CN105264694B - 一种给锂‑硫电池单元充电的方法 - Google Patents
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- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
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- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
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Abstract
一种用于给锂‑硫电池单元充电的方法,所述方法包括:确定在充放电周期n期间电池单元的放电容量Qn,计算a·Qn的值,其中a=1.05到1.4,以及在后续的充放电周期n+x中,将电池单元充电至容量Qn+x,其中,Qn+x等于a·Qn,x为1到5的整数。
Description
技术领域
本发明涉及一种给锂-硫电池充电的方法。本发明还涉及一种用于给锂-硫电池充电的电池管理系统。
背景技术
锂-硫电池单元通常包括由锂金属或者锂金属合金形成的阳极(负电极)以及由元素硫或者其它电活性硫材料形成的阴极(正电极)。硫或者其它电活性含硫材料可以与诸如碳之类的导电材料混合以提高硫或者其它电活性含硫材料的导电性。通常,将碳和硫研磨并且然后与溶剂和粘合剂混合以形成浆液。将该浆液涂抹到集电器(current collector)并使其干燥以除去溶剂。将得到的结构进行压延以形成复合结构,该复合结构被切割成期望的形状以形成阴极。在阴极上放置隔膜,并且在该隔膜上放置锂阳极。然后将电解质导入到组装的电池单元中以浸湿阴极和隔膜。
锂-硫电池单元是二次电池单元,并且可以通过将外部电流施加到电池单元来再次充电。通常,将电池单元充电至固定的截止电压,例如2.45-2.8V。然而,随着长时间的重复循环,电池单元的容量会衰减。因此,通过反复地将电池单元充电至选定的截止电压,最终电池单元会被反复地过充电。由于不期望的化学反应可能导致对例如电池单元的电极和/或电解质的损害,因此反复地过充电会对电池单元的寿命具有不利的影响。
在WO 2007/111988中描述了用于终止锂-硫电池单元的充电的方法。具体地,该参考文献描述了将诸如硝酸锂之类的N-O添加剂添加到电池单元的电解质中。根据该参考文献第16页第29到31行处的段落,添加剂有效地在完全充电时提供电压的急剧上升的充电曲线。因此,如果在充电期间对电池单元电压进行监测,则一旦观察到电压的快速上升就可以停止充电。
WO 2007/111988的方法依赖于当电池单元达到满容量时电池单元的电压急剧上升。然而,不是所有的锂-硫电池单元都呈现出这样的充电曲线分布。
发明内容
根据本发明,提供一种给锂-硫电化电池单元充电的方法,所述方法包括:
确定在充放电周期n期间电池单元的放电容量Qn,
计算a·Qn的值,其中a=1.1到1.3,以及
在后续的充放电周期n+x中,将电池单元充电至容量Qn+x,其中Qn+x等于a·Qn,x为1到5的整数。
优选地,x等于1、2或3,更优选地,x等于1或2,最优选地,x等于1。因此,在一优选实施例中,电池单元被充电至根据前一周期的放电容量来确定的容量。
优选地,a是选自1.1到1.2的值。
在一优选实施例中,x等于1或2,优选等于1,并且a为1.1到1.2。
在本发明的方法中,根据较早的(优选地前一)周期的放电容量来确定电池单元的充电容量。由于对电池单元的放电容量进行监测,因此电池单元可以被充电至取决于电池单元所经历的充放电周期的数量的水平。这样,可以以这种方式给电池单元充电以避免或者降低由于容量衰减而造成的过充电的风险。通过降低过充电的风险,容量衰减的风险也可以被降低。有利地,这可以提高整个电池单元的寿命。这与给锂硫电池单元充电的传统方法形成了鲜明对比,在传统方法中,不管电池单元已经经历了何种程度的容量衰减,电池都被充电至预定的电压或者容量。
在一个实施例中,从电池单元的第一放电周期起应用本发明的方法。换句话说,放电容量Qn为电池单元的寿命中首次放电容量(Qbol)。在一替代实施例中,在电池单元已经被充电了不止一次之后应用本发明的方法。在一个实施例中,可以在观察到容量衰减的迹象之后,例如,在电池单元的5个或更多个周期之后应用本方法。在一个实施例中,在电池单元的10个或更多个周期之后应用本发明的方法。在实施本发明的方法之前,可以使用不同的方法来给电池单元充电,例如,使用恒定电流将电池单元充电至固定的、预定的电压。
在一个实施例中,所述方法还包括下述步骤:确定电池单元的阈值放电容量Qt。该阈值放电容量可以是电池单元的生命期中早期的周期期间电池单元的放电容量,例如,在观察到容量衰减的任何明显的迹象之前。这可以是第五周期或者更早的周期,例如第四、第三、第二或者第一周期时的放电容量。在一个实施例中,这可以是电池单元组装之后电池单元的第一个放电周期期间电池单元的容量(即,寿命中的首次放电容量Qbol,或者在第一周期的放电容量)。在一优选实施例中,阈值放电容量是电池单元在第一周期或者第二周期的放电容量。
一旦确定了阈值放电容量,则在后续的放电周期中对电池单元的放电容量Q进行监测。当电池单元的放电容量Qm降至低于0.8Qt(例如,低于0.7Qt或者低于0.6Qt)时,电池单元可以被充电至(i)b.Qt,其中b为1.05到1.3,或者充电至(ii)2.45V,取两者中较低者。在电池单元被充电至b·Qt的情况下,b优选地为1.1到1.2,更优选地为大约1.1。通过根据上述的步骤(i)或者(ii)给电池单元充电,一旦电池单元的放电容量降至低于0.8Qt,就可以给电池单元给予充电补充,将比例较大的短链多硫化物转变成长链多硫化物。这可以降低由于电池单元的充电不足而造成的容量的后续损失率。
一旦根据上述的步骤(i)或者(ii)给电池单元充电,则后续的周期的放电容量是Qm+1。Qm+2周期的充电容量优选为a·Qm+1,其中a为1.1到1.3,优选为1.1到1.2。后续的周期的充电容量可以按这种方式基于前一周期的放电容量,直到电池单元的放电容量再一次降至低于0.8Qt(例如,低于0.7Qt或者低于0.6Qt)。此时,可以重复步骤(i)或者(ii)。
本发明还提供一种用于实现上述方法的电池管理系统。另一方面,本发明提供一种用于锂-硫电池的电池管理系统,所述系统包括:
用于确定在充放电周期(n)期间电池单元的放电容量Qn的装置,
用于计算a·Qn的值的装置,其中a=1.1到1.3,以及
用于在后续的充放电周期n+x中将电池单元充电至容量Qn+x的装置,其中,Qn+x等于a·Qn,x为1到5的整数。
该系统还可以包括用于将该系统耦接到锂-硫电池的装置。在一个实施例中,该系统包括锂-硫电池。
在一优选实施例中,通过以恒定电流进行供电来给锂-硫电池单元充电。可以提供该电流,以便在从30分钟到12小时,优选地8到10小时的时间范围内给电池单元充电。可以在从0.1到3mA/cm2,优选地0.1到0.3mA/cm2的电流密度范围下提供该电流。作为以恒定电流进行充电的替代方案,还可以将锂-硫电池单元充电至恒定电压直到达到相关容量。适合的电压范围从2.35V到2.8V。
电化电池单元可以是任何适合的锂-硫电池单元。该电池单元通常包括阳极、阴极和电解质。有利地,可以将多孔隔膜放置在阳极与阴极之间。阳极可以由锂金属或者锂金属合金构成。优选地,阳极是金属箔电极,例如锂箔电极。锂箔可以由锂金属或者锂金属合金构成。
电化电池单元的阴极包括电活性硫材料与导电材料的混合物。该混合物形成电活性层,该电活性层可以被放置成与集电器接触。
可以将电活性硫材料与导电材料的混合物以溶剂(例如,水或者有机溶剂)中浆液的形式涂抹到集电器。然后可以除去该溶剂,并且得到的结构经压延形成复合结构,该复合结构被切割成期望的形状以形成阴极。可以在阴极上放置隔膜并且在隔膜上放置锂阳极。然后可以将电解质导入到组装的电池单元中以浸湿阴极和隔膜。
电活性硫材料可以包括元素硫、基于硫的有机化合物、基于硫的无机化合物和含硫聚合物。优选地,使用元素硫。
固体导电材料可以是任何适合的传导材料。优选地,该固体导电材料可以由碳制成。示例包括碳黑、碳纤维和碳纳米管。其他适合的材料包括金属(例如,薄片、锉屑和粉末)和导电聚合物。优选地,采用碳黑。
电活性硫材料(例如,元素硫)与导电材料(例如,碳)的重量比可以是1:1到30:1;优选地2:1到8:1,更优选地5:1到7:1。
电活性硫材料与导电材料的混合物可以是颗粒混合物。该混合物可以具有50nm到20μm,优选地100nm到5μm的平均粒度。
电活性硫材料与导电材料的混合物(即,电活性层)可以可选地包括粘合剂。适合的粘合剂可以由以下各项中的至少一种制成:例如,聚氧化乙烯、聚四氟乙烯、聚偏二氟乙烯、三元乙丙橡胶、甲基丙烯酸酯(例如,UV固化甲基丙烯酸酯)以及二乙烯基酯(例如,热固化二乙烯基酯)。
如上所述,电化电池单元的阴极还可以包括与电活性硫材料和固体导电材料的混合物接触的集电器。例如,电活性硫材料和固体导电材料的混合物沉积在集电器上。隔膜也设置在电化电池单元的阳极与阴极之间。例如,隔膜可以与电活性硫材料和固体导电材料的混合物接触,该电活性硫材料和固体导电材料的混合物又与集电器接触。
适合的集电器包括金属衬底,例如箔、由金属或者金属合金制成的片状物或者网状物。在一优选实施例中,集电器是铝箔。
隔膜可以是允许离子在电池单元的电极之间移动的任何适合的多孔衬底。衬底的孔隙率应该至少是30%,优选地至少50%,例如,60%以上。适合的隔膜包括由聚合材料制成的网状物。适合的聚合物包括聚丙烯、尼龙和聚乙烯。特别优选非织造聚丙烯。可以采用多层式隔膜。
优选地,电解质包括至少一种锂盐和至少一种有机溶剂。适合的锂盐包括下述各项中的至少一种:六氟磷酸锂(LiPF6)、六氟砷酸锂(LiAsF6)、高氯酸锂(LiClO4)、三氟甲基磺酰亚胺锂(LiN(CF3SO2)2)、四氟硼酸锂以及三氟甲烷磺酸锂(CF3SO3Li)。优选地,锂盐是三氟甲烷磺酸锂。
适合的有机溶剂有:四氢呋喃、2-甲基四氢呋喃、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、甲基丙基丙酸酯、乙基丙基丙酸酯、乙酸甲酯、二甲氧基乙烷、1,3-二氧戊环(2-甲氧基乙醚)、四乙二醇二甲醚、碳酸亚乙酯、碳酸丙烯酯、γ-丁内酯、二氧戊环、六甲基磷酰胺、吡啶、二甲基亚砜、磷酸三丁酯、磷酸三甲酯、N,N,N,N-四乙基磺酰胺以及砜及其混合物。优选地,有机溶剂为砜或者砜的混合物。砜的示例有二甲基砜和环丁砜。环丁砜可以用作单一溶剂或者可以例如与其他砜类结合。
用在电解质中的有机溶剂应该能够使诸如分子式Sn 2-之类的多硫化物物质溶解,其中n=2到12,该多硫化物物质形成于在电池单元放电期间电活性硫材料减少时。
电解质中锂盐的浓度优选为0.1到5M,更优选为0.5到3M,例如,1M。锂盐优选地以至少70%、优选至少80%、更优选至少90%、例如95%-99%的饱和度的浓度存在。
在一个实施例中,电解质包括三氟甲烷磺酸锂和环丁砜。
电解质与电活性硫材料和导电材料的总量的重量比是1-15:1;优选是2-9:1、更优选是6-8:1。
比较例1
在该示例中,锂-硫电池单元经过200+个周期被充电至固定的电压。图1示出了在电池单元的使用寿命内的充电和放电容量曲线。如可以从图中看出的那样,随着周期寿命增加,容量衰减。
示例2
在该示例中,锂-硫电池单元被充电至固定的电压,直到在周期15结束时观察到容量衰减的最初迹象。确定周期15的放电容量Q15,并且在周期16,将电池单元充电至等于a·Q15的容量,其中a=1.10。然后确定周期16的放电容量Q16,并且在周期17,将电池单元充电至a·Q16,以此类推。如可以从图2中看出的那样,通过使用该充电方法,降低了容量衰减率。
Claims (7)
1.一种用于给锂-硫电池单元充电的方法,所述方法包括:
确定在充放电周期n期间所述电池单元的放电容量Qn,
计算a·Qn的值,其中a=1.05到1.4,以及
在后续的充放电周期n+x中,将所述电池单元充电至容量Qn+x,其中,Qn+x等于a·Qn,x为1到5的整数,
其特征在于,所述方法还包括:
确定所述电池单元的阈值放电容量Qt,其中,所述阈值放电容量是第五周期或者更早周期时的放电容量,以及
当所述电池单元的放电容量Qm降至低于0.8Qt时,将所述电池单元充电至(i)b·Qt,其中b为1.05到1.3,或者充电至(ii)2.45V,取两者中较低者。
2.根据权利要求1所述的方法,其中,x为选自1、2或3的整数。
3.根据权利要求2所述的方法,其中,x为1。
4.根据前述权利要求中任一项所述的方法,其中,a为选自1.1到1.3的值。
5.根据权利要求4所述的方法,其中,a选自1.1到1.2。
6.根据权利要求1所述的方法,其中,所述电池单元的阈值容量为所述电池单元的第一个放电周期期间的容量。
7.根据权利要求1所述的方法,其中,b为1.1到1.2。
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