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CN1185743C - 氧化还原胶体电池 - Google Patents

氧化还原胶体电池 Download PDF

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Publication number
CN1185743C
CN1185743C CNB998072117A CN99807211A CN1185743C CN 1185743 C CN1185743 C CN 1185743C CN B998072117 A CNB998072117 A CN B998072117A CN 99807211 A CN99807211 A CN 99807211A CN 1185743 C CN1185743 C CN 1185743C
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CN
China
Prior art keywords
battery
redox gel
redox
battery according
ion
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Expired - Fee Related
Application number
CNB998072117A
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English (en)
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CN1305649A (zh
Inventor
史蒂芬·韦恩·霍尔顿
克里斯·梅尼克特兹
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Farnow Technologies Pty Ltd
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Farnow Technologies Pty Ltd
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Priority claimed from AUPP3992A external-priority patent/AUPP399298A0/en
Priority claimed from AUPP8260A external-priority patent/AUPP826099A0/en
Application filed by Farnow Technologies Pty Ltd filed Critical Farnow Technologies Pty Ltd
Publication of CN1305649A publication Critical patent/CN1305649A/zh
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Publication of CN1185743C publication Critical patent/CN1185743C/zh
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Abstract

氧化还原胶体电池(10)由正氧化还原电解质(13)，负氧化还原电解质(14)和位于两者之间的隔膜(15)构成。与正氧化还原电解质(13)作电连接的正电极(11)：与负氧化还原电解质(14)作电连接的负电极(12)。氧化还原胶体电池的运行能够通过电池管理系统得以增强，电池管理系统将极化的影响最小化。

Description

氧化还原胶体电池
发明所属领域
本发明涉及一种电池，尤其是提高了运行特性的电池。
背景技术
电池工业现在对电池管理技术的需求提高了。首先，由于消费者对电池供电的便携设备(如便携式电话、膝上型电脑等)的需求日益增长。其次，电池工业现在增长的趋向重点在于电动机驱动工具和零排放交通工具(电池为这新一代交通工具的主要动力来源)。这种趋向的原因是政府法令的迅速增加和消费者对空气及噪音污染的担忧。另外的要求高效电池的蓄能应用领域是，例如用于敏感电子元件的负荷均衡、应急/备用功率和功率质量系统。
作为电池能源设备需求增长的结果，电池厂家需在竞争压力下生产出理想的电池。理想电池应该是超轻，超小，具有优秀的周期寿命和理想的充、放电性能，并在寿命结束后其自身不会产生环境污染。电池工业采用的最普遍的技术工艺是铅酸电池，它正在面对向更高能量密度、更小体积、更好的性能水准、更长周期寿命和保证回收等方面挑战。
传统的铅酸电池组，其容量利用率有限、放电深度低、周期寿命短、能量密度低、存在热管理问题并且需要不断提升充电来维持电池单元均衡。
铅酸电池组还要求充电时间长，高充电电流仅能在极低充电状态下使用几分钟。如果使用高电流，通常将导致电压高于允许值，从而导致电解质丧失和电池容量减小。如果遵从适当的充电形式，以提升充电进行铅酸电池的再充电时间最大可提高到4小时。
铅酸电池组的周期寿命在极大程度上取决于周期过程中所达到的放电深度(DOD)。电动交通工具应用中90-100％的放电深度并不罕见，在这样的放电深度水准下，传统深度周期铅酸电池组的周期寿命能达到接近300个周期。大多数控制器的运行是针对总的电池电压。通常个别电池单元会放电低于能接受的极限，因为整个电池电压技术所依靠的假定是所有电池单元处于同一充电状态，而这，通常不符合实际情况。在高负荷下，电池系统将严重失衡，个别电池单元在放电过程中可能实际上反置，甚至冒烟。这似乎有些极端，然而，当大型电池组在较高电压下提供电力时，可能会发生电池单元反向，而最初不会被检测到。
传统的镍氢电池(NiMH)采用先进的加工和高纯度的原料，导致电池系统的成本非常高。采用高纯度氢氧化镍化合物的扩展镍泡沫和经处理的金属合金原料都需要高度的质量控制以得到高性能电池。
NiMH氢化物电池也存在自放电问题并且也易受到温度的影响。在某些系统用高电流萃取会破坏电池单元，而必须注意不要使电池组过充电。在这一方面，需要高档的电池充电器来确保完全充电。
氧化还原电池组经过多年研究，大体上是按照流体电池组的形式。氧化还原流体电池组将能量储存在液体电解质中，其电解质被分开地保存在电池槽中。在运行时，电解质通过系统再循环，能量在电解质中往复传递。在充电时，电量流入并存储在电解质中；在放电时，电解质向负载释放出所存储的能量。氧化还原流体电池组的代表性缺点是低能量密度、因电解质通过系统再循环引起泵吸损失。在某些情况下，高自放电率可能取决于隔膜或存在有内泄漏以及旁路电流。
发明简述
本发明提供了一种氧化还原胶体电池，它至少包含一个电池单元，该单元包括正氧化还原胶体电解质，负氧化还原胶体电解质，位于正、负氧化还原电解质之间的隔膜，与正氧化还原胶体电解质连在一起的正电极，与负氧化还原电解质连在一起的负电极。
附图简要说明
图一是本发明的一个实施例的一个单氧化还原胶体电池的示意图；
图二是本发明另一实施例的一个多单元氧化还原胶体电池的示意图；
图三是本发明又一实施例的一个螺旋盘绕型单氧化还原胶体电池的示意图；
图四是本发明的氧化还原胶体电池的电池管理系统框图；
图五是图四中所示电池管理系统的阻抗控制模块的框图。
发明的详细描述
传统电池系统采用某种形式的固体金属电极，其包含有相位转移反应，导致重量增大和效率损失。本发明的氧化还原胶体电池采用超浓缩胶体，它包含有各自胶体中的高浓缩正、负活性离子。所有活性元素或反应物质都包含在胶体中，并且无相位转移反应。由于损失最小，从而达到高的效率。
以铈/铬电池(典型的铈氯化物CeCL3，和铬氯化物CrCL3)为作为氧化还原胶体电池的实例，其典型的反应如方程1和2所示：
    E0＝1.44V                (1)
    E0＝-0.41V               (2)
在充电状态，正极胶体电解质包含Ce4+离子，负极胶体电解质包含Cr2+离子。当电池被放电时，负极胶体电解质中的Cr2+离子被氧化为Cr3+离子，正极胶体电解质中的Ce4+离子被还原为Ce3+离子。
下面方程3给出了完整的放电反应，理论上电池电压基于方程1和方程2的标准电极电位，例如对于在25 ℃时对NHE计算的水溶液，此电压为1.85V。充电反应是方程3的逆反应。
    E0＝1.85V        (3)
实际的电池电压将取决于氧化还原胶体介质中用于反应物的支持电解质。
如图1所示，一个单氧化还原胶体电池10包括一个惰性正电极11，一个惰性负电极12，正氧化还原胶体电解质13，负氧化还原胶体电解质14，以及位于13和14之间的隔膜15。电极11和电极12最好选用非金属物质。
隔膜15的电阻抗极低，它以极低的电阻抗将氧化还原胶体电解质13和14隔离。氧化还原胶体电解质13和14可以由任何金属离子、金属离子混合物、无机和有机化合物等构成，当电池在特征电压下接上负载后，能够使胶体导电并产生电流。胶体中还可以包含一些能提高性能的添加剂。
胶体电解质还包含某些凝胶剂，如二氧化硅，或者任何其他无活性成分沉淀有助于稳定胶体结构的物质。
氧化还原胶体电池与氧化还原流体电池的区别在于，其电解质为超浓缩胶体，包含在电池之中，无需进行再循环，如图1所示。
氧化还原胶体电池可以是如图1所示的单电池结构，图2所示的双极多单元电池组，或者是图3所示的螺旋盘绕式电池结构。
如图2所示，双极多单元电池组20由电池单元1，2…………N-1，N组成。从1到N，每个单元都包括一正氧化还原胶体电解质13和一负氧化还原胶体电解质14，以及位于13和14之间的隔膜15。公共电极16位于各单元之间。惰性负电极12位于单元1的外表面，惰性正电极11位于单元N的外表面。
如图3所示，单元螺旋盘绕型氧化还原胶体电池30包括一个如图1所示的电池单元结构以及隔离电池结构的盘绕段的绝缘膜17。
如图4所示，氧化还原胶体电池可以采用一个电池管理系统，它包含一个可以集成到电池组中的模块，以使极化的影响最小。因为电池管理系统的加速和监控，从而限制了极化现象并提供了一种高度的个别单元控制，氧化还原胶体电池的运行得以加强。
由于采用了超浓缩胶体，当电池系统应用在高负荷时，极化将趋向于增高，而电池管理系统能够减轻氧化还原胶体设计时的约束，特别适合于氧化还原胶体电池。
专为氧化还原胶体电池设计的电池管理系统还可执行许多监控功能。例如监控个别电池电压和温度。可以监控密封电池组的内压和确定各种给定条件下系统容许负荷的极限。电池管理系统还具有一个附加能力，能够在任意充电状态采取积极行动来保持最佳的电池性能。这种高程度的系统控制下，本发明的氧化还原胶体电池，能够重复地在一非常长的周期寿命中利用它的全部容量。
优先选用的电池管理系统如图4框图所示，包括一个微处理器40和管理后述所有功能的相关软件57。此例采用的是8位(bit)微处理器，运行速度为8MHz，但也可采用4、16、32或64位处理器。处理器的速度可以是4MHz～166MHz。也可根据个别电池需要选择数字信号处理芯片。微处理器包含电可擦除只读存储器(EEPROM)、只读存储器(ROM)和随机存取存储器(RAM)，也可选用特定用途集成电路(ASIC)。
个别电池电压测量模块41采用一个单独导线连接每个电池的接点，这条导线单独用来测电压。每个电池单元电压以电池组接地为参考量起，可达到24伏特。也可根据精确度要求和需要，通过直接测量每个电池单元的电压实现。
单元电池电压测量调节由模块42实现。它包括一个电路，在该电路中，电池电压被电阻网络分压，并通过连接在分压器接地电阻两端的滤波电容器加以平滑。可采用应用运算放大器的有源滤波器或其他滤波设备。电压通过分压器和滤波器定标到适合作模数转换的电压。在此例中，4.95伏特表示电池每个连接的预期的最大电压。一个12位的模数转换器用于测量每个电池单元的电压。模数转换器由微处理器串行控制，它通过定标各处电势，并从各电池单元的正极电势中减去其负极电势，将每一测量的电势转换为电池的电压。这种对每个电池单元的处理方法可应用于达到24伏特的电池电压。
高于24伏特时，可通过光耦合串行通信(从而隔离电池单元电压)的设备传递连续的数字数据，将上述方法多级使用。另外，可采用跨接每个单元的电压频率转换器，直接测量电池单元电势并将此信息作为频率信号发送到微处理器。上述的电压频率转换器可以是电或光耦合到微处理器，用来测量频率信号并将其转换成电压值。
电流测量模块43是测量旁路电阻两端的电压，并用带有源滤波的电流读出放大器定标该值。也可选择利用霍耳效应器通过适当的信号波形调整来测定电流。
电流测量调节由电流模块44实现，此时，将测量的旁路电压转换成一个0～5伏特的信号，而不管随后被传送到被用于测量上述电压时的相同的12位模数转换器的入口的电流的方向。调节电路还向微处理器提供数字输入来指示电流方向。这可通过具有最少外部元件的集成电路实现。在这方面离散部件方案也可降低成本。
温度由电路模块45使用一个装在电路板上的集成温度传感器来测量。任何数量的这些可用来安置在不同的区域，如电池组，个别电池单元或者外部的环境温度。
温度测量调节由电路模块46实现。其中，温度值是一个电压的输出量，通过使用一个低补偿电压运算放大器将此值定标到0～5伏特的数值，以适合与同样的模数转换器接口的连接，该模数转换器用于测量电压和电流。
一个液晶显示器47用来显示诸如剩余容量、剩余千米数以及其他信息等。
显示驱动器48可通过根据存储在微处理器40内的查找表对存储单元写入适当的值来，由微处理器直接驱动。取决于微处理器的要求和液晶显示器的复杂性，可以采用一个单独的集成电路驱动器。也可使用发光二极管或气体等离子显示器，或者一个液晶显示模块。
声音指示器模块49包括一个压电蜂鸣器，能向用户提供声音讯号。声音指示器理想的由微处理器直接驱动，或在必要时也可采用晶体管驱动器。
距离传感器50装在使用本电池的运动车辆的轮子上。它采用电磁传感器的形式，其磁体位于轮子上，或霍耳效应传感装置装在车辆的固定部件或光传感器。
距离传感器调节由电路模块51实现。其中，距离传感器输出的频率值通过微处理器定标和测量，再将其转换成速度值或距离值。
压力传感器模块52位于电池中，包括一个能输出低电压(0～100mV)的压力传感器。
压力传感器调节模块53通过精密运算放大器将输出结果转化到0～5伏特之间并输出到模数转换器。
通信模块54确保所有控制和电池充电器发出的通讯信号能够通过串行总线直接由微处理器40传递。此串行总线为校准目的也可访问PC。
为保证长的电池寿命，所有优化程序的组件都选择用于低电流消耗。通过微处理器向低电流模式模块55发出的信号，微处理器、模数转换器、以及其他所有电路都被设置在低电流消耗模式。
为达到要求的精确度，微处理器的模拟输入通过校准模块56来校准，校准系数和残留偏差存储在电可擦除存储器中。
软件模块57最好是面向查询的以及用于时间紧急事件，例如能量利用积累的电流监控的中断。更可取的是，软件能确定个别单电池是否有故障，并通知电池充电器。
此软件包括一个电压电流算法的多项式，以打开开关防止电池过放电。此软件适用于以下方面：
(1)计算电池自放电并能启动电池均衡过程。
(2)记录循环次数，并将此信息发送给电池充电器。
(3)监控、传递和启动安全措施防止过电压或者电压不足。
(4)按规律的时间间隔采样电流，并相对时间将电流求积分，以提供已使用的安时和剩余量。
(5)根据电流循环期间的负荷校正已使用的安时和剩余量。
微处理器40可通过驱动FETS或IGBT来控制电动机58的电流。这能够向有刷电动机提供单个脉冲宽度调制控制。或者通过多输出，向无刷多类型电动机如磁阻电动机、无刷直流电动机等提供准正弦信号控制。
可采用一个FET或者IGBT开关59用来提供电池安全和保护。采用的是一个低阻值FETS。
开关59由开关控制模块60控制。开关控制模块由微处理器40驱动，FETS或IGBTS的驱动采用开关电源以提升高压来使能高侧驱动。
在阻抗控制模块61中，微处理器控制着一块FET。该FET的功能是周期性向一个电容充电直到电压值超出电池电压，然后向电池中释放此电容电量，在此同时转换到另一电容器充电，以保持负载电流。
能量计62的输出显示在液晶显示器上，表示剩余容量，此值由电流对时间积分求得。电流按等时间间隔采样，并从累加器中减去此值，再转化成百分数给出剩余容量的输出值。
内阻／阻抗模块63，采用测定电流改变前后电压的变化的方法来计算内阻和阻抗。在充电和放电的过程中都可以进行。交流电流或电压可能会注入电池，最后的电压或电流被测量来计算内阻和阻抗。
电池均衡模块64的运行，使得在当一个电池单元的自放电超过其他同组的其他电池单元时，将从整个电池组中提出电量，通过开关模式电源转换器被转化成适当的电压值，然后分配给最弱的电池单元，从而使电池达到平衡。
氧化还原胶体电池采用的电极的功能在于允许能量传入和传出胶体电解质。电极是惰性的，可以用专门开发的非金属导电物质制成，这些物质可以形成或铸塑成几乎任何特定形状。
电解质是用来存储所有包含在氧化还原胶体电池中的能量。胶体中所含的特定的离子可以根据应用和能量密度要求选择，并可利用单个的或多电子半电池单元反应。胶体电解质可制成带有或不带有总合为胶体的电极矩阵。在此二种情形下，胶体存储电能这一主要功能保持不变。
因为胶体电解质的稳定性，氧化还原胶体电池具有很长的周期寿命。在胶体的基本形态下，电解质在存储能量时，无相位转移发生，电解后不产生降解，从而大大节省了整个系统的成本。由于轻便、稳定耐用的特性，氧化还原胶体电池非常适合用于“租赁能量”型车辆的电池更换过程，紧急备用和便携电源组。
参照图5，下面进一步描述控制极化和因而电池输出的方式。
如图5所示的控制系统100适用于提供从氧化还原电池系统111向终端或连接有负载如电动车等的输出装置112预定的能源输出。控制装置114位于输出终端112和氧化还原胶体电池系统111的终端113之间，来检测电池系统111的预定运行参数。在第一运行模式期间，控制装置114从电池系统111向输出终端112供电。
第一电容装置115连接在电池系统111和控制装置114之间，当控制装置114在第一运行模式下时，它存储电池系统111的预定电量；当控制装置114在第二运行模式下时，它响应控制装置114发出的指令信号，向电池系统111提供所存储的电量。
第二电容装置116连接在输出终端112和控制装置114之间，当控制装置114处于第一运行模式时，它存储由电池系统111提供的预定电量总量；当控制装置114处于第二运行模式时，它向输出终端112提供其所存储的电量，以响应控制装置114发出的指令信号。
因而，电源控制系统与两个电容网路相结合，当控制装置检测到异常时，例如在电池系统111中极化程度过高或自最初将电力加到负载开始过去了预置时间间隔，它将启动向电池系统111返回充电。在这放电周期中，控制装置114允许存储在第一电容网路115中的电能向电池系统111充电，与此同时，第二电容装置116向输出终端112以不间断电源供电。反此逆向周期即放电周期的时间间隔非常小，所以它可以有效的以定时间隔运行。
反向充电具有瓦解和最小化系统内的极化效应及相应的损失的能力。
电源控制系统还可以与充电器协同工作以在运行过程中提供最佳性能和随时电池维护。电源控制系统还适用于防止将未经许可的充电器连接到电池系统，由此防止了潜在的误用并确保车主在家里不会使用不正确的充电器来尝试为电池系统充电。
电源控制系统、充电器和车辆可以结合各个人的电子签名，从而能够高精度跟踪和监控整体系统。每当电池系统被装入充电装置，电源控制系统将自我识别，确认是否已从车辆中卸下以及用户在使用。
充电装置可用来监控电池的能量水平，再加上汇兑成本，电力和电池的月租费，并将这一数值通知用户。无论是使用支票还时信用卡，根据收到的这项支付金额，就可以发放新的电池并装入车辆。如果顾客违章使用或损害了电池，总而言之，都会在充电器中被鉴别出来。
控制系统不仅适用于鉴别电池的能量水平，还可以根据电流能量的使用程度来估计剩余的行程。因此，车辆司机可以得知靠剩余的电量还能够行驶多少公里路程。
每个充电装备都通过一个遥测系统连接到操作中心，该中心能够持续检测充电站网中所有位置的充电站。
电源控制系统还包含速度控制模块的功能和特征，这意味着车量管理者可以从车上去除速度控制装置，仅仅通过电源控制系统来控制输出，从而减少车辆成本，减少制造厂商的风险担保，而且还可通过遥控信息系统提供持续的性能检测监测。
电源控制系统可应用于很多电池系统，如阀调节铅酸电池组，镍氢电池组和氧化还原胶体电池组等，对每个系统都有特定的应用和益处。电源控制系统还可应用于改善边远程区电力系统，负荷均衡以及紧急后备电池系统的后备性能。应用在边远地区的电力系统和紧急后备应用中的稳定的电池系统，能维持在延长期间内满充电。由于电池单元自放电的速率不同，可将电源控制系统编程来定期扫描单个电池单元的状态，并使用电池平衡技术在内部平衡电池。充电系统还可以作为后备设备或者根据要求用电源控制系统来控制。

Claims (13)

1.一种氧化还原胶体电池，包括至少一个电池单元，所述电池单元组成包括：
(i)正胶体电解质，包含在所述电池运行期间被还原但不经历相位转移的活性离子，
(ii)负胶体电解质，包含在所述电池运行期间被氧化但不经历相位转移的活性离子，
(iii)分隔所述正和负胶体电解质的隔膜，
(iv)与所述正胶体电解质电连接的正电极，以及
(v)与所述负胶体电解质电连接的负电极。
2.根据权利要求1所述的氧化还原胶体电池，其中，所述胶体是超浓缩的。
3.根据权利要求1所述的氧化还原胶体电池，其是铈/铬氧化还原胶体电池。
4.根据权利要求1所述的氧化还原胶体电池，其是铈氯化物/铬氯化物氧化还原胶体电池。
5.根据权利要求4所述的氧化还原胶体电池，其中，所述正胶体电解质包含Ce4+离子，所述负胶体电解质包含Cr2+离子，并且其中在所述电池的放电期间所述Ce4+离子被还原为Ce3+离子，所述Cr2+离子被氧化为Cr3+离子。
6.根据权利要求1所述的氧化还原胶体电池，其中，每种胶体都包含凝胶剂。
7.根据权利要求6所述的氧化还原胶体电池，其中，所述凝胶剂是二氧化硅。
8.根据权利要求1所述的氧化还原胶体电池，其中，所述电池单元被盘绕成螺旋形。
9.根据权利要求1所述的氧化还原胶体电池，具有N个叠式的电池单元，其中相邻的电池单元被公共的电极分隔，在第一个电池单元的外表面有一个负电极，在第N个电池单元的外表面有一个正电极。
10.根据权利要求1所述的氧化还原胶体电池，其中，所述电极是非金属的。
11.根据权利要求1所述的氧化还原胶体电池，其中，所述电极是惰性的。
12.根据权利要求9所述的氧化还原胶体电池，其中，所述电极是非金属的。
13.根据权利要求9所述的氧化还原胶体电池，其中，所述电极是惰性的。
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ID27342A (id) 2001-04-05
BR9911519A (pt) 2001-03-20
US6720107B1 (en) 2004-04-13
WO1999065131A1 (en) 1999-12-16
MXPA00012257A (es) 2002-04-24
WO1999065100A1 (en) 1999-12-16
HK1038651A1 (zh) 2002-03-22
CA2333048A1 (en) 1999-12-16
EP1095419A1 (en) 2001-05-02
MY124056A (en) 2006-06-30
EA200001256A1 (ru) 2001-08-27
JP2002518969A (ja) 2002-06-25
HK1038643A1 (zh) 2002-03-22
AU4589099A (en) 1999-12-30
BR9911520A (pt) 2001-03-20
AU744894B2 (en) 2002-03-07
EP1095419A4 (en) 2005-06-15
CN1305655A (zh) 2001-07-25
CA2333043A1 (en) 1999-12-16
KR20010071363A (ko) 2001-07-28
EA200001257A1 (ru) 2001-08-27
ID28115A (id) 2001-05-03
EP1095419B1 (en) 2007-07-18
CN1305649A (zh) 2001-07-25
DE69936586D1 (en) 2007-08-30

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