CN108140801B - 涂覆有活性氧化物材料的金属泡沫阳极 - Google Patents
涂覆有活性氧化物材料的金属泡沫阳极 Download PDFInfo
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- CN108140801B CN108140801B CN201680043033.1A CN201680043033A CN108140801B CN 108140801 B CN108140801 B CN 108140801B CN 201680043033 A CN201680043033 A CN 201680043033A CN 108140801 B CN108140801 B CN 108140801B
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- sintering
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Abstract
用活性氧化物材料制造三维金属泡沫用作锂电池的阳极。使用可以通过冷冻铸造工艺制造的多孔金属泡沫作为锂电池的阳极集电体。多孔金属泡沫可以被热处理以形成活性氧化物材料在金属泡沫的表面上。氧化物材料充当在充电和放电期间与锂离子反应的三维活性材料。
Description
说明书
相关申请的交叉引用
本专利申请要求于2016年7月20日提交的美国专利申请62/194,564和62/194,677的优先权,该美国专利申请通过引用与本申请中所引用的所有其它引用文献一起被并入本申请中。
背景技术
本发明涉及可再充电电池技术领域,更具体地涉及可再充电锂离子电池技术。
在各种类型的二次电池中,锂离子电池(LIB)是具有相对高的能量密度和优异的循环寿命的环境友好型储能装置。锂离子电池技术通常使用石墨材料作为阳极,使用金属氧化物材料例如LiCoO2作为阴极。
虽然石墨现已主要用作锂离子电池阳极的活性材料,但是其小比容量(372毫安小时/克)对需要高能量密度的下一代应用而言有局限性。而且,石墨还具有低输送率和相应的低功率密度。因此,石墨阳极不被认为是对于需要高容量和功率密度的电池应用而言的有前途的解决方案。
为了克服这些限制,已经进行了很大的努力来开发先进的阳极和阴极材料。例如,诸如金属氧化物和锂合金之类的高容量的阳极材料已经被认为可以代替石墨。对于活性材料而言,可以使用包括Co3O4、Fe2O3、NiO、CuO和TiO2的过渡金属氧化物(TMO)。例如,上述氧化物材料中的一些可以在每个化学式中嵌入合计至少六个锂离子,显示出比石墨材料更大的可逆容量。这种过渡金属氧化物在首次放电过程中与锂离子发生反应,形成Li2O,并遵循在充电过程中可逆地回到初始状态的转换反应机理。
但是,这些材料也显示出若干问题。一些TMO’s在锂离子嵌入/提取期间的容量保持能力差,倍率性能(rate capability)差,导致体积膨胀严重。众所周知,过渡金属氧化物的构造和集电体的结构对电化学性能有很大的影响。
因此,需要具有改进的能量和功率能力的改进的锂离子电池。
发明内容
用氧化物材料涂层制造三维金属泡沫结构以用作锂离子电池的阳极。制造技术相对简单而不复杂。经涂覆的金属泡沫阳极减少了活性材料的体积膨胀并且提高了电化学反应的速率,导致阳极材料的改进的循环性能和更高的容量。
本发明旨在实现以下目的:使用孔径为数百纳米至数百微米的多孔金属泡沫作为锂离子电池的集电体;以及在多孔金属泡沫的表面上形成具有纳米级表面粗糙度的活性氧化物材料层。
提供了一种制造多孔金属泡沫的方法以及通过高温处理涂覆活性材料的方法,所述方法包括以下步骤:(a)用冷表面铜棒冷冻模具中的金属浆料;(b)在减压和低温下使冷冻样品升华,形成多孔的生坯体;(c)烧结多孔生坯体以获得多孔金属泡沫;(d)将多孔金属泡沫切成薄层;(e)通过将金属泡沫暴露于高温热处理而形成活性氧化物材料层。
具有活性氧化物材料的三维(3D)金属泡沫在结构上有利于限制循环过程中阳极的剧烈体积变化并且由于较大的表面积而增强电化学反应。因此,其预计具有高容量。
在一个实施方式中,锂电池装置包括多孔金属泡沫集电体和活性氧化物材料,活性氧化物材料形成在多孔金属泡沫集电体的表面上。活性氧化物材料可以是阳极活性材料。阳极活性材料可以是包括Fe2O3、Fe3O4、Co3O4、CoO、SnO2、Cu2O、CuO、TiO2或NiO中的至少一种的氧化物基材料。
金属泡沫集电体可以由以下金属中的至少一种制成:铁、钴、镍、铜、钛、金、铝、镁或不锈钢,或这些金属的合金。制造过程可以使用冷冻铸造法来形成多孔金属泡沫集电体。
活性材料是氧化物基材料,可以包括Fe2O3、Fe3O4、Co3O4、CoO、Cu2O、CuO、NiO和TiO2中的至少一种。并且集电体是包括铁、钴、铜、镍或钛中的至少一种的三维多孔金属基材料。
在一个实施方式中,使用冷冻铸造工艺制造多孔金属泡沫的方法包括:将含氟聚合物树脂或Teflon(聚四氟乙烯)模具放置在浸入液氮中的铜棒上;用冷冻铸造装置将金属浆料浇注在含氟聚合物树脂模具中;冷冻金属浆料,在金属浆料中形成并生长冰枝晶,并在生长的冰晶之间堆积金属或金属氧化物颗粒;通过在低温和减压下干燥冷冻金属浆料的冰晶形成具有中空孔的生坯体金属泡沫;在惰性气体或氢气气氛下高温烧结生坯体金属泡沫以形成多孔金属泡沫;以及将多孔金属泡沫加工成薄层,其中多孔金属泡沫薄层可以被用作锂电池中的阳极。金属浆料包括蒸馏水、粘合剂和金属或金属氧化物粉末。Teflon是一种合成含氟树脂或含氟聚合物树脂。Teflon是Chemours Company FC,LLC的商标。
在一个实施方式中,制造用于锂电池的金属泡沫阳极的方法包括在金属泡沫集电体的表面上形成活性氧化物材料。进行高温热处理以在金属泡沫集电体的表面上形成活性氧化物材料。热处理在空气炉中约100摄氏度至约800摄氏度的高温范围内进行。热处理在空气炉中约400摄氏度至约800摄氏度的高温范围内进行。额外的碳或辅助材料可以与金属泡沫集电体和活性氧化物材料结合。
在一个实施方式中,一种方法包括:在液氮下,将钛金属浆料浇注到置于容器a中的铜棒上;冷冻金属浆料,其中钛金属颗粒堆积并物理附着在生长的冰晶之间;通过在足够低的温度和减压下干燥冷冻浆料的冰晶来形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;通过在足够高的温度下在真空中还原和烧结多孔生坯体来构造多孔金属泡沫;并通过在空气炉中氧化形成用于多孔金属泡沫的锐钛矿氧化层。
在各种实施方式中,锐钛矿氧化层可以通过在大约100摄氏度(例如,100度或以上,100度或以下,55、95、105或150度,加或减5、10或20、25、50,或75度,或加或减1%、2%、5%、10%或20%)下将多孔金属泡沫在过氧化氢(H2O2)中预浸泡约3小时(例如3小时或以下,或3小时或以上,1、2、4、5、7或8小时,加或减0.5、1或2小时,或加或减1%、2%、5%、10%或20%)。
烧结多孔生坯体可以包括在约300摄氏度(例如,300度或以上,300度或以下,200、240、245、250、295、298、305、310、325、350、380或400度,加或减5、10或20、25、50,或75度,或加或减1%、2%、5%、10%或20%)下烧结或预烧结约3小时(例如3小时或以下,3小时或以上,1、2、4、5、7或8小时,加或减0.5、1或2小时,或加或减1%、2%、5%、10%或20%);并且在约1100摄氏度(例如,1100度或以上,1100度或以下,1000、1050、1080、1090、1098、1102、1110、1150或1200度,加或减5、10,或20、25、50或75度,或加或减1%、2%、5%、10%或20%)下烧结约7小时(例如7小时或以下,7小时或以上,1、2、3、5、6、9或10小时,加或减0.5、1、2或3小时,或加或减1%、2%、5%、10%或20%)。
所述方法可以包括:在溶液中,将聚乙烯醇溶解在水中;并将钛粉添加到该溶液中以形成钛金属浆料。通过干燥冰晶而形成多孔生坯体是在约0摄氏度或以下(例如0度或以上,0度或以下,加或减5、10或20度,或加或减1%、2%、5%、10%或20%)进行约24小时(例如,24小时或以下,24小时或以上,18、19、20、22、23、25、26、28或30小时,加或减0.5、1、2、3、4、5、6或7小时,或加或减1%、2%、5%、10%或20%)。
在一个实施方式中,一种方法包括:将铜棒上的模具放入液氮中,并将铁金属浆料浇注到模具中;冷冻铁金属浆料,其中铁金属颗粒堆积并物理附着在生长的冰晶之间;通过在足够低的温度下干燥冷冻浆料的冰晶形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;通过在氢气气氛下在足够高的温度下还原和烧结多孔生坯体来构造多孔金属泡沫。
在各种实施方式中,烧结多孔生坯体可以包括:在约300摄氏度(例如,300度或以上,300度或以下,200、240、245、250、295、298、305、310、325、350、380或400度,加或减5、10,或20、25、50或75度,或加或减1%、2%、5%、10%或20%)下烧结约2小时(例如2小时或以下,2小时或以上,1、3、4、5、7或8小时,加或减0.5、1或1.5小时,或加或减1%、2%、5%、10%或20%);并且在约950摄氏度(例如950度或以上,950度或以下,900、940、945、948、952、955、995、1000或1050度,加或减5、10,或20、25、50或75度,或加或减1%、2%、5%、10%或20%)下烧结约2小时(例如2小时或以下,2小时或以上,1、3、4、5、7或8小时,加或减0.5、1或1.5小时,加或减1%、2%、5%、10%或20%)。氢气气氛可以包括氢气(例如约5%)和约95%的氩气。
形成多孔生坯体可以通过在约-90摄氏度(例如-90度或以上,-90度或以下,-90度加或减5、10或20度,或加或减1%、2%、5%、10%或20%)冷冻干燥约48小时(例如,48小时或以下,48小时或以上,38、39、40、42、43、45、46、53、55、58或60小时,加或减0.5、1、2、3、4、5、6或7小时,或加或减1%、2%、5%、10%或20%)来实现。
铜棒可以在大约-15摄氏度(例如,-15度或以上,-15度或以下,-15度加或减5、10或20度,或加或减1%、2%、5%、10%或20%)。
在一个实施方式中,一种方法包括:将铜棒上的模具放入液氮中,并将钴金属浆料浇注到模具中;冷冻钴金属浆料,其中钴金属颗粒堆积并物理附着在生长的冰晶之间;通过在足够低的温度下干燥冷冻浆料的冰晶形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;通过在氢气气氛下在足够高的温度下还原和烧结多孔生坯体来构造多孔金属泡沫。
在各种实施方式中,烧结多孔生坯体可以包括:在约550摄氏度(例如550度或以上,550度或以下,500、540、545、555、560、580、590或600度,加或减5、10,或20、25、50或75度,或加或减1%、2%、5%、10%或20%)下烧结约4小时(例如,4小时或以下,4小时或以上,1、2、3、5、7或8小时,加或减0.5、1、2或3小时,或加或减1%、2%、5%、10%或20%);并在约1000摄氏度(例如,1000度或以上,1000度或以下,900、940、945、948、952、955、995、1000、1105、1110、1050或1100度,加或减5、10,或20、25、50或75度,或加或减1%、2%、5%、10%或20%)下烧结约9小时(例如,9小时或以下,9小时或以上,1、2、3、5、7、8、10、11或12小时,加或减0.5、1、2、3、4、5或6小时,或加或减1%、2%、5%、10%或20%)。
氢气气氛可以具有约5%的氢气(例如,5%或以上,5%或以下,1、2、3、4、6、7、8、9%,或加或减0.25、0.5、1、1.5、2或3%)。形成多孔生坯体可包括在约-88摄氏度(例如,-88度或以上,-88度或以下,-88度加或减5、10或20度,或加或减1%、2%、5%、10%或20%)下冷冻干燥约24小时(例如24小时或以下,24小时或以上,18、19、20、22、23、25、26、28或30小时,加或减0.5、1、2、3、4、5、6或7小时,或加或减1%、2%、5%、10%或20%)。对于冷冻而言,铜棒可以在大约-10摄氏度(例如,-10度或以上,-10度或以下,-10度加或减5、10或20度,或加或减1%、2%、5%、10%或20%)。
考虑以下详细描述和附图,本发明的其它目的、特征和优点将变得明显,其中相同的附图标记在所有附图中表示相同的特征。
附图说明
图1A是由具有活性氧化物材料的三维金属泡沫制成的阳极电极的图示。
图1B示出了制造由具有活性氧化物材料的金属泡沫制成的电极的流程图。
图2是具有在铁表面上形成的活性氧化铁层的三维铁泡沫的扫描电子显微镜(SEM)显微照片。
图3是三维铁泡沫的X射线衍射(XRD)谱,其证实在铁泡沫的表面上形成纯氧化铁层。
图4是具有在钛表面上形成的活性氧化钛层的三维钛泡沫的SEM显微照片。
图5是三维钛泡沫的XRD谱,其证实在钛泡沫的表面上形成纯氧化钛层。
图6示出了三维钴泡沫的安装和抛光的顶部和横截面的光学显微照片。
图7A-7C示出了具有在表面上形成的活性氧化钴层的三维钴泡沫的SEM显微照片和能量分散X射线(EDX)谱。
图8示出了三维钴泡沫的XRD谱。
图9示出了具有在其表面上形成的活性氧化钴层的三维钴泡沫的XRD谱。
图10示出了具有在其表面上形成的活性氧化物层的三维钴泡沫体的循环性能和库仑效率。
具体实施方式
金属泡沫结构被制造以用作锂离子电池的阳极。一种方法包括:制作孔径为几纳米至几百微米的多孔金属泡沫作为集电体;以及通过热处理形成活性氧化物材料层,对锂离子进行充放电。
图1A示出了本发明的一个实施例,其描述了在用作锂离子电池的集电体的多孔金属泡沫的表面上形成具有纳米级表面粗糙度的活性氧化物材料层。在具体实施中,锂离子电池的集电体为阳极集电体。集电体由多个多孔金属泡沫板制成,活性氧化物材料层围绕多个板。因此,阳极集电体的表面积增加,并且能够以更大的速率加速电化学反应,并且能比传统的阳极集电体存储更多的锂离子。
在2015年7月20日提交的美国专利申请62/194,564中描述了制造三维多孔阳极电极的技术,该美国专利申请通过引用与本申请中所引用的所有其它引用文献一起被并入本申请中。
多孔金属可以根据许多技术制造。在一种实施方式中,多孔金属泡沫具有通过冷冻铸造法制造的三维多孔结构。例如,通过冷冻铸造法制造三维铜泡沫作为示例制造工艺。美国专利申请13/930,887描述了一种冷冻铸造技术,并且通过引用并入本文。该工艺的特征是以简单、低成本的处理方法来制造多孔结构。具有纳米级表面粗糙度的活性氧化物材料被形成在多孔金属泡沫的表面上,多孔金属泡沫可以用作集电体。
本专利中呈现了具体的流程实现,但是应该理解,本发明不限于所给出的具体流程和步骤。本发明的流程可以具有其他步骤(本申请中不一定描述)、代替所呈现的步骤中的一些步骤的不同步骤、更少的步骤或呈现步骤的子集,或者按照与呈现的顺序不同的顺序的步骤,或者这些的任何组合。此外,本发明的其它实施方式中的步骤可能与所给出的步骤不完全相同,并且可以根据具体应用或基于其他因素适当地修改或改变。
图1B示出了制造多孔金属泡沫并形成金属氧化物层的详细方法130,包括:
(a)参考步骤132,将铜棒(具有高导热性)浸入液氮中,并用冷冻铸造装置将金属浆料浇注到模具中。
(b)参照步骤135,冷冻金属浆料,其中金属颗粒堆积在生长的冰晶之间。
(c)参照步骤138,通过在低温和减压下干燥冷冻样品的冰晶(在其位置留下孔隙)形成多孔结构。
(d)参照步骤141,通过在氢气气氛下烧结多孔结构来形成三维连接的多孔金属泡沫。
(e)参考步骤144,将多孔金属泡沫切割成薄层以用作锂离子电池的阳极的集电体。
(f)参照步骤147,通过热处理在用作锂离子电池的阳极的集电体的金属泡沫的表面上形成活性氧化物材料层。所形成的氧化物材料可以是Co3O4、CoO、Fe2O3、Fe3O4、CuO、Cu2O、NiO或TiO2作为阳极活性材料。
在本发明中,提供了三个示例性实施例:在其表面上形成有氧化物层的钴、钛和铁泡沫。然而,金属泡沫的选择不限于此,而是对其他金属材料如铜、镍泡沫等是开放的。金属泡沫可以用作具有高导电性和质量传输效率的三维集电体。
下面介绍一些具体的实施例。提供这些实施例仅仅是为了描述具体实施方式的一些示例,并且其对于本领域技术人员显而易见本发明的范围不受这些实施例的限制。
示例性实施例1(三维多孔氧化铁或铁阳极)
选择铁泡沫作为确认这种实施方式的模型材料,并通过冷冻铸造工艺制造。通过将氧化铁粉末与去离子水和粘合剂混合来制备金属浆料。氧化铁粉末通过搅拌和超声处理的组合被充分分散在浆料中。然后将浆料浇注到铜棒上的含氟聚合物树脂或聚四氟乙烯(Teflon)模具中,使用液氮(N2)冷却铜棒。铜棒顶部的温度由加热器控制,并且固定在-15摄氏度。
冷冻后,冷冻的浆料在-90摄氏度下冷冻干燥约两天(例如约48小时),形成多孔的生坯体。将生坯体在氢气(H2)-95%氩气混合物中在管式炉中还原和烧结。在300摄氏度下2小时以及在500摄氏度下2小时逐步进行还原,并且在950摄氏度下进行14小时的烧结。
图2示出了具有在铁泡沫表面上形成的活性氧化铁层的三维铁泡沫的SEM显微照片。图3示出了三维铁泡沫的XRD谱,证实在铁泡沫的表面上形成了纯氧化铁层,并且其比没有氧化铁层的铁泡沫具有更高的峰值强度。
示例性实施例2(三维多孔氧化钛或钛阳极)
选择钛泡沫作为模型材料,并通过冷冻铸造工艺制造。在冷冻铸造之前,将聚乙烯醇(PVA)溶解在蒸馏水中,并且将钛粉加入到制备的溶液中以制成浆料。然后在液氮(N2)下将浆料直接浇注到放置在不锈钢容器中的铜冷却棒的顶部。
通过在零度以下(例如,小于0摄氏度)升华约一天(例如,约24小时)将冷冻的生坯体冻干以去除冰。然后将冻干的坯体在真空炉中通过两步热处理工艺烧结:在300摄氏度下烧结3小时,然后在1100摄氏度下烧结7小时。
最后,为了形成锐钛矿氧化层,将钛泡沫在过氧化氢(H2O2)中在100摄氏度下预浸3小时。然后将钛泡沫在空气炉中在400摄氏度下氧化6小时。
图4示出了具有在钛泡沫表面上形成的活性氧化钛层的三维钛泡沫的SEM显微照片。图5是三维钛泡沫的XRD谱,证实在钛泡沫表面上形成了纯氧化钛层,并且具有比没有氧化钛层的钛泡沫更高的峰值强度。
示例性实施例3(三维多孔氧化钴或钴阳极)
基于30毫升去离子水的钴粉末浆料由7体积百分比的氧化钴粉末和8重量百分比的PVA粘合剂组成。通过使用搅拌和超声处理的组合来溶解浆料以改善分散度。然后将浆料浇注到铜棒上的含氟聚合物树脂或Teflon(聚四氟乙烯)模具中。铜棒顶部的温度通过液氮和加热器固定在-10摄氏度。
浆料完全冷冻后,冷冻的样品在冷冻干燥器中于-88摄氏度下真空升华24小时,从而去除冰晶,形成具有定向孔的生坯体。然后在氢气气氛中将生坯体从氧化钴还原成钴,然后烧结。还原和烧结工艺包括在5%氢气混合气体下在管式炉中在550摄氏度下预烧结4小时以及在1000摄氏度下实际烧结9小时。
图6示出了三维钴泡沫的安装和抛光的顶部和横截面的光学显微照片(径向和纵向视图)。更具体地说,图6示出了钴泡沫实际上是具有规则分布的数十微米量级的层状结构孔的三维结构。图7A-7C还示出了如通过SEM图像和能量分散X射线图所证实的,具有纳米级表面粗糙度的氧化钴层被形成在钴泡沫的表面上。
图8是三维钴泡沫的XRD谱。图9示出了在600摄氏度下热处理的三维多孔钴泡沫的XRD图案,并验证了钴泡沫表面上的Co3O4和CoO相的形成,并且这两种钴氧化物具有比如图7A-7C所示的纯钴泡沫更高的峰值强度。特别是,钴表明由钴泡沫集电体和氧化钴活性材料组成的阳极系统可以显示出优异的纽扣电池性能。
图10示出了在600摄氏度下热处理的三维多孔钴泡沫的循环性能,证实了在本发明中制造的三维多孔钴泡沫确实适合用作锂-离子电池的阳极。在600摄氏度下热处理的三维多孔钴泡沫的初始放电容量是每平方厘米8.7毫安-小时,比传统的阳极高。此外,在600摄氏度下热处理的三维多孔钴泡沫的库仑效率也很高,在第30次循环后保持接近99.8%的电荷。
已经出于说明和描述的目的呈现了本发明的描述。这并不意味着穷举或将本发明限制于所描述的精确形式,并且鉴于上述教导,许多修改和变化是可能的。选择和描述实施例是为了最好地解释本发明的原理及其实际应用。该描述将使得本领域的其他技术人员能够在各种实施例中以及以适合于特定用途的各种修改来最佳地利用和实践本发明。本发明的范围由所附权利要求限定。
Claims (17)
1.一种用于制造多孔金属泡沫的方法,包括:
在液氮下将钛金属浆料浇注到放置在容器中的铜棒上;
冷冻金属浆料,其中钛金属颗粒堆积并物理附着在生长的冰晶之间;
通过在0摄氏度或以下的温度和减压下干燥冷冻浆料的冰晶来形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;
通过在300摄氏度或以上的温度下在真空中还原和烧结多孔生坯体来构造多孔金属泡沫;以及
通过在空气炉中进行氧化来形成针对多孔金属泡沫的锐钛矿氧化层。
2.根据权利要求1所述的方法,其中形成锐钛矿氧化层包括:
在100摄氏度下将多孔金属泡沫在过氧化氢(H2O2)中预浸泡3小时。
3.根据权利要求1所述的方法,其中烧结所述多孔生坯体包括:
在300摄氏度下烧结3小时;以及
在1100摄氏度下烧结7小时。
4.根据权利要求1所述的方法,包括:
在溶液中,将聚乙烯醇溶解在水中;以及
将钛粉添加到所述溶液中以形成钛金属浆料。
5.根据权利要求1所述的方法,其中通过干燥所述冰晶形成多孔生坯体在0摄氏度或以下的温度进行24小时。
6.一种用于制造多孔金属泡沫的方法,包括:
将铜棒上的模具放入液氮中,并将铁金属浆料浇注到所述模具中;
冷冻所述铁金属浆料,其中铁金属颗粒堆积并物理附着在生长的冰晶之间;
通过在-90摄氏度或以下的温度下干燥冷冻浆料的冰晶来形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;以及
通过在氢气气氛下在300摄氏度下还原所述多孔生坯体2小时以及在950摄氏度下烧结所述多孔生坯体14小时来构造多孔金属泡沫。
7.根据权利要求6所述的方法,其中所述氢气气氛包含氢气和95%的氩气。
8.根据权利要求6所述的方法,其中形成多孔生坯体包括:
在-90摄氏度下冷冻干燥48小时。
9.根据权利要求6所述的方法,其中所述铜棒为-15摄氏度。
10.根据权利要求6所述的方法,其中还原和烧结所述多孔生坯体包括:
在300摄氏度下进行第一次还原;并且
在所述第一次还原之后,在500摄氏度下进行第二次还原。
11.根据权利要求10所述的方法,包括:
在所述第二次还原之后,在950摄氏度下进行烧结。
12.根据权利要求11所述的方法,其中所述第一次还原的持续时间为2小时,所述第二次还原的持续时间为2小时,并且所述烧结的持续时间为14小时。
13.一种用于制造多孔金属泡沫的方法,包括:
将铜棒上的模具放入液氮中,并将钴金属浆料浇注到所述模具中;
冷冻钴金属浆料,其中钴金属颗粒堆积并物理附着在生长的冰晶之间;
通过在-88摄氏度或以下的温度下干燥冷冻浆料的冰晶来形成多孔生坯体,在具有物理附着的冰晶的位置处留下孔隙;以及
通过在氢气气氛下在550摄氏度下烧结所述多孔生坯体4小时以及在1000摄氏度下烧结所述多孔生坯体9小时来构造多孔金属泡沫。
14.根据权利要求13所述的方法,其中所述氢气气氛包含5%的氢气。
15.根据权利要求13所述的方法,其中形成多孔生坯体包括:
在-88摄氏度下冷冻干燥24小时。
16.根据权利要求13所述的方法,其中所述铜棒为-10摄氏度。
17.根据权利要求13所述的方法,其中所述多孔生坯体包括氧化钴,并且还原和烧结所述多孔生坯体包括在氢气气氛下将所述氧化钴生坯体还原为钴生坯体,然后对所述钴生坯体进行烧结。
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Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3063921B1 (fr) * | 2017-03-16 | 2022-07-29 | Office National Detudes Et De Rech Aerospatiales Onera | Materiau metallique fritte a porosite orientee comprenant au moins une partie ferromagnetique et procede de fabrication |
WO2019070767A1 (en) * | 2017-10-02 | 2019-04-11 | Cellmobility, Inc. | PROCESS FOR PRODUCING ALUMINUM NITRIDE FOAM |
CN107732204B (zh) * | 2017-10-16 | 2020-07-07 | 中国科学院宁波材料技术与工程研究所 | 金属锂复合材料及其制备方法、多层金属锂复合材料及其制备方法 |
WO2019173849A1 (en) * | 2018-03-09 | 2019-09-12 | Cellmobility, Inc. | Method of making copper-nickel alloy foams |
CN112368092A (zh) * | 2018-07-06 | 2021-02-12 | 赛莫必乐公司 | 镁基合金泡沫 |
CN109103458A (zh) * | 2018-09-10 | 2018-12-28 | 深圳市华慧品牌管理有限公司 | 一种新型可充电锂电池及其制造方法 |
JP2022522530A (ja) * | 2019-03-25 | 2022-04-19 | セルモビリティ・インコーポレイテッド | 金属発泡体キャパシタおよびスーパーキャパシタ |
US20220155247A1 (en) * | 2019-03-26 | 2022-05-19 | Cellmobility, Inc. | Gas Sensor Device Based on Metal Oxide Foam |
CN110523957B (zh) * | 2019-10-14 | 2020-12-11 | 哈尔滨工业大学 | 一种镁锂合金铸造用铸型及铸造方法 |
US20220389962A1 (en) * | 2019-11-12 | 2022-12-08 | Cellmobility, Inc. | Method of Making Copper Foam Ball |
JP7078658B2 (ja) * | 2020-02-18 | 2022-05-31 | 本田技研工業株式会社 | リチウムイオン二次電池用電極、およびリチウムイオン二次電池 |
KR102379999B1 (ko) | 2020-02-28 | 2022-03-29 | 한국에너지기술연구원 | 티타늄 다공질 소결체 및 이의 제조방법 |
CN112054208B (zh) * | 2020-03-17 | 2022-06-28 | 安徽理士新能源发展有限公司 | Cu3Pt铜网-锂金属电极及其制法及锂电池制法 |
JP2023519821A (ja) * | 2020-03-31 | 2023-05-15 | セルモビリティ・インコーポレイテッド | 軽量の金属発泡体を使用する電磁波の低減 |
US20230346641A1 (en) * | 2020-08-20 | 2023-11-02 | Hoffmann-La Roche Inc. | Lyophilisate retainer, method of manufacturing thereof and procedure of drying a substrate |
CN112103514B (zh) * | 2020-08-28 | 2022-05-17 | 深圳供电局有限公司 | 集流体、电池电极、制备方法及电池 |
JP2022155900A (ja) * | 2021-03-31 | 2022-10-14 | 三菱マテリアル株式会社 | チタン基材、水電解用電極、および、固体高分子形水電解装置 |
CN113427002B (zh) * | 2021-06-25 | 2022-06-21 | 哈尔滨工业大学 | 一种三维多孔结构的无压烧结制备方法 |
CN113564524B (zh) * | 2021-07-13 | 2023-08-01 | 南京邮电大学 | 一种制备碳包覆三维多孔铜集流体的方法 |
CN113953088A (zh) * | 2021-11-23 | 2022-01-21 | 昆明理工大学 | 冶炼烟气高效除尘协同选择性催化还原脱硝一体化方法 |
CN114220943B (zh) * | 2021-12-20 | 2024-03-29 | 远景动力技术(江苏)有限公司 | 一种三明治结构极片及其生产系统装置 |
KR20230116285A (ko) | 2022-01-28 | 2023-08-04 | 한국에너지기술연구원 | 수전해 기액 배출 특성이 향상된 금속분말소결 확산체, 금속분말소결 확산체의 제조방법 및 금속분말소결 확산체를 포함하는 수전해 장치 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6087024A (en) * | 1996-12-17 | 2000-07-11 | Whinnery; Leroy Louis | Method for forming porous sintered bodies with controlled pore structure |
KR101410061B1 (ko) * | 2012-12-24 | 2014-06-30 | 국민대학교산학협력단 | 염료감응형 태양전지 및 그 제조방법 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS572886A (en) | 1980-06-05 | 1982-01-08 | Agency Of Ind Science & Technol | Production of electrode |
US7507502B2 (en) | 2003-03-28 | 2009-03-24 | Hitachi Maxell, Ltd. | Negative electrode having intermetallic compound that occludes/desorbs lithium as an active material layer on collector for non-aqueous secondary battery and non-aqueous secondary battery using the same |
KR100559364B1 (ko) | 2003-05-09 | 2006-03-10 | 한국과학기술연구원 | 다공성의 3차원 집전체로 구성된 전극과 이를 이용한리튬전지, 및 그 제조방법 |
JP4515948B2 (ja) | 2005-03-31 | 2010-08-04 | 株式会社東芝 | ゲル状電解質用原料キット、ゲル状電解質用電解質組成物及び光増感型太陽電池 |
US7804736B2 (en) * | 2006-03-30 | 2010-09-28 | Aloka Co., Ltd. | Delay controller for ultrasound receive beamformer |
JP5300191B2 (ja) | 2006-11-02 | 2013-09-25 | キヤノン株式会社 | 固体高分子型燃料電池用膜電極接合体及び固体高分子型燃料電池 |
JP2008152925A (ja) | 2006-12-14 | 2008-07-03 | Sumitomo Electric Ind Ltd | 電池構造体およびそれを用いたリチウム二次電池 |
JP2009199744A (ja) | 2008-02-19 | 2009-09-03 | Sumitomo Electric Ind Ltd | リチウム二次電池用負極とその製造方法。 |
US20100133110A1 (en) | 2008-10-08 | 2010-06-03 | Massachusetts Institute Of Technology | Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other, electrochemical techniques |
IN2012DN02063A (zh) * | 2009-08-28 | 2015-08-21 | Sion Power Corp | |
US20120121976A1 (en) | 2010-11-16 | 2012-05-17 | Panasonic Corporation | Porous network negative electrodes for non-aqueous electrolyte secondary battery |
US8822081B2 (en) * | 2011-02-14 | 2014-09-02 | Samsung Sdi Co., Ltd. | Electrode structure and electrochemical cell using the same |
KR101321463B1 (ko) * | 2012-06-28 | 2013-10-28 | 주식회사 셀모티브 | 연료전지 및 연료전지의 제조방법 |
KR101353262B1 (ko) * | 2013-04-19 | 2014-01-23 | 주식회사 셀모티브 | 리튬이차전지 전극용 메탈폼, 상기 메탈폼의 제조방법 및 상기 메탈폼을 포함하는 리튬이차전지 |
US20150221930A1 (en) * | 2014-02-03 | 2015-08-06 | Ayyakkannu Manivannan | ELECTROLESS DEPOSITION OF Bi, Sb, Si, Sn, AND Co AND THEIR ALLOYS |
US10068717B2 (en) * | 2014-04-01 | 2018-09-04 | Sumitomo Seika Chemicals Co., Ltd. | Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus |
KR102112746B1 (ko) * | 2015-04-09 | 2020-06-04 | 커창 린 | 전극 재료 및 에너지 저장 장치 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6087024A (en) * | 1996-12-17 | 2000-07-11 | Whinnery; Leroy Louis | Method for forming porous sintered bodies with controlled pore structure |
KR101410061B1 (ko) * | 2012-12-24 | 2014-06-30 | 국민대학교산학협력단 | 염료감응형 태양전지 및 그 제조방법 |
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CN108140813A (zh) | 2018-06-08 |
US10343213B2 (en) | 2019-07-09 |
CN108140813B (zh) | 2021-09-07 |
US20170025683A1 (en) | 2017-01-26 |
US11642723B2 (en) | 2023-05-09 |
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