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锂电池电解质衰降原理

2022-10-18

锂电池

如果(guo)没有副反(fan)应的(de)(de)锂(li)电池(chi)电解(jie)液,锂(li)离子电池(chi)可以实现(xian)无限循环(huan)。然(ran)而,由于常(chang)规碳(tan)酸酯电解(jie)液不稳定的(de)(de)表(biao)面(mian)上的(de)(de)正电极和(he)负电极,电解(jie)质的(de)(de)分解(jie)表(biao)面(mian)上的(de)(de)正电极和(he)负电极在使用过程中,导致电池(chi)容(rong)量持续下降(jiang)。

研究较多的(de)(de)分(fen)(fen)解(jie)反响电(dian)(dian)(dian)解(jie)质表面(mian)上的(de)(de)正(zheng)电(dian)(dian)(dian)极和(he)负电(dian)(dian)(dian)极,但大部分(fen)(fen)的(de)(de)测试实验室(shi)条件下进行。重复充电(dian)(dian)(dian)和(he)放(fang)电(dian)(dian)(dian)的(de)(de)电(dian)(dian)(dian)池(chi)与固定周期(qi)系统引起的(de)(de)衰减的(de)(de)电(dian)(dian)(dian)池(chi),然后分(fen)(fen)析(xi)了(le)衰减机制的(de)(de)电(dian)(dian)(dian)池(chi);然而,在实际使用中,其工(gong)作状(zhuang)态(tai)的(de)(de)锂(li)离子(zi)电(dian)(dian)(dian)池(chi)要(yao)复杂(za)得多,例(li)如短期(qi)快(kuai)速(su)加速(su),快(kuai)速(su)充电(dian)(dian)(dian),长期(qi)搁置(zhi)等(deng)原因引起电(dian)(dian)(dian)解(jie)质的(de)(de)分(fen)(fen)解(jie)。

锂电池电解质衰减包含DMC、EMC等溶(rong)剂组分。这两种溶(rong)剂将(jiang)发生酯交换(huan)反应,这也是为什么我们(men)发现有少量DEC在(zai)大多(duo)数电解质 (0.3-1.3%)。

LiPF6电(dian)(dian)解(jie)(jie)(jie)(jie)液(ye)也将发生(sheng)分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie)反(fan)应。通常,我们认为,所分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie)的锂盐主要(yao)是由于(yu)电(dian)(dian)解(jie)(jie)(jie)(jie)质含有(you)(you)微量(liang)水分(fen)(fen)(fen)(fen)。一般来(lai)说,含水率在(zai)(zai)电(dian)(dian)解(jie)(jie)(jie)(jie)液(ye)商业化锂离子电(dian)(dian)池(chi)低于(yu)20mg/L,但含水量(liang)电(dian)(dian)池(chi)拆(chai)卸从电(dian)(dian)动汽车(che)远远高(gao)(gao)于(yu)这个值 (995,643,113 mg/dl和290 mg L-1)。LiPF6在(zai)(zai)水分(fen)(fen)(fen)(fen)作用下(xia)分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie)产生(sheng)的产物POF3,具有(you)(you)相对较高(gao)(gao)的反(fan)应活性(xing),所以POF3仅存在(zai)(zai)于(yu)部(bu)分(fen)(fen)(fen)(fen)的电(dian)(dian)解(jie)(jie)(jie)(jie)质,但POF3电(dian)(dian)解(jie)(jie)(jie)(jie)液(ye)中进一步(bu)分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie)成(cheng)(cheng)产品DFP。虽(sui)然DFP的分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie)产物的LiPF6,DFP实际上有(you)(you)助于(yu)形(xing)成(cheng)(cheng)更(geng)稳定的SEI膜,从而提(ti)高(gao)(gao)了循环电(dian)(dian)池(chi)的性(xing)能(neng)。在(zai)(zai)LiPF6分(fen)(fen)(fen)(fen)解(jie)(jie)(jie)(jie),少量(liang)HF也形(xing)成(cheng)(cheng),HF终(zhong)形(xing)成(cheng)(cheng)LiF在(zai)(zai)负电(dian)(dian)极,成(cheng)(cheng)为SEI膜的一部(bu)分(fen)(fen)(fen)(fen)。

在(zai)(zai)分解(jie)进(jin)程(cheng)中(zhong),LiPF6不仅会产生(sheng)上述分解(jie)产物,但也与电解(jie)质(zhi)(zhi)溶剂(ji)反(fan)应产生(sheng)二(er)氟磷酸(suan) (DMFP),二(er)氟磷酸(suan) (DEFP) 等分解(jie)产物的(de)(de)毒性相似有机(ji)磷毒剂(ji),有机(ji)磷毒剂(ji)可以进(jin)入人体皮肤,这意味着在(zai)(zai)动力电池(chi)拆解(jie)和再利用的(de)(de)过(guo)程(cheng)中(zhong)需要格外注意相关人员的(de)(de)防(fang)护,以避(bi)免(mian)过(guo)度与电解(jie)质(zhi)(zhi)接触(chu)。


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