CN108448038B - 层合的氧化受保护性隔板 - Google Patents
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Abstract
一种用于铅酸电池的电池隔板,解决了由污染物引起的酸分层和隔板氧化的问题。该隔板包括微孔膜和附于其上的扩散毡。扩散毡的三小时芯吸为至少约2.5cm。扩散毡可由合成纤维、玻璃纤维、天然纤维以及它们的组合制成。扩散毡可包括二氧化硅。隔板可包括橡胶。
Description
本申请为分案申请,原申请日是2014年3月7日;原申请号是201480012624.3;原发明名称是《层合的氧化受保护性隔板》。
相关申请
本申请要求享有2013年3月7日提交的序号为61/774144的待审美国临时申请的权益,该临时申请的内容以引用的方式并入本文。
发明领域
本发明涉及用于铅/酸电池的电池隔板,其具有附于微孔膜上的扩散毡。
背景技术
在过度热应用中(例如,具有高交通量的拥挤区域、热带或沙漠区域、外部储存应用等),电池(例如,铅酸电池,特别是淹没式铅酸(FLA)电池)易于发生电解质损失。电解质可以是水和酸(例如,硫酸)的混合物。电解质的损失使电极暴露于电池顶部空间内所含有的气态环境以及热量,这可最终导致电极板的干涸,并且继而电极加速腐蚀,其导致过早的电池失效。
进一步地,在电池(例如,铅酸电池)的充电期间,电解质中的酸可能会发生分层。酸分层不利地影响电池的性能及寿命。现有技术对电池(例如,铅酸电池)中酸分层问题的解决方案包括使用附于隔板上的“玻璃毡”。然而,这些玻璃毡显著地抬高了隔板的成本,具有大孔(因此,芯吸情况不好),并且在一些情况下使其本身不适合高速制造技术(例如,形成“袋”并熔接于隔板)。
在世界上的一些地区,例如在亚洲,铅/酸电池是以“干荷”电池的形式出售的。购买的这些干荷电池没有包括水/酸。干荷电池具有较长的保存期。然而,使用者在用未被污染的水/酸填充电池时可能会不小心。被污染的水/酸将会导致隔板的氧化,并最终导致电池失效。水/酸中的污染物可能来源于水/酸容器,例如钢桶。
另外,隔板(如用于铅/酸电池的隔板)的氧化可能会缩短电池的循环寿命,并因此缩短电池的有效寿命。这种氧化可能是由对“干荷”电池添加的水或酸中的污染物引起的。氧化使隔板脆化(通过例如%伸长率的损失测定),其可导致电池的部分或完全失效。
污染物通常起源于对电池添加的水和/或硫酸以及构成电极板的合金及活性材料中的杂质,并且这类污染物可引起氧化。这类污染物通常包括周期表的过渡金属,例如:铬(Cr)、锰(Mn)、钛(Ti)、铜(Cu)等。污染物水平(Cr、Mn和/或Ti)超过约2.0ppm[2.0mg/L]是不可取的。Cu污染物水平超过26ppm[26mg/L]是不可取的。
USPN5221587公开了在隔板中使用乳胶以防止铅/酸电池的锑(Sb)中毒。锑来源于电池的铅板(电极)。锑被用作铅中的合金化剂以改进板的制造并延长电池的循环寿命。普通技术人员将不会考虑USPN5221587的教导来达成上文提到的隔板氧化问题的解决方案。
USPN6242127公开了在常规的聚烯烃隔板中使用固化的多孔橡胶以提高隔板的电化学性质(锑抑制)。
需要开发解决前述酸分层及氧化问题的新型隔板(例如,用于铅/酸电池)。
CN1064969A没有公开“扩散毡”,其第11-12跨页段表明其涉及“玻璃毡”,与本发明的“扩散毡”完全不是一回事。
发明内容
一种用于铅酸电池的电池隔板解决了由污染物引起的酸分层和/或隔板氧化的问题。该隔板包括微孔膜和附于其上的扩散毡。扩散毡的三小时芯吸为至少约2.5cm。扩散毡可由合成纤维、玻璃纤维、天然纤维以及它们的组合制成。扩散毡可包括二氧化硅。隔板可包括橡胶。
本申请的具体实施方式部分的第3自然段记载,“扩散毡(DM)不是常规的玻璃毡”。
“玻璃毡”与本发明的“扩散毡”之间的多个不同的物理性质。本申请的具体实施方式部分的第4自然段记载了其中一个不同特性,即通过“三小时芯吸”进行测量。
根据这样的试验,“玻璃毡”与本发明的“扩散毡”之间的比较结果列入了说明书的表中。该表的注释部分记载,传统的玻璃毡是由Johns-Manville市售的DURA GLASS垫,其三小时芯吸为0.5cm。而玻璃毡恰恰是由Johns Manville市售的DURAGLASS垫。
本发明的“扩散毡”的一个关键参数是吸附液体的能力,这涉及材料、孔径、厚度,而三小时芯吸很好地表达了这样的性质。现有技术公开的孔径范围与本发明有重叠,但不能说明就公开了本发明,因为孔径仅仅是一个参数,但不是所有参数。
CN1064969A第11页末段至第12页第2段记载,CN1064969A的孔径是从约160微米(ps1)至约80微米(ps2)的范围;而本发明的表中记载,传统的DURAGLASS垫的三小时芯吸为0.5cm(wt1)。一般地,孔径越小,液体吸附能力越强,吸附能力与孔径成反比,wt∝1/ps,因此,wt1/wt2=ps2/ps1。因此,CN1064969A的吸附能力(wt2)应该仅仅是约1cm。
然而,本发明三小时芯吸为至少2.5cm,明显超出CN1064969A的范围。
附图说明
为了例示本发明的目的,附图中显示了目前优选的形式;然而要理解的是,本发明并不限于所示的精确布置及实施手段。
图1是本发明隔板(扩散毡)INV对比带有常规玻璃毡的隔板PA的图示比较。
图2是本发明隔板(扩散毡)INV对比另一带有常规玻璃毡的隔板PA的图示比较。
图3是本发明隔板(扩散毡)INV对比另一带有常规玻璃毡的隔板PA的图示比较。
图4是本发明隔板(扩散毡)INV对比另一带有常规玻璃毡的隔板PA的图示比较。
图5是本发明隔板(扩散毡)INV对比另一带有常规玻璃毡的隔板PA的图示比较。
具体实施方式
铅/酸电池是公知的,参见例如Linden,Hand book of Batteries,第2版,McGraw-Hill,Inc.New York,NY(1995)和/或Besenhard,Hand book of Battery Materials,Wiley-VCH Verlag GmbH,Weinheim,Germany(1999),两者均以引用的方式并入本文。隔板可用在任何铅/酸电池中。在一个实施方案中,铅/酸电池是淹没式铅/酸(FLA)电池,如用作逆变器电池、增强型淹没式电池(EFB)、ISS电池、固定电池、高尔夫球车电池等的那些。
在本发明的第一方面中,包括了扩散毡(DM)与微孔膜,以通过例如赋予阻止酸分层的优异扩散性质、减少锑中毒、提高耐氧化性和提高微短路保护性(由枝晶生长引起)而提高电池性能。DM和微孔膜的层合体还通过保持电极不藉由电解质芯吸作用干涸而防止水损失,从而通过扩散性质的改进而解决干涸状况并防止酸分层。
扩散毡(DM)不是常规的玻璃毡。常规的玻璃毡是被动性的,并且没有扩散或芯吸能力。比起常规的湿式或干式玻璃毡,DM可具有芯吸25倍或更多的能力。芯吸速率与酸分层是反比的关系。常规玻璃毡的“三小时芯吸”不超过0.6cm,而DM的“三小时芯吸”为至少约2.5cm。或者,DM的“三小时芯吸”可为至少约2.5cm或至少约3.0cm或至少约4.0cm或在约2.5-约10.0cm范围内或在约3.0-约10.0cm范围内或在约4.0-约10.0cm范围内或为它们的各种子组合。
通过以下方式进行“三小时芯吸”的测试,将标准尺寸的材料件插在液体(比重为1.280的硫酸)中,等待三个小时,并测量液体沿材料的上行高度。“标准尺寸件”意指具有相同的宽度和长度,但厚度可根据被测试材料的自然厚度而有所变化,以便可以进行有意义的比较。对于“三小时芯吸”测试,样品具有1英寸的宽度和至少40cm的长度。沿样品的垂直轴向上标示样品的每一厘米。将保持在液体上方的夹具中的样品***液体里到2cm的深度。在一分钟、五分钟、十分钟和十五分钟由样品上的刻度测量芯吸高度,并且测量三小时后的最大芯吸高度。DM可进一步包括粒状填料,如二氧化硅。
可以按任意方式将DM层合到微孔膜上。可以通过熔接或胶合使DM附于微孔膜上。可以将DM形成为“S”包套的袋、套筒、叶片。DM可以是由纤维制成的非织造或织造或编织织物。DM可由玻璃纤维、合成纤维、天然纤维或它们的组合制成。在一个实施方案中,DM可由玻璃纤维及合成纤维制成。DM具有足以担当正极活性材料(PAM)保留毡并防止PAM脱落的物理整体性。DM保护隔板免受强氧化剂(例如,Cr、Mn、Ti)影响。合适的DM(INV)的若干例子列于下表中,连同与常规玻璃毡(现有技术)的比较。
在电池中使用时,将隔板放置在电池中,以便DM面对电池的正电极(或板)或与之接触。在一个实施方案中,隔板可包封负极和/或正极板。在另一实施方案中,隔板可包封负极板。
表
1由Johns-Manville市售的DURAGLASSB-20(20密耳厚的标准玻璃毡)。
微孔膜可以由以下材料制成:聚烯烃(例如,聚乙烯、聚丙烯、超高分子量聚乙烯(UHMWPE)以及它们的组合)、聚氯乙烯(PVC)、酚醛树脂(包括例如浸有酚醛树脂的纤维素和/或合成纤维)、交联橡胶或非织造物(例如,惰性纤维,包括纤维素纤维或玻璃纤维)的片材。在一个实施方案中,微孔膜可由聚乙烯、UHWMPE或这两者的组合制成,并且可包括粒状填料,如已知的那样。微孔膜可具有带肋的外形。肋可以是常规的,例如在对着正电极的那侧上按机器方向(MD)延展(例如,以(除了其它方面外)将隔板与正电极分开,并形成在处于过充电条件期间允许气体逸出及促进混合的气体通道),但肋也可以在对着负电极的那侧上按机器横方向(CMD)延伸(以阻止酸分层)。
在本发明的另一方面中,可以对隔板添加橡胶以解决由污染物引起的氧化问题。如本文所用的橡胶是指橡胶乳胶、轮胎屑以及它们的组合。在一个实施方案中,橡胶可以是未交联或未固化的橡胶。在另一实施方案中,橡胶乳胶可以是天然或合成的橡胶乳胶。在另一实施方案中,橡胶可以是天然橡胶乳胶。在又一实施方案中,橡胶可以是轮胎屑。天然橡胶可以包括例如任意等级(例如,乳胶等级),如皱纹烟化胶片、白绉胶和浅色绉胶、纯毡绉胶或再炼胶、厚褐绉胶或琥珀及平树皮绉胶。天然橡胶可包括三叶橡胶。合成橡胶可包括例如甲基橡胶、聚丁二烯、氯丁二烯(chloropene)橡胶和共聚物橡胶。共聚物橡胶可包括例如苯乙烯/丁二烯橡胶、丙烯腈/丁二烯橡胶、乙烯/丙烯橡胶(ELM和PERM)及乙烯/乙酸乙烯酯橡胶。其它橡胶可包括例如丁基橡胶、溴化丁基橡胶、聚氨酯橡胶、环氧氯丙烷橡胶、聚硫橡胶、氯磺酰聚乙烯、聚降冰片烯橡胶、丙烯酸酯橡胶、氟化橡胶、异戊二烯橡胶和硅酮橡胶。可以单独或按各种组合的方式使用这些橡胶。
在一个实施方案中,可以使橡胶浸到微孔膜里。如本文所用的浸意指橡胶是被掺入到隔板的主体里的,而非形成到隔板上面的层。所以,可以将橡胶混合或共混到用来形成隔板的一种或多种材料里。橡胶(例如乳胶)在挤出后仍然是化学活性的(即,未固化和/或未交联)。因此,橡胶是与隔板的材料一体或分布在其内或在其所有各处均匀共混或紧密共混在其中的组分。
如上所述的橡胶可占微孔膜的任意部分。在一个实施方案中,当将橡胶添加到配方中时,按微孔膜的重量计其可占不超过约12%(即,按挤出前原材料的“重量”计)。在另一实施方案中,按微孔膜的重量计橡胶可占约1-12%。在另一实施方案中,按微孔膜的重量计橡胶可占约1.2-6%。在又一实施方案中,按微孔膜的重量计橡胶可占约2-4%。在又另一实施方案中,按微孔膜的重量计橡胶可占约2.5-3.5%。在另一实施方案中,按微孔膜的重量计橡胶可占约3%。
可以按任意常规的方式来制成微孔膜。例如,在PE微孔膜中,可以在挤出期间使橡胶与加工油混合并与PE混合。
实施例
图(图表)1-5是带有扩散毡(DM)的本发明隔板与带有常规玻璃毡的隔板的比较。隔板是相当的,但一个隔板具有DM,而另外的具有常规的玻璃毡。这些图表中给出的信息是采用常规逆变器电池模拟产生的,使用的是12V 150Ah电池(放电深度DoD≈100%),正极板被包封(图1-2)或负极板被包封(图3-5),并且在10.50V下以43A放电1小时54分钟,接下来在13.80V下以15A的限流再充电10小时6分钟。
可以其它形式实施本发明而不偏离其实质及基本属性,并且因此应当参考所附的权利要求而不是前述说明书来指示本发明的范围。
Claims (10)
1.一种用于铅酸电池的电池隔板,其包括:
微孔膜和附于其上的扩散毡,所述微孔膜包含聚烯烃、聚氯乙烯或酚醛树脂制成的微孔片,所述微孔膜浸渍有未固化的橡胶;所述未固化的橡胶被掺入到隔板的主体里的,而非形成到隔板上面的层;
所述扩散毡不是常规的玻璃毡,所述扩散毡的三小时芯吸为2.5-10.0cm,所述扩散毡的基重大于35gsm,所述铅酸电池至少18个循环的放电持续时间大于1.5小时。
2.如权利要求1所述的隔板,其中,所述扩散毡具有大于90mN的MD刚度和/或大于45mN的CMD刚度。
3.如权利要求1所述的隔板,其中,所述扩散毡由玻璃纤维、合成纤维、天然纤维或它们的组合制成。
4.如权利要求1所述的隔板,其中,所述扩散毡包括二氧化硅。
5.如权利要求1所述的隔板,其中,按所述隔板的重量计所述橡胶占不超过12%;或者,按所述隔板的重量计所述橡胶占不超过2.5-3.5%。
6.如权利要求1所述的隔板,适合于降低由污染物引起的酸分层和/或隔板氧化。
7.一种电池,包括如权利要求1所述的隔板。
8.一种用于铅酸电池的电池隔板,其包括如权利要求1所述的电池隔板,该电池隔板包封电池的正极板。
9.一种用于铅酸电池的电池隔板,其包括如权利要求1所述的电池隔板,该电池隔板包封电池的负极板。
10.一种用于铅酸电池的电池隔板,其包括:
微孔膜,所述微孔膜包含:
聚烯烃、聚氯乙烯或酚醛树脂制成的微孔片,所述微孔膜浸渍有未固化的橡胶,所述未固化的橡胶被掺入到隔板的主体里的,而非形成到隔板上面的层;和
附于其上的扩散毡;
所述扩散毡的三小时芯吸为2.5-10.0cm,所述扩散毡的基重大于35gsm,所述铅酸电池至少18个循环的放电持续时间大于1.5小时,
所述扩散毡不是常规的玻璃毡,常规的玻璃毡是被动性的,并且没有扩散或芯吸能力,比起常规的湿式或干式玻璃毡,所述扩散毡具有芯吸25倍或更多的能力,芯吸速率与酸分层是反比的关系;
所述扩散毡是由纤维制成的非织造或织造或编织织物,由玻璃纤维、合成纤维、天然纤维或它们的组合制成。
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- 2014-03-07 KR KR1020157027483A patent/KR20150126903A/ko active Application Filing
- 2014-03-07 US US14/200,066 patent/US20140255752A1/en active Pending
- 2014-03-07 CN CN201480012624.3A patent/CN105378974A/zh active Pending
- 2014-03-07 JP JP2015561689A patent/JP2016513861A/ja active Pending
- 2014-03-07 KR KR1020217010226A patent/KR20210041128A/ko not_active IP Right Cessation
- 2014-03-07 BR BR112015021454-1A patent/BR112015021454B1/pt active IP Right Grant
- 2014-03-07 KR KR1020227017232A patent/KR20220071298A/ko not_active IP Right Cessation
- 2014-03-07 EP EP14760775.8A patent/EP2965368A4/en active Pending
- 2014-03-07 WO PCT/US2014/021480 patent/WO2014138509A1/en active Application Filing
-
2015
- 2015-09-03 PH PH12015501950A patent/PH12015501950B1/en unknown
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2016
- 2016-11-29 US US15/363,591 patent/US20170077479A1/en active Pending
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2020
- 2020-05-07 JP JP2020081986A patent/JP7219244B2/ja active Active
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2021
- 2021-08-27 US US17/458,921 patent/US20210399385A1/en active Pending
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EP2965368A4 (en) | 2016-11-30 |
KR20220071298A (ko) | 2022-05-31 |
US20140255752A1 (en) | 2014-09-11 |
KR20210041128A (ko) | 2021-04-14 |
JP7219244B2 (ja) | 2023-02-07 |
PH12015501950A1 (en) | 2016-01-11 |
BR112015021454B1 (pt) | 2021-11-23 |
BR112015021454A2 (pt) | 2017-07-18 |
JP2020115490A (ja) | 2020-07-30 |
US20210399385A1 (en) | 2021-12-23 |
CN105378974A (zh) | 2016-03-02 |
JP2023052625A (ja) | 2023-04-11 |
EP2965368A1 (en) | 2016-01-13 |
PH12015501950B1 (en) | 2016-01-11 |
WO2014138509A1 (en) | 2014-09-12 |
KR20150126903A (ko) | 2015-11-13 |
CN108448038A (zh) | 2018-08-24 |
KR20230152786A (ko) | 2023-11-03 |
JP2016513861A (ja) | 2016-05-16 |
US20170077479A1 (en) | 2017-03-16 |
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