CN1401143A - 新型燃料 - Google Patents

新型燃料 Download PDF

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CN1401143A
CN1401143A CN01804609A CN01804609A CN1401143A CN 1401143 A CN1401143 A CN 1401143A CN 01804609 A CN01804609 A CN 01804609A CN 01804609 A CN01804609 A CN 01804609A CN 1401143 A CN1401143 A CN 1401143A
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fuel
fuel cell
direct oxidation
oxalic acid
dimethyl oxalate
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CN1255894C (zh
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E·匹莱德
T·杜德瓦尼
A·枚尔曼
A·阿哈隆
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Tel Aviv University Future Technology Development LP
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RAMOT UNIV AUTHORITY FOR APPLIED RESEARCH AND INDUSTRIAL DEVELOPMENT Ltd
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Abstract

本发明公开了草酸二甲酯、乙二醇、其草酸、乙醛酸和甲酸酯、二羟乙酸及其甲酯、乙二醛和聚草酸乙二醇酯在供给燃料电池燃料中的应用，通过这些化合物供给燃料的燃料电池，含有这些燃料电池的混合能源，以及评估其在溶液中的浓度的方法。

Description

新型燃料
技术领域
本发明涉及燃料电池和在燃料电池中应用的有机燃料。
发明背景
烃类和脂肪醇非常难于完全电氧化(J.WANG，S.Wasmus和R.F.Savinell，J.Electrochem.Soc.142，4218(1995))，其中脂肪醇氧化的主要产品是醛或酮、CO2和酸或酯。甚至在190℃下，在聚合物-电解质膜(PEM)燃料电池中，乙醇的氧化是不完全的，其主要氧化产品(超过60％)是乙醛，而CO2小于氧化产品的40％。不能以80％或更高比例电氧化的化合物被认为不是有效的燃料。就发明者所知，从来没有过关于具有C-C键的化合物完全电氧化的报道，其中草酸例外(V.S.Bagotzky和Y.B.Vasilyev，Electrochemica Acta 9，869(1964))。存在数种公开出版物，其中教导了在燃料电池中应用的燃料。在它们当中，US5599638提及应用甲醇、甲醛、甲酸、二甲氧基甲烷、三甲氧基甲烷和三噁烷。NASA进行了对约150种作为潜在燃料的用于燃料电池的有机化合物的筛选(NASA报告No.SP-120(1967)，第15章，225页)，其中检验到仅甲醇是有效的燃料。测试其它有机分子在酸性、中性或碱性溶液中的半电池电势，和在不同电流和温度下测量电极电压，并在假设一种理论的氧电极下，计算每平方厘米的最大功率，所筛选的所有分子显示出介于1-250mW/cm2的某一最大功率。然而，这一参数并没有教导化合物是否是作为燃料的良好候选者。例如，被认为是良好有机燃料的甲醇和几乎不可能被认为是燃料的乙醇在酸性介质中显示出相似的最大功率值(分别为13和15mW/cm2)。在SP-120(第6章，第262页)中报道了乙二醇和尿素在30％KOH燃料电池中表现不好。在此NASA报道中提及的其它一些分子是甘油、乙二醛和二羟乙酸。
发明概述
本发明提供了燃料电池用的有机燃料。本发明的有机燃料选自草酸二甲酯(DMO)、乙二醇(EG)、其草酸酯、乙醛酸酯和甲酸酯、二羟乙酸及其甲酯、乙二醛(glyoxylic aldehyde)和聚草酸乙二醇酯，后者是草酸与乙二醇的聚酯。本发明的有机燃料在非碱性燃料电池中，特别在酸性燃料电池中进行清洁和有效的氧化。本发明优选的燃料是草酸二甲酯、乙二醇、其甲酸酯、草酸乙二醇酯和聚草酸乙二醇酯。本发明最优选的燃料是乙二醇和草酸二甲酯。本发明优选的燃料是当在燃料电池中用作燃料时，转化成CO2的转化率超过80％，且仅留下可忽略量的非挥发副产物的那些。
在使用本发明燃料的情况下，可满意地工作的燃料电池的非限制性实施例是液体原料燃料电池、气体原料燃料电池、高温燃料电池、固体氧化物燃料电池、熔融碳酸盐燃料电池和使用质子交换或质子传导膜的燃料电池。优选使用质子交换或质子传导膜的燃料电池或者固体氧化物燃料电池。
本发明还提供本发明燃料的混合物，以及本发明燃料与在燃料电池中作为燃料应用的已知有机燃料(如甲醇)的混合物。
特别地在高温下，本发明的一些燃料在碱性燃料电池情况下也可以是有用的。然而，当使用碱性电解质时，由于在碱性环境下燃料的不完全电氧化，以及这种不完全电氧化导致的碳酸盐或其它有机盐的累积，从而需要不时地更换燃料。
当燃料电池借助本发明的燃料工作时，它们显示的交叉(crossover)电流密度低于借助甲醇(它是目前在这种电池中最常用的燃料)工作的相同燃料电池所显示的交叉电流密度。低的交叉电流导致高的效率。在未受理论束缚的情况下，可认为低的交叉电流归功于与甲醇相比，本发明燃料的分子尺寸大。大的分子尺寸与小的扩散系数有关，而小的扩散系数导致小的交叉电流密度。
此外，本发明的燃料具有比甲醇高的沸点，从而主要在其液相中通过质子传导膜进行运输。自然地，液相中的扩散系数低于气相。
本发明的固体燃料(如DMO和聚草酸乙二醇酯)比起象甲醇类的液体燃料来，由于数种原因(如它们较容易操作和它们在水中的溶解度低)可以是有利的。因此，它们维持低浓度，而低浓度辅助保持低交叉电流。此外，例如在燃料电池的阳极室中，可将其饱和溶液与大量固体燃料一起储藏，其中当电池在使用中以及燃料被消耗时，所述固体燃料会溶解，而未溶解的固体燃料充当燃料储存器。
根据本发明的另一方面，本发明提供了一种直接氧化燃料电池，它具有阳极、阴极、排列在所述阳极和所述阴极之间的质子传导膜；向阳极供应有机燃料的装置以及向阴极供应氧气的装置，其中所述有机燃料选自草酸二甲酯(DMO)、乙二醇(EG)、其草酸酯、乙醛酸酯和甲酸酯、二羟乙酸及其甲酯、乙二醛和聚草酸乙二醇酯。根据本发明的这一方面，优选的电池是其中燃料选自草酸二甲酯、乙二醇、其草酸酯和甲酸酯以及聚草酸乙二醇酯的那些。根据本发明的这一方面，最优选的电池是其中燃料选自乙二醇和草酸二甲酯的那些。
根据一个实施方案，本发明这一方面的燃料电池的特征进一步在于在其使用过程中，通过位于阳极室或燃料罐中的薄的疏水多孔基质释放所产生的CO2，从而使得在没有损失溶液的情况下放出气体。
根据本发明另一实施方案，本发明提供了一种燃料电池，它特别适用于与本发明的燃料一起工作。这种燃料电池的特征在于阴极除了含氧气还原催化剂之外，还含有燃料氧化催化剂，其非限制性实例是Pt-Ru、Pt-Sn、Pt-Ru-Sn、Pt-Ag-Ru、Pt-Os催化剂或这些催化剂的结合。在阴极处的燃料氧化催化剂改进穿越过膜的燃料的氧化性并防止阴极的氧气还原催化剂(典型地为Pt或Pt合金催化剂)失活。还原催化剂与氧化催化剂的实际比介于1％-50％，优选5％-20％(w/w)或介于0.01-5mg，优选介于0.05-0.2mg氧化催化剂/cm2氧气电极。
根据本发明的另一实施方案，本发明提供一种在预先设定温度下，评估新型燃料浓度的方法，该方法包括下述步骤：
(a)在燃料电池中，在所述预先设定温度下，制作交叉电流对燃料浓度的校正曲线；
(b)在所述燃料电池中，在所述预先设定温度下，测量交叉电流；和
(c)由步骤(b)中测量的电流和步骤(a)中制作的校正曲线来评估燃料浓度。
这一方法是基于本发明者发现的本发明燃料电池中的交叉电流与燃料浓度直接成正比。例如，发现在80℃下，1M EG的交叉电流密度是在相同温度下，0.5M EG的约2倍(分别是41和19mA/cm2)，以及发现在60℃下0.25M DMO的交叉电流密度是在相同温度下，0.1M DMO的约2.5倍(分别是2.5和0.9mA/cm2)。在确保在其测量中，所测量的电流与电压无关的条件下，这一发现是正确的。
本发明的方法可用于测量在工作的燃料电池中燃料溶液的燃料浓度。这可通过测量在工作的燃料电池中的交叉电流得以进行。或者可提供进行测量用的小的辅助燃料电池。这一可供选择的方案使得可根据本发明进行测量，而没有必须在测量所要求的电压下操作整个燃料电池。辅助燃料电池可与燃料电池物理地分离，或安装在其中，或与其相连接或与燃料罐相连接。
本发明还提供一种混合能源，它包括至少一种本发明的燃料电池、一种DC到DC的变换器和一种可再充电的电池。
直接的甲醇燃料电池(DMFC)和液体原料燃料电池(LFFC)的能量低。然而，象蜂窝电话、计算机和小型电子设备之类的仪器在短时间内需要高的能量。对于这些和类似的应用来说，可将本发明的燃料电池与小型高功率可再充电电池结合，所述小型高功率可再充电电池在所需时可供应高能量。这一结合比起现有技术的混合能源来是有利的，这种有利特别归功于小的交叉电流。目前，DC到DC的变换器可从0.7V起开始工作。正因为如此，可通过DC到DC的变换器尽可能使电池组结合少至两种或三种燃料电池(串联结合)。若交叉电流密度足够小，如15mA/cm2或更低，则不必经常地供给这一混合能源燃料。因此，这种混合能源优选使用低交叉电流密度的燃料电池如本发明的燃料电池。燃料电池使电池组充电并供应低的能量要求，而高能电池组则供应大的负荷。这种所要求的燃料电池的数量少，使得能使用平而薄的燃料电池体系。
本发明提供一种用本发明燃料供给燃料的这种混合能源。用本发明的固体燃料供应这种混合能源燃料将是最有利的。
例如，可使用由2节薄的燃料电池、DC到DC的变换器以及小的高能锂离子电池组成的混合能源向蜂窝电话供应能量，其中这2节燃料电池以串联结合的方式连接，并通过本发明的液体燃料(如EG)或通过本发明的固体燃料(如DMO)来供应燃料。
附图的简要说明
为了更好地理解本发明和为了明白它实际上如何工作，在参考下述附图的情况下，将更详细地描述本发明的数个实施方案，其中：
图1是显示本发明的一些燃料以及一些现有技术的燃料的极化曲线图；和
图2是本发明的固体原料有机燃料电池的示意图。
一些实施方案的详细描述
实施例1：获得一些燃料的极化曲线
在使用纯的金属催化剂替代碳上承载的催化剂的情况下，制造燃料电池。通过下述工艺制备阴极催化剂墨水(ink)：
按照下述重量比混合Pt纳米粉末(Pt黑，购于“Johnson Matthey”)、TeflonTM乳液和5％NafionTM溶液：60％Pt、25％Teflon乳液和15％Nafion。首先通过声波处理混合Pt粉末和Teflon乳液15分钟。在两次声波处理周期后，将所得墨水放置在磁搅拌器上至少一个晚上。
通过下述工艺制备阳极催化剂墨水：按照下述重量比混合Pt∶Ru纳米粉末(Pt∶Ru黑，50％，购于“Johnson Matthey”)和PVDF：91％催化剂粉末和9％ PVDF。以等于催化剂体积30-70％的量加入碳酸异丙烯酯，然后加入环戊酮，和搅拌所得墨水至少一个晚上。
制备电极：将阴极催化剂墨水涂敷到特氟隆化的TorayTM碳纤维纸上，形成4mg Pt/cm2。分层铺展墨水(呈糊状形式)，使得在涂敷下一层之前，各层干燥约1小时。重复这种操作，直到获得所需量的催化剂。以相同的方式，将阳极催化剂墨水涂敷到没有特氟隆化的TorayTM碳纤维纸上，直到获得5-10mg催化剂/cm2。用3M硫酸，然后用水洗涤两种电极。
将阴极和阳极放置在厚度为100-300μm的PCM两侧，彼此互相平行，且在10-70Kg/cm2的压力和85-130℃的温度下热压。图1示出了在下述条件下这种类型燃料电池的极化曲线：将燃料溶液和3M硫酸以9ml/min的速度循环通过阳极。氧气以比大气压高0.25atm.的压力下循环流过阴极。电池温度为65℃。PCM为300微米厚，它由(V/V)16％SiO2的纳米尺寸粉末、24％PVDF和60％的1.5nm典型直径的孔隙体积组成。在0.4V下电池证明了超过100小时的稳定操作。所测试的燃料是：甲醇(1M)、草酸(0.1M与1M甲醇、0.1M草酸、0.1M草酸二甲酯、0.5M乙二醇和0.5M甘油，(根据本发明，在这些当中，甘油草酸和甲醇不是n)。如图中所示，在这些条件下，DMO和EG具有最佳的性能。然而，人们应当记住在此实验中的任何条件都不是最优化的，因此其它浓度和/或其它催化剂可定性地导致不同的观察结果。
通过在恒定电压下进行50ml燃料溶液的电化学滴定，直到电流降到3mA来测试燃料利用率。估计在此电流下仅残留有百分之几的燃料未被氧化。通过实验的容量与理论值的比较，计算利用率。通过将滴定曲线外推到电流为0，得出进一步的校正。这种校正使利用率值增加3-6％(表1)。
发现在0.2V下，DMO的燃料利用率为95％，EG的燃料利用率为94％和甲醇的燃料利用率仅为85％(参见表1)。在更实际的0.4V电压下，发现EG的燃料利用率为89％，DMO的燃料利用率为67％，和甲醇的燃料利用率为81％。
由于燃料不会跨越到阴极一侧，这些高的燃料利用率值表明燃料的电氧化接近100％。
通过向阴极室内供入氮气替代氧气(在环境温度下)和向阳极室内供入有机燃料-酸溶液，在不同温度下进行燃料跨越的测量。使电池电压反向；在燃料电极处产生氢气，同时跨越到阴极一侧的燃料被氧化。发现在1V下流动的电流是所有燃料氧化的极限电流。
表2总结了燃料跨越试验结果。交叉电流密度取决于燃料的渗透性、温度、浓度，同时取决于氧化中所包含的电子总数。1M甲醇的交叉电流密度(在80℃下)是1M EG和0.25M DMO的2倍。然而，当考虑电子数和用单位mol·s-1·cm-2表示的燃料通量(flux)(在80℃和控制扩散的条件下)归一化为1M燃料时，可看出EG的渗透性(通量)是甲醇的1/3，而DMO的渗透性几乎与甲醇一样大。
                            表1：不同燃料利用率的比较
    电子数   理论容量[Ah/g]    在0.4V下的利用率*[％]    在0.2V下的利用率*[％]
    Exp.    Corr.    Exp.     Corr.
    草酸     2     0.43     91
    甲醇     6     5.03     79     81     82     85
    乙二醇     10     4.32     83     89     89     94
  草酸二甲酯     14     3.18     64     67     93     95
*至少两次试验的平均；Exp.-实验值；Corr.-校正值，参见正文。
                           表2：不同燃料的跨越
    1.燃料                   跨越试验
    温度[℃]   浓度[M] 交叉电流密度[A/cm2]     燃料通量*[mol·s-1·cm-2]1×10-8
  草酸二甲酯     60     0.10      0.009           6.7
    60     0.25      0.025           7.4
    80     0.25      0.038           11
    乙二醇     80     0.5      0.019           3.9
    80     1.0      0.041           4.2
    甲醇     80     1.0      0.076           13
*归一化到1M
实施例2：本发明燃料在NafionTM基燃料电池中的应用
由购于Globetech Inc.的合成石墨层制造燃料电池壳，其中在所述石墨层中可刻录流场。
使用Pt-Ru墨水形成阳极，其中所述Pt-Ru墨水铺展在可商购的TorayTM纸张的碳纤维片材上。催化剂层由15％Teflon(DuPont)、15％NafionTM和70％Pt-Ru纳米粉末(Pt∶Ru黑，50％，购于“JohnsonMatthey”)组成。阳极的负荷是5mg/cm2。所使用的阴极是可商购的ELAT E-TEKTM，它由4mg Pt/cm2和0.6mg nafion/cm2组成。阳极和阴极被热压到117 Nafion膜(获自DuPont)上，形成膜电极组件(MEA)，正如实施例1所述。
在冷却后，将MEA放置在石墨流场片之间，插入聚丙烯密封并组装电池。
在操作过程中，选自草酸、草酸二甲酯、乙二醇、甘油的浓度介于0.1-0.5M的燃料含水溶液在4-15ml/min的流速下循环流过阳极(在使用蠕动的Masterflex L/S Cole-Parmer Instrument Co.泵的情况下)。
在环境压力和7-40ml/min的流速下，氧气直接地或通过水起泡器供入阴极室。在60℃下对电池进行实验。发现极化曲线类似于图1的那些。
实施例3：固体原料的有机燃料电池
图2说明了一种固体原料的有机燃料电池，它具有一个塑料容器501、一个阳极509、一个阴极511和一种固体聚合物电解质膜510。膜510是WO99/44245中公开的PCM类型，它由12％SiO2、28％PVDF和60％孔隙(将酸性溶液引入到所述孔隙中)组成。如实施例1制备阳极、阴极和MEA。通过燃料孔502填充固体有机燃料并用软木塞503密封。燃料溶解在罐中，且通过哈斯特洛伊耐蚀镍基合金(hastaHoy)C-276(Cabot)网507在多孔碳布508处吸收燃料。通过排气嘴504排出在阳极室中形成的二氧化碳。由于液体燃料可通过排气嘴渗漏，用薄的疏水多孔层506覆盖排气嘴。疏水层仅可使气体渗透，而燃料溶液仍保留在罐中。阴极通过第二块哈斯特洛伊耐蚀镍基合金网513敞开于空气中。为了防止燃料从阴极一侧漏出，用衬垫512密封MEA。第二块哈斯特洛伊耐蚀镍基合金网513还用于覆盖整个组件。200mg DMO溶解在含1M硫酸溶液的燃料罐中。燃料电池在0.35V下传递30mA的电流。交叉电流密度在室温下为2mA/cm2。

Claims (24)

1.在非碱性燃料电池中用作燃料的有机化合物，它们选自草酸二甲酯、乙二醇、其草酸酯、乙醛酸酯和甲酸酯、二羟乙酸及其甲酯、乙二醛和聚草酸乙二醇酯。
2.用于在权利要求1所定义的应用中使用的权利要求1的有机化合物，它们选自草酸二甲酯、乙二醇、其甲酸酯、二羟乙酸、草酸乙二醇酯和聚草酸乙二醇酯及其混合物。
3.用于在权利要求1所定义的应用中使用的权利要求1的有机化合物，它们选自乙二醇、草酸二甲酯及其混合物。
4.用于在权利要求1所定义的应用中使用的权利要求1的有机化合物，它们选自草酸二甲酯、聚草酸乙二醇酯及其混合物。
5.用于在权利要求1所定义的应用中使用的权利要求1-4任一项的有机化合物与已知燃料的混合物。
6.用于在权利要求1所定义的应用中使用的权利要求5的混合物，其中所述已知的燃料是甲醇。
7.用于在权利要求1所定义的应用中使用的权利要求1-6任一项的化合物，其中所述燃料电池是酸性电解质燃料电池。
8.用于在权利要求1所定义的应用中使用的权利要求1-6任一项的化合物，其中所述燃料电池具有质子传导膜。
9.用于在权利要求7或8所定义的应用中使用的权利要求5的混合物。
10.一种直接氧化燃料电池，它具有阳极、阴极、排列在所述阳极和所述阴极之间的质子传导膜；向阳极储存或供应有机燃料的装置以及向阴极供应氧气的装置，其中所述有机燃料选自草酸二甲酯、乙二醇、其草酸酯、乙醛酸酯和甲酸酯、二羟乙酸及其甲酯、乙二醛和聚草酸乙二醇酯。
11.权利要求10的直接氧化燃料电池，其中所述燃料选自草酸二甲酯、乙二醇、其草酸酯和甲酸酯、聚草酸乙二醇酯及其混合物。
12.权利要求11的直接氧化燃料电池，其中所述燃料选自草酸二甲酯、乙二醇、其甲酸酯、草酸乙二醇酯、聚草酸乙二醇酯及其混合物。
13.权利要求12的直接氧化燃料电池，其中燃料选自草酸二甲酯、乙二醇及其混合物。
14.权利要求10-13任一项的液体原料的直接氧化燃料电池，其中所述燃料电池是液体原料。
15.权利要求13的液体原料的直接氧化燃料电池，其中燃料选自聚草酸乙二醇酯、草酸二甲酯及其混合物。
16.权利要求14或15任一项的液体原料的直接氧化燃料电池，其进一步的特征在于在其使用过程中，通过位于阳极室或燃料罐中的薄的疏水多孔基质释放所产生的CO2。
17.一种直接氧化燃料电池，它具有含氧气还原催化剂和燃料氧化催化剂的阴极。
18.权利要求17的直接氧化燃料电池，其中所述燃料氧化催化剂选自Pt-Ru、Pt-Sn、Pt-Ru-Sn、Pt-Ag-Ru、Pt-Os催化剂或这些催化剂的任意结合。
19.权利要求18的直接氧化燃料电池，其中燃料氧化催化剂与氧气还原催化剂之比介于1％-50％(w/w)。
20.权利要求19的直接氧化燃料电池，其中所述比例介于5％-20％(w/w)。
21.权利要求14-17任一项的直接氧化燃料电池，其中所述燃料是权利要求5或6所定义的混合物。
22.在预先设定温度下评估溶液中燃料浓度的方法，其中燃料是权利要求1-6任何一项的化合物，它包括下述步骤：
(a)在给定的燃料电池中，在所述预先设定的温度下，制作交叉电流对燃料浓度的校正曲线；
(b)在所述给定的燃料电池中，在所述预先设定的温度下，测量交叉电流；和
由步骤(b)中测量的交叉电流和步骤(a)中制作的校正曲线来评估燃料浓度。
23.一种混合能源，它包括至少一种权利要求10-21任一项的燃料电池、一种DC到DC的变换器和一种可再充电的电池。
24.一种混合能源，它包括至少一种权利要求15的燃料电池、一种DC到DC的变换器和一种可再充电的电池。
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