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鋰電池的二次利用

正負極集流體,一般,正極用鋁箔,負極用銅箔,還可能焊一些鎳帶做連接導電用。這些基本沒有毒性。現在出現的一些廢舊鋰電池回(hui)收(shou)單位就是靠回(hui)收(shou)這些(xie)和鋼殼(ke)鋁殼(ke)掙(zheng)錢(qian)。標簽:可回(hui)收(shou)利用(yong),無污染。

負極一(yi)般是(shi)(shi)(shi)(shi)石(shi)(shi)(shi)墨(mo)(mo)(mo),少數可能是(shi)(shi)(shi)(shi)鈦(tai)酸鋰(li)或(huo)是(shi)(shi)(shi)(shi)硅基材(cai)料(liao),當然(ran)(ran)錫基負極也有,但(dan)是(shi)(shi)(shi)(shi)成本就有點高了(le)(le),現(xian)在沒人(ren)用。石(shi)(shi)(shi)墨(mo)(mo)(mo)分為天(tian)(tian)然(ran)(ran)石(shi)(shi)(shi)墨(mo)(mo)(mo)和人(ren)造石(shi)(shi)(shi)墨(mo)(mo)(mo),天(tian)(tian)然(ran)(ran)石(shi)(shi)(shi)墨(mo)(mo)(mo)來(lai)源(yuan)于石(shi)(shi)(shi)墨(mo)(mo)(mo)礦,然(ran)(ran)后(hou)再進(jin)行一(yi)些加工(gong),這個天(tian)(tian)然(ran)(ran)石(shi)(shi)(shi)墨(mo)(mo)(mo)的(de)(de)開(kai)采,污(wu)染(ran)(ran)還(huan)是(shi)(shi)(shi)(shi)比較嚴重(zhong)的(de)(de),主要是(shi)(shi)(shi)(shi)對呼吸道的(de)(de)損(sun)壞,大家(jia)可以(yi)搜一(yi)下;人(ren)造石(shi)(shi)(shi)墨(mo)(mo)(mo),是(shi)(shi)(shi)(shi)用石(shi)(shi)(shi)油焦或(huo)是(shi)(shi)(shi)(shi)瀝青(qing)等高分子物(wu)高溫石(shi)(shi)(shi)墨(mo)(mo)(mo)化制成,基本無(wu)(wu)污(wu)染(ran)(ran)。有一(yi)些鋰(li)電池中(zhong)(zhong)石(shi)(shi)(shi)墨(mo)(mo)(mo)浮(fu)選的(de)(de)回(hui)收(shou)方法(fa),但(dan)是(shi)(shi)(shi)(shi)不知道現(xian)在應(ying)用的(de)(de)怎么樣(yang)了(le)(le),肯定可以(yi)回(hui)收(shou)。鈦(tai)酸鋰(li)的(de)(de)生產流(liu)程不清(qing)楚(chu)。硅基負極基本無(wu)(wu)污(wu)染(ran)(ran)。按照用量最大的(de)(de)石(shi)(shi)(shi)墨(mo)(mo)(mo)進(jin)行評估。標(biao)簽:中(zhong)(zhong)度污(wu)染(ran)(ran),回(hui)收(shou)情況(kuang)不明。

正極:目前(qian)的(de)正極有磷酸(suan)(suan)(suan)鐵鋰(li)(li)、錳酸(suan)(suan)(suan)鋰(li)(li)、三元(yuan)材(cai)料(liao)、鈷(gu)(gu)(gu)酸(suan)(suan)(suan)鋰(li)(li)、鎳(nie)(nie)鈷(gu)(gu)(gu)鋁酸(suan)(suan)(suan)鋰(li)(li)。磷酸(suan)(suan)(suan)鐵鋰(li)(li),一(yi)般用(yong)作汽車(che)電池或是儲能電池,無(wu)毒(du)性(xing)。錳酸(suan)(suan)(suan)鋰(li)(li),電動自行車(che)電池,無(wu)毒(du)性(xing)。三元(yuan)材(cai)料(liao):鎳(nie)(nie)鈷(gu)(gu)(gu)錳酸(suan)(suan)(suan)鋰(li)(li),用(yong)途廣泛,電動自行車(che)、電子產品(pin)、航模(mo)等(deng),鈷(gu)(gu)(gu)元(yuan)素有毒(du)。鈷(gu)(gu)(gu)酸(suan)(suan)(suan)鋰(li)(li),數碼類的(de)產品(pin),手機、pad等(deng),中等(deng)毒(du)性(xing)。鎳(nie)(nie)鈷(gu)(gu)(gu)鋁酸(suan)(suan)(suan)鋰(li)(li):不(bu)明,猜測和鎳(nie)(nie)鈷(gu)(gu)(gu)錳酸(suan)(suan)(suan)鋰(li)(li)一(yi)樣(yang)。

鋰電池

電解(jie)液為有機(ji)溶(rong)劑(ji)(ji)和鋰鹽組成,有機(ji)溶(rong)劑(ji)(ji)一般有PC、EC、DEC、DMC、DME等,其中(zhong)DMC為微度,其他是(shi)無毒(du)。鋰鹽是(shi)六氟磷(lin)酸鋰(用的最多(duo),也(ye)有其他鋰鹽),遇水則(ze)水解(jie)生成HF,有毒(du)。外殼(ke)(ke)有幾大(da)類:鋁(lv)(lv)殼(ke)(ke)、鋼殼(ke)(ke)、塑(su)料(liao)殼(ke)(ke)、鋁(lv)(lv)塑(su)膜(mo)(mo)。其中(zhong)鋁(lv)(lv)殼(ke)(ke)、鋼殼(ke)(ke)無毒(du)。塑(su)料(liao)殼(ke)(ke)和鋁(lv)(lv)塑(su)膜(mo)(mo)則(ze)是(shi)白色(se)污染。隔膜(mo)(mo),一般是(shi)聚烯烴(jing)類的微孔薄膜(mo)(mo),PP、PE,白色(se)污染。

粘(zhan)結劑(ji)(ji),目(mu)(mu)前(qian)一(yi)(yi)般有(you)丁(ding)苯橡膠SBR、聚偏氟乙烯PVdF、還有(you)一(yi)(yi)些(xie)丙烯酸(suan)類的(de)(de)粘(zhan)結劑(ji)(ji)。這(zhe)些(xie)就當做是(shi)白色(se)污(wu)染(ran)吧。另外鋰(li)電(dian)(dian)(dian)加工過(guo)程(cheng)(cheng)中(zhong)(zhong)(zhong)使(shi)用到(dao)的(de)(de)物質主(zhu)要(yao)是(shi)NMP(微毒(du)),用作(zuo)是(shi)正負(fu)(fu)極的(de)(de)溶劑(ji)(ji),在制造過(guo)程(cheng)(cheng)中(zhong)(zhong)(zhong)蒸發掉,企業需要(yao)控(kong)制其(qi)排放量,并(bing)且回收。我(wo)認為,目(mu)(mu)前(qian)鋰(li)電(dian)(dian)(dian)存在的(de)(de)污(wu)染(ran)問題主(zhu)要(yao)有(you)三大類:第(di)一(yi)(yi)、生(sheng)產過(guo)程(cheng)(cheng)中(zhong)(zhong)(zhong)清洗正負(fu)(fu)極制漿的(de)(de)設備和涂布設備造成的(de)(de)污(wu)染(ran),這(zhe)兩個是(shi)包括正極負(fu)(fu)極材(cai)料(liao)、NMP、膠等物質,一(yi)(yi)些(xie)企業控(kong)制不(bu)好(惡意(yi)揣測(ce)不(bu)想控(kong)制)導致含毒(du)廢水(shui)(shui)(shui)泄露(lu)。第(di)一(yi)(yi)點一(yi)(yi)、生(sheng)產過(guo)程(cheng)(cheng)中(zhong)(zhong)(zhong)清洗注電(dian)(dian)(dian)解液時的(de)(de)用品,可(ke)能導致含電(dian)(dian)(dian)解液的(de)(de)水(shui)(shui)(shui)流(liu)入下(xia)水(shui)(shui)(shui)道。一(yi)(yi)般情(qing)況下(xia),技術研發人員(yuan)很(hen)可(ke)能將(jiang)水(shui)(shui)(shui)直接排入下(xia)水(shui)(shui)(shui)道。第(di)二、NMP回收不(bu)徹底。第(di)三、市場上(shang)流(liu)通的(de)(de)鋰(li)電(dian)(dian)(dian)池(chi)確(que)實很(hen)少(shao)有(you)回收的(de)(de),一(yi)(yi)是(shi)鋰(li)電(dian)(dian)(dian)本身(shen)污(wu)染(ran)小,大家重視程(cheng)(cheng)度不(bu)夠;二是(shi)、鋰(li)電(dian)(dian)(dian)回收收益低。

目(mu)前鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi),越來(lai)(lai)越貼近平民(min)生活(huo)了(le)(le),主(zhu)(zhu)要是手(shou)機(ji)數碼電(dian)(dian)(dian)(dian)子產(chan)品(pin)的(de)(de)普及(ji),鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)應用也逐(zhu)漸擴張到電(dian)(dian)(dian)(dian)動(dong)自(zi)行(xing)車(che)、混動(dong)轎車(che)等(deng),原先一(yi)些鉛(qian)酸(suan)電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)市(shi)場逐(zhu)漸被鋰(li)(li)電(dian)(dian)(dian)(dian)侵蝕,但(dan)不(bu)(bu)可(ke)能(neng)完全(quan)被取代。雖然家(jia)(jia)(jia)家(jia)(jia)(jia)戶戶都有(you)(you)(you)不(bu)(bu)少(shao)鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi)(廢(fei)棄(qi)手(shou)機(ji)電(dian)(dian)(dian)(dian)池(chi)(chi)等(deng)),但(dan)是其(qi)回(hui)(hui)收(shou)目(mu)前還(huan)局(ju)限在制造企(qi)業(ye)內部(bu),主(zhu)(zhu)要是正極(ji)(ji)材料鈷(gu)酸(suan)鋰(li)(li)、鎳鈷(gu)錳酸(suan)鋰(li)(li)中的(de)(de)貴金屬鈷(gu)鎳,負極(ji)(ji)石墨,集流體(ti)鋁、銅(超高(gao)純度),殼體(ti)等(deng)。就(jiu)好比大街小巷見到的(de)(de)廢(fei)品(pin)回(hui)(hui)收(shou)一(yi)樣,有(you)(you)(you)價(jia)值自(zi)然就(jiu)有(you)(you)(you)人回(hui)(hui)收(shou),但(dan)是這(zhe)其(qi)中的(de)(de)污染(ran)(ran)完全(quan)沒有(you)(you)(you)減少(shao)。目(mu)前鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi)為(wei)液體(ti)電(dian)(dian)(dian)(dian)解質(zhi)(zhi),即多種有(you)(you)(you)機(ji)溶(rong)劑、鋰(li)(li)鹽等(deng)組分,其(qi)中不(bu)(bu)乏有(you)(you)(you)毒(du)(du)有(you)(you)(you)害甚(shen)至(zhi)致癌物(wu);未來(lai)(lai)固態電(dian)(dian)(dian)(dian)解質(zhi)(zhi)鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi)或許會(hui)普及(ji),這(zhe)是另話。而對(dui)(dui)比鉛(qian)酸(suan),大家(jia)(jia)(jia)都有(you)(you)(you)了(le)(le)解,電(dian)(dian)(dian)(dian)動(dong)自(zi)行(xing)車(che)賣家(jia)(jia)(jia)對(dui)(dui)回(hui)(hui)收(shou)鉛(qian)酸(suan)電(dian)(dian)(dian)(dian)池(chi)(chi)非常(chang)(chang)有(you)(you)(you)積(ji)極(ji)(ji)性且民(min)眾也很樂意(yi),原因就(jiu)是免維護(hu)鉛(qian)酸(suan)電(dian)(dian)(dian)(dian)池(chi)(chi)回(hui)(hui)收(shou)已(yi)經(jing)非常(chang)(chang)成熟(shu),社會(hui)和企(qi)業(ye)都對(dui)(dui)其(qi)回(hui)(hui)收(shou)盡到了(le)(le)義務和責任。在用戶端,只要不(bu)(bu)破壞就(jiu)不(bu)(bu)會(hui)有(you)(you)(you)污染(ran)(ran)。鉛(qian)酸(suan)電(dian)(dian)(dian)(dian)池(chi)(chi)生產(chan)也一(yi)樣,污染(ran)(ran)物(wu)主(zhu)(zhu)要是鉛(qian)粉,不(bu)(bu)接觸不(bu)(bu)吸(xi)入也就(jiu)不(bu)(bu)會(hui)中毒(du)(du);電(dian)(dian)(dian)(dian)解液是水溶(rong)劑,硫(liu)酸(suan)。另者(zhe),鉛(qian)酸(suan)企(qi)業(ye)經(jing)過(guo)國(guo)家(jia)(jia)(jia)大力整(zheng)治,已(yi)經(jing)形成了(le)(le)寡(gua)頭壟斷,產(chan)品(pin)質(zhi)(zhi)量都較可(ke)靠。而鋰(li)(li)電(dian)(dian)(dian)(dian)池(chi)(chi)企(qi)業(ye)參差不(bu)(bu)齊(qi),應該所有(you)(you)(you)人都經(jing)歷過(guo)手(shou)機(ji)電(dian)(dian)(dian)(dian)池(chi)(chi)氣鼓、容量驟減、壽命超短等(deng)類似情況,嚴重(zhong)的(de)(de)甚(shen)至(zhi)出現爆炸事(shi)故,鋰(li)(li)離(li)(li)子電(dian)(dian)(dian)(dian)池(chi)(chi)一(yi)旦過(guo)充(chong)過(guo)放(fang),受(shou)沖擊很容易出現燃燒危(wei)險(xian)。制造過(guo)程同(tong)樣也是,有(you)(you)(you)機(ji)溶(rong)劑毒(du)(du)性形成污水、粉塵(chen)污染(ran)(ran)、多次發生著火事(shi)故。

團隊使用(yong)濕法冶金(jin)技術,在實驗室級的(de)測試(shi)(shi)中,可以(yi)從(cong)48.8Wh鋰電池(chi)中還(huan)原出鈷和鋰。這個(ge)工藝包括:首先,在700攝氏度的(de)烤(kao)箱(xiang)中烘烤(kao)電池(chi),“煅燒”鈷、鋰和銅,破壞有機化合(he)物(wu)(wu)例如(ru)塑料(liao)和泡沫。這種煅燒物(wu)(wu)質攜帶金(jin)屬(shu)(shu)(shu)和金(jin)屬(shu)(shu)(shu)化合(he)物(wu)(wu)(鹽和氧(yang)(yang)化物(wu)(wu)),然后加以(yi)強酸(suan)、鹽酸(suan)和硫酸(suan),萃(cui)取(qu)金(jin)屬(shu)(shu)(shu)離(li)子。團隊使用(yong)過氧(yang)(yang)化氫(qing)作為還(huan)原劑(ji)進行實驗,以(yi)測試(shi)(shi)這種試(shi)(shi)劑(ji)是否可以(yi)提高(gao)浸出工藝。他(ta)們能(neng)夠(gou)以(yi)約50%的(de)效率提取(qu)鋰,以(yi)約25%效率提取(qu)鈷。

可行性

因為這些金屬分別(bie)代表(biao)48.8Wh電(dian)池(chi)重量的41%和8.5%,所以整(zheng)體來說(shuo)提取率是較高的,另外再加(jia)上熱(re)和酸的作用(yong)(yong),構成了(le)一種具有商業可行性的方(fang)案,用(yong)(yong)于(yu)回收(shou)這些電(dian)池(chi)的電(dian)極。然后,這種淋溶(rong)金屬可以用(yong)(yong)于(yu)制造新電(dian)池(chi),或者用(yong)(yong)于(yu)其他(ta)工(gong)業應用(yong)(yong)。這種受污染的液體廢料,可進一步地進行更(geng)加(jia)安全地回收(shou)處(chu)理(li)。

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