CN117317166A - 正极活化物质及其制备方法、延长浮充寿命铅酸蓄电池的制备方法 - Google Patents
正极活化物质及其制备方法、延长浮充寿命铅酸蓄电池的制备方法 Download PDFInfo
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Abstract
本发明涉及电池技术领域,尤其是一种正极活化物质及其制备方法、延长浮充寿命铅酸蓄电池的制备方法。将正极活性物质填涂在板栅网格中经固化、干燥后形成蓄电池正极板;正极板和负极板在直流电的作用下与稀硫酸通过氧化还原反应生产氧化铅,再通过清洗、干燥即可用于电池装配所用的正负极板;正极板和负极板放入壳体焊接组装成铅蓄电池,加酸后化成。活性物质与板栅有较好结合力,较低腐蚀速率,电池充电接受能力、耐高温、耐过充效果明显,浮充寿命是普通铅酸电池的2倍多,成本大约是普通铅酸电池的1.2倍,综合性价比是普通铅酸电池的2倍以上;预留极板变形伸缩空间,防止引起活物质脱落,降低充电转化效率,正、负极板产生短路,影响浮充寿命。
Description
技术领域
本发明涉及电池技术领域,尤其是一种正极活化物质及其制备方法、延长浮充寿命铅酸蓄电池的制备方法。
背景技术
近十年来,阀控密封铅酸蓄电池技术取得了较大的发展,在电力、光伏、风能行业得到了广泛应用,对经济的快速发展起到了重要支柱作用。我国储能商业化应用面临储能成本偏高,储能技术在系统容量、转换率、寿命、安全性等问题上还有待进一步提高,储能设备至少要有10年的寿命期,才能收回投资成本,才具有投资价值。锂离子电池由于制作工艺因素,安全性问题、回收问题制约了发展,因此,提高铅酸蓄电池环境温度适应性,延长高温浮充寿命成为新能源能否快速发展的关键。
现有技术主要是针对后备通信后备电源,对蓄电池使用环境温度要求为25℃,电池的浮充使用寿命6年左右。而电力系统、太阳能、光伏贮能系统环境比较恶劣,温度变化相对较大,环境温度较高,有时会达到45℃,电池放电状态或欠充状态不够固定。
现有的铅酸电池无法满足贮能场景寿命要求。由于蓄电池的使用环温度变化较大,放电深度不稳定,充放电循环次数较多,活性物质与板栅的结合力随着循环次数的增加会逐渐下降、电极性会恶化,充电效率严重下降,容量衰减较快,高温浮充寿命会大幅减少,制约了贮能技术的的发展,因此,开发一种温度适应性较好,能延长铅酸蓄电池浮充寿命的方法,能解决现有铅酸蓄电池在循环使用过程中,因温度上升,板栅腐蚀加快,充电后期电流增大,失水加快,寿命缩短的难题。
发明内容
本发明要解决的技术问题是:为了解决上述背景技术中的现有技术存在的问题,提供一种现有铅酸蓄电池在循环充放电使用过程中,充电效率随温度变化而变化,充放电不稳定,特别是环境温度高时,加速板栅腐蚀及活性物质的软化,大幅降低使用寿命的正极活化物质及其制备方法、延长浮充寿命铅酸蓄电池的制备方法。
本发明解决其技术问题所采用的技术方案是:一种正极活化物质,其特征在于:所述的正极活性物质的组分为:三氧化二锰、氧化钼以及石墨烯,三氧化二锰、氧化钼、石墨烯三者之间的质量百分比为1.1:1:0.5。
一种铅酸蓄电池中正极活化物质的制备方法,包括如下制备步骤:
S1.将三氧化二锰、氧化钼、石墨烯按1.1:1:0.5的质量百分比配制,经真空预混5至10分钟;
S2.将S1中配置的混合物按0.1%~0.24%的质量百分比加入到铅及铅的多相混合物中,并加入丙纶纤维进行干混;
S3.在S2所得的混合物中,在10分钟内边搅拌边匀速加入去离子水,继续搅拌5分钟,再加入密度为1.25~1.32 g/cm3硫酸,加酸时间8~10分钟,继续搅拌5分钟,制成正极活化物质;
在规定温度下,产生电化学反应,形成铅酸电池活性物质所需的组织结构,目的是让电池在充放电过程中,活性物质充分转化、还原。
一种延长浮充寿命的铅酸蓄电池的制备方法,采用正极活化物质,包括如下步骤:
Sa.正极板制备
将正极活性物质填涂在板栅网格中经固化、干燥后形成蓄电池正极板;
Sb. 极板化成
正极板和负极板在直流电的作用下与稀硫酸通过氧化还原反应生产氧化铅,再通过清洗、干燥即可用于电池装配所用的正负极板;
Sc.装配电池、化成
正极板和负极板放入壳体焊接组装成铅蓄电池,加酸后化成。
进一步的,正极板和负极板的上边框与汇流排底部之间具有间距,该间距大于25mm,是考虑电池在充放过程中极板会伸长或变形,通过预留极板变形伸缩空间,当极板伸长或变形、弯曲,减少内应力产生,防止正、负极弯曲形成局部短路,造成壳体产生变形或开裂,漏酸导致电池寿命终止。
进一步的,正极板中正极活物质与负极板中负极活物质质量百分比为1:0.8,正极活性物质干量为14~16g/AH,负极活性物质干量为11.2~12.8g/AH。
进一步的,壳体内腔底部设有若干筋条,筋条为R2筋条,筋条高6~12mm,宽5~10mm,在连接处有R2~3过渡圆角。
进一步的,壳体内腔底部设有垫块,垫块为6~12mm弹性泡沫垫块。
进一步的,Sc中电池化成前注酸密度为1.18~1.20g/cm3,电池化成后开路电压静置96h后,平均不大于2.12V,化成后的硫酸密度为1.25~1.29g/cm3。
进一步的,Sc中化成后的电池成品的开路电压低于普通电池电压。
进一步的,Sc中化成后的电池成品的浮充电压设计为2.21V/单体。
进一步的,负极板的制备为铅粉中按常规工艺配方加入短纤维、木素、碳黑、硫酸钡经充分混合后,加酸、加水等湿混进行负极活性物质制备,并将负极活性物质填涂在负板栅网格中经固化、干燥后形成蓄电池负极板。
本发明的有益效果是:(1)本发明制备的电池在-10℃~35℃环境下正常充电,能保持活性物质与板栅有较好的结合力,较低的腐蚀速率,板栅保持良好的导电性,活性物质具有足够的强度。
(2)通过本技术方案,制备的铅酸电池充电接受能力、耐高温、耐过充效果明显,浮充寿命是普通铅酸电池的2倍多,使用寿命达12年以上,成本大约是普通铅酸电池的1.2倍,综合性价比是普通铅酸电池的2倍以上;
(3)本发明壳体内腔底部若干筋条或垫块,极板上边框与汇流排底部间距大于25mm,预留了极板变形伸缩空间,有效防止蓄电池在高温环境下充、放电,有效防止正极板伸长,变形较大,引起活物质脱落,降低了充电转化效率,正、负极板产生短路,影响浮充寿命。
(4)本发明加入的氧化钼,使铅膏金相组织均匀,缓蚀效果好,提高铅膏与板栅结合力;加入的三氧化二锰,提高过度放电及再充电接受能力;加入片状石墨烯,提高导电性、快速充电能力;通过上述材料的有机结合,提高活性材料的再充电恢复能力;和膏时加入低酸密度1.25-1.32 g/cm3,降低了电液密度,延缓对板栅的腐蚀速率,延长板栅的耐腐蚀寿命;
(5)本发明通过设计创新,正、负极活性物质质量百分比为1:0.8,正极活性物质干量为14~16g/AH,负极活性物质干量为11.2-12.8g/AH,正、负极活性物质相对普通电池,设计量富余,预留有部分活性物质,待后期有活性物质失效时逐渐补充,同时正、负极活性物质比例提高,保证正极产生的氧气与负极产生的氢气得到有效复合,减少电池的失水,提高电池浮充寿命;
(6)本发明电池化成前注酸密度为1.18~1.20g/cm3,电池化成后开路电压静置96h后,平均不大于2.12V, 化成后的硫酸密度为1.25~1.29g/cm3,由于降低了注酸密度,减少化成过程中的总充入电量,使极板活性物质中的α二氧化铅的含量由普通电池3%以下,增加至15%~20%,这些α二氧化铅在蓄电池循环使用过程中逐渐转化为β二氧化铅,补充并参与电化学反应的活性物质的活度,从而提高蓄电池放电容量,延缓容量衰减,延长寿命;
(7)本发明的电池成品的开路电压比普通电池低0.03V,电池在25℃下使用过程中浮充电压设计为2.21V/单体,使电池在较低电压下浮充运行,与电池内的低电液密度相对应,减少了电池充电电压差,有利减少充电过程中产生的热量,减少失水,减少对板栅的腐蚀,从而延长电池的浮充寿命。
具体实施方式
现在对本发明作进一步详细的说明。
延长浮充寿命的铅酸蓄电池:
一种正极活化物质,正极活性物质的组分为:三氧化二锰、氧化钼以及石墨烯,三氧化二锰、氧化钼、石墨烯三者之间的质量百分比为1.1:1:0.5。
延长浮充寿命的铅酸蓄电池的制备包括:
一、铅酸蓄电池中正极活化物质的制备,包括如下制备步骤:将三氧化二锰、氧化钼、片状石墨烯按1.1:1:0.5的质量百分比配制,经真空预混5至10分钟;将S1中配置的混合物按0.24%的质量百分比加入到铅及铅的多相混合物中,并加入丙纶纤维进行干混,混合10分钟;在S2混合10分钟内边搅拌边匀速加入去离子水,继续搅拌5分钟,再加入密度为1.28 g/cm3硫酸,加酸时间8分钟,继续搅拌5分钟,制成正极活化物质;
二、正极板的制备,将正极活性物质填涂在板栅网格中经固化、干燥后形成蓄电池正极板;
三、负极板的制备,负极板的制备为铅粉中按常规工艺配方加入短纤维、木素、碳黑、硫酸钡经充分混合后,加酸、加水等湿混进行负极活性物质制备,并将负极活性物质填涂在负板栅网格中经固化、干燥后形成蓄电池负极板;
四、极板化成,正极板和负极板在直流电的作用下与稀硫酸通过氧化还原反应生产氧化铅,再通过清洗、干燥即可用于电池装配所用的正负极板,正极板中正极活物质与负极板中负极活物质质量百分比为1:0.8,正极活性物质干量为16g/AH,负极活性物质干量为12.8g/AH;
五、装配电池、化成,将正极板、负极板、隔膜放入专用工装中,通过焊接方式组装成极群,并装入电池桶体中,并将上盖密封,形成半成品电池12只,壳体内腔底部垫厚为8mm的弹性泡沫垫块或若干条筋条,在极板上部与汇流排底部保持间距26mm。
在组装好的半成品电池中,注入密度为1.185g/cm3稀硫酸,通过三充、二放内化成工艺对极板的活性物质进行活化,形成成品GFD-200电池12 只,电池化成后电解液密度为1.261g/cm3 ,下线后,静置96小时,平均不大于2.12V,化成后的电池成品的开路电压低于普通电池电压0.03V,化成后的电池成品的浮充电压设计为在25℃条件下,每个电池单体的电压应设置为2.21V,随机抽取9只配成3组,其中2组分别进行高温循环寿命,1组进行高温浮充寿命试验,2只进行充电接受能力试验,1只备用。
对比例电池:
采用本企业生产的GFM-200AH电池12只,随机抽取9只配成3组,2组进行高温循环寿命,1组进行高温浮充寿命试验,2只进行充电接受能力试验,1只备用。
其中,GFM-200AH电池的主要设计指标:
设计寿命:浮充寿命10 年 (25℃正常使用充足电的条件下),深循环寿命1200 次(25℃放电深度 80%,且及时补充足电条件下);
充电接受能力:电池100%深度放电后,以 2.35V/单体恒压限流 0.15C 10 (A)充电 10h,充得电量在放出电量的98% 以上;
密封反应效率:大于99%;
容量保存率:静置 90 天后剩余容量大于 90%;
额定容量:10h 率容量 0.1C 10 A 放电至终压 1.80V/单体 ≥C 10,3h 率容量0.25C 10 A 放电至终压 1.80V/,单体 ≥0.75 C 10,1h 率容量 0.55C 10 A 放电至终压1.75V/单体 ≥0.55 C 10容量恢复性能(短接性能):以 0.1C 10 A 放电至 0V,短接 24h,以 2.35V/单体恒压限流 0.15C 10 (A)充电10h,再以 2.25V/单体恒压限流 0.15C 10(A)充电 24h,检测 C 10 容量,连续 5 次,其剩余容量不小于初始容量的 90%。
电池性能检测对比:
随机抽取电池6只配成2组,进行高温不同荷电态循环、高温浮充寿命循环测试,2只分别进行充电接受能力测试,检测设备采用48V 、100A型蓄电池循环检测设备。
1、10%DOD-80%DOD-40%DOD高温循环寿命
将配好电池组1(3只),在环境温度为45℃±2℃下,进行10%DOD-80%DOD-40%DOD高温循环寿命测试。循环制式为:
a)0.1C放1h;
b)2.35V/单体,限流0.15C10充6h;
c)0.1C放8h;
d)2.35V/单体,限流0.15C10充6h;
e)0.1C放4h;
f)2.35V/单体,限流0.15C10充6h;
g)重复第a)、f)步骤循环30次;
h)循环30次结束后,以2.35V/单体,进行限流0.1 C10充电24h,充电结束,再进行C10容量检测;
i)重复a)-h)直至核对性容量检测小于80%C10为止,
j)当核对性容量检测小于80%C10 时,需要再次确认一次。
10%DOD-80%DOD-40%DOD高温循环寿命对比试验结果见下表:
从表中可发现,本发明的容量衰减率与对比电池相比明显减小,在10%-40%-80%高温(55℃)循环寿命明显提高。
2、高温浮充寿命
将配好组的蓄电池组3(3只),保持在55℃±2℃环境中进行高温浮充寿命测试。循环制式为:对蓄电池以6.63V/单体浮充电压连续充电42d,将蓄电池取出,在25℃±2℃环境中进行3h率放电检测,为1次循环,直至容量低于3h率额定容量的80%时,寿命试验结束。
按上述高温浮充循环寿命制式进行浮充循环直至整组电池的3h率放电容量低于额定容量的80%时,本发明制作的电池组高温浮充循环寿命次数为12次,现有技术的电池高温浮充循环寿命次数一般在6次左右。
其中,现有技术的电池正极活化物质的制备步骤:在铅及铅的多相混合物中,加入5%-10%红丹及1-2%丙纶纤维进行干混,混合5分钟,后边搅拌边在3分种内匀速加入去离子水,继续搅拌5分钟,再加入密度为1.4g/cm3硫酸,加酸时间约10分钟,继续搅拌10分钟,制成正极活化物质。
3、充电接受能力试验
从样品电池中抽取2只电池,分别以20A电流放电5h,再放入0℃的低温室中24h,取出在1min内,以恒定电压2.35V/单体充电对蓄电池进行充电,10min后,测得最大充电电流分别为90A、96A,现有技术的电池最大充电电流一般在28A、32A,本发明充电接受能力为现有技术的电池的3倍以上。
上述试验结果说明,采用本发明制作的蓄电池10%-40%-80%高温(55℃)循环寿命是普通电池2.4倍以上,容量衰减率明显低于普通电池,高温55℃浮充寿命是普通电池2倍以上,充电接受能力是普通电池的3倍以上,综合性价比是普通铅酸电池的2倍以上,高温浮充循环寿命次数达12次,本发明适应在高温环境下长期浮充使用和不同荷电态下的循环使用。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (10)
1.一种正极活化物质,其特征在于:所述的正极活性物质的组分为:三氧化二锰、氧化钼以及石墨烯,三氧化二锰、氧化钼、石墨烯三者之间的质量百分比为1.1:1:0.5。
2.一种铅酸蓄电池中正极活化物质的制备方法,其特征在于:包括如下制备步骤:
S1.将三氧化二锰、氧化钼、石墨烯按1.1:1:0.5的质量百分比配制,经真空预混5至10分钟;
S2.将S1中配置的混合物按0.1%~0.24%的质量百分比加入到铅及铅的多相混合物中,并加入丙纶纤维进行干混;
S3.在S2所得的混合物中,在10分钟内边搅拌边匀速加入去离子水,继续搅拌5分钟,再加入密度为1.25~1.32 g/cm3硫酸,加酸时间8~10分钟,继续搅拌5分钟,制成正极活化物质。
3.一种延长浮充寿命的铅酸蓄电池的制备方法,采用如权利要求1所述的正极活化物质,其特征在于:包括如下步骤:
Sa.正极板制备
将正极活性物质填涂在板栅网格中经固化、干燥后形成蓄电池正极板;
Sb. 极板化成
正极板和负极板在直流电的作用下与稀硫酸通过氧化还原反应生产氧化铅,再通过清洗、干燥即可用于电池装配所用的正负极板;
Sc.装配电池、化成
正极板和负极板放入壳体焊接组装成铅蓄电池,加酸后化成。
4.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的正极板和负极板的上边框与汇流排底部之间具有间距,该间距大于25mm。
5.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的正极板中正极活物质与负极板中负极活物质质量百分比为1:0.8,正极活性物质干量为14~16g/AH,负极活性物质干量为11.2~12.8g/AH。
6.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的壳体内腔底部设有若干筋条。
7.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的壳体内腔底部设有垫块。
8.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的Sc中电池化成前注酸密度为1.18~1.20g/cm3,电池化成后开路电压静置96h后,平均不大于2.12V,化成后的硫酸密度为1.25~1.29g/cm3。
9.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的Sc中化成后的电池成品的浮充电压设计为2.21V/单体。
10.根据权利要求3所述的延长浮充寿命的铅酸蓄电池的制备方法,其特征在于:所述的负极板的制备为铅粉中按常规工艺配方加入短纤维、木素、碳黑、硫酸钡经充分混合后,加酸、加水等湿混进行负极活性物质制备,并将负极活性物质填涂在负板栅网格中经固化、干燥后形成蓄电池负极板。
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