CN101821883A - 碱金属电池 - Google Patents

碱金属电池 Download PDF

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CN101821883A
CN101821883A CN200880103959A CN200880103959A CN101821883A CN 101821883 A CN101821883 A CN 101821883A CN 200880103959 A CN200880103959 A CN 200880103959A CN 200880103959 A CN200880103959 A CN 200880103959A CN 101821883 A CN101821883 A CN 101821883A
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alkali metal
storage battery
mercury
battery
lead
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CN101821883B (zh
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约翰·斯托弗
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/20—Semi-lead accumulators, i.e. accumulators in which only one electrode contains lead
    • H01M10/22—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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    • H01M2300/0002—Aqueous electrolytes
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    • Y02E60/10—Energy storage using batteries

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Abstract

提供了一种蓄电池，该蓄电池包含铅正极、汞负极以及由碱金属盐的水溶液组成的电解液。对电池充电时，铅转变为二氧化铅，而碱金属与汞一起形成汞齐。放电期间，二氧化铅被还原成二价铅状态，而碱金属被氧化成正离子且进入溶液中。以若干替代方式之一固定所述汞。

Description

碱金属电池
发明领域
本发明涉及一种新型蓄电池，该电池的特征在于其独特的电化学。该电池的正极由铅基材料制成；即，二氧化铅和一氧化铅或二价铅盐。负极由汞组成。电池的电解液是碱金属盐的水溶液，包括：锂、钠、钾、铷和铯。对电池充电时，铅基材料转变为二氧化铅，而由汞和碱金属形成汞齐。当电池放电时，二氧化铅被还原成二价铅形式，并且汞齐中的碱金属被氧化形成正离子，所述正离子进入溶液中。
背景技术
用于几乎各种机动车辆中的最常见的蓄电池是铅-酸电池。这种电池包含二氧化铅正极、铅金属负极和作为电解液的硫酸。
多年来，已开发出许多铅酸电池的替代电池用于其它应用。这些替代电池中的两种使用锌作为负极而使用苛性钾作为电解质。一种电池的正极为氧化镍，而另一种使用氧化银。
为了结合铅酸电池和常见碱性电池的最佳特征，开发出铅-碱性电池。如上述共同待审的专利申请中所述，该电池具有铅正极、由已证实的材料如锌、镉、铅和铁制成负极以及碱性电解质。
本发明的目的是提供进一步改良的蓄电池。从下面的描述将认识到本发明的这些和其它目的、特征和优点。
发明概述
本发明是一种可再充电的电池，在该电池中正极包含铅基材料，负极包含汞，以及碱金属盐水溶液的电解液。对电池充电时，铅基材料转变为二氧化铅，而由汞和碱金属形成汞齐。当电池放电时，二氧化铅被还原成一氧化铅或铅(II)盐，并且来自汞齐的碱金属被氧化形成正离子，所述正离子进入溶液中。
碱金属可以选自锂、钠、钾、铷或铯。这些金属的盐包括硫酸盐、碳酸盐、碳酸氢盐、磷酸盐、硅酸盐和硼酸盐。这些盐可以单独使用或者组合使用。
为了维持液态汞(尤其在移动应用中)的稳定性，可以使用若干装置。例如可以使用半透性隔膜来限制汞的移动。这样的隔膜可透过电解液，然而将汞限制在其隔间中。作为替代，汞可以被涂覆、镀覆、吸附或以其它形式施用到导电的固态基材上。另一替代装置的是用万向架固定(gimbal)该电池以抵抗所有方向或一些方向上的加速度。
附图简述
图1是包括本发明关键特征的电池样品的示意图；和
图2是替代性实施方案的示意图。
具体实施方式
可以通过将硫酸钠溶液用作电解液的情形来说明本发明的碱金属电池的电化学。放电时，可预测到下列反应：
在正极处：
PbO2+Na2SO4+2H2O+2e→PbSO4+2NaOH+2OH
而在负极处：
2Na(Hg)→2Na++Hg+2e 
在电池再充电期间，上述反应反向。
任何碱金属可以用于本发明的电池。因此，除上述方程所示的钠之外，还可以使用锂、钾、铷或铯。尽管所有碱金属的反应相似，但是它们在性能上却不相同。已发现负极的单电极电位取决于所用的具体碱金属。
这些碱金属在另一方面相互不同；即，它们的盐的溶解度不同。例如，硫酸铯在0℃水中的溶解度为每100份水167克。相比之下，相同温度下硫酸钾在水中的溶解度为每100份水7.25克。
考虑用于电解液的盐的溶解度还取决于具体的阴离子。为了说明，0℃下硫酸锂的溶解度为每100份水35.34克，然而硅酸锂是不溶解的。锂特别地非常受限于适宜的可用盐的数目。
除了硫酸盐，本发明的电池可以使用许多其它盐，包括：碳酸盐、碳酸氢盐、磷酸盐、硅酸盐和硼酸盐。这些盐可以单独使用或者作为添加剂以获得理想的结果。
当使用硫酸盐以外的盐时，电化学与方程式1所示的不同。由于这些盐往往在溶液中为碱性，电化学领域的技术人员将理解，当电池放电时二氧化铅被还原为氧化铅。这个结果影响正极的单电极电位。
图1中示出本发明的工作中的电池。电池壳1容钠汞池2，该汞池2覆盖容器底部。该汞充当负极。正极由铅片3制成。至汞池的电引线穿过玻璃管4以使其与电解液隔离。两个电极(即汞池和铅片)都浸入在含水电解液5中。半透性隔膜6将汞2保持在适当位置。
图2显示了本发明的替代性实施方案，其中汞2与石墨基材8相结合以将其固定。所有其它部件与图1的相同并且类似编号。
实施例
由直径2-1/2英寸、高2英寸的玻璃罐制成实验电池。正极是直径2-1/2英寸的铅圆盘。负极是覆盖罐底部的汞池。借助玻璃管内的铜线将负极电引线与汞相连。通过在100ml水中溶解26.0克的硫酸钠制备电解液。
在3.7V下对电池充电3分钟之后，获得3.38V的开路电位。对电池进行反复地充电和放电得到可重复的结果。在操作的最后，电极处于良好状态并且电解液是水-白色。
使用其它碱金属替代钠来重复上文描述的实验。结果如下。在3.5V下充电3分钟之后，电解液包含硫酸锂的电池产生3.33V的开路电位。在3.7V充电7分钟之后，以硫酸钾溶液作为电解液的电池获得3.45V的开路电位。最后，在3.9V充电22分钟之后，在电解液中使用硫酸铯的电池获得3.50V的开路电位。

Claims (15)

1.蓄电池，其包含：
a.铅基材料的正极；
b.汞负极，和
c.由碱金属盐的水溶液组成的电解液。
2.根据权利要求1的蓄电池，其中所述碱金属是锂。
3.根据权利要求1的蓄电池，其中所述碱金属是钠。
4.根据权利要求1的蓄电池，其中所述碱金属是钾。
5.根据权利要求1的蓄电池，其中所述碱金属是铷。
6.根据权利要求1的蓄电池，其中所述碱金属是铯。
7.根据权利要求1的蓄电池，其中所述碱金属是硫酸盐。
8.根据权利要求1的蓄电池，其中所述碱金属是碳酸盐。
9.根据权利要求1的蓄电池，其中所述碱金属是磷酸盐。
10.根据权利要求1的蓄电池，其中所述碱金属是硅酸盐。
11.根据权利要求1的蓄电池，其中所述碱金属是硼酸盐。
12.根据权利要求1的蓄电池，其中提供固定汞的装置。
13.根据权利要求2的蓄电池，其中所述固定装置包括结合汞的固体基材。
14.根据权利要求13的蓄电池，其中所述固体基材为石墨。
15.根据权利要求12的蓄电池，其中所述固定装置是汞和电解液之间的半透性隔膜。
CN2008801039590A 2007-08-22 2008-08-22 碱金属电池 Expired - Fee Related CN101821883B (zh)

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US11/842,980 US7608361B2 (en) 2007-08-22 2007-08-22 Alkali metal battery
US11/842,980 2007-08-22
PCT/US2008/073990 WO2009026500A1 (en) 2007-08-22 2008-08-22 Alkali metal battery

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EP2201630B1 (en) 2016-03-09
JP2010537388A (ja) 2010-12-02
US20090053596A1 (en) 2009-02-26
CA2695352A1 (en) 2009-02-26
EP2201630A4 (en) 2011-11-02
WO2009026500A1 (en) 2009-02-26
CN101821883B (zh) 2012-08-22
EP2201630A1 (en) 2010-06-30

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