CN1237649C - 镍－金属氢化物蓄电池以及使用该蓄电池的混合电动车辆 - Google Patents

镍－金属氢化物蓄电池以及使用该蓄电池的混合电动车辆 Download PDF

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CN1237649C
CN1237649C CNB2004100282625A CN200410028262A CN1237649C CN 1237649 C CN1237649 C CN 1237649C CN B2004100282625 A CNB2004100282625 A CN B2004100282625A CN 200410028262 A CN200410028262 A CN 200410028262A CN 1237649 C CN1237649 C CN 1237649C
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storage battery
positive pole
reserve capacity
electric vehicle
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CN1531132A (zh
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池添通则
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Nissan Motor Co Ltd
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Abstract

一种密封型镍-金属氢化物蓄电池，包括：含有镍作为正极活性材料的正极；含有吸氢合金作为负极活性材料的负极，插在正极和负极之间的隔板，以及将正极和负极浸入其中的电解液。负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量、当正极处于完全放电状态时提供放电备用容量。充电备用容量与放电备用容量之比在1∶0至1∶0.5的范围内。

Description

镍-金属氢化物蓄电池以及 使用该蓄电池的混合电动车辆
技术领域
本发明涉及密封型镍-金属氢化物蓄电池以及具有这种蓄电池的混合电动车辆。
背景技术
JP特开平9-204931公开了一种密封型镍-金属氢化物蓄电池，该蓄电池的正极和负极分别含有镍和吸氢合金作为活性材料。为了避免增加电池内部压力、并使电池尺寸、重量和生产成本减少，把在充电完成后蓄电池中存储的电量设置为小于正极的理论容量。
发明内容
然而，当使蓄电池的充电容量小于其额定值时，上述蓄电池的容量是不足的。因此，易于使这种蓄电池的成本效率和能量密度方面的改善受到影响。
鉴于上述原因，本发明的目的是提供一种能够以比较低的成本获得高能量密度的密封型镍-金属氢化物蓄电池。
本发明的另一目的是提供一种具有这种密封型镍-金属氢化物蓄电池的混合电动车辆。
根据本发明的第一种方案，提供一种密封型镍-金属氢化物蓄电池，包括：含有镍作为正极活性材料的正极；含有吸氢合金作为负极活性材料的负极，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量、当正极处于完全放电状态时提供放电备用容量，放电备用容量与充电备用容量之比在0至0.5的范围内；插在正极和负极之间的隔板；以及正极和负极浸入其中的电解液。
根据本发明的第二种方案，提供一种包括多个密封型镍-金属氢化物蓄电池的混合电动车辆，各蓄电池具有：含有镍作为正极活性材料的正极；含有吸氢合金作为负极活性材料的负极，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量、当正极处于完全放电状态时提供放电备用容量，放电备用容量与充电备用容量之比在0至0.5的范围内；插在正极和负极之间的隔板；以及正极和负极浸入其中的电解液。
根据本发明的第三种方案，提供一种混合电动车辆，包括：内燃式发动机；具有多个镍-金属氢化物蓄电池的电池组件，各蓄电池具有分别含有镍和吸氢合金作为电化学活性材料的正极和负极、插在正极和负极之间的隔板、以及正极和负极浸入其中的电解液，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量、当正极处于完全放电状态时提供放电备用容量，放电备用容量小于充电备用容量；由发动机驱动以对蓄电池再充电的发电机；用于检测各蓄电池的充电状态的装置；以及用于控制发动机和发电机以使蓄电池充电状态的平均值保持在给定值或更高的装置。
本发明的其它目的和特点从下面的描述中更易理解。
附图说明
图1是表示在根据本发明的一个典型实施例的密封型镍-金属氢化物蓄电池的正、负极容量之间关系的示意图。
图2是设置有多个根据本发明一个典型实施例的密封型镍-金属氢化物蓄电池的混合电动车辆的示意图。
具体实施方式
参考图1和2详细描述本发明。
根据本发明的一个典型实施例，混合电动汽车(HEV)10具有电池组件17，此电池组件17设置有多个密封的镍-金属氢化物蓄电池1。
各蓄电池1包括至少一个正极、至少一个负极、至少一个隔板、电解液和电解容器。在本实施例中，设置有十个正极、十一个负极和二十个隔板。正极和负极交替设置在电解容器中，各隔板插在两个相邻的电极之间。将电解液密封在电解容器中，从而使正极和负极浸在电解液中。
对蓄电池1的正极没有特别地限制，只要正极含有镍作为正极活性材料即可。例如，可通过下述方法提供正极：将75wt.％的氢氧化镍与25wt.％的甲基纤维素水溶液(作为粘度改进剂)混合；将得到的膏状物填充到泡沫镍基片中(550g/m2)；以70-80℃烘干填充有膏状物的基片；辊压烘干后的基片；然后利用裁剪刀将辊压后的基片裁成20mm×50mm的大小。
同样，对蓄电池1的负极没有特别地限制，只要负极含有吸氢合金作为负极活性材料即可。例如，可通过下述方法提供负极：将吸氢合金(主要由混合稀土构成)粉末化为100目或更小的尺寸；将75wt.％的吸氢合金粉末与25wt.％的聚乙烯醇水溶液(作为粘度改进剂)混合；将得到的膏状物涂覆到镀镍打孔金属基片上，使得涂层具有0.5mm的厚度；以70-80℃烘干涂覆后的基片；辊压烘干后的基片；然后利用裁剪刀将辊压后的基片裁成19mm×49mm的大小。
蓄电池1的隔板可由磺化聚丙烯无纺织物制成。
蓄电池1的电解液可以是6-N的氢氧化钾水溶液。
蓄电池1的电解容器可以由树脂制成并形成为矩形形状。
如图1所示，使负极的理论容量大于正极的理论容量。在此将电极的理论容量定义为以电极中所含的活性材料的总量为基础的容量。当正极处于完全充电状态时，负极含有剩余量的未充电活性材料，以便提供充电备用容量CR(即，能够进一步储存在负极中的过剩安培-小时数)。当正极处于完全放电状态时，负极含有剩余量的充电活性材料，以便提供放电备用容量DR(即，能够进一步从负极中提取出的过剩安培-小时数)。
也就是说，将蓄电池1划分为所谓的“正极调节型”，其中，负极容量大于正极容量。这种正极调节型蓄电池1的完全充电状态一般由蓄电池1的电压或温升速率判断出来。然而，在蓄电池1达到完全充电状态之后，蓄电池1的电压降低或保持不变。由于这种不稳定的电压特性，导致了从电池电压不能精确地检测出蓄电池1的完全充电状态，从而经常导致过充电。此外，在周围温度的影响下难以准确地确定出蓄电池1的温升速率。蓄电池1的完全充电状态不能从电池的温升速率精确地检测出来，因而也导致了过充电。另一方面，蓄电池1的完全放电状态一般由蓄电池1的电压判断出来。由于蓄电池1电压中的变化程度由放电容量唯一地确定，因此能够比较精确地检测出蓄电池1的完全放电状态。不会如此经常地发生蓄电池1的过放电。基于上述因素，人们认为过放电的频率远远低于过充电的频率。通过将蓄电池1应用于HEV 10，这样就可以进行充、放电控制，在这种控制下蓄电池1具有更大的充电可能性。
通过下述电化学反应(1)和(2)对上面构成的镍-金属氢化物蓄电池1进行充电：
正极：     (1)
负极：          (2)
这里M代表吸氢合金，MH代表它的金属氢化物。
在充电结束时，通过下面的反应(3)在正极中生成氧。生成的氧通过下面的反应(4)与负极中的氢再结合，这样就防止了由于氧气的产生引起的蓄电池1内压的升高。
正极：          (3)
负极：       (4)
                     (5)
此外，随着充电电流的增加，负极吸氢合金吸收氢的趋势降低。在充电结束时，氢通过上述反应(5)与充电备用容量CR的吸氢合金再结合，这样就防止了由于氢气的产生引起的蓄电池1内压的升高。
通过这些反应(2)、(4)和(5)，蓄电池1保持平衡，从而保持蓄电池1的密封。
虽然蓄电池1的负极通常比蓄电池1的正极放电效率低、循环寿命短，但是放电备用容量DR弥补了这种不利的负极特性，从而在没有增加正极容量的条件下保持了蓄电池1的性能。这里，在反应(5)中吸收氢的充电备用容量CR的负极活性材料不再用于蓄电池1的充、放电循环，但有助于放电备用容量DR。
考虑到由于蓄电池1完全放电状态检测的简便性使得过放电的频率低于过充电的频率，在本实施例中使放电备用容量DR小于充电备用容量CR。最好将充电备用容量CR与放电备用容量DR之比控制为(CR∶DR)＝(1.0∶0)至(1.0∶0.5)。通过如上所述将放电备用容量DR设定为小于充电备用容量CR，可以减少在负极中采用的高价吸氢合金的量，由此降低蓄电池1的尺寸、重量和生产成本。并且由于蓄电池1重量的降低还可以使它获得高能量密度。
在蓄电池1过充电的情况下，放电备用容量DR可能变得不足。但在这种情况下，放电备用容量DR由对应于由上述反应(5)吸收氢的负极活性材料的一部分充电备用容量CR补充，由此避免了放电备用容量DR的短缺。因此，蓄电池1能够保持其性能，增加其使用寿命。
可按下述方式在负极中形成充、放电备用容量CR和DR。在负极的制造中，加入过量的吸氢合金以形成充电备用容量CR。为了形成放电备用容量DR，加入其氧化还原电位低于镍的金属(例如，二价钴)。在最初充电过程中，适当量的电能输送给负极。于是，优先于正极中镍的氧化，所加入的金属氧化成作为放电备用容量DR的该金属的氢化物。
作为示例，本实施例的镍-金属氢化物蓄电池1形成有7Ah的额定容量、1.3的理论容量比(理论负极容量[Ah]/理论正极容量[Ah])、以及10的备用容量比(充电备用容量CR[Ah]/放电备用容量DR[Ah])。
如图2所示，HEV 10具有：发动机11和马达12，以通过行星齿轮系16驱动车轮19；电池组件17，以通过换流器13将电能提供给马达12；发电机14，通过转换器15连接到发动机1以产生用于对电池组件17进行再充电的电能；以及控制器18，控制发动机11、马达12、换流器13、转换器15和发电机14的工作。将HEV 10设计为所谓的“并行混合电动车辆(PHEV)”，这种车辆的发动机11和马达12同时工作或者发动机11和马达12各自单独工作，从而产生驱动功率。
发动机11可以是内燃式发动机(例如汽油发动机或柴油发动机)。
马达12可以是交流(AC)马达、感应马达、同步马达或直流(DC)马达。在马达12是DC马达的情况下，换流器13由DC-DC转换器替代。
发电机14可以是产生三相交变电流的三相交流发电机，转换器15将三相交变电流转换为直流。作为选择，发电机14可以是直流发电机。在这种情况下，不需要转换器15。
电池组件17具有以串联方式电连接的镍-金属氢化物蓄电池1。各蓄电池1的端子电压(terminal voltage)由电压传感器20检测并输出到控制器18。
控制器18根据蓄电池1的输出电压确定蓄电池1的充电(SOC)状态，计算蓄电池1充电状态的平均值，并检查算出的平均值是否为55％或更高。当算出的平均值低于55％时，控制器18按发动机11驱动发电机14以产生电能并由此对电池组件17再充电的方式对发动机11和发电机14进行操作。在控制器18的控制下，蓄电池1的充电状态的平均值在任何时候都保持在55％或更高。各蓄电池1的充电状态的计算方法不限于以上所述。例如，温度传感器或电流传感器可选择性地提供给各蓄电池1，以便根据蓄电池1的电流或温度计算蓄电池1的充电状态。当蓄电池1的充电状态的平均值在任何时候都保持在55％或更高时，蓄电池1具有被充电的更大可能性。这样成功地避免了蓄电池1的过放电。这使得在电池性能和使用寿命没有恶化的情况下、在HEV 10的电池组件17中蓄电池1的有效利用成为可能，在所述蓄电池1中把放电备用容量DR设置为小于充电备用容量CR。
此外，控制器18检查各蓄电池1的电压是否高于或等于放电电压限值。在本实施例中，放电电压限值设为1.15V/电池。当任何蓄电池1的电压低于放电电压限值时，控制器18按发动机11驱动发电机14以产生电能并由此对电池组件17再充电的方式对发动机11和发电机14进行操作。在控制器18的控制下，蓄电池1的电压在任何时候都保持在放电电压限值或更高。由于放电电压限值对于完全放电电压提供了足够的电压余量，因此能够更可靠地避免蓄电池1的过放电。这使得在电池性能和使用寿命没有恶化的情况下、对在HEV 10的电池组件17中的蓄电池1合理地有效利用成为可能。
最理想地，在最初充电过程中(例如，在工厂出货或交货过程中)蓄电池1基本上保持在过充电状态。可以通过下述方式进行在最初充电过程中蓄电池1的充电状态的等同化：将蓄电池1过充电到基本上相同的状态；然后，向蓄电池1施加涓流充电。控制器18可具有通过例如在最初充电过程中控制涓流充电的采用使蓄电池1的充电状态大致等同的功能。通过这种蓄电池1的充电等同化，从而可以防止在从电池组件17的完成直到将HEV 10提供给用户的这段时间内由于蓄电池1的自放电引起的最初充电容量的变化，由此可以从蓄电池1的使用开始时就正确地表现出蓄电池1的性能。此外，在最初充电时蓄电池1的过充电将一部分充电备用容量CR提前转化为放电备用容量DR，从而防止了在过放电情况下放电备用容量DR的短缺，避免了电池性能和使用寿命的恶化。
申请号为2003-063056(2003年3月10日提交)的日本专利申请的全部内容在此引作参考。
虽然参考本发明的具体实施例描述了本发明，但本发明并不限于上述实施例。鉴于上述教导，本领域的技术人员可对上述实施例进行各种修改和变化。参考权利要求限定本发明的范围。

Claims (13)

1.一种密封型镍-金属氢化物蓄电池(1)，包括：
含有镍作为正极活性材料的正极；
含有吸氢合金作为负极活性材料的负极，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量，当正极处于完全放电状态时提供放电备用容量，DR/CR的比值在0至0.5的范围内，其中DR是放电备用容量，CR是充电备用容量；
插在正极和负极之间的隔板；以及
正极和负极浸入其中的电解液。
2.根据权利要求1的密封型镍-金属氢化物蓄电池(1)，其中在最初充电过程中蓄电池(1)过充电。
3.一种包括多个密封型镍-金属氢化物蓄电池(1)的混合电动车辆(10)，各蓄电池(1)具有：
含有镍作为正极活性材料的正极；
含有吸氢合金作为负极活性材料的负极，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量，当正极处于完全放电状态时提供放电备用容量，DR/CR的比值在0至0.5的范围内，其中DR是放电备用容量，CR是充电备用容量；
插在正极和负极之间的隔板；以及
正极和负极浸入其中的电解液。
4.根据权利要求3的混合电动车辆(10)，还包括：
内燃式发动机(11)；
由发动机(11)驱动以产生用于对蓄电池(1)充电的电能的发电机(14)；以及
对发动机(11)和发电机(14)进行控制以对蓄电池(1)进行再充电的控制器(18)。
5.根据权利要求4的混合电动车辆(10)，还包括检测各蓄电池(1)的充电状态的充电状态检测单元，
其中控制器(18)按使蓄电池(1)的充电状态平均值保持在55％或更高的方式控制发动机(11)和发电机(14)。
6.根据权利要求4或5的混合电动车辆(10)，还包括用于检测各蓄电池(1)的端子电压的电压传感器(20)，
其中控制器(18)按使蓄电池(1)的端子电压保持在1.15V或更高的方式控制发动机(11)和发电机(14)。
7.根据权利要求3的混合电动车辆(10)，其中在最初充电过程中将所述多个蓄电池(1)过充电成基本上相同的状态。
8.一种混合电动车辆(10)，包括：
内燃式发动机(11)；
具有多个镍-金属氢化物蓄电池(1)的电池组件(17)，各蓄电池(1)具有分别含有镍和吸氢合金作为电化学活性材料的正极和负极、插在正极和负极之间的隔板、以及正极和负极浸入其中的电解液，负极具有比正极的理论容量更大的理论容量，从而当正极处于完全充电状态时提供充电备用容量，当正极处于完全放电状态时提供放电备用容量，DR/CR的比值在0至0.5的范围内，其中DR是放电备用容量，CR是充电备用容量；
由发动机(11)驱动以对蓄电池(1)再充电的发电机(14)；
用于检测各蓄电池(1)的充电状态的装置；以及
用于控制发动机(11)和发电机(14)以使蓄电池(1)充电状态的平均值保持在给定值或更高的装置。
9.根据权利要求8的混合电动车辆(10)，其中所述给定值是55％。
10.根据权利要求8的混合电动车辆(10)，还包括用于检测各蓄电池(1)的电压的装置(20)，
其中控制器(18)控制发动机(11)和发电机(14)以使各蓄电池(1)的电压保持在放电电压极限值或更高。
11.根据权利要求10的混合电动车辆(10)，其中放电电压极限值为1.15V。
12.根据权利要求8或10的混合电动车辆(10)，其中在最初充电过程中蓄电池(1)过充电。
13.根据权利要求12的混合电动车辆(10)，还包括在最初充电过程中使所述多个蓄电池的充电状态基本上相同的装置(18)。
CNB2004100282625A 2003-03-10 2004-03-10 镍－金属氢化物蓄电池以及使用该蓄电池的混合电动车辆 Expired - Fee Related CN1237649C (zh)

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