電解液不足對電池有什么危害?
電解液注液量的“略少、少、嚴重少”這是一般說法,沒有嚴格要求。電解液即使是略少,電池也(ye)已經是不(bu)良品(pin)了(le)。電(dian)解液略少(shao)(shao)的電(dian)芯(xin),不(bu)容易(yi)被(bei)發(fa)現,這個時候,電(dian)芯(xin)的容量(liang)和內阻都是正常的,檢測(ce)出電(dian)解液略少(shao)(shao)電(dian)芯(xin)有三類方(fang)法:拆電(dian)芯(xin)、稱(cheng)重、測(ce)試(shi)。
拆電(dian)芯:此(ci)時滿充(chong)負極(ji)會出現類似于下面圖(tu)片的樣(yang)子:
拆開屬(shu)于破(po)壞性試驗且一(yi)次(ci)只能檢測(ce)一(yi)個電(dian)芯,雖然可(ke)以直觀和準(zhun)確的確定(ding)問題,但實(shi)際用(yong)(yong)此方法篩選電(dian)芯的基本不用(yong)(yong)。
稱重:這(zhe)一(yi)方(fang)法準確(que)性較低,因(yin)為極片、鋁(lv)塑膜(mo)等也(ye)會有重量(liang)(liang)差異;電(dian)(dian)(dian)解(jie)液(ye)既然是“略(lve)少”,那么實際每個(ge)電(dian)(dian)(dian)芯(xin)(xin)的(de)保液(ye)量(liang)(liang)也(ye)就不(bu)會差距很(hen)大(da),這(zhe)樣其他材料的(de)重量(liang)(liang)差異,很(hen)可能大(da)于電(dian)(dian)(dian)解(jie)液(ye)重量(liang)(liang)的(de)差異。當然,可以通過注液(ye)時(shi)實測(ce)每個(ge)電(dian)(dian)(dian)芯(xin)(xin)的(de)注液(ye)量(liang)(liang)或者保液(ye)量(liang)(liang)來(lai)準確(que)的(de)、及時(shi)的(de)得知問題電(dian)(dian)(dian)芯(xin)(xin),但(dan)是與其對全電(dian)(dian)(dian)芯(xin)(xin)稱重,不(bu)如增加注液(ye)設(she)備的(de)準確(que)性和優化工藝,從(cong)而治(zhi)(zhi)標(biao)治(zhi)(zhi)本(ben)。
測試:這個是問題的重點,用何種測試方法能夠篩選出電解液“略少”的電芯,等價于電解液“略少”的電芯會有何種異常。目前(qian)文武僅知道兩種方法(fa)可(ke)以測出容量、內(nei)阻皆正常的,但是電解液卻(que)略少的電芯。這(zhe)兩個(ge)方法(fa)分別是:循環、倍(bei)率放(fang)電平臺。
循環(huan)(huan)(huan),可以(yi)(yi)說(shuo)(shuo)是(shi)(shi)檢(jian)查(cha)鋰離子(zi)(zi)電(dian)(dian)(dian)池(chi)電(dian)(dian)(dian)性能的(de)(de)(de)(de)(de)(de)(de)(de)終極(ji)方法,縱(zong)觀鋰離子(zi)(zi)電(dian)(dian)(dian)池(chi)材料和制成時的(de)(de)(de)(de)(de)(de)(de)(de)近乎無(wu)數(shu)種的(de)(de)(de)(de)(de)(de)(de)(de)異常,絕大(da)多數(shu)的(de)(de)(de)(de)(de)(de)(de)(de)最終影響都是(shi)(shi)兩個字(zi):循環(huan)(huan)(huan)。電(dian)(dian)(dian)解液(ye)(ye)(ye)略少(shao)(shao)(shao)時,容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)或是(shi)(shi)說(shuo)(shuo)正極(ji)克發(fa)揮是(shi)(shi)正常的(de)(de)(de)(de)(de)(de)(de)(de),前幾十次循環(huan)(huan)(huan)的(de)(de)(de)(de)(de)(de)(de)(de)話,容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)并(bing)不(bu)(bu)會(hui)(hui)明(ming)顯(xian)衰(shuai)減(jian);隨著電(dian)(dian)(dian)解液(ye)(ye)(ye)缺失(shi)的(de)(de)(de)(de)(de)(de)(de)(de)程(cheng)度的(de)(de)(de)(de)(de)(de)(de)(de)加重,能夠保(bao)持較高容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)保(bao)持率的(de)(de)(de)(de)(de)(de)(de)(de)循環(huan)(huan)(huan)次數(shu)會(hui)(hui)逐漸減(jian)少(shao)(shao)(shao);或者(zhe)說(shuo)(shuo),電(dian)(dian)(dian)解液(ye)(ye)(ye)“略少(shao)(shao)(shao)”中(zhong)電(dian)(dian)(dian)解液(ye)(ye)(ye)相對較多的(de)(de)(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)芯(xin),可能會(hui)(hui)以(yi)(yi)正常容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)衰(shuai)減(jian)速率循環(huan)(huan)(huan)幾十次甚至上百次才會(hui)(hui)明(ming)顯(xian)衰(shuai)減(jian);電(dian)(dian)(dian)解液(ye)(ye)(ye)“略少(shao)(shao)(shao)”中(zhong)電(dian)(dian)(dian)解液(ye)(ye)(ye)相對較少(shao)(shao)(shao)的(de)(de)(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)芯(xin),可能循環(huan)(huan)(huan)十次二(er)十次容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)就開始(shi)明(ming)顯(xian)跳水(shui)。但(dan)不(bu)(bu)論(lun)在容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)跳水(shui)前電(dian)(dian)(dian)芯(xin)能按正常容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)衰(shuai)減(jian)速度循環(huan)(huan)(huan)多少(shao)(shao)(shao)次,跳水(shui)開始(shi)后(hou)(hou),電(dian)(dian)(dian)芯(xin)的(de)(de)(de)(de)(de)(de)(de)(de)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)都會(hui)(hui)快(kuai)速衰(shuai)減(jian);衰(shuai)減(jian)過(guo)程(cheng)中(zhong),電(dian)(dian)(dian)芯(xin)的(de)(de)(de)(de)(de)(de)(de)(de)表現是(shi)(shi)能充(chong)入容(rong)(rong)(rong)(rong)(rong)量(liang)(liang),但(dan)是(shi)(shi)放出容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)較低(di)(很像氣(qi)(qi)數(shu)已盡的(de)(de)(de)(de)(de)(de)(de)(de)人“有(you)進氣(qi)(qi)兒沒(mei)出氣(qi)(qi)兒”的(de)(de)(de)(de)(de)(de)(de)(de)樣(yang)子(zi)(zi)哦(e)),如果做充(chong)電(dian)(dian)(dian)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)/放電(dian)(dian)(dian)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)圖的(de)(de)(de)(de)(de)(de)(de)(de)話,跳水(shui)期間(jian)二(er)者(zhe)的(de)(de)(de)(de)(de)(de)(de)(de)比(bi)值會(hui)(hui)明(ming)顯(xian)高于1;跳水(shui)之后(hou)(hou),電(dian)(dian)(dian)芯(xin)的(de)(de)(de)(de)(de)(de)(de)(de)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)并(bing)不(bu)(bu)會(hui)(hui)馬上降為0,而是(shi)(shi)相對穩定的(de)(de)(de)(de)(de)(de)(de)(de)維持在其初始(shi)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)的(de)(de)(de)(de)(de)(de)(de)(de)20%~40%中(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)位置一段時間(jian);再往后(hou)(hou),文(wen)武就沒(mei)有(you)測過(guo)了。以(yi)(yi)下是(shi)(shi)一個因電(dian)(dian)(dian)解液(ye)(ye)(ye)不(bu)(bu)足而容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)跳水(shui)的(de)(de)(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)芯(xin)的(de)(de)(de)(de)(de)(de)(de)(de)循環(huan)(huan)(huan)容(rong)(rong)(rong)(rong)(rong)量(liang)(liang)曲線和C/D曲線,
循(xun)(xun)(xun)環(huan)性(xing)能(neng)的(de)(de)(de)(de)(de)(de)(de)(de)降低,是(shi)電(dian)(dian)解(jie)(jie)液(ye)缺失的(de)(de)(de)(de)(de)(de)(de)(de)一個必然結果,只(zhi)要電(dian)(dian)解(jie)(jie)液(ye)的(de)(de)(de)(de)(de)(de)(de)(de)量(liang)足夠維持(chi)電(dian)(dian)芯(xin)(xin)循(xun)(xun)(xun)環(huan)到規格書中規定的(de)(de)(de)(de)(de)(de)(de)(de)循(xun)(xun)(xun)環(huan)次數,就(jiu)可(ke)以認為(wei)(wei)電(dian)(dian)解(jie)(jie)液(ye)是(shi)充足的(de)(de)(de)(de)(de)(de)(de)(de)。但(dan)(dan)(dan)是(shi),循(xun)(xun)(xun)環(huan)性(xing)能(neng)無法作(zuo)為(wei)(wei)篩選電(dian)(dian)解(jie)(jie)液(ye)量(liang)少的(de)(de)(de)(de)(de)(de)(de)(de)電(dian)(dian)芯(xin)(xin)的(de)(de)(de)(de)(de)(de)(de)(de)手段,原因很簡單(dan),不(bu)再多說(shuo)。倍(bei)(bei)率(lv)放電(dian)(dian)平(ping)臺,這里所說(shuo)的(de)(de)(de)(de)(de)(de)(de)(de)平(ping)臺,一定要是(shi)相對較高(gao)倍(bei)(bei)率(lv)的(de)(de)(de)(de)(de)(de)(de)(de)平(ping)臺,0.2C/0.5C是(shi)看(kan)不(bu)出來差異的(de)(de)(de)(de)(de)(de)(de)(de)。文武比(bi)較了同設計下,實際平(ping)均保液(ye)量(liang)分(fen)別為(wei)(wei)0.002g/mAh和(he)0.0023g/mAh兩批電(dian)(dian)芯(xin)(xin)的(de)(de)(de)(de)(de)(de)(de)(de)0.5C/3.6V、1C/3.6V和(he)2C/3.4V的(de)(de)(de)(de)(de)(de)(de)(de)平(ping)臺容量(liang),二(er)者0.5C平(ping)臺幾乎一致,但(dan)(dan)(dan)電(dian)(dian)解(jie)(jie)液(ye)充足的(de)(de)(de)(de)(de)(de)(de)(de)第二(er)組1C和(he)2C平(ping)臺容量(liang)要高(gao)于電(dian)(dian)解(jie)(jie)液(ye)不(bu)足的(de)(de)(de)(de)(de)(de)(de)(de)第一組約8%(文武做的(de)(de)(de)(de)(de)(de)(de)(de)是(shi)容量(liang)型卷繞軟包(bao)電(dian)(dian)芯(xin)(xin),倍(bei)(bei)率(lv)型或者疊片(pian)電(dian)(dian)芯(xin)(xin)所用(yong)測(ce)試倍(bei)(bei)率(lv)肯定要再高(gao)才可(ke)以)。與全檢稱(cheng)重、測(ce)循(xun)(xun)(xun)環(huan)、拆電(dian)(dian)芯(xin)(xin)相比(bi),用(yong)高(gao)倍(bei)(bei)率(lv)放電(dian)(dian)對比(bi)平(ping)臺容量(liang)這一方(fang)法預(yu)測(ce)電(dian)(dian)解(jie)(jie)液(ye)略少的(de)(de)(de)(de)(de)(de)(de)(de)電(dian)(dian)芯(xin)(xin),可(ke)行性(xing)顯然更大。但(dan)(dan)(dan)問(wen)題是(shi),對于制成較差的(de)(de)(de)(de)(de)(de)(de)(de)廠子,高(gao)倍(bei)(bei)率(lv)下,電(dian)(dian)芯(xin)(xin)平(ping)臺容量(liang)本(ben)身就(jiu)可(ke)能(neng)相差很多,這樣的(de)(de)(de)(de)(de)(de)(de)(de)話定標準是(shi)很難的(de)(de)(de)(de)(de)(de)(de)(de)。
對(dui)于(yu)電(dian)(dian)解(jie)液“略(lve)少(shao)”的電(dian)(dian)芯,由于(yu)正極(ji)克(ke)發(fa)(fa)(fa)揮(hui)還是足夠的(克(ke)發(fa)(fa)(fa)揮(hui)不足,在本文叫做“嚴重少(shao)”),因(yin)而最開(kai)始極(ji)片(pian)可(ke)能僅是比較干,但(dan)是還沒(mei)有析鋰。但(dan)隨(sui)著循(xun)環的進行(xing),析鋰會越(yue)來越(yue)嚴重。“少(shao)”時的情況與(yu)“略(lve)少(shao)”相比,“少(shao)”的時候,問題就(jiu)要簡單的多了。依照(zhao)文武的定義來說,當電(dian)(dian)解(jie)液少(shao)到讓電(dian)(dian)芯高(gao)內阻的時候,就(jiu)可(ke)以稱(cheng)呼為“少(shao)”了。這個時候,電(dian)(dian)芯的正極(ji)克(ke)發(fa)(fa)(fa)揮(hui)依舊是正常(chang)的,但(dan)是循(xun)環、倍率平臺容量(liang)都要明顯的差(cha)于(yu)“略(lve)少(shao)”的情況。
平臺容量低,即使是0.2C的平臺容量,也要明顯低于內阻正常的電芯,更不用說高倍率平臺容量了。
無(wu)法完成循環,這(zhe)是對實際(ji)現象(xiang)的描述,當測過這(zhe)幾個高內阻電(dian)(dian)芯(xin)(xin)的倍率后(hou),將電(dian)(dian)芯(xin)(xin)擱置了幾天,然后(hou)有了空(kong)余測試通(tong)(tong)道(dao)(dao)準備測1C循環,上(shang)下限(xian)保(bao)護(hu)電(dian)(dian)壓(ya)分別為(wei)4.5V和2.5V,這(zhe)時發現,不論是充電(dian)(dian)還是放電(dian)(dian),通(tong)(tong)道(dao)(dao)都會馬上(shang)進入保(bao)護(hu)(這(zhe)種析鋰電(dian)(dian)芯(xin)(xin),此時處于高電(dian)(dian)壓(ya)狀態)。更換通(tong)(tong)道(dao)(dao)也沒有改善,測了一下電(dian)(dian)芯(xin)(xin)的重量,發現比正常電(dian)(dian)芯(xin)(xin)低0.5~1g,室外拆開電(dian)(dian)芯(xin)(xin),全部(bu)起火!
由于電解液“少”的電芯,內阻已然偏高,而內阻基本是所有電池廠都會關注的參數,所以篩選出電解液“少”的電芯,并不難。需要再一次強調的是,電解液“少”的電芯,會遇到電解液“略少”的電芯的一切問題,同時也會增加一個問題:內阻偏高。“嚴重少”的情況拋開一切不看,電解液“嚴重少”時,最為明顯的結果就是:低容。電芯的內阻往往是由電芯廠制定的,一般的話,偶有高內阻也可能出貨,但是容量不足的話,可就完全沒有補救的可能性了。
處于“嚴重(zhong)少”的電(dian)(dian)芯(xin),克發揮、內阻、平臺、循環(huan)等(deng)問題,將會一起(qi)爆發。當看到電(dian)(dian)芯(xin)低容且高(gao)內阻時,就(jiu)很有(you)可能是電(dian)(dian)解(jie)液(ye)“嚴重(zhong)少”的情況;如果再與正常電(dian)(dian)芯(xin)對比(bi)一下(xia)重(zhong)量,則可以幾(ji)乎確(que)認問題所在。此時,就(jiu)不要拆(chai)電(dian)(dian)芯(xin)了,起(qi)火的可能性非常大。
如果將電(dian)芯分開來看(kan)的(de)(de)話,電(dian)解(jie)液(ye)(ye)“嚴(yan)重(zhong)少(shao)”時(shi)還可(ke)以分為正(zheng)極(ji)(ji)吸(xi)液(ye)(ye)不(bu)足(zu)和負(fu)(fu)極(ji)(ji)吸(xi)液(ye)(ye)不(bu)足(zu)這兩個方(fang)面(mian)來看(kan)。當正(zheng)極(ji)(ji)吸(xi)液(ye)(ye)不(bu)足(zu)時(shi),沒(mei)有足(zu)夠(gou)的(de)(de)鋰(li)(li)離(li)(li)子能(neng)夠(gou)從正(zheng)極(ji)(ji)脫嵌,但(dan)是(shi)(shi)(shi)負(fu)(fu)極(ji)(ji)吸(xi)液(ye)(ye)充足(zu),只要是(shi)(shi)(shi)脫嵌的(de)(de)鋰(li)(li)離(li)(li)子,就可(ke)以嵌入負(fu)(fu)極(ji)(ji)。結果就是(shi)(shi)(shi)正(zheng)負(fu)(fu)極(ji)(ji)都(dou)很干,但(dan)是(shi)(shi)(shi)負(fu)(fu)極(ji)(ji)并沒(mei)有析鋰(li)(li)。當負(fu)(fu)極(ji)(ji)吸(xi)液(ye)(ye)不(bu)足(zu)、正(zheng)極(ji)(ji)充足(zu)時(shi),正(zheng)極(ji)(ji)可(ke)以提供充足(zu)的(de)(de)鋰(li)(li)離(li)(li)子給負(fu)(fu)極(ji)(ji),但(dan)是(shi)(shi)(shi)負(fu)(fu)極(ji)(ji)沒(mei)有辦法接(jie)受,于(yu)是(shi)(shi)(shi)負(fu)(fu)極(ji)(ji)析鋰(li)(li)。但(dan)不(bu)論是(shi)(shi)(shi)哪(na)種情況,電(dian)芯的(de)(de)外在表現都(dou)是(shi)(shi)(shi):低容(rong)、高內阻、低平臺(tai)、低循(xun)環(huan)。電(dian)解(jie)液(ye)(ye)“嚴(yan)重(zhong)少(shao)”的(de)(de)電(dian)芯拿去做(zuo)循(xun)環(huan),十(shi)次就可(ke)能(neng)掉10%的(de)(de)容(rong)量(liang),且循(xun)環(huan)后由于(yu)嚴(yan)重(zhong)析鋰(li)(li),電(dian)芯會變得異常的(de)(de)厚(hou)。





