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鋰電池電解質衰降原理

2022-10-18

鋰電池

如果沒有副反應的鋰電池電解液,鋰離子電池可以實現無限循環(huán)。然而,由于常規(guī)碳酸酯電解液不穩(wěn)定的表面上的正電極和負電極,電解質的分解表面上的正電極和負電極在使用過程中,導致電池容量持續(xù)下降。

研究較多的分解反響電解質表面上的正電極和負電極,但大部分的測試實驗室條件下進行。重復充電和放電的電池與固定周期系統引起的衰減的電池,然后分析了衰減機制的電池;然而,在實際使用中,其工作狀態(tài)的鋰離子電池要復雜得多,例如短期快速加速,快速充電,長期擱置等原因引起電解質的分解。

鋰電池電解質衰減包含DMC、EMC等溶劑組分。這兩種溶劑將發(fā)生酯交換反應,這也是為什么我們發(fā)現有少量DEC在大多數電解質 (0.3-1.3%)。

LiPF6電解液也將發(fā)生分解反應。通常,我們認為,所分解的鋰鹽主要是由于電解質含有微量水分。一般來說,含水率在電解液商業(yè)化鋰離子電池低于20mg/L,但含水量電池拆卸從電動汽車遠遠高于這個值 (995,643,113 mg/dl和290 mg L-1)。LiPF6在水分作用下分解產生的產物POF3,具有相對較高的反應活性,所以POF3僅存在于部分的電解質,但POF3電解液中進一步分解成產品DFP。雖然DFP的分解產物的LiPF6,DFP實際上有助于形成更穩(wěn)定的SEI膜,從而提高了循環(huán)電池的性能。在LiPF6分解,少量HF也形成,HF終形成LiF在負電極,成為SEI膜的一部分。

在分解進程中,LiPF6不僅會產生上述分解產物,但也與電解質溶劑反應產生二氟磷酸 (DMFP),二氟磷酸 (DEFP) 等分解產物的毒性相似有機磷毒劑,有機磷毒劑可以進入人體皮膚,這意味著在動力電池拆解和再利用的過程中需要格外注意相關人員的防護,以避免過度與電解質接觸。


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