顶的储存瓶。
实施例5
将20.175g 27%未经稳定的锂在油中的分散体放入装有磁力搅拌器的1120ml hastelloy合金罐。在搅拌下将0.514g全氟1,3-二甲基环已烷一次加入且温度升高为约60℃并将样品保持在约85℃下约1小时。使样品冷却并转移到储存瓶中。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密封顶的储存瓶。
实施例6
将6.472g 27%未经稳定的锂在油中的分散体放入装有磁力搅拌器的120ml hastelloy合金罐。在搅拌下将37.3ml 8.74%的全氟己烷在环己烷中的溶液以超过20次加入(20 times excess in one shot),没有观察到反应热。在10小时内将样品加热到180℃。使样品冷却并转移到储存瓶中。进一步在密闭、烧结玻璃过滤漏斗中将锂分散体过滤并用己烷洗涤三次、用正戊烷洗涤一次以除去烃油介质。用加热枪加热所述漏斗以除去微量溶剂并将所得自由流动的粉转移到紧密封顶的储存瓶。
实施例7
将干燥的1升三颈圆底烧瓶装上磁力搅拌器、热电偶和带有氩气入口的加料漏斗。用氩气吹扫烧瓶并装入已用FC-70稳定的金属锂粉(20.00g,2.2当量)。加入己烷(195g)并将浆液加热到37℃。加入少量正丁基氯来引发反应。几分钟后,将余下的正丁基氯(共121g)以一定速率加入以保持混合物缓和回流。加完后,将混合物搅拌1小时,然后冷却和过滤。过滤速度快且丁基锂溶液接近无色。滴定表明该产率对低钠分散体(low sodium dispersion)是典型的。
已这样对本发明某些实施方案进行描述,应理解的是,通过随附的利要求书限定的本发明不局限于以上说明书中所列的具体细节,因此在不偏离权利要求的精神和范围的条件下,可能有许多明显的变体。
Claims (10)
1.一种使金属锂粉稳定的方法,所述方法包括以下步骤:
a)将金属锂加热到超过其熔点的温度;
b)搅动所述熔融金属锂;和
c)使所述金属锂与氟化剂接触以提供经稳定的金属锂粉。
2.权利要求1的方法,其中步骤(a)在烃油中进行。
3.权利要求2的方法,其中所述经稳定的金属锂粉经过处理以除去残余烃油。
4.权利要求1的方法,其中所述金属锂粉的中值粒径为10-500微米。
5.权利要求1的方法,其中将所述熔融金属锂冷却到24℃-200℃。
6.一种使金属锂粉稳定的方法,所述方法包括以下步骤:
a)将金属锂加热到超过其熔点的温度;
b)将所述熔融金属锂通过雾化器喷嘴喷出以提供小滴;和
c)在小滴飞行过程中将其氟化以提供经稳定的金属锂粉。
7.权利要求1的方法,其中步骤(a)在烃油中进行。
8.权利要求2的方法,其中所述经稳定的金属锂粉经过处理以除去残余烃油。
9.权利要求1的方法,其中所述金属锂粉的中值粒径为10-500微米。
10.权利要求1的方法,其中将所述熔融金属锂冷却到24℃-200℃。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102642024A (zh) * | 2012-03-06 | 2012-08-22 | 宁德新能源科技有限公司 | 锂离子电池及其阳极片和稳定化锂金属粉末 |
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Families Citing this family (72)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7968233B2 (en) | 2004-02-18 | 2011-06-28 | Solicore, Inc. | Lithium inks and electrodes and batteries made therefrom |
US7588623B2 (en) * | 2005-07-05 | 2009-09-15 | Fmc Corporation Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
US20090035663A1 (en) | 2006-10-13 | 2009-02-05 | Fmc Corporation, Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
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US8236452B2 (en) * | 2009-11-02 | 2012-08-07 | Nanotek Instruments, Inc. | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
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US20110135810A1 (en) * | 2009-12-03 | 2011-06-09 | Marina Yakovleva | Finely deposited lithium metal powder |
US9073120B2 (en) * | 2009-12-18 | 2015-07-07 | Chemetall Gmbh | Surface-passivated lithium metal and method for the production thereof |
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US9166222B2 (en) | 2010-11-02 | 2015-10-20 | Envia Systems, Inc. | Lithium ion batteries with supplemental lithium |
US9601228B2 (en) | 2011-05-16 | 2017-03-21 | Envia Systems, Inc. | Silicon oxide based high capacity anode materials for lithium ion batteries |
CN102437310A (zh) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | 一种粉末锂电极的制备方法 |
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US9601762B2 (en) | 2012-01-13 | 2017-03-21 | Rockwood Lithium GmbH | Phosphorous-coated lithium metal products, method for production and use thereof |
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US10553871B2 (en) | 2012-05-04 | 2020-02-04 | Zenlabs Energy, Inc. | Battery cell engineering and design to reach high energy |
US9780358B2 (en) | 2012-05-04 | 2017-10-03 | Zenlabs Energy, Inc. | Battery designs with high capacity anode materials and cathode materials |
JP6306013B2 (ja) | 2012-08-21 | 2018-04-04 | クラトス・エル・エル・シー | 官能化iva族粒子およびその使用方法 |
US9461309B2 (en) | 2012-08-21 | 2016-10-04 | Kratos LLC | Group IVA functionalized particles and methods of use thereof |
US8920925B2 (en) * | 2012-11-09 | 2014-12-30 | Corning Incorporated | Stabilized lithium composite particles |
WO2016048850A1 (en) | 2014-09-23 | 2016-03-31 | Corning Incorporated | Encapsulated lithium particles and methods of making and use thereof |
US9183994B2 (en) * | 2012-11-28 | 2015-11-10 | Corning Incorporated | Lithium ion capacitors and methods of production |
CN103021675B (zh) * | 2012-12-30 | 2015-08-19 | 万裕三信电子(东莞)有限公司 | 锂离子电容器及其负极极片及制备方法 |
KR102258042B1 (ko) | 2013-04-19 | 2021-05-27 | 알베마를 저머니 게엠베하 | 질소 함유 쉘로 코팅된 안정화된 리튬 금속 형성물 및 이를 생산하는 방법 |
WO2015024004A1 (en) | 2013-08-16 | 2015-02-19 | Envia Systems, Inc. | Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics |
US11038165B2 (en) | 2014-05-29 | 2021-06-15 | Sila Nanotechnologies, Inc. | Ion permeable composite current collectors for metal-ion batteries and cell design using the same |
CN106001585A (zh) * | 2015-03-31 | 2016-10-12 | Tdk株式会社 | 稳定化锂粉和使用其的锂离子二次电池 |
CN107305941B (zh) * | 2016-04-21 | 2019-12-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | 锂-碳复合材料、其制备方法与应用以及锂补偿方法 |
JP2019520682A (ja) | 2016-07-05 | 2019-07-18 | クラトス・エル・エル・シー | 不動態化されたプレリチウム化ミクロン及びサブミクロンiva族元素粒子及びこの調製方法 |
US10756340B2 (en) | 2016-12-01 | 2020-08-25 | Lg Chem, Ltd. | Negative electrode for lithium metal secondary battery and method for manufacturing the same |
US11637280B2 (en) | 2017-03-31 | 2023-04-25 | Kratos LLC | Precharged negative electrode material for secondary battery |
KR102187719B1 (ko) | 2017-09-29 | 2020-12-08 | 나이키 이노베이트 씨.브이. | 구조색을 갖는 물품 및 구조색을 갖는 물품을 제조하고 사용하기 위한 방법 |
CN108176859B (zh) * | 2017-12-05 | 2021-06-04 | 天齐锂业股份有限公司 | 钝化锂粉的制备方法 |
CN108161016A (zh) * | 2017-12-13 | 2018-06-15 | 天齐锂业股份有限公司 | 制备钝化锂粉的方法 |
US11094925B2 (en) | 2017-12-22 | 2021-08-17 | Zenlabs Energy, Inc. | Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance |
KR102601605B1 (ko) * | 2017-12-27 | 2023-11-14 | 삼성전자주식회사 | 음극, 이를 포함하는 리튬전지 및 음극 제조방법 |
DE102018104291A1 (de) | 2018-02-26 | 2019-08-29 | Volkswagen Aktiengesellschaft | Beschichtung für ein Werkzeug zur Handhabung von Lithiummetall, Werkzeug und Verfahren zum Herstellen eines solchen Werkzeugs |
US11264598B2 (en) | 2018-03-22 | 2022-03-01 | Fmc Lithium Usa Corp. | Battery utilizing printable lithium |
US20190214631A1 (en) * | 2018-03-22 | 2019-07-11 | Fmc Lithium Usa Corp. | Methods of applying printable lithium compositions for forming battery electrodes |
WO2019183368A1 (en) | 2018-03-22 | 2019-09-26 | Fmc Lithium Usa Corp. | Solid-state battery |
US20200014033A1 (en) * | 2018-03-22 | 2020-01-09 | Fmc Lithium Usa Corp. | Printed lithium foil and film |
CN108923046B (zh) * | 2018-07-03 | 2021-08-31 | 江苏乐能电池股份有限公司 | 一种纳米多孔富锂磷酸铁锂材料的制备方法 |
WO2020068134A1 (en) * | 2018-09-30 | 2020-04-02 | Seeo, Inc. | High-energy cathode material particles with oxy-fluoride surfaces for aqueous processing |
KR102287354B1 (ko) * | 2019-02-19 | 2021-08-06 | 한국과학기술연구원 | 조성과 융점이 제어된 저융점 합금 입자의 제조방법, 및 이에 의해 제조된 저융점 합금 입자를 이용한 저(低)퍼콜레이션 복합체 및 그 제조방법 |
BR112021015924A2 (pt) | 2019-03-20 | 2021-10-05 | Fmc Lithium Usa Corp. | Lâmina e película de lítio impressas |
CN113597691A (zh) | 2019-03-20 | 2021-11-02 | Fmc锂业美国公司 | 使用可印刷锂的电池 |
JP2020158834A (ja) * | 2019-03-27 | 2020-10-01 | Tdk株式会社 | ハロゲン化金属粒子、これを用いた全固体電池及び非水系リチウムイオン電池 |
US11600853B1 (en) | 2019-05-14 | 2023-03-07 | Ampcera Inc. | Systems and methods for storing, transporting, and handling of solid-state electrolytes |
CN114008493A (zh) | 2019-06-26 | 2022-02-01 | 耐克创新有限合伙公司 | 结构着色的物品以及用于制造和使用结构着色的物品的方法 |
US20210022444A1 (en) | 2019-07-26 | 2021-01-28 | Nike, Inc. | Structurally-colored articles and methods for making and using structurally-colored articles |
CN110556509A (zh) * | 2019-08-14 | 2019-12-10 | 南京大学 | 一种利用含氟有机物进行金属锂负极表面保护和钝化处理的方法、产品及应用 |
CN110534706B (zh) * | 2019-09-06 | 2021-06-25 | 燕山大学 | 一种钝化锂粉及其制备方法和应用 |
EP4044860A1 (en) | 2019-10-21 | 2022-08-24 | Nike Innovate C.V. | Structurally-colored articles |
CN112993251B (zh) * | 2019-12-16 | 2023-12-12 | 比亚迪股份有限公司 | 一种补锂材料及其制备方法、负极和锂离子电池 |
WO2021168063A1 (en) | 2020-02-19 | 2021-08-26 | Fmc Lithium Usa Corp. | Fast charging pre-lithiated silicon anode |
CN115551720A (zh) | 2020-05-29 | 2022-12-30 | 耐克创新有限合伙公司 | 结构着色的物品以及用于制造和使用结构着色的物品的方法 |
CN111725515A (zh) * | 2020-06-30 | 2020-09-29 | 昆山宝创新能源科技有限公司 | 稳定锂粉及其制备方法和应用 |
CN111725494B (zh) * | 2020-06-30 | 2021-11-09 | 蜂巢能源科技有限公司 | 锂材料、含锂材料分散液、电极材料及其制备方法和应用 |
US11241062B1 (en) | 2020-08-07 | 2022-02-08 | Nike, Inc. | Footwear article having repurposed material with structural-color concealing layer |
US11129444B1 (en) | 2020-08-07 | 2021-09-28 | Nike, Inc. | Footwear article having repurposed material with concealing layer |
US11889894B2 (en) | 2020-08-07 | 2024-02-06 | Nike, Inc. | Footwear article having concealing layer |
CN113013398A (zh) * | 2021-02-22 | 2021-06-22 | 昆山宝创新能源科技有限公司 | 稳定化锂粉及其制备方法、负极片的预锂化工艺、极片和锂离子电池 |
WO2022216460A1 (en) | 2021-04-08 | 2022-10-13 | Fmc Lithium Usa Corp. | Dry process for forming an electrode |
WO2023076011A1 (en) | 2021-10-29 | 2023-05-04 | Livent USA Corp. | Dry process for forming an electrode |
FR3134396A1 (fr) | 2022-04-12 | 2023-10-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de fluoration d’une surface de lithium métallique |
FR3134395B1 (fr) | 2022-04-12 | 2024-03-29 | Commissariat Energie Atomique | Procédé de fluoration d’une surface de lithium métallique |
WO2023239686A1 (en) | 2022-06-07 | 2023-12-14 | Livent Lithium Llc | Solid-state battery |
CA3169823A1 (fr) * | 2022-08-05 | 2024-02-05 | Hydro-Quebec | Poudre de lithium metallique, son procede de preparation et applications |
Family Cites Families (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3271196A (en) * | 1961-11-08 | 1966-09-06 | Leesona Corp | Fuel cell electrodes |
US3788906A (en) * | 1961-12-28 | 1974-01-29 | Minnesota Mining & Mfg | Solid propellant compositions containing lithium passivated by a coating of polyethylene |
US3508967A (en) * | 1967-09-22 | 1970-04-28 | Gulton Ind Inc | Negative lithium electrode and electrochemical battery containing the same |
JPH0789483B2 (ja) * | 1984-05-07 | 1995-09-27 | 三洋化成工業株式会社 | 二次電池 |
DE3680249D1 (de) * | 1985-05-10 | 1991-08-22 | Asahi Chemical Ind | Sekundaerbatterie. |
JPH063745B2 (ja) | 1986-07-02 | 1994-01-12 | シャープ株式会社 | 非水電解液型二次電池 |
US4770697A (en) * | 1986-10-30 | 1988-09-13 | Air Products And Chemicals, Inc. | Blanketing atmosphere for molten aluminum-lithium alloys or pure lithium |
US4945014A (en) | 1988-02-10 | 1990-07-31 | Mitsubishi Petrochemical Co., Ltd. | Secondary battery |
US5028500A (en) * | 1989-05-11 | 1991-07-02 | Moli Energy Limited | Carbonaceous electrodes for lithium cells |
JPH0439859A (ja) | 1990-06-04 | 1992-02-10 | Mitsubishi Petrochem Co Ltd | 二次電池用電極 |
US5153082A (en) * | 1990-09-04 | 1992-10-06 | Bridgestone Corporation | Nonaqueous electrolyte secondary battery |
JP3133318B2 (ja) | 1990-09-18 | 2001-02-05 | 三洋電機株式会社 | 二次電池 |
JP3162437B2 (ja) * | 1990-11-02 | 2001-04-25 | セイコーインスツルメンツ株式会社 | 非水電解質二次電池 |
JP3126030B2 (ja) | 1990-11-22 | 2001-01-22 | 大阪瓦斯株式会社 | リチウム二次電池 |
US5244757A (en) * | 1991-01-14 | 1993-09-14 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
DE4101533A1 (de) * | 1991-01-19 | 1992-07-23 | Varta Batterie | Elektrochemisches sekundaerelement |
JP3291750B2 (ja) | 1992-02-25 | 2002-06-10 | 松下電器産業株式会社 | 非水電解液二次電池およびその製造法 |
EP0573266B1 (en) | 1992-06-01 | 1999-12-08 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method of manufacturing carbonaceous material for negative electrode of the battery |
EP0601832B1 (en) | 1992-12-07 | 1999-05-19 | Honda Giken Kogyo Kabushiki Kaisha | Alkaline ion-absorbing/desorbing carbon material, electrode material for secondary battery using the carbon material and lithium battery using the electrode material |
US5776369A (en) * | 1993-02-18 | 1998-07-07 | Fmc Corporation | Alkali metal dispersions |
AU6128994A (en) | 1993-02-18 | 1994-09-14 | Fmc Corporation | Alkali metal dispersions |
US5312623A (en) * | 1993-06-18 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | High temperature, rechargeable, solid electrolyte electrochemical cell |
CA2127621C (en) * | 1994-07-08 | 1999-12-07 | Alfred Macdonald Wilson | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
JPH08213052A (ja) | 1994-08-04 | 1996-08-20 | Seiko Instr Inc | 非水電解質二次電池 |
US5543021A (en) * | 1994-09-01 | 1996-08-06 | Le Carbone Lorraine | Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator |
FR2724490B1 (fr) | 1994-09-09 | 1996-10-25 | Lorraine Carbone | Electrode composite carbone/polymere pour generateur electrochimique rechargeable au lithium |
US5707756A (en) * | 1994-11-29 | 1998-01-13 | Fuji Photo Film Co., Ltd. | Non-aqueous secondary battery |
US5595837A (en) * | 1995-04-12 | 1997-01-21 | Valence Technology, Inc. | Process for prelithiation of carbon based anodes for lithium batteries |
US5753387A (en) * | 1995-11-24 | 1998-05-19 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
US5672446A (en) * | 1996-01-29 | 1997-09-30 | Valence Technology, Inc. | Lithium ion electrochemical cell |
US5958622A (en) * | 1996-03-28 | 1999-09-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Negative electrode material for lithium secondary batteries |
JPH10117406A (ja) | 1996-06-14 | 1998-05-06 | Fuji Photo Film Co Ltd | 電気自動車及びその駆動電源装置 |
US6270926B1 (en) * | 1996-07-16 | 2001-08-07 | Murata Manufacturing Co., Ltd. | Lithium secondary battery |
DE69705428T2 (de) * | 1996-12-20 | 2001-10-11 | Danionics As Odense S | Lithium sekundärbatterie mit einer negativen elektrode enthaltend natürlichen schuppengraphit |
JPH10223259A (ja) | 1997-02-03 | 1998-08-21 | Toyota Central Res & Dev Lab Inc | リチウム二次電池及びその製造方法 |
DE69836820T2 (de) * | 1997-02-28 | 2007-10-11 | Asahi Kasei Emd Corporation | Nichtwässrige sekundärbatterie und verfahren zu deren herstellung |
US6156457A (en) * | 1997-03-11 | 2000-12-05 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method for manufacturing a negative electrode |
JP3200025B2 (ja) | 1997-03-26 | 2001-08-20 | セイコーインスツルメンツ株式会社 | 非水電解質二次電池 |
US5807645A (en) * | 1997-06-18 | 1998-09-15 | Wilson Greatbatch Ltd. | Discharge promoter mixture for reducing cell swelling in alkali metal electrochemical cells |
JPH1125975A (ja) | 1997-07-02 | 1999-01-29 | Toyota Central Res & Dev Lab Inc | 負極活物質 |
US5948569A (en) * | 1997-07-21 | 1999-09-07 | Duracell Inc. | Lithium ion electrochemical cell |
KR100245808B1 (ko) * | 1997-12-30 | 2000-03-02 | 박찬구 | 리튬이온 전지용 양극재료의 제조방법 |
US6168885B1 (en) * | 1998-08-21 | 2001-01-02 | Sri International | Fabrication of electrodes and devices containing electrodes |
JP2000067853A (ja) | 1998-08-18 | 2000-03-03 | Matsushita Battery Industrial Co Ltd | リチウム二次電池用負極 |
DE19839217C2 (de) | 1998-08-28 | 2001-02-08 | Fraunhofer Ges Forschung | Pastöse Massen, Schichten und Schichtverbände, Zellen und Verfahren zur Herstellung |
JP2000164210A (ja) | 1998-11-24 | 2000-06-16 | Fuji Photo Film Co Ltd | 非水二次電池 |
KR100326457B1 (ko) * | 1999-03-10 | 2002-02-28 | 김순택 | 리튬 이차 전지용 양극 활물질 및 그 제조 방법 |
SE516891C2 (sv) * | 1999-06-14 | 2002-03-19 | Ericsson Telefon Ab L M | Bindemedel och/eller elektrolytmateriel för en elektrod i en battericell, elektrod för en battericell samt förfarande för framställning av ett bindemedel och/eller elektrolytmaterial för en elektrod |
US6541156B1 (en) * | 1999-11-16 | 2003-04-01 | Mitsubishi Chemical Corporation | Negative electrode material for non-aqueous lithium secondary battery, method for manufacturing the same, and non-aqueous lithium secondary battery using the same |
US8980477B2 (en) * | 2000-12-22 | 2015-03-17 | Fmc Corporation | Lithium metal dispersion in secondary battery anodes |
US6706447B2 (en) * | 2000-12-22 | 2004-03-16 | Fmc Corporation, Lithium Division | Lithium metal dispersion in secondary battery anodes |
US7276314B2 (en) * | 2000-12-22 | 2007-10-02 | Fmc Corporation | Lithium metal dispersion in secondary battery anodes |
CN1410203A (zh) * | 2001-09-21 | 2003-04-16 | 吴庆林 | 一种金属锂粉深加工工艺 |
FR2833760B1 (fr) | 2001-12-19 | 2011-03-25 | Fmc Corp | Dispersion de metal lithium dans des anodes de batterie secondaire |
CN1195602C (zh) * | 2002-11-19 | 2005-04-06 | 中国石化集团巴陵石油化工有限责任公司 | 一种锂砂的制备方法 |
US20050130043A1 (en) * | 2003-07-29 | 2005-06-16 | Yuan Gao | Lithium metal dispersion in electrodes |
US7588623B2 (en) * | 2005-07-05 | 2009-09-15 | Fmc Corporation Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
-
2006
- 2006-07-03 US US11/480,606 patent/US7588623B2/en active Active
- 2006-07-05 WO PCT/US2006/026238 patent/WO2007005983A2/en active Application Filing
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- 2006-07-05 CA CA2613485A patent/CA2613485C/en not_active Expired - Fee Related
-
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- 2009-08-14 US US12/541,229 patent/US20100024597A1/en not_active Abandoned
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---|---|---|---|---|
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CN102642024A (zh) * | 2012-03-06 | 2012-08-22 | 宁德新能源科技有限公司 | 锂离子电池及其阳极片和稳定化锂金属粉末 |
CN105489870A (zh) * | 2014-10-03 | 2016-04-13 | Tdk株式会社 | 稳定化锂粉 |
CN105489870B (zh) * | 2014-10-03 | 2019-01-08 | Tdk株式会社 | 稳定化锂粉 |
CN105826545A (zh) * | 2016-05-23 | 2016-08-03 | 天津巴莫科技股份有限公司 | 锂粉或锂合金粉的制备方法 |
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CN108015294A (zh) * | 2017-12-13 | 2018-05-11 | 天齐锂业股份有限公司 | 钝化金属锂粉的制备方法及装置 |
CN108538642A (zh) * | 2018-01-26 | 2018-09-14 | 南昌大学 | 一种稳定化金属锂粉的制备方法 |
CN108461724A (zh) * | 2018-03-05 | 2018-08-28 | 苏州大学 | 一种高安全性金属复合负极的制备方法 |
CN109037627A (zh) * | 2018-07-20 | 2018-12-18 | 浙江大学 | 一种碱金属基复合负极及其应用 |
CN114242946A (zh) * | 2021-12-13 | 2022-03-25 | 四川启睿克科技有限公司 | 复合金属锂负极及其制备方法和用途 |
CN114242946B (zh) * | 2021-12-13 | 2023-09-05 | 四川启睿克科技有限公司 | 复合金属锂负极及其制备方法和用途 |
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US7588623B2 (en) | 2009-09-15 |
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GB201019834D0 (en) | 2011-01-05 |
CA2613485A1 (en) | 2007-01-11 |
RU2008104147A (ru) | 2009-08-10 |
EP2246134A2 (en) | 2010-11-03 |
EP2246134A3 (en) | 2011-04-06 |
KR101379477B1 (ko) | 2014-04-01 |
WO2007005983A3 (en) | 2007-04-05 |
KR20080023703A (ko) | 2008-03-14 |
KR101335000B1 (ko) | 2013-11-29 |
CN101213039B (zh) | 2012-06-20 |
CN102601376A (zh) | 2012-07-25 |
EP1899094A2 (en) | 2008-03-19 |
DE112006001699T5 (de) | 2009-04-30 |
JP5713532B2 (ja) | 2015-05-07 |
GB2439517B (en) | 2011-02-09 |
GB2472357A (en) | 2011-02-02 |
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