铅酸电池失效模式与修复的电化学研究
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摘要
铅酸电池作为最古老的二次电池,因其优良的性价比,仍然是世界上应用最广泛的电池。但是由于负极硫酸盐化、正极板栅腐蚀等失效模式限制了它的使用寿命,而电动汽车的日趋发展,也需要铅酸电池能够实现快速充电。本文研究的目的即是围绕铅在硫酸电解液中的电化学特性,挖掘铅电极在电化学氧化还原过程中的现象与铅酸电池性能之间的对应关系,探究负极硫酸盐化的本质及修复方法,寻找提高快速充电的新方法,研究阳极腐蚀膜及相关现象与机理。
采用循环伏安法研究了电极表面初始状态及结构对二氧化铅特征峰和析氧峰的影响。发现正向扫描前,电极表面硫酸铅的来源,对二氧化铅形成峰影响非常大,当硫酸铅源自纯铅氧化时,正向阳极氧化过程二氧化铅形成过电位非常高；相反,硫酸铅源自上一循环中二氧化铅的还原时,正向阳极过程二氧化铅特征峰凸显,氧化过电位降低了0.7V。并因此发现了两种反应活性的硫酸铅,即由二氧化铅还原得到的PbSO4(R)具有高反应活性的,而由铅氧化得到的PbSO4(O)反应活性很低。
采用电化学方法制备了PbSO4(O)和PbSO4(R)两种硫酸铅,并进行了循环伏安和电化学阻抗谱等电化学测试,扫描电镜(SEM)和X射线衍射(XRD)等物理表征。结果发现,PbSO4(O)结构致密,离子传导率低,电化学活性低,成钝化状态；而PbSO4(R)电化学活性高,离子传导率是PbSO4(O)的6倍,且具有疏松的表面结构；X射线衍射结果表明,两种硫酸铅属于同一晶型,反应活性的巨大差异仅是由其结构导致的。认为在电池放电过程,正极表面形成的是活性高的PbSO4(R),而负极形成的是低反应活性的PbSO4(O),这正是负极硫酸盐化的本质。提出将硫化电池进行反向充电,可将负极的PbSO4(O)转换成PbSO4(R),实现活化,进而修复硫化电池。反向充电修复硫化电池的实验结果表明,修复后的电池容量增加了1倍以上。因此,这两种不同反应活性的硫酸铅的发现为反向充电方法修复电池或正电位下反复氧化还原活化电极提供了理论依据,并且还可以指导产生其它修复硫化电池的新方法,只要PbSO4(O)能够在修复过程转变成PbSO4(R),都可以活化硫酸盐化的负极。
采用循环伏安法、线性电势扫描法和线性电势扫描联合电位阶跃法等多种方法,详细研究了偏移氧化峰(AEPs)产生的条件。得出,AEPs现象与铅阳极腐蚀膜的组成有密切关系,且AEPs的产生依赖电极表层的PbSO4(O)钝化层和能使Pb(II)向高价铅氧化的正极化过程。在高电位短时极化处理后,在阴极负向扫描过程第一次发现了四个AEPs脱离二氧化铅还原峰而独立出现,现存的所有AEPs理论都不能合理解释此现象。第一次提出AEPs的“中间态PbO。理论”,即AEPs是中间价态的PbOn氧化成Pb02的氧化峰。给出了AEPs形成过程的反应模型,认为PbSO4层的致密程度和PbSO4层中的电场强度决定了OH离子在PbSO4层中的传输难易程度,进而决定了AEPs的产生与否。在铅电极正电位极化时,外层的高致密PbSO4(O)钝化层阻碍了OH离子向内层的传输,内层的PbO仅被氧化成了中间价态的PbOn,在阴极回扫时继续被氧化产生AEPs。同时,提出四个AEPs峰是具有不同“n”值的PbOn化合物,在氧化时生成Pb02的氧化峰。同时,认为在不同硫酸浓度中AEPs相对二氧化铅还原峰位置的变化,是由于二氧化铅还原峰的峰电位受硫酸浓度的影响而偏移导致的,而AEPs氧化峰电位不受硫酸浓度的影响。
通过伏安法测试,研究了多元醇和卤族离子两类添加剂对AEPs的影响。结果表明,以葡萄糖为代表的多羟基化合物提高了AEPs峰；而以氟化钠为例的卤族离子化合物几乎消除了AEPs峰。在添加多元醇的体系中,当羟基数小于6时,AEPs峰随多羟基化合物中羟基数量的增加成线性增加。通过扫描电镜表征二氧化铅的表面形貌特征得出,铅电极在含葡萄糖或山梨醇的电解液中腐蚀后,晶粒都较小,表面结构致密,这将会阻止内层PbO向Pb02氧化,形成大量中间态的PbOn,导致AEPs峰的上升。认为葡萄糖等多元醇可以用作铅电极正极板栅的缓蚀剂或者干荷电池负极板的抗氧化剂。
通过循环伏安方法研究了铅电极在不同浓度山梨醇的硫酸溶液中的AEPs的变化规律,采用动电位极化方法研究了山梨醇对铅电极在硫酸溶液中的缓蚀作用。得出,随着硫酸溶液中山梨醇浓度的增加,循环伏安曲线中AEPs峰电流的增高趋势,和动电位极化测试结果中腐蚀电流的下降趋势是一致的,都是先随浓度线性变化,后趋于平缓,说明AEPs确实与铅电极的腐蚀受到抑制有关。继而表明可以通过循环伏安测试中的AEPs峰电流的高低,来表征添加剂对铅电极的缓蚀效果,即能够提高AEPs的添加剂就能起到缓蚀作用。通过动电位极化结果拟合出腐蚀电流,来计算山梨醇在铅表面的覆盖度,并进而得出山梨醇的吸附等温线,符合Langmuir吸附等温线模型,经吸附自由能测试证明吸附是一个自发进行过程。提出山梨醇等具有邻羟基结构的多元醇分子可以与铅、氧化铅和二氧化铅产生配位化学作用,进而对铅电极起缓蚀作用,促进AEPs峰的提高。
研究了添加剂对Pb/PbSO4电化学反应的可逆性的影响。发现,四丁基溴化铵明显提高了Pb/PbSO4电化学反应的可逆性,且使硫酸铅还原峰变短,这意味着加入四丁基溴化铵后硫酸铅的还原变得更彻底,使硫酸铅还原更快,预示着四丁基溴化铵可以提高铅酸电池的充电速度。电池充电测试结果表明,采用常规的恒流恒压充电方法,添加四丁基溴化铵后电池充电时间从空白电池的10小时以上缩短到4.5小时。这大大缩短了电池的充电时间。这意味着采用电解液添加剂的这种简单易操作的方法,无需复杂的充电模式,就可以实现快速充电。这将大大降低快速充电的成本及能耗。
Lead acid battery is the most wildely-used secondary battery for its high cost performace, even though it is the oldest one. However, some failure modes such as sufation of negative plate and corrosion of positive grid lead to the end of service life of lead acid battery. Also, the rapid development of electric vehicles needs lead acid battery could be charged quickly. The aim of this thesis is to mine the relationships between the behavior during the electrochemical redox process of lead electrode and the performance of lead acid battery, probe into the essence of sufation and to find the restoring method, investigate the corrosion film of positive grid and some other relative phenomena, and find the simple and effective fast charging method through the investigation of electrochemical behavior of lead in sulfuric acid solution.
The influence of the oxidative status and structure of the surface of lead electrode on the anodic peaks for Pb(Ⅱ) to PbO2 and oxygen evolution was investigated via cyclic voltammetry. It was found that the source of lead sulfate on the surface of lead electrode has significant influence on its anodic peaks. When lead sulfate was from the oxidation of metallic lead, the overpotential of oxidation of PbSO4 to PbbO2 was so high and the characteristic peak of PbbO2 formation overlapped with the anodic peak of oxygen evolution. On the contrary, when lead sulfate came from the reduction of PbO2, the anodic peaks for oxidation of PbSO4 to PbbO2 appeared and the overpotential was reduced about 0.7V. Therefore, two types of PbSO4 with different reaction activity were found. The PbSO4 from the oxidation of pure Pb is denoted as PbSO4(O) and has low reaction activity; and the PbSO4 from the reduction of PbO2 is denoted as PbSO4(R) and has high reaction activity.
The samples of PbSO4(O) and PbSO4(R) were prepared by electrochemical method and were characterized though cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electronic microscopy (SEM) and X-ray diffraction (XRD). The results showed that PbSO4(O) had compact structure, high ion-transfer resistance and low electrochemical reaction activity, whereas PbSO4(R) had loose structure, high electrochemical reaction activity and low ion-transfer resistance. The XRD results showed that the two types of PbSO4 belong to the orthorhombic PbSO4, which suggests that the significant difference in reaction activity of the two types of PbSO4 should not be attributed to the different crystal forms of PbSO4. It was proposed that during the discharge process, PbSO4(R) was formed on positive plate and PbSO4(O) with low activity was formed on negative plate, which is the essence of sufation of negative plate. It is sugguested that the inert PbSO4(O) on negative plate could be transformed to active PbSO4(R) via inverse charging. The restore test result showed that the new capacity after inverse charging was more than twice of the initial value. The discovery of the different reaction activity of the two types of PbSO4 provides the mechanism for the methods of the inverse charging or repeating redox process at positive potential ranges to reactivate sulfated negative electrode, and can also bring other novel recovering method, which means as long as PbSO4(O) is transformed to PbSO4(R), the sulfated negative electrode could be reactivated.
The occurrence of "anodic excursion peaks "(AEPs) was investigated in detail via cyclic voltammetry (CV), linear sweep voltammetry (LSV) and low rate linear sweep voltammetry combined with potential step method. It was obtained that AEPs was closely related to the corrosion film of lead electrode formed at positive polarization potential, and the occurrence of AEPs depended on the passivated PbSO4(O) layer on the surface of lead electrode and positive polarization enabling the oxidation of Pb(Ⅱ) to Pb(Ⅳ). It was found for the first time that four AEPs occurred without reduction of PbbO2 to PbSCO4, which is in confliction with the conventional understanding that AEPs would appear accompanying with a large reduction peak for PbbO2 discharge. Therefore, we gave the mold for the formation of AEPs and proposed that AEPs corresponds to the oxidation of intermidate PbOn compounds which is the incomplete oxidation product of PbO. The compactness of PbSO4(O) layer and the electric field strength in PbSO4 layer determines the electro-migration rate of OH- through PbSO4(O) layer, which determines the oxidation degree of PbO and therefore determines the occurrence of AEPs. When lead electrode was polarized at high anodic potential, due to the inhibition of the transfer of OH" by passivated PbSO4(O) layer, the inner PbO was only oxidized to PbOn, and in the cathodic scanning, PbOn was continuely oxidized to PbO2, forming AEPs. Also it was suggested that the four AEPs correspond to the oxidation of PbOn compounds with different values of "n". About the phenomenon that AEPs is situated before and after the peak for reduction of PbO2, we propsed that it is attributed to the excursion of peak potential of reduction of PbO2 caused by the concentration of H2SO4, but which has no effect on AEPs.
The effects of polyhydroxyl compounds and halide ion on AEPs were investigated through voltammetry. The results showed that polyol increased AEPs, but halide ion eliminated AEPs. When the amount of OH groups of polyols is less than 6, AEPs increased linearly with the increasing of amount of OH groups of added polyols. The SEM results showed that the lead electrode corroded in electrolyte containing glucose or sorbitol had a compact structure, which prevented the oxidation of PbO to PbO2, forming lots of PbOn, and therefore AEPs was increased. So, it was concluded that polyols such as glucose could be used as corrosion inhibitor of positive grid or the antioxidant of dry charged negative plate.
The variation of AEPs with the concentration of added sorbtiol was investigated through CV and the inhibition of sorbitol on corrosion of lead electrode was investigated via Tafel polarization measurements. It was obtained that as the concentration of added sorbtiol was increased, the trend of the increase of AEPs and the trend of the decrease of corrocion current were similar, both of which varied linearly first and then became stable, which means that AEPs is surely relative with the inhibition of corrosion of lead electrode. Therefore, the measurement of AEPs could be applied to characterize the effect on additives on corrosion resistance of lead alloy grid, which means the additives that could increase AEPs have good anticorrosion effect. The coverage of sorbitol on lead electrode was calculated via the corrosion current from Tafel curves, and the adsorption isotherms was obtained from the coverage which obeyed Langmuir adsorption isotherm mold. The obtained adsorption free energy was a negative value, which means that the adsorption of sorbitol on lead electrode was a spontaneous process. It was proposed that the 2-hydroxy in polyols could be interacted with Pb resulting in the adsorption of polyols on the surface of lead electrode. So, the corrosion was inhibited and therefore AEPs was increased.
The reversibility of Pb/PbSO4 electrode was studied through adding additives. It was found that tetrabutylammonium bromide (TBAB) increased the reversibility of Pb/PbSO4 electrode and shortened the reduction peak of PbSO4, which means that TBAB may shorten the charging time and could recover the capacity quickly. The result of charging test showed that the charging time of battery with TBAB was less than half that of the blank battery, which means that this simple method could be effective on fast charging and does not need complicated charging mode. This method would decrease the cost and energy consumption of fast charging.
采用循环伏安法研究了电极表面初始状态及结构对二氧化铅特征峰和析氧峰的影响。发现正向扫描前,电极表面硫酸铅的来源,对二氧化铅形成峰影响非常大,当硫酸铅源自纯铅氧化时,正向阳极氧化过程二氧化铅形成过电位非常高；相反,硫酸铅源自上一循环中二氧化铅的还原时,正向阳极过程二氧化铅特征峰凸显,氧化过电位降低了0.7V。并因此发现了两种反应活性的硫酸铅,即由二氧化铅还原得到的PbSO4(R)具有高反应活性的,而由铅氧化得到的PbSO4(O)反应活性很低。
采用电化学方法制备了PbSO4(O)和PbSO4(R)两种硫酸铅,并进行了循环伏安和电化学阻抗谱等电化学测试,扫描电镜(SEM)和X射线衍射(XRD)等物理表征。结果发现,PbSO4(O)结构致密,离子传导率低,电化学活性低,成钝化状态；而PbSO4(R)电化学活性高,离子传导率是PbSO4(O)的6倍,且具有疏松的表面结构；X射线衍射结果表明,两种硫酸铅属于同一晶型,反应活性的巨大差异仅是由其结构导致的。认为在电池放电过程,正极表面形成的是活性高的PbSO4(R),而负极形成的是低反应活性的PbSO4(O),这正是负极硫酸盐化的本质。提出将硫化电池进行反向充电,可将负极的PbSO4(O)转换成PbSO4(R),实现活化,进而修复硫化电池。反向充电修复硫化电池的实验结果表明,修复后的电池容量增加了1倍以上。因此,这两种不同反应活性的硫酸铅的发现为反向充电方法修复电池或正电位下反复氧化还原活化电极提供了理论依据,并且还可以指导产生其它修复硫化电池的新方法,只要PbSO4(O)能够在修复过程转变成PbSO4(R),都可以活化硫酸盐化的负极。
采用循环伏安法、线性电势扫描法和线性电势扫描联合电位阶跃法等多种方法,详细研究了偏移氧化峰(AEPs)产生的条件。得出,AEPs现象与铅阳极腐蚀膜的组成有密切关系,且AEPs的产生依赖电极表层的PbSO4(O)钝化层和能使Pb(II)向高价铅氧化的正极化过程。在高电位短时极化处理后,在阴极负向扫描过程第一次发现了四个AEPs脱离二氧化铅还原峰而独立出现,现存的所有AEPs理论都不能合理解释此现象。第一次提出AEPs的“中间态PbO。理论”,即AEPs是中间价态的PbOn氧化成Pb02的氧化峰。给出了AEPs形成过程的反应模型,认为PbSO4层的致密程度和PbSO4层中的电场强度决定了OH离子在PbSO4层中的传输难易程度,进而决定了AEPs的产生与否。在铅电极正电位极化时,外层的高致密PbSO4(O)钝化层阻碍了OH离子向内层的传输,内层的PbO仅被氧化成了中间价态的PbOn,在阴极回扫时继续被氧化产生AEPs。同时,提出四个AEPs峰是具有不同“n”值的PbOn化合物,在氧化时生成Pb02的氧化峰。同时,认为在不同硫酸浓度中AEPs相对二氧化铅还原峰位置的变化,是由于二氧化铅还原峰的峰电位受硫酸浓度的影响而偏移导致的,而AEPs氧化峰电位不受硫酸浓度的影响。
通过伏安法测试,研究了多元醇和卤族离子两类添加剂对AEPs的影响。结果表明,以葡萄糖为代表的多羟基化合物提高了AEPs峰；而以氟化钠为例的卤族离子化合物几乎消除了AEPs峰。在添加多元醇的体系中,当羟基数小于6时,AEPs峰随多羟基化合物中羟基数量的增加成线性增加。通过扫描电镜表征二氧化铅的表面形貌特征得出,铅电极在含葡萄糖或山梨醇的电解液中腐蚀后,晶粒都较小,表面结构致密,这将会阻止内层PbO向Pb02氧化,形成大量中间态的PbOn,导致AEPs峰的上升。认为葡萄糖等多元醇可以用作铅电极正极板栅的缓蚀剂或者干荷电池负极板的抗氧化剂。
通过循环伏安方法研究了铅电极在不同浓度山梨醇的硫酸溶液中的AEPs的变化规律,采用动电位极化方法研究了山梨醇对铅电极在硫酸溶液中的缓蚀作用。得出,随着硫酸溶液中山梨醇浓度的增加,循环伏安曲线中AEPs峰电流的增高趋势,和动电位极化测试结果中腐蚀电流的下降趋势是一致的,都是先随浓度线性变化,后趋于平缓,说明AEPs确实与铅电极的腐蚀受到抑制有关。继而表明可以通过循环伏安测试中的AEPs峰电流的高低,来表征添加剂对铅电极的缓蚀效果,即能够提高AEPs的添加剂就能起到缓蚀作用。通过动电位极化结果拟合出腐蚀电流,来计算山梨醇在铅表面的覆盖度,并进而得出山梨醇的吸附等温线,符合Langmuir吸附等温线模型,经吸附自由能测试证明吸附是一个自发进行过程。提出山梨醇等具有邻羟基结构的多元醇分子可以与铅、氧化铅和二氧化铅产生配位化学作用,进而对铅电极起缓蚀作用,促进AEPs峰的提高。
研究了添加剂对Pb/PbSO4电化学反应的可逆性的影响。发现,四丁基溴化铵明显提高了Pb/PbSO4电化学反应的可逆性,且使硫酸铅还原峰变短,这意味着加入四丁基溴化铵后硫酸铅的还原变得更彻底,使硫酸铅还原更快,预示着四丁基溴化铵可以提高铅酸电池的充电速度。电池充电测试结果表明,采用常规的恒流恒压充电方法,添加四丁基溴化铵后电池充电时间从空白电池的10小时以上缩短到4.5小时。这大大缩短了电池的充电时间。这意味着采用电解液添加剂的这种简单易操作的方法,无需复杂的充电模式,就可以实现快速充电。这将大大降低快速充电的成本及能耗。
Lead acid battery is the most wildely-used secondary battery for its high cost performace, even though it is the oldest one. However, some failure modes such as sufation of negative plate and corrosion of positive grid lead to the end of service life of lead acid battery. Also, the rapid development of electric vehicles needs lead acid battery could be charged quickly. The aim of this thesis is to mine the relationships between the behavior during the electrochemical redox process of lead electrode and the performance of lead acid battery, probe into the essence of sufation and to find the restoring method, investigate the corrosion film of positive grid and some other relative phenomena, and find the simple and effective fast charging method through the investigation of electrochemical behavior of lead in sulfuric acid solution.
The influence of the oxidative status and structure of the surface of lead electrode on the anodic peaks for Pb(Ⅱ) to PbO2 and oxygen evolution was investigated via cyclic voltammetry. It was found that the source of lead sulfate on the surface of lead electrode has significant influence on its anodic peaks. When lead sulfate was from the oxidation of metallic lead, the overpotential of oxidation of PbSO4 to PbbO2 was so high and the characteristic peak of PbbO2 formation overlapped with the anodic peak of oxygen evolution. On the contrary, when lead sulfate came from the reduction of PbO2, the anodic peaks for oxidation of PbSO4 to PbbO2 appeared and the overpotential was reduced about 0.7V. Therefore, two types of PbSO4 with different reaction activity were found. The PbSO4 from the oxidation of pure Pb is denoted as PbSO4(O) and has low reaction activity; and the PbSO4 from the reduction of PbO2 is denoted as PbSO4(R) and has high reaction activity.
The samples of PbSO4(O) and PbSO4(R) were prepared by electrochemical method and were characterized though cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electronic microscopy (SEM) and X-ray diffraction (XRD). The results showed that PbSO4(O) had compact structure, high ion-transfer resistance and low electrochemical reaction activity, whereas PbSO4(R) had loose structure, high electrochemical reaction activity and low ion-transfer resistance. The XRD results showed that the two types of PbSO4 belong to the orthorhombic PbSO4, which suggests that the significant difference in reaction activity of the two types of PbSO4 should not be attributed to the different crystal forms of PbSO4. It was proposed that during the discharge process, PbSO4(R) was formed on positive plate and PbSO4(O) with low activity was formed on negative plate, which is the essence of sufation of negative plate. It is sugguested that the inert PbSO4(O) on negative plate could be transformed to active PbSO4(R) via inverse charging. The restore test result showed that the new capacity after inverse charging was more than twice of the initial value. The discovery of the different reaction activity of the two types of PbSO4 provides the mechanism for the methods of the inverse charging or repeating redox process at positive potential ranges to reactivate sulfated negative electrode, and can also bring other novel recovering method, which means as long as PbSO4(O) is transformed to PbSO4(R), the sulfated negative electrode could be reactivated.
The occurrence of "anodic excursion peaks "(AEPs) was investigated in detail via cyclic voltammetry (CV), linear sweep voltammetry (LSV) and low rate linear sweep voltammetry combined with potential step method. It was obtained that AEPs was closely related to the corrosion film of lead electrode formed at positive polarization potential, and the occurrence of AEPs depended on the passivated PbSO4(O) layer on the surface of lead electrode and positive polarization enabling the oxidation of Pb(Ⅱ) to Pb(Ⅳ). It was found for the first time that four AEPs occurred without reduction of PbbO2 to PbSCO4, which is in confliction with the conventional understanding that AEPs would appear accompanying with a large reduction peak for PbbO2 discharge. Therefore, we gave the mold for the formation of AEPs and proposed that AEPs corresponds to the oxidation of intermidate PbOn compounds which is the incomplete oxidation product of PbO. The compactness of PbSO4(O) layer and the electric field strength in PbSO4 layer determines the electro-migration rate of OH- through PbSO4(O) layer, which determines the oxidation degree of PbO and therefore determines the occurrence of AEPs. When lead electrode was polarized at high anodic potential, due to the inhibition of the transfer of OH" by passivated PbSO4(O) layer, the inner PbO was only oxidized to PbOn, and in the cathodic scanning, PbOn was continuely oxidized to PbO2, forming AEPs. Also it was suggested that the four AEPs correspond to the oxidation of PbOn compounds with different values of "n". About the phenomenon that AEPs is situated before and after the peak for reduction of PbO2, we propsed that it is attributed to the excursion of peak potential of reduction of PbO2 caused by the concentration of H2SO4, but which has no effect on AEPs.
The effects of polyhydroxyl compounds and halide ion on AEPs were investigated through voltammetry. The results showed that polyol increased AEPs, but halide ion eliminated AEPs. When the amount of OH groups of polyols is less than 6, AEPs increased linearly with the increasing of amount of OH groups of added polyols. The SEM results showed that the lead electrode corroded in electrolyte containing glucose or sorbitol had a compact structure, which prevented the oxidation of PbO to PbO2, forming lots of PbOn, and therefore AEPs was increased. So, it was concluded that polyols such as glucose could be used as corrosion inhibitor of positive grid or the antioxidant of dry charged negative plate.
The variation of AEPs with the concentration of added sorbtiol was investigated through CV and the inhibition of sorbitol on corrosion of lead electrode was investigated via Tafel polarization measurements. It was obtained that as the concentration of added sorbtiol was increased, the trend of the increase of AEPs and the trend of the decrease of corrocion current were similar, both of which varied linearly first and then became stable, which means that AEPs is surely relative with the inhibition of corrosion of lead electrode. Therefore, the measurement of AEPs could be applied to characterize the effect on additives on corrosion resistance of lead alloy grid, which means the additives that could increase AEPs have good anticorrosion effect. The coverage of sorbitol on lead electrode was calculated via the corrosion current from Tafel curves, and the adsorption isotherms was obtained from the coverage which obeyed Langmuir adsorption isotherm mold. The obtained adsorption free energy was a negative value, which means that the adsorption of sorbitol on lead electrode was a spontaneous process. It was proposed that the 2-hydroxy in polyols could be interacted with Pb resulting in the adsorption of polyols on the surface of lead electrode. So, the corrosion was inhibited and therefore AEPs was increased.
The reversibility of Pb/PbSO4 electrode was studied through adding additives. It was found that tetrabutylammonium bromide (TBAB) increased the reversibility of Pb/PbSO4 electrode and shortened the reduction peak of PbSO4, which means that TBAB may shorten the charging time and could recover the capacity quickly. The result of charging test showed that the charging time of battery with TBAB was less than half that of the blank battery, which means that this simple method could be effective on fast charging and does not need complicated charging mode. This method would decrease the cost and energy consumption of fast charging.
引文
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