CN101836324A - 重组混合储能装置 - Google Patents

重组混合储能装置 Download PDF

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CN101836324A
CN101836324A CN200880113398A CN200880113398A CN101836324A CN 101836324 A CN101836324 A CN 101836324A CN 200880113398 A CN200880113398 A CN 200880113398A CN 200880113398 A CN200880113398 A CN 200880113398A CN 101836324 A CN101836324 A CN 101836324A
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hybrid accumulator
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爱德华·布伊尔
维克多·叶仕克纳兹
列昂尼德·拉宾诺维奇
孙伟
弗拉迪米尔·维什雅科夫
亚当·斯维奇
约瑟夫·科尔
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Axion Power International Inc
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Abstract

混合储能装置具有至少一个铅基正电极和至少一个碳基负电极，电极之间的分隔部，将包含电极、分隔部和酸性电解质的壳体。分隔部是可透气的，并能够吸收并携带酸性电解质。分隔部具有对酸性电解质的有限的吸收容量，并且存在于电池内的酸性电解质的量小于分隔部的有限容量。一旦电池被组装，壳体便被密封，组装的电池内没有液态酸性电解质。

Description

重组混合储能装置
本国际申请要求于2007年10月22日向美国专利商标局提交的序列号为11/876,005的专利申请的优先权。
技术领域
本发明涉及一种混合储能装置，该混合储能装置包括至少一个电池，该至少一个电池具有至少一个正电极、至少一个负电极、可透气分隔部、酸性电解质和壳体。放置在该至少一个电池内的酸性电解质的量小于可透气分隔部、至少一个正电极和至少一个负电极对酸性电解质的有限吸收容量。
背景技术
混合储能装置，也作为非对称超级电容器或者混合电池/超级电容器为人所知，将电池电极和超级电容器电极组合以产生具有包括循环寿命、能量密度、能量容量、快速再充电性能以及大范围温度可操作性在内的独特的特征组的装置。混合碳酸铅储能装置采用酸性铅电池正电极以及超级电容器负电极。例如，参见第6,466,429、6,628,504、6,706,079、7,006,346和7,110,242号美国专利。
公知的常识是，组合的并且意欲用于商业使用的混合储能装置需要装置内的电池被酸性电解质浸没。
当混合铅-碳-酸储能装置被液态酸性电解质浸没时，正电极和负电极电势可能变得不稳定，尤其是在深度放电或者过度充电的条件中。因此，存在腐蚀的风险，尤其对于铅基正电极来说。还可能有在充电条件期间生成气体的风险。特别地，由于液态酸性电解质的水分的电解而产生的足够的氧气和氢气在壳体内加压使得阀门打开。如果阀门打开，酸性电解质通常从壳体喷出，装置变干并且损坏电极。该装置通常从操作中被取出并被丢弃。
发明人已经证明了，与公知的常识相反，没有必要浸没混合储能装置的电池。为确保电池不被浸没，放置在电池内的液态酸性电解质的量小于可透气分隔部、至少一个正电极和至少一个负电极对电解质的有限吸收容量。
发明内容
本发明的目的是减少混合储能装置的电极在深度放电或者过度充电的情形中的不稳定性。
本发明的另一个目的是减少或消除由于液态酸性电解质的水分的电解所引起的氧化和氢气的产生。
本发明的另一个目的是减少或防止铅基正电极的腐蚀。
本发明的优势在于，可以使用比传统的混合储能装置中采用的分隔部更薄的分隔部。
上述目的和优势由这样的混合储能装置满足，该混合储能装置包括至少一个电池，该至少一个电池包括至少一个铅基正电极、至少一个碳基负电极、电极之间的分隔部、容纳电极、分隔部和酸性电解质的壳体。分隔部是能够透气的。至少一个电池中酸性电解质的量小于该可透气分隔部、至少一个正电极和至少一个负电极对酸性电解质的有限吸收容量。
这里所使用的“实质上”、“通常”、“相关的”、“近似”以及“约”是相对的修改量，该修改量意欲表示修改的特征所允许的偏差。并非意欲限制其修改的绝对值或者特征，而是接近或近似于这样的物理的或功能的特征。
提到的“一个实施例”、“实施例”或“实施例中”意指被提及的特征被包括在本发明的至少一个实施例中。而且，单独地提及“一个实施例”、“实施例”或者“实施例中”并非必须指同样的实施例；但是，除非这样声明了，并且除非对于本领域技术人员来说是非常明显的，这样的实施例不是互相排斥的。如此，本发明可以包括这里所描述的实施例的任意种的结合和/或综合。
在随后的说明书中，附图用作参考，其以图解可以实施本发明的具体实施例的方式被展示。随后图解的实施例被足够详细地描述以似的本领域技术人员能够实施本发明。要理解的是，可以使用其他实施例并且可以在不脱离本发明的宗旨的前提下做出基于当前已知的结构上和/或功能上的等价物的结构改变。
附图说明
图1图解混合储能装置的电池，该混合储能装置在正电极和负电极之间具有电压电势。
图2图解混合储能装置的组装的电池，该混合储能装置具有预定量的放置在电池中而没有浸没电池的液态酸性电解质。
图3是显示在恒流充电操作期间电池的正负电极的电极电势的曲线图。
图4图解根据本发明的实施例的混合储能装置的负电极。
具体实施方式
根据本发明，混合储能装置包括至少一个电池，该电池具有至少一个铅基正电极、至少一个碳基负电极、电极之间的分隔部、酸性电解质和壳体。该至少一个电池实质上不包括富余的液态酸性电解质。因为至少一个电池未被完全地浸没，所以并没有气态氧形成气泡而从至少一个电池溢出的趋势。
通常被储存在分隔部内的酸性电解质的至少一部分可以被储存在本发明的至少一个负电极内。根据本发明，酸性电解质实质上被分隔部和至少一个碳基负电极所吸收。因而，分隔部可以被做得比通常使用的分隔部更薄。例如，分隔部可以具有约0.5mm的厚度，而不是传统装置所使用的约2mm。
分隔部的减小的厚度允许当电极之间的通道长度被减小时，电极之间有更大的气体通道。结果，在至少一个正电极处任何逸出的氧传到至少一个负电极，并且以比传统的混合储能装置更高的效率与氢再结合从而形成水。
根据本发明，比传统的混合能量装置更多的电解质可以被添加到至少一个电池。由可透气分隔部、至少一个正电极和至少一个负电极吸收并带走的酸性电解质的量在电池对酸性电解质的有限吸收容量的约92％至98％，更优选的是约95％至98％。通过填充至少一个电池直至可以看见电解质的聚集(填充的电解质的mL)，来测量分隔部和电极中吸收的电解质的量。或者，至少一个电池中的电解质可能会满溢并且过渡的堆积(前后至少一个电池的重量)。混合能量装置的能量密度同样被增加。
图1图解了用于电池10的其间具有分隔部16的正电极12和负电极14。在电极12和14之间存在电压差，如箭头18所示。
根据现有技术，在充电循环期间，氧逸出出现在正电极12的表面处，气态氧作为气泡通过可透气分隔部16转移至负电极14的表面，在那里被电化学地减少。同时，当充电差不多完成时，气态氢可能在负电极14的表面处产生。
氧气和氢气的产生是可透气分隔部16的结构内部携带的液态酸性电解质的水分的电解的结果。并且，主要是氧朝向负电极转移，很少可能是任何氢气朝向正电极转移。箭头40所示的氧的转移导致它的去极化从而形成水，水将回到电池内部携带的液态电解质。这符合以下的反应：
O2+4H++4e-→2H2O
图2图解根据本发明的混合储能装置的电池10示意图。
根据本发明，正电极12主要是铅基的。铅基正电极可包括铅集电器和活性材料，活性材料包括与铅集电器电接触的二氧化铅。
根据本发明的负电极14主要是碳基的。如图4所示，碳基负电极14可包括集电器45、抗腐蚀导电涂层50和活性材料55。负电极也可具有包住突出部分65的铅突缘60，以及铸造带70。在某些实施例中，突出部分可以是与集电器相同或不相同的材料。
负电极的集电器包括导电材料。例如，集电器可包括诸如铍、青铜、商用含铅青铜、铜、铜合金、银、金、钛、铝、铝合金、铁、钢、镁、不锈钢、镍、它们的混合物或者它们的合金的金属材料。优选地，集电器包括铜或铜合金。集电器20的材料可以由网状材料(例如，铜网)制成。集电器可包括任意具有大于约10×105西门子(siemens)/m的导电率的导电材料。如果材料呈现各向异性的导电，它应该在任何方向上呈现比约1.0×105西门子/m更大的导电率。
抗腐蚀导电涂层可以被施加到集电器。在有电解质存在的情况下，例如诸如硫酸或者其他任何包括硫磺的电解质的酸性电解质中，抗腐蚀导电涂层是化学稳定并且电化学稳定的。如此，至集电器或者来自集电器的离子流被排除，同时电子电导率被允许。
抗腐蚀涂层优选地包括浸渍石墨材料。用使得石墨片或金属薄片抗酸性的物质来浸渍石墨。该物质可以是诸如石蜡或者糠醛的非聚合物。优选地，用石蜡和松香浸渍石墨。
负电极的活性材料包括活性碳。活性碳指的是呈现出比使用传统的单点BET技术(例如，使用Micromeritics FlowSorb III 2305/2310的设备)测量的约100m2/g要大，例如约100m2/g至约2500m2/g的表面面积的任何主流的碳基材料。在某些实施例中，活性材料可以包括活性碳、铅和导电碳。例如，活性材料可以包括5-95wt.％的活性碳、95-5wt.％的铅和5-20wt.％的导电碳。
活性材料可以呈粘附至抗腐蚀导电涂层材料并与抗腐蚀导电涂层材料电接触的薄片的形式。为了使活性碳被粘附至抗腐蚀导电涂层并与该抗腐蚀导电涂层电接触，活性碳微粒可以混合有合适的粘合物质，诸如PTFE或者超高分子量聚乙烯(例如，具有数以百万计的分子量，通常在约200万和约600万之间)。优选地，粘合材料不呈现热特性或者呈现出最小的热特性。
分隔部16是可透气的。分隔部16能够吸收并携带酸性电解质。分隔部可包括吸收性玻璃纤维板材料、熔融石英凝胶体或者它们的组合中的至少一个。
电池还包含具有盖28的壳体26。在电池已经被组装并被放置在其内之后，盖28密封壳体26。如此，电池10是封闭系统。任何在电池内逐渐形成的气体被包含在电池内。
图3是显示电极电势(V)与时间(T)的曲线图。曲线30所示的正电极电势和曲线32所示的负电极的电势之间的增加的电势差18在恒定电流充电操作期间出现。
在传统的浸没电池中，如果正电极12的电势增加成超过34所示的特定电势，则在正电极处的氧逸出将非常严重以致正电极进入磨蚀状态36。还可能的是，当电极的电势达到38所示的特定电势时，在负电极处可能发生显著的氢逸出。
实例
组合27(BCI标准电池尺寸)PbC混合能量装置采用大约680ml的硫酸电解质，该组合27具有五个包含82份活性碳、10份碳黑和8份PTFE的负电极；6个包含铅的正电极和每个都具有0.5mm厚度的10个分隔部。由于负电极的结构，被吸收并被携带的硫酸电解质的量是硫酸电解质的有限吸收容量的92.5％。
传统的组27铅酸电池采用735ml的硫酸电解质，该传统的组27铅酸电池具有8个包含铅/硫酸铅活性材料的负电极、7个包含二氧化铅的正电极和14个各自具有2mm厚度的分隔部。被吸收并被携带的硫酸电解质的量是硫酸电解质的有限吸收容量的72％。现有的常识建议使用10块0.5mm的分隔部只有大约四分之一的吸收容量(约18％)。
工业实用性
本发明提供一种混合储能装置，该混合储能装置包括至少一个电池，该电池具有至少一个正电极，至少一个负电极，可透气分隔部，酸性电解质以及壳体。放置在至少一个电池内的酸性电解质的量小于可透气分隔部、至少一个正电极和至少一个负电极对酸性电解质的有限吸收容量。混合储能装置尤其适合于储能应用。
虽然本文已经详细的描述了本发明的具体实施例，本领域技术人员要理解的是，得益于前述的说明书和相关的附图中陈述的教导，从属于本发明的本发明的许多其他的变形和实施例是显而易见的。
因此要理解的是，本发明并不限于本文所公开的具体实施例，本发明的多个变形例和其他实施例也意欲被包括在本发明的范围内。而且，虽然本文采用的专用名词，它们只是基于通常的和说明性的意义而被使用，并不是为了限制说明本发明。

Claims (9)

1.一种混合储能装置，其特征在于：
至少一个电池，所述至少一个电池包括至少一个正电极、至少一个负电极、所述正电极和负电极之间的分隔部、酸性电解质和壳体；
其中，由所述分隔部、所述至少一个正电极和所述至少一个负电极吸收并携带的酸性电解质的量在由所述电池对所述酸性电解质的有限吸收容量的约95％至约98％的范围内，
其中，所述至少一个电池在所述壳体内包括对于所述至少一个电池实质上并不富余的液态酸性电解质。
2.如权利要求1所述的混合储能装置，其特征在于，所述分隔部具有约0.5mm的厚度。
3.如权利要求1-2中任意一个所述的混合储能装置，其特征在于，所述至少一个正电极包括集电器，所述集电器包括铅或者铅合金。
4.如权利要求1-3中任意一个所述的混合储能装置，其特征在于，所述至少一个正电极进一步包括活性材料，所述活性材料包括与所述集电器电接触的二氧化铅。
5.如权利要求1-4中任意一个所述的混合储能装置，其特征在于，所述至少一个负电极包括集电器、抗腐蚀导电涂层和活性材料。
6.如权利要求1-5中任意一个所述的混合储能装置，其特征在于，所述集电器包括铜或者铜合金。
7.如权利要求1-5中任意一个所述的混合储能装置，其特征在于，所述抗腐蚀涂层包括石蜡或者糠醛浸渍的石墨。
8.如权利要求5所述的混合储能装置，其特征在于，所述活性材料包括混合有PTFE或者超高分子量聚乙烯的活性碳。
9.如权利要求1-8中任意一个所述的混合储能装置，其特征在于，所述分隔部选自包含吸收性的玻璃纤维板分隔材料、熔融石英凝胶体和它们的组合的集合。
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