CN105340115A - 能量存储的方法和装置 - Google Patents
能量存储的方法和装置 Download PDFInfo
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Abstract
依照本发明的示例性实例,提供一种包括第一和第二电极、第一和第二集电体、电解质以及第一接触层的装置,其中所述电解质被配置为分隔所述第一和第二电极;并且其中所述第一接触层被配置为在所述第一集电体与所述第一电极之间形成电气接触。
Description
技术领域
本申请通常涉及用于使用电池或超级电容器的能量存储的方法和装置。
背景技术
存在对可印刷的能量存储装置的越来越多的兴趣,诸如由于低成本和机械灵活性的超级电容器和电池。对于任何种类的能量存储装置,传统的或可印刷的装置,最小化内部电容非常重要,由于装置的功率输出很大程度上依赖于等效的串联电阻(ESR)。任何减少的ESR中将产生直接的功率输出的改进。对于超级电容器,低ESR特别重要,因为它主要用于高电流应用。在电极与集电体之间的界面电阻贡献超级电容器的整体ESR的显著部分。对于可印刷的能量存储装置,降低界面电阻的工序应该与印刷技术兼容。
铝箔通常被用作用于超级电容器的集电体,并且对于电池,铝被典型地用于阴极集电体,而铜箔用于阳极集电体,然而,对于这些金属,界面电阻和电极可能存在问题。铝和铜箔具有平滑的表面并且在电极和箔之间的接触区域受限,以及在电极和铝表面之间的粘附通常欠佳的。此外,铝和铜容易形成绝缘氧化层,其增加了界面电阻。表面蚀刻和其它工序可以被用于扩大用于铝和铜集电体的接触区域并且去除表面氧化物,但是当电池或超级电容器在使用中时,氧化物层将重组并且作为结果,ESR将随着这样的使用逐步增加。也应当注意,以增加集电体的表面区域的化学蚀刻,同样涉及强酸的使用,这通常不适合于可印刷的电池或超级电容器制造。
发明内容
本发明的实例的各方面被在权利要求书中陈述。
根据本发明的第一方面,提供一种包括第一和第二电极、第一和第二集电体、电解质以及第一接触层的装置;其中所述电解质被配置为分隔所述第一和第二电极;并且其中所述第一接触层被配置为在所述第一集电体与所述第一电极之间形成电气接触。
根据本发明的第二方面,一种方法包括:在第一集电体上沉积第一接触层;在所述第一接触层上沉积第一电极;在第二集电体之上沉积第二电极;以及在所述第一与第二电极之间沉积电解质以形成包括通过所述电解质分隔的所述第一和第二电极的装置;其中将所述第一接触层配置为使形成在所述第一集电体与所述第一电极之间电气接触。
附图说明
为了更完全的理解本发明的示例性实施例,现在与附图结合做出引用到下文的描述,其中:
图1示出根据本发明的一方面的装置;
图2示出根据本发明的另一方面的装置;
图3为示出用于制造根据本发明的一方面的装置的操作的流程图;以及
图4示出对于根据本发明的装置的实验结果。
具体实施方式
通过参考附图的图1到4理解本发明的示例性实施例和其潜在优势。
图1示出根据本发明的装置,在第一实例中为电池100。电池100包含通过电解质101分隔的第一电极102、第二电极103。电池100也包含第一集电体104和第二集电体105;第一和第二集电体104、105支撑第一和第二电极102、103,并且提供在电池100与外部电路107之间的电气连接。电池100也包含分隔物110以阻止在第一与第二电极102、103之间的直接接触。
在第一电极102(电池100的阳极)处,可以发生产生电子的氧化反应。这些电子可以从第一电极102(电池100的阳极)围绕外部电路107(通过箭头108表示)流动到第二电极103(电池100的阴极)以在阴极103处发生还原反应。
电子108的流动可以被用于驱动在外部电路105中的一个或多个电气部件109。氧化和还原反应可以继续直到反应物完全转化。除非经由外部电路107,电子能够从阳极102流动到阴极103,否则电化学反应不可能发生。在没有外部电路107连接阳极102到阴极103时,化学反应的抑制允许电池100在相当一段时间内存储电。随着电子围绕外部电路107从阳极102流动到阴极103,负电荷云在电解质101中围绕阴极103产生,并且正电荷云在电解质101中围绕阳极102产生。在电解质101中的正和负离子(在图中没有示出)移动以中和这些电荷云,允许反应和电子的流动继续。没有来自电解质101的离子,围绕每个电极102、103的电荷云将抑制电的生成。到电气部件109的功率输出很大程度上依赖电池100的等效串联电阻(ESR)。在第一电极102与第一集电体之间的界面电阻贡献整体ESR的显著部分。本发明提供在第一电极102与第一集电体105之间并且与其电气接触的接触层106,以减少在第一电极102与第一集电体105之间的界面电阻。
在一个实例中,电池100可能为锂离子电池,其电解质101包含在电池100的充电或放电期间插入或移出第一和第二电极102、103的锂离子(在图1中没有示出)。这样的锂-离子电池100,包含诸如石墨的碳阳极102、包括锂金属氧化物的阴极103、包括铝箔的阴极集电体104和包括铜箔的阳极集电体105以及包括锂盐和有机溶剂的电解质101。接触层106包含平均颗粒尺寸在0.1与10微米之间的多样性的铜、银或金颗粒,并且接触层106具有在10与20微米之间的平均厚度。形成阴极的锂金属氧化物包含一种或多种:锂钴氧化物、锂铁磷酸盐以及诸如锂锰氧化物的尖晶石。电解质包含诸如碳酸亚乙酯或碳酸二乙酯的有机碳酸酯的混合物。锂盐包含一种或多种:六氟磷酸锂(LiPF.sub.6)、六氟砷酸锂一水合物(LiAsF.sub.6)、高氯酸锂(LiClO.sub.4)、四氟硼酸锂(LiBF.sub.4)以及三氟甲磺酸锂(LiCF.sub.3SO.sub.3)。
与电池对比,电容器静电存储电荷。被称为“超级电容器”(也被称为电双层电容器、超级电容器以及电化学双层电容器)的相对新类型的电容器比常规的或电解质电容器提供更大能量存储,并且因为便携式电子应用变得越来越流行。
图2示意性示出根据本发明的装置,在该实例中其为超级电容器300。超级电容器300包含第一和第二铝集电体301、302连同第一和第二电极303、304。第一和第二电极303、304包含多孔碳层,因为电极孔隙度增加与电解质305接触的电极表面区域,其产生更大的电荷存储。当电源311在第一与第二电极303、304之间施加电势差时,电解质305变得极化。在第一电极303上的电势吸引在电解质305中的正离子,而在第二电极304上的电势吸引负离子。当电容器被充电时,在电解质305中的离子设置它们自己在电极304、303的表面以镜像表面电荷316并且形成绝缘“电双层”。在第一和第二电极303、304的表面上的电双层和高表面积材料的使用的结合允许电荷载流子被存储在电极-电解质界面。
关于在图1中所示的电池100,到在图2中所示的电气部件310的功率输出很大程度上依赖超级电容器300的等效串联电阻(ESR)。在电极303、304与集电体301、302之间的界面电阻贡献整体ESR的显著部分。本发明提供在第一电极303与第一集电体302之间并且与其电气接触的第一接触层306,以减少在第一电极303与第一集电体302之间的界面电阻。本发明也提供在第二电极304与第二集电体301之间并且与其电气接触的第二接触层308,以减少在第二电极304与第二集电体301之间的界面电阻。第一和第二接触层306、308包含平均颗粒尺寸在0.1与10微米之间的多样性的铜、银或金颗粒,并且接触层306、308具有在10与20微米之间的平均厚度。
根据本发明的装置38被通过在图3中示意性示出的整体过程制造。在第一步骤35中处理集电体31,以在集电体31上通过印刷金属墨沉积接触层32。对于电池,集电体31为阴极集电体31a,并且包含铜箔,或者集电体31为阳极集电体31b,并且包含铝箔。对于超级电容器,集电体31包含铝箔。通过以下的一种或更多种方法沉积金属墨:棒式涂敷、丝网印刷、凹版印刷、柔性版印刷以及喷墨印刷。金属墨包含金属纳米粒子,金属选自一种或多种:铜、银、铂或金。第一步骤35包含在墨沉积之后在充有氮的炉中以100℃持续1小时干燥。对于铝和铜集电体,第一步骤35也包含在印刷金属墨之前蚀刻箔以去除氧化物层。如果使用银墨,那么它包含在丁二酸二甲酯中固体含量65wt%的微米级Ag薄片。如果使用铜墨,那么它包含在1-(2-丁氧基乙氧基)乙醇中浓度含量60-90wt%的铜薄片。
在第二步骤36中,在已经通过第一步骤35在接触层32上沉积电极33。如果电极33为电池的阳极33b,电极33被以石墨墨的形式沉积,该石墨墨已经被通过在水中或有机溶剂中混合石墨粉末、10%碳黑以及5%结合剂来制备。如果电极33为电池的阴极33a,那么电极33被以锂金属氧化物墨的形式沉积,该锂金属氧化物墨包括锂金属氧化物(例如,LiCoO2、LiMnO4或LiFePO4)和在有机溶液中的5%结合剂。如果电极33为超级电容器的电极中的一个,那么电极33被以活性碳墨的形式沉积,该活性碳墨包括活性碳粉末和在水中的5%结合剂。将墨棒式涂敷到通过集电体31支撑的接触层32上,随后以100℃持续1小时干燥。
在第三步骤37中,分隔物34被浸在电解质中并且被夹在电极33a与33b之间以产生装置38。如果装置38为电池,那么电解质34包含在碳酸亚丙酯(proplycarbonate)中的1M六氟磷酸锂(LiPF6)。如果器件为超级电容器,那么电解质34包含在碳酸亚丙酯中的1.25M四乙基四氟硼酸(TEABF4)。
图4a示出用于具有铝集电体而没有接触层的超级电容器的充电和放电曲线,而图4b示出用于除了具有银接触层基本上相同于图4a器件的超级电容器的充电和放电曲线。图4a和4b示出随时间函数跨超级电容器的电势差,对于图4a,观测到25.6mV的电势降ΔVa,然而对于图4b装置为4.4mV的电势降ΔVb。该变化反映在电阻上的减少,从12.8到2.2Ω,由于银接触层的存在。
没有以任何方式限制下文出现的权利要求书的范围、解释或应用,此处公开的示例性实施例的一种或多种的技术效果为减少超级电容器或电池的ESR。因为根据本发明的装置包含包括金属纳米粒子的薄接触层,此处公开的示例性实施例的一种或多种的另一技术效果为电池或超级电容器可以被通过普通地可得到的印刷技术制造。
如果需要,可以以不同顺序和/或彼此同时地执行此处讨论的不同功能。而且,如果需要,可选的或组合一种或多种上文描述的功能。
尽管在独立权利要求中陈述本发明的各方面,本发明的其它方面包含来自描述的实施例和/或非独立权利要求的特征与独立权利要求的特征的其它组合,而非唯一地在权利要求书中明确陈述的组合。
此处同样应注意,虽然上文描述了本发明的示例性实施例,但这些说明不应该被认为是限制的意义。当然,可以做出没有脱离如在附加的权利要求中限定的本发明的范围的各种变化和修改。
Claims (14)
1.一种装置,所述装置包括第一和第二电极、第一和第二集电体、电解质以及第一接触层;其中所述电解质被配置为分隔所述第一和第二电极;并且其中所述第一接触层被配置为在所述第一集电体与所述第一电极之间形成电气接触。
2.根据权利要求1所述的装置,其中,所述装置包含第二接触层,并且其中所述第二接触层被配置为在所述第二电极与第二集电体之间形成电气接触。
3.根据权利要求1所述的装置,其中,所述第一和第二电极中的一种或两种包含至少一种:活性碳、石墨烯、石墨烯片、银纳米线网、硅纳米线、碳纳米管以及金属氧化物。
4.根据权利要求1所述的装置,其中,所述电解质包含聚合物电解质。
5.根据权利要求1所述的装置,其中,所述第一和第二所述集电体中的至少一种包含铝或铜。
6.根据权利要求1所述的装置,其中,所述第一接触层包含一种或多种铜、银、金以及铂。
7.根据权利要求1所述的装置,其中,所述第一接触层包含平均颗粒尺寸在0.1与10微米之间的多样性的颗粒。
8.根据权利要求1所述的装置,其中,所述第一接触层具有在10与20微米之间的平均厚度。
9.根据权利要求1所述的装置,其中,所述装置为电池、超级电容器或混合电池-电容器。
10.一种包括权利要求1所述的装置的设备。
11.根据权利要求10所述的设备,其中,所述设备为以下的至少一种:电子设备、便携式电子设备、便携式电信设备以及用于任何前文描述的设备的模块。
12.一种方法,所述方法包括:在第一集电体上沉积第一接触层;在所述第一接触层上沉积第一电极;在第二集电体之上沉积第二电极;以及在所述第一与第二电极之间沉积电解质,以形成包括通过所述电解质分隔的所述第一与第二电极的装置;其中将所述第一接触层配置为在所述第一集电体与所述第一电极之间形成电气接触。
13.根据权利要求12所述的方法,其中,在所述第二集电体之上沉积所述第二电极包含在所述第二集电体上沉积所述第二电极。
14.根据权利要求12所述的方法,其中,所述方法进一步包含在所述第二集电体上沉积第二接触层,并且其中在所述第二集电体之上沉积所述第二电极包含在已经被沉积在所述第二集电体上的所述第二接触层上沉积所述第二电极。
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US7382602B2 (en) * | 2004-12-27 | 2008-06-03 | Matsushita Electric Industrial Co., Ltd. | Polarizable electrode member, process for producing the same, and electrochemical capacitor utilizing the member |
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JPH11251200A (ja) * | 1998-03-06 | 1999-09-17 | Meidensha Corp | 電極及びこれを用いた電気二重層キャパシタ |
CN1471741A (zh) * | 2000-10-23 | 2004-01-28 | �Դ���� | 电化学电池阳极组件 |
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