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淺析鈣鈦礦太陽能電池產業化發展趨勢

發布時(shi)間:2024-01-31 來源:元祿光(guang)電(dian)

一、鈣鈦礦電池材料成本低廉,生產流程較短


1.1 鈣鈦礦材料體系、電池結構概述

鈣(gai)(gai)鈦(tai)(tai)礦(kuang)本指化學式為 CaTiO3 的礦(kuang)物(wu)(wu)質(zhi)以(yi)及(ji)擁有(you) CaTiO3 結(jie)(jie)構(gou)的金(jin)屬(shu)氧化物(wu)(wu),現指結(jie)(jie)構(gou)式為 ABX3 形(xing)式且具(ju)有(you)與 CaTiO3 相(xiang)似晶體(ti)結(jie)(jie)構(gou)的材料(liao)。1839 年,俄(e)羅斯地質(zhi)學家(jia)L.Perovskite 在烏(wu)拉(la)爾山脈(mo)發現了鈣(gai)(gai)鈦(tai)(tai)礦(kuang)這種(zhong)礦(kuang)石,而(er)后就以(yi)他的名字(zi)來命名這種(zhong)礦(kuang)物(wu)(wu)。后將結(jie)(jie)構(gou)式為 ABX3 形(xing)式且具(ju)有(you)與 CaTiO3 相(xiang)似晶體(ti)結(jie)(jie)構(gou)的材料(liao)統稱(cheng)為鈣(gai)(gai)鈦(tai)(tai)礦(kuang)。鈣(gai)(gai)鈦(tai)(tai)礦(kuang)一般采用(yong) ABX3 八(ba)面(mian)體(ti)結(jie)(jie)構(gou) 。光伏用(yong)的鈣(gai)(gai)鈦(tai)(tai)礦(kuang)材料(liao)中,A 位一般選擇(ze)甲胺(CH3NH3+,MA+)、甲脒(NH2-HC=NH2+,FA+)和銫(Cs+)等一價陽離(li)子(zi);B位一般選擇(ze)鉛(Pb2+)、錫(xi)(Sn2+)等二(er)價陽離(li)子(zi),X 位可選擇(ze)碘(I-)、氯(Cl-)和溴(Br-)等鹵素陰離(li)子(zi)。

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鈣鈦礦光(guang)伏電(dian)(dian)池(chi)的發電(dian)(dian)原理(li)是光(guang)生(sheng)(sheng)伏特效應。其物(wu)理(li)過(guo)程為:鈣鈦礦吸(xi)(xi)光(guang)層(ceng)(ceng)吸(xi)(xi)收光(guang)子之后,入(ru)射光(guang)將(jiang)電(dian)(dian)子從價帶躍遷到(dao)導帶,形(xing)成電(dian)(dian)子-空(kong)(kong)穴對,然(ran)后電(dian)(dian)子-空(kong)(kong)穴對在(zai)(zai)吸(xi)(xi)光(guang)層(ceng)(ceng)內部(bu)迅速(su)分開,接著(zhu)電(dian)(dian)子通過(guo)電(dian)(dian)子傳(chuan)輸層(ceng)(ceng)輸送到(dao)陽(yang)(yang)極(ji)(ji)(ji),空(kong)(kong)穴通過(guo)空(kong)(kong)穴傳(chuan)輸層(ceng)(ceng)輸送到(dao)陰極(ji)(ji)(ji),隨著(zhu)電(dian)(dian)子和空(kong)(kong)穴不斷在(zai)(zai)陽(yang)(yang)極(ji)(ji)(ji)和陰極(ji)(ji)(ji)的堆積,兩級之間產生(sheng)(sheng)了光(guang)生(sheng)(sheng)電(dian)(dian)動勢2。若(ruo)此(ci)時裝置與外部(bu)電(dian)(dian)路相連,便有光(guang)電(dian)(dian)流輸出。

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常見的(de)單(dan)結(jie)(jie)鈣(gai)鈦(tai)(tai)礦(kuang)電(dian)(dian)(dian)(dian)池(chi)由透明(ming)電(dian)(dian)(dian)(dian)極(ji)、電(dian)(dian)(dian)(dian)子傳輸層(ceng)(ceng)(ceng)、鈣(gai)鈦(tai)(tai)礦(kuang)吸(xi)光層(ceng)(ceng)(ceng)、空(kong)穴傳輸層(ceng)(ceng)(ceng)與金屬(shu)電(dian)(dian)(dian)(dian)極(ji)構(gou)成。單(dan)結(jie)(jie)鈣(gai)鈦(tai)(tai)礦(kuang)電(dian)(dian)(dian)(dian)池(chi)根據(ju)電(dian)(dian)(dian)(dian)荷傳輸層(ceng)(ceng)(ceng)的(de)形貌結(jie)(jie)構(gou),可(ke)分為(wei)介孔(kong)結(jie)(jie)構(gou)和(he)(he)平面(mian)結(jie)(jie)構(gou)兩(liang)種類(lei)型(xing)(xing),介孔(kong)能夠擴(kuo)大 TCO 與鈣(gai)鈦(tai)(tai)礦(kuang)的(de)接觸面(mian)積,有(you)利于電(dian)(dian)(dian)(dian)荷提(ti)(ti)取,提(ti)(ti)升高轉換(huan)效率,但制造(zao)介孔(kong)需要 450 ℃以上的(de)高溫加(jia)工,且會由于紫外光引起(qi)的(de)表(biao)面(mian)吸(xi)附氧的(de)解吸(xi)而導致電(dian)(dian)(dian)(dian)池(chi)不穩定。若根據(ju)電(dian)(dian)(dian)(dian)荷傳輸層(ceng)(ceng)(ceng)類(lei)型(xing)(xing)分類(lei),平面(mian)鈣(gai)鈦(tai)(tai)礦(kuang)太陽能電(dian)(dian)(dian)(dian)池(chi)結(jie)(jie)構(gou)又可(ke)以分為(wei)正式結(jie)(jie)構(gou)(n-i-p)和(he)(he)倒置結(jie)(jie)構(gou)(p-i-n)兩(liang)種類(lei)型(xing)(xing),其中(zhong) n 代表(biao)電(dian)(dian)(dian)(dian)子傳輸層(ceng)(ceng)(ceng)(ETL),i 代表(biao)鈣(gai)鈦(tai)(tai)礦(kuang)吸(xi)光層(ceng)(ceng)(ceng),p代表(biao)空(kong)穴傳輸層(ceng)(ceng)(ceng)(HTL)。

電(dian)子(zi)(zi)(zi)(zi)傳(chuan)(chuan)(chuan)輸(shu)(shu)層(ceng)(ceng)(ETL):電(dian)子(zi)(zi)(zi)(zi)傳(chuan)(chuan)(chuan)輸(shu)(shu)層(ceng)(ceng)用于接收由(you)鈣(gai)鈦(tai)(tai)礦層(ceng)(ceng)傳(chuan)(chuan)(chuan)輸(shu)(shu)的(de)電(dian)子(zi)(zi)(zi)(zi),并將(jiang)其傳(chuan)(chuan)(chuan)輸(shu)(shu)到(dao)電(dian)極中,同時防(fang)止(zhi)空(kong)(kong)穴的(de)傳(chuan)(chuan)(chuan)輸(shu)(shu)。電(dian)子(zi)(zi)(zi)(zi)傳(chuan)(chuan)(chuan)輸(shu)(shu)層(ceng)(ceng)必須滿足(zu)與(yu)鈣(gai)鈦(tai)(tai)礦層(ceng)(ceng)良(liang)好接觸(chu),使得電(dian)子(zi)(zi)(zi)(zi)在傳(chuan)(chuan)(chuan)輸(shu)(shu)過(guo)程(cheng)中的(de)潛在勢壘降低,并且在完成電(dian)子(zi)(zi)(zi)(zi)傳(chuan)(chuan)(chuan)輸(shu)(shu)的(de)同時阻止(zhi)空(kong)(kong)穴向陰極傳(chuan)(chuan)(chuan)輸(shu)(shu),這對提高電(dian)池的(de)光電(dian)轉換效率具有(you)重要作用。ETL 必須滿足(zu)與(yu)鈣(gai)鈦(tai)(tai)礦層(ceng)(ceng)能帶匹配,目前ETL常(chang)用的(de)材料(liao)有(you)兩大類:1)金屬氧(yang)化物(wu):通常(chang)包括(kuo) TiO2、SnO2、ZnO以及一些摻雜的(de)氧(yang)化物(wu),主(zhu)要用于 n -i-p 結構。2)有(you)機材料(liao):通常(chang)是富(fu)勒烯及其衍生物(wu)例如PCBM和C60 等(deng),主(zhu)要用于 p - i - n 結構。

空(kong)(kong)穴傳(chuan)輸(shu)(shu)(shu)層(HTL):用(yong)(yong)(yong)(yong)于(yu)接收由鈣鈦礦(kuang)層傳(chuan)輸(shu)(shu)(shu)的(de)(de)(de)(de)空(kong)(kong)穴,并將其傳(chuan)輸(shu)(shu)(shu)到電(dian)(dian)(dian)極中(zhong),同(tong)時防止電(dian)(dian)(dian)子(zi)的(de)(de)(de)(de)傳(chuan)輸(shu)(shu)(shu)。HTL 需要與鈣鈦礦(kuang)層有(you)(you)(you)良好(hao)(hao)的(de)(de)(de)(de)異質(zhi)結接觸界面,減少空(kong)(kong)穴傳(chuan)輸(shu)(shu)(shu)過(guo)程中(zhong)的(de)(de)(de)(de)潛在(zai)(zai)(zai)勢(shi)壘,完(wan)成空(kong)(kong)穴傳(chuan)輸(shu)(shu)(shu)的(de)(de)(de)(de)同(tong)時阻止電(dian)(dian)(dian)子(zi)向陽(yang)極移(yi)動,對(dui)(dui)提高太陽(yang)能(neng)電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)光(guang)電(dian)(dian)(dian)轉換(huan)效率(lv)具(ju)有(you)(you)(you)重要作用(yong)(yong)(yong)(yong)。一般(ban)常用(yong)(yong)(yong)(yong)材料包括有(you)(you)(you)機(ji)小分子(zi)、有(you)(you)(you)機(ji)聚合(he)(he)(he)物(wu)以及無機(ji)材料。用(yong)(yong)(yong)(yong)在(zai)(zai)(zai) p-i-n 結構(gou)中(zhong)的(de)(de)(de)(de) HTL 主(zhu)要是(shi)有(you)(you)(you)機(ji)聚合(he)(he)(he)物(wu) PTAA、PEDOT:PSS;用(yong)(yong)(yong)(yong)在(zai)(zai)(zai)n-i-p結構(gou)中(zhong)的(de)(de)(de)(de)HTL 主(zhu)要是(shi)有(you)(you)(you)機(ji)小分子(zi)和(he)無機(ji)物(wu)材料:Spiro-OMeTAD、NiO、CuSCN、CuO、CuI、P3HT 等1。鈣鈦礦(kuang)吸光(guang)層:電(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)核心層。用(yong)(yong)(yong)(yong)于(yu)吸收光(guang)能(neng)生成電(dian)(dian)(dian)子(zi)-空(kong)(kong)穴對(dui)(dui),一般(ban)采用(yong)(yong)(yong)(yong)ABX3八面體結構(gou)。透明(ming)電(dian)(dian)(dian)極:透明(ming)電(dian)(dian)(dian)極一般(ban)選(xuan)用(yong)(yong)(yong)(yong)商業(ye)化(hua)的(de)(de)(de)(de) ITO 或(huo)(huo)者 FTO 氧化(hua)物(wu)導(dao)(dao)電(dian)(dian)(dian)玻璃(li)。其在(zai)(zai)(zai)可見(jian)光(guang)波(bo)段的(de)(de)(de)(de)透光(guang)率(lv)高達 80-90%、導(dao)(dao)電(dian)(dian)(dian)能(neng)力強、功函數合(he)(he)(he)適(shi),這些(xie)優異的(de)(de)(de)(de)特(te)性(xing)使得(de)透明(ming)電(dian)(dian)(dian)極在(zai)(zai)(zai)在(zai)(zai)(zai)保證(zheng)透過(guo)率(lv)的(de)(de)(de)(de)同(tong)時還擁(yong)有(you)(you)(you)出色的(de)(de)(de)(de)電(dian)(dian)(dian)荷橫(heng)縱向傳(chuan)輸(shu)(shu)(shu)能(neng)力,有(you)(you)(you)利于(yu)電(dian)(dian)(dian)荷收集。金(jin)屬電(dian)(dian)(dian)極:選(xuan)擇導(dao)(dao)電(dian)(dian)(dian)性(xing)良好(hao)(hao)的(de)(de)(de)(de)金(jin)屬或(huo)(huo)具(ju)有(you)(you)(you)金(jin)屬性(xing)質(zhi)的(de)(de)(de)(de)導(dao)(dao)電(dian)(dian)(dian)物(wu),如金(jin)、銀、銅、碳(tan)等,通過(guo)熱蒸發沉積的(de)(de)(de)(de)方式制(zhi)成。

1.2 鈣鈦礦電池實驗室效率進步迅速

2009 年(nian), 日本人(ren)(ren) Kojima 等人(ren)(ren)將(jiang)有機、無(wu)機雜化(hua)的(de)鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)材(cai)料應用到量子點敏化(hua)太(tai)(tai)陽(yang)(yang)(yang)(yang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)中(zhong)。制備出了(le)鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)太(tai)(tai)陽(yang)(yang)(yang)(yang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi),并實現了(le) 3.8% 的(de)效(xiao)(xiao)(xiao)(xiao)率(lv)。但(dan)是這(zhe)種鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)材(cai)料在液(ye)態(tai)電(dian)(dian)(dian)(dian)解質中(zhong)很容易(yi)溶解,該電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)僅(jin)僅(jin)存(cun)在了(le)幾(ji)分(fen)鐘(zhong)。隨后(hou),Park 等人(ren)(ren)在2011年(nian)將(jiang)MAPbI3 納米晶粒改(gai)為(wei) 2—3 nm, 效(xiao)(xiao)(xiao)(xiao)率(lv)提高到 6.5%。但(dan)是由(you)于仍然(ran)采用液(ye)態(tai)電(dian)(dian)(dian)(dian)解質, 僅(jin)僅(jin)經(jing)過 10 分(fen)鐘(zhong)后(hou)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)效(xiao)(xiao)(xiao)(xiao)率(lv)就衰(shuai)減了(le) 80%。2 為(wei)解決鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)太(tai)(tai)陽(yang)(yang)(yang)(yang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)穩定性問題(ti), 2012 年(nian) Kim 等人(ren)(ren)將(jiang)一種固態(tai)的(de)空穴傳(chuan)輸材(cai)料(spiro-OMeTAD)引(yin)入到鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)太(tai)(tai)陽(yang)(yang)(yang)(yang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)中(zhong), 制備出全(quan)固態(tai)鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)太(tai)(tai)陽(yang)(yang)(yang)(yang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi), 電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)效(xiao)(xiao)(xiao)(xiao)率(lv)達(da)到9.7%,即使未經(jing)封裝, 電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)在經(jing)過 500 h 后(hou), 效(xiao)(xiao)(xiao)(xiao)率(lv)衰(shuai)減依舊(jiu)很小。通過對(dui)鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)組分(fen)以及制備方(fang)法(fa)的(de)優化(hua)和改(gai)進(jin)(jin)、傳(chuan)輸層的(de)改(gai)良與(yu)修飾(shi)、鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)與(yu)傳(chuan)輸層之間界(jie)面(mian)的(de)鈍(dun)化(hua),使得(de)光(guang)電(dian)(dian)(dian)(dian)轉換效(xiao)(xiao)(xiao)(xiao)率(lv)不斷突破,自(zi)此以后(hou),鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)太(tai)(tai)陽(yang)(yang)(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)進(jin)(jin)入迅(xun)猛發展階(jie)段(duan):2013 年(nian),Michael Gratzel 等人(ren)(ren)采用兩步旋涂法(fa)獲得(de)多晶薄膜(mo)MAPbl3,并且使得(de)鈣(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)效(xiao)(xiao)(xiao)(xiao)率(lv)提高到 15 %;2014 年(nian),加州大學洛(luo)杉磯分(fen)校(xiao) Yang Yang 等人(ren)(ren)使用溶液(ye)沉(chen)積法(fa)獲得(de)多晶薄膜(mo)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)獲得(de)了(le)光(guang)電(dian)(dian)(dian)(dian)轉換效(xiao)(xiao)(xiao)(xiao)率(lv)為(wei) 19.3%的(de)平面(mian)結(jie)構(gou)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi);

2016 年,瑞士洛桑(sang)聯邦(bang)理工學院 Anders Hagfeldt 等(deng)人(ren)通過一(yi)步旋(xuan)涂法制備(bei)的多晶薄膜電(dian)池(chi)光(guang)電(dian)轉(zhuan)換效(xiao)率達到(dao) 20.8%;2021 年,Sang ll Seok 等(deng)人(ren)通過一(yi)步旋(xuan)涂法制備(bei)了多晶薄膜FAPbl3,并且在吸光(guang)層和電(dian)子(zi)傳(chuan)輸層之間(jian)形成相干(gan)界面降(jiang)低缺陷,獲(huo)得(de)了 25.5%的光(guang)電(dian)轉(zhuan)換效(xiao)率。2022 年 12 月,根據(ju) NREL,目前單結鈣鈦礦電(dian)池(chi)世界紀錄由韓(han)國(guo)蔚山科學技術院(UNIST)保持,光(guang)電(dian)轉(zhuan)換效(xiao)率達到(dao) 25.8%。

1.3 鈣鈦礦優勢:理論轉換效率高,材料、制造成本低廉

鈣鈦礦電(dian)(dian)池(chi)(chi)的研究起步較晚,但其轉換(huan)效率進步速度遠快于晶(jing)(jing)硅(gui)電(dian)(dian)池(chi)(chi)。鈣鈦礦電(dian)(dian)池(chi)(chi)僅用(yong)十余年時(shi)(shi)間就將轉換(huan)效率從 3.8%提升至 25.8%,相(xiang)(xiang)對短時(shi)(shi)間獲(huo)得了主流(liu)晶(jing)(jing)硅(gui)電(dian)(dian)池(chi)(chi)近(jin)40年才取得的成績,這與其材料本身的性能優勢密(mi)切相(xiang)(xiang)關。

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鈣(gai)鈦(tai)(tai)礦電(dian)(dian)(dian)池突飛猛進(jin)的(de)發(fa)展(zhan)得益于(yu)其(qi)(qi)優秀的(de)光電(dian)(dian)(dian)性質。對比晶(jing)硅材料(liao),鈣(gai)鈦(tai)(tai)礦材料(liao)具有更高(gao)的(de)光吸收(shou)系數。較高(gao)的(de)光捕獲效(xiao)率(lv)(lv)使鈣(gai)鈦(tai)(tai)礦厚(hou)度僅(jin)為百納(na)米時可(ke)就(jiu)實現對光的(de)全吸收(shou);另一方(fang)面,對于(yu)幾乎沒有晶(jing)界(jie)的(de)鈣(gai)鈦(tai)(tai)礦單晶(jing)材料(liao),電(dian)(dian)(dian)子(zi)(zi)和(he)空(kong)穴(xue)的(de)擴散長度大于(yu)百微(wei)米,其(qi)(qi)擴散長度遠遠大于(yu)鈣(gai)鈦(tai)(tai)礦材料(liao)對光子(zi)(zi)的(de)吸收(shou)深(shen)度,有利于(yu)自由電(dian)(dian)(dian)子(zi)(zi)和(he)空(kong)穴(xue)的(de)輸運,可(ke)被(bei)陰陽電(dian)(dian)(dian)極完全收(shou)集,進(jin)而實現高(gao)效(xiao)的(de)光電(dian)(dian)(dian)轉(zhuan)化效(xiao)率(lv)(lv)。鈣(gai)鈦(tai)(tai)礦電(dian)(dian)(dian)池擁有更高(gao)的(de)理論(lun)轉(zhuan)換(huan)效(xiao)率(lv)(lv),未(wei)來(lai)發(fa)展(zhan)空(kong)間更大。追求(qiu)持續的(de)降本增效(xiao)一直是光伏行業發(fa)展(zhan)的(de)主旋(xuan)律,目前晶(jing)硅電(dian)(dian)(dian)池越來(lai)越接近(jin) 29.4%的(de)理論(lun)值(zhi),發(fa)展(zhan)潛力有限;而鈣(gai)鈦(tai)(tai)礦電(dian)(dian)(dian)池擁有更高(gao)的(de) 31%理論(lun)轉(zhuan)換(huan)效(xiao)率(lv)(lv)上限,且可(ke)與(yu)其(qi)(qi)他(ta)電(dian)(dian)(dian)池進(jin)行雙節、三節疊層,分(fen)別達(da)到 35%和(he) 45%的(de)轉(zhuan)換(huan)效(xiao)率(lv)(lv)。

鈣鈦礦(kuang)帶隙滿足單結太陽電池(chi)(chi)發電的(de)帶隙值(1.40 eV),且帶隙可調,能組成(cheng)(cheng)(cheng)更高效(xiao)率的(de)層電池(chi)(chi)。例如由 MAPbI(3-x)Br(x)構(gou)成(cheng)(cheng)(cheng)的(de)鈣鈦礦(kuang)材(cai)料可隨x 的(de)變化(hua)可實現帶隙1.5 ~ 2. 3 eV 連(lian)續可調。根據調整(zheng) ABX3 中各個元素的(de)配比,可以(yi)得到需要的(de)所需要的(de)帶隙并與其他電池(chi)(chi)結合組成(cheng)(cheng)(cheng)轉換效(xiao)率更高的(de)疊層電池(chi)(chi)1。

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疊(die)層(ceng)(ceng)電(dian)池(chi)(chi)通過(guo)(guo)將寬帶(dai)(dai)隙電(dian)池(chi)(chi)與(yu)窄帶(dai)(dai)隙電(dian)池(chi)(chi)串聯,能(neng)更(geng)加合(he)理(li)地利用全光譜(pu)范(fan)圍內的光子,減少能(neng)量損失。硅電(dian)池(chi)(chi)帶(dai)(dai)隙為 1.1 eV,非(fei)常適(shi)合(he)作疊(die)層(ceng)(ceng)電(dian)池(chi)(chi)底電(dian)池(chi)(chi),通過(guo)(guo)理(li)論(lun)計算,再與(yu)一種(zhong)帶(dai)(dai)隙 1.7 eV 的頂電(dian)池(chi)(chi)相結合(he),可以實(shi)現效率超過(guo)(guo) 30%的疊(die)層(ceng)(ceng)電(dian)池(chi)(chi)。而(er)鈣鈦礦電(dian)池(chi)(chi)具(ju)有優(you)秀的材料(liao)性(xing)質(zhi),是制造頂電(dian)池(chi)(chi)的候選材料(liao)之(zhi)一2。

其(qi)中(zhong)(zhong)工藝(yi)開發簡單的(de)(de)(de)(de)(de)(de)是機械堆疊的(de)(de)(de)(de)(de)(de)四(si)端(duan)結(jie)(jie)(jie)構(gou)(a),將(jiang)兩(liang)個(ge)(ge)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)獨(du)立制(zhi)備(bei)后(hou)堆疊在(zai)一起,相(xiang)互(hu)之間(jian)只(zhi)有光(guang)學(xue)耦合作用。這個(ge)(ge)結(jie)(jie)(jie)構(gou)的(de)(de)(de)(de)(de)(de)優(you)點是各個(ge)(ge)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)(de)(de)(de)制(zhi)備(bei)工藝(yi)不互(hu)相(xiang)制(zhi)約,能(neng)(neng)各自采用好的(de)(de)(de)(de)(de)(de)工藝(yi)條件。但是四(si)端(duan)疊層電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)對電(dian)(dian)(dian)(dian)極有較(jiao)高(gao)(gao)的(de)(de)(de)(de)(de)(de)要(yao)(yao)(yao)求,要(yao)(yao)(yao)求四(si)個(ge)(ge)電(dian)(dian)(dian)(dian)極中(zhong)(zhong)其(qi)中(zhong)(zhong)三個(ge)(ge)為透(tou)明(ming)電(dian)(dian)(dian)(dian)極,進光(guang)面(mian)電(dian)(dian)(dian)(dian)極需(xu)要(yao)(yao)(yao)具備(bei)在(zai)寬(kuan)光(guang)譜范圍內(nei)的(de)(de)(de)(de)(de)(de)高(gao)(gao)透(tou)過(guo),中(zhong)(zhong)間(jian)兩(liang)個(ge)(ge)電(dian)(dian)(dian)(dian)極需(xu)要(yao)(yao)(yao)具備(bei)在(zai)紅外(wai)光(guang)譜范圍內(nei)的(de)(de)(de)(de)(de)(de)高(gao)(gao)透(tou)過(guo)。兩(liang)端(duan)引出的(de)(de)(de)(de)(de)(de)鈣鈦(tai)礦/晶(jing)硅(gui)疊層電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)也被廣泛(fan)研究(d)。這種(zhong)結(jie)(jie)(jie)構(gou)是在(zai)晶(jing)硅(gui)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)上直接生長鈣鈦(tai)礦電(dian)(dian)(dian)(dian)池(chi)(chi)(chi),中(zhong)(zhong)間(jian)通(tong)過(guo)復合層或隧道結(jie)(jie)(jie)將(jiang)兩(liang)個(ge)(ge)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)串聯(lian)起來(lai)。與四(si)端(duan)疊層電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)相(xiang)比,兩(liang)端(duan)疊層電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)僅需(xu)要(yao)(yao)(yao)一個(ge)(ge)寬(kuan)光(guang)譜透(tou)明(ming)電(dian)(dian)(dian)(dian)極,有利(li)于降低制(zhi)造(zao)成本。但該結(jie)(jie)(jie)構(gou)的(de)(de)(de)(de)(de)(de)限制(zhi)在(zai)于1)要(yao)(yao)(yao)求兩(liang)個(ge)(ge)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)具有近似的(de)(de)(de)(de)(de)(de)電(dian)(dian)(dian)(dian)流(liu),這個(ge)(ge)電(dian)(dian)(dian)(dian)流(liu)匹配要(yao)(yao)(yao)求將(jiang)頂電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)理想帶隙(xi)限制(zhi)在(zai)1.7-1.8eV的(de)(de)(de)(de)(de)(de)狹(xia)窄范圍內(nei);2)要(yao)(yao)(yao)求頂電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)功(gong)能(neng)(neng)層的(de)(de)(de)(de)(de)(de)制(zhi)備(bei)不能(neng)(neng)影響底(di)(di)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)(de)(de)(de)性能(neng)(neng),同(tong)時底(di)(di)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)表(biao)面(mian)成為頂電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)(de)(de)(de)襯底(di)(di),傳統絨面(mian)結(jie)(jie)(jie)構(gou)的(de)(de)(de)(de)(de)(de)晶(jing)硅(gui)底(di)(di)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)為制(zhi)備(bei)高(gao)(gao)性能(neng)(neng)鈣鈦(tai)礦電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)帶來(lai)了挑(tiao)戰1。

疊層(ceng)電(dian)池近年(nian)來實驗(yan)室效率進步(bu)明顯(xian),效率已(yi)達(da) 32.5%。在兩(liang)端疊層(ceng)電(dian)池方面,2015年(nian), Mailoa 和(he) Bailie 采用銀納米線(xian)作為鈣(gai)鈦礦電(dian)池的透明電(dian)極,結(jie)合n++/p++硅薄膜隧道(dao)結(jie),制備出(chu)效率為 13.7%的兩(liang)端疊層(ceng)電(dian)池;2018 年(nian)牛津光(guang)伏的鈣(gai)鈦礦/硅基電(dian)池效率突破(po) 28%;2020 年(nian)德(de)國柏林亥姆霍茲中心(HZB)打破(po)其紀錄(lu)達(da)到29.15%;在2022年(nian) 12 月(yue) 18 日(ri),HZB 又(you)刷新自己(ji)的紀錄(lu)將轉換效率提升至32.5%,該紀錄(lu)已(yi)獲(huo)得美國能源(yuan)部國家可再(zai)生能源(yuan)實驗(yan)室(NREL)的權威(wei)認證(zheng)。

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鈣鈦礦(kuang)電(dian)池制備過(guo)(guo)(guo)程(cheng)(cheng)與(yu)晶(jing)硅電(dian)池有(you)較大(da)差異(yi)。不(bu)同于晶(jing)硅電(dian)池組(zu)(zu)件的硅料(liao)(liao)-硅片-電(dian)池-組(zu)(zu)件的長產(chan)業鏈流程(cheng)(cheng),鈣鈦礦(kuang)電(dian)池從基礎的原(yuan)材料(liao)(liao)開始到最終組(zu)(zu)件出(chu)廠(chang)全生產(chan)過(guo)(guo)(guo)程(cheng)(cheng)均在組(zu)(zu)件廠(chang)完成,特點為高度的一(yi)體(ti)化生產(chan)。精簡的生產(chan)過(guo)(guo)(guo)程(cheng)(cheng)可以使鈣鈦礦(kuang)組(zu)(zu)件生產(chan)時(shi)(shi)間大(da)大(da)減少,根據(ju)能鏡公眾號報(bao)道(dao),協鑫光電(dian)等頭部(bu)公司其(qi)產(chan)品從玻璃、膠膜、靶材、化工原(yuan)料(liao)(liao)進入到組(zu)(zu)件成型(xing)的全過(guo)(guo)(guo)程(cheng)(cheng)時(shi)(shi)間可控(kong)制在 45 分鐘之內,而(er)從傳(chuan)統晶(jing)硅電(dian)池從硅料(liao)(liao)到組(zu)(zu)件整個(ge)過(guo)(guo)(guo)程(cheng)(cheng)約需要 3 天以上時(shi)(shi)間。

鈣(gai)鈦(tai)礦組(zu)(zu)(zu)(zu)件的(de) GW 級別產(chan)(chan)能投(tou)資僅(jin)約(yue)為晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)組(zu)(zu)(zu)(zu)件的(de)一半(ban)。根據協鑫光電測算(suan),晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)組(zu)(zu)(zu)(zu)件全產(chan)(chan)業鏈(lian)(lian)(lian)的(de)投(tou)資成(cheng)本(ben)約(yue)為 9.6 億(yi)元/GW,而鈣(gai)鈦(tai)礦組(zu)(zu)(zu)(zu)件的(de)產(chan)(chan)能投(tou)資約(yue)為5 億(yi)元/GW,僅(jin)為晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)組(zu)(zu)(zu)(zu)件的(de)一半(ban)左右。其主要(yao)原因(yin)有:1)鈣(gai)鈦(tai)礦材(cai)料(liao)(liao)成(cheng)本(ben)低(di)(di)(di)廉,且對材(cai)料(liao)(liao)純(chun)度要(yao)求低(di)(di)(di)。鈣(gai)鈦(tai)礦材(cai)料(liao)(liao)構(gou)成(cheng)元素均為常(chang)見元素,成(cheng)本(ben)相比硅(gui)(gui)(gui)材(cai)料(liao)(liao)低(di)(di)(di)廉,且材(cai)料(liao)(liao)對雜質不敏感,通常(chang)只(zhi)需(xu)(xu)(xu)要(yao) 95%的(de)純(chun)度即可滿足使用(yong)需(xu)(xu)(xu)求,而硅(gui)(gui)(gui)料(liao)(liao)純(chun)度需(xu)(xu)(xu)達(da)到 99.9999%或 99.99999%。2)產(chan)(chan)業鏈(lian)(lian)(lian)更(geng)短,所需(xu)(xu)(xu)設(she)備(bei)更(geng)少,投(tou)資成(cheng)本(ben)與能耗(hao)(hao)(hao)更(geng)低(di)(di)(di)。晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)電池的(de)硅(gui)(gui)(gui)料(liao)(liao)-硅(gui)(gui)(gui)片(pian)-電池-組(zu)(zu)(zu)(zu)件的(de)長產(chan)(chan)業鏈(lian)(lian)(lian)流程所需(xu)(xu)(xu)設(she)備(bei)更(geng)多,硅(gui)(gui)(gui)料(liao)(liao)、硅(gui)(gui)(gui)片(pian)的(de)制備(bei)也需(xu)(xu)(xu)要(yao)高溫環境,能耗(hao)(hao)(hao)更(geng)高。每(mei)1瓦晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)組(zu)(zu)(zu)(zu)件制造(zao)的(de)能耗(hao)(hao)(hao)約(yue)為 1.52 kWh,而鈣(gai)鈦(tai)礦組(zu)(zu)(zu)(zu)件的(de)能耗(hao)(hao)(hao)為0.12 kWh,單瓦能耗(hao)(hao)(hao)約(yue)為晶(jing)(jing)(jing)(jing)硅(gui)(gui)(gui)組(zu)(zu)(zu)(zu)件的(de) 1/10。

鈣(gai)鈦礦電池擁有豐富(fu)的(de)下(xia)游應用場景。除了大型地(di)面(mian)(mian)電站和(he)工商(shang)業(ye)屋頂(ding)光伏(fu)等傳統光伏(fu)發電領域(yu),由于鈣(gai)鈦礦可以做到自然半(ban)透,同時顏色可調,所以可以作(zuo)為發電幕墻,在光伏(fu)建筑(zhu)一(yi)體化(BIPV)領域(yu)具有潛力,是鈣(gai)鈦礦商(shang)業(ye)化的(de)重(zhong)(zhong)要(yao)切入點之(zhi)一(yi);另一(yi)方面(mian)(mian),由于鈣(gai)鈦礦可做成(cheng)柔(rou)性材料,所以可以制成(cheng)可穿戴的(de)移動電源。而類似太陽(yang)能汽(qi)車這種對于面(mian)(mian)積和(he)重(zhong)(zhong)量(liang)敏感的(de)應用場景,鈣(gai)鈦礦與晶硅疊層電池將是理想(xiang)的(de)選(xuan)擇。

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1.4 目前大面積鈣鈦礦電池穩定性仍有挑戰

在(zai)鈣(gai)(gai)鈦(tai)礦(kuang)大(da)規模產業化的(de)(de)過程中,仍然有許(xu)多問(wen)題(ti)需(xu)要(yao)解(jie)決:1)穩(wen)定(ding)(ding)(ding)性(xing)(xing)問(wen)題(ti)。由于鈣(gai)(gai)鈦(tai)礦(kuang)材料(liao)(liao)不穩(wen)定(ding)(ding)(ding),濕、熱、光均(jun)(jun)會引(yin)起鈣(gai)(gai)鈦(tai)礦(kuang)材料(liao)(liao)降解(jie),雖(sui)(sui)然目前(qian)(qian)已能夠(gou)采取部(bu)分(fen)措施(shi)提升(sheng)穩(wen)定(ding)(ding)(ding)性(xing)(xing),例(li)如準二維 PSCs、全(quan)無機PSCs、采用無機電荷(he)傳輸層等,但(dan)都會以(yi)犧牲電池效(xiao)率(lv)為代價,尚需(xu)進一步發展。2)大(da)面(mian)(mian)積(ji)(ji)制備(bei)問(wen)題(ti)。雖(sui)(sui)然目前(qian)(qian)鈣(gai)(gai)鈦(tai)礦(kuang)電池的(de)(de)實(shi)驗室(shi)效(xiao)率(lv)成(cheng)績矚目,但(dan)均(jun)(jun)是在(zai)小面(mian)(mian)積(ji)(ji)(1平方厘米以(yi)下)下實(shi)現,一旦大(da)面(mian)(mian)積(ji)(ji)制備(bei)則難以(yi)控制其鈣(gai)(gai)鈦(tai)礦(kuang)薄膜(mo)均(jun)(jun)勻(yun)性(xing)(xing),導致光電轉換(huan)效(xiao)率(lv)和(he)穩(wen)定(ding)(ding)(ding)性(xing)(xing)都會出現明顯(xian)下降。這其中的(de)(de)難點在(zai)于晶(jing)體的(de)(de)結晶(jing)質量(liang),讓溶(rong)液層揮發成(cheng)均(jun)(jun)勻(yun)結晶(jing)層仍具有挑(tiao)戰性(xing)(xing)。目前(qian)(qian)業界(jie)多采用添加(jia)劑來解(jie)決相(xiang)關問(wen)題(ti):南(nan)京工(gong)業大(da)學秦(qin)天石教授團隊(dui)(dui)設計合成(cheng)了一種(zhong)多功能氟取代分(fen)子作為添加(jia)劑來誘(you)導鈣(gai)(gai)鈦(tai)礦(kuang)薄膜(mo)形成(cheng)更(geng)加(jia)有序(xu)的(de)(de)結晶(jing);香港城(cheng)市大(da)學的(de)(de)科研團隊(dui)(dui)通(tong)過在(zai)鈣(gai)(gai)鈦(tai)礦(kuang)前(qian)(qian)驅體溶(rong)液中添加(jia) 4-胍基(ji)苯(ben)甲酸鹽(yan)酸鹽(yan),使之能形成(cheng)一個(ge)氫鍵橋接的(de)(de)中間相(xiang)并調節結晶(jing)過程,從而形成(cheng)高質量(liang)的(de)(de)鈣(gai)(gai)鈦(tai)礦(kuang)薄膜(mo),形成(cheng)具有大(da)顆粒(li)、從底(di)部(bu)到表面(mian)(mian)呈(cheng)現連貫晶(jing)粒(li)生長的(de)(de)鈣(gai)(gai)鈦(tai)礦(kuang)薄膜(mo)。

3)材(cai)料(liao)含鉛(qian)。目前鉛(qian)元素(su)是鈣鈦礦(kuang)電(dian)(dian)池不可或(huo)缺的組成部(bu)分,但由于(yu)含鉛(qian)材(cai)料(liao)對環(huan)境的不友好性,必然(ran)會限(xian)制鈣鈦礦(kuang)實(shi)際應用的方(fang)向。目前有部(bu)分研究采用錫元素(su)替(ti)代(dai)鉛(qian)元素(su),但二價錫容易被氧(yang)化成四價錫,會導致電(dian)(dian)池性能下降。要(yao)完全(quan)實(shi)現無鉛(qian)化依然(ran)是鈣鈦礦(kuang)電(dian)(dian)池領域一件充(chong)滿(man)挑戰的難題。1 4)實(shi)驗室(shi)高(gao)效電(dian)(dian)荷傳輸(shu)(shu)層、金(jin)屬(shu)電(dian)(dian)極原(yuan)材(cai)料(liao)昂(ang)貴。為追求效率,實(shi)驗室(shi)大多采用金(jin)、銀(yin)等貴金(jin)屬(shu)作為電(dian)(dian)極,電(dian)(dian)荷傳輸(shu)(shu)層采用 spiro-OMeTAD、PEDOT : PSS、PCBM等昂(ang)貴材(cai)料(liao),難以大規(gui)模用于(yu)工業化生產中。因此仍(reng)需開發成本低、適合大規(gui)模制備、能保(bao)障電(dian)(dian)池效率的功(gong)能層材(cai)料(liao)。

二、鈣鈦礦電池產業化發展加速


2.1 國家政策支持鈣鈦礦電池發展

鈣鈦(tai)礦電(dian)(dian)池(chi)是具有高轉換效率的清潔能源(yuan),符合我國碳(tan)(tan)達峰、碳(tan)(tan)中(zhong)(zhong)和的綠(lv)色發展(zhan)要求,受到(dao)政(zheng)策(ce)大力支持(chi)。在“十四五”開(kai)局之年 2021 年,開(kai)展(zhan)鈣鈦(tai)礦等先進(jin)高效電(dian)(dian)池(chi)技術應用就已經寫在了可(ke)再(zai)生(sheng)能源(yuan)規(gui)劃中(zhong)(zhong),在后續(xu)政(zheng)策(ce)中(zhong)(zhong)也不斷提(ti)及,持(chi)續(xu)促進(jin)產業發展(zhan)進(jin)步。

2.2 鈣鈦礦企業備受資本市場關注

2.2.1 鈣鈦礦產業融資情況

鈣(gai)(gai)鈦(tai)(tai)礦具備(bei)高轉換(huan)效率、低成本(ben)、應用場(chang)景多元(yuan)的優勢,在技術不斷發展過程中也受到了資本(ben)市場(chang)的不斷加碼。近(jin)年(nian)來鈣(gai)(gai)鈦(tai)(tai)礦產(chan)業(ye)進展迅速,相關鈣(gai)(gai)鈦(tai)(tai)礦企(qi)業(ye)開始(shi)越(yue)來越(yue)多受到資本(ben)市場(chang)的青睞,資本(ben)市場(chang)巨頭如 IDG、騰(teng)訊、紅衫等也加入了產(chan)業(ye)投資行列中。

2.2.2 鈣鈦礦企業產線推進情況

隨著鈣鈦礦企業(ye)自(zi)身工(gong)藝進(jin)步與產(chan)(chan)業(ye)資本的(de)(de)持續高漲投入,行業(ye)內(nei)公司的(de)(de)產(chan)(chan)線(xian)(xian)推進(jin)迅速(su),頭(tou)部企業(ye)大多已投產(chan)(chan)百兆瓦級量產(chan)(chan)中試(shi)線(xian)(xian),并在產(chan)(chan)品穩定性得到驗證后進(jin)一步探索GW級產(chan)(chan)線(xian)(xian);新進(jin)入者也在跟進(jin)布局百兆瓦級中試(shi)線(xian)(xian)。

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三、鈣鈦礦產業化發展帶來相關設備投資分析


3.1 產業化帶來新關鍵設備投資機會

鈣(gai)(gai)鈦(tai)礦(kuang)電池產品結(jie)構原理和硅基電池差異(yi)較大(da),需全(quan)新(xin)的工(gong)藝流(liu)程(cheng)和產線設(she)備(bei)(bei)(bei)(bei)(bei),目前產線所需的設(she)備(bei)(bei)(bei)(bei)(bei)主要分(fen)為鍍膜(mo)設(she)備(bei)(bei)(bei)(bei)(bei)、涂(tu)布(bu)設(she)備(bei)(bei)(bei)(bei)(bei)、激光(guang)設(she)備(bei)(bei)(bei)(bei)(bei)與封裝設(she)備(bei)(bei)(bei)(bei)(bei)。鈣(gai)(gai)鈦(tai)礦(kuang)電池在(zai)(zai)結(jie)構上(shang)(shang)由多個(ge)功能薄(bo)膜(mo)疊加而成(cheng),其制(zhi)備(bei)(bei)(bei)(bei)(bei)在(zai)(zai)方法(fa)上(shang)(shang)也是在(zai)(zai)基底(di)上(shang)(shang)一層(ceng)(ceng)層(ceng)(ceng)累置薄(bo)膜(mo)而成(cheng)。整個(ge)過(guo)程(cheng)中(zhong)三層(ceng)(ceng)薄(bo)膜(mo)(空穴傳輸(shu)層(ceng)(ceng)、鈣(gai)(gai)鈦(tai)礦(kuang)層(ceng)(ceng)、電子傳輸(shu)層(ceng)(ceng))制(zhi)備(bei)(bei)(bei)(bei)(bei)關(guan)鍵,涂(tu)布(bu)機(ji)、鍍膜(mo)設(she)備(bei)(bei)(bei)(bei)(bei)(PVD、RPD)和激光(guang)設(she)備(bei)(bei)(bei)(bei)(bei)為核心(xin)設(she)備(bei)(bei)(bei)(bei)(bei),制(zhi)備(bei)(bei)(bei)(bei)(bei)大(da)面積、高性能、均(jun)勻穩(wen)定、高質量(liang)的薄(bo)膜(mo)是其中(zhong)關(guan)鍵。

3.2 激光刻蝕、鍍膜為鈣鈦礦生產核心環節

激(ji)(ji)光(guang)(guang)工藝涉及(ji)到整個(ge)鈣(gai)鈦(tai)礦(kuang)(kuang)薄膜電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)制備流(liu)程,是(shi)整個(ge)生(sheng)產(chan)流(liu)程中的(de)(de)必(bi)備環節。鈣(gai)鈦(tai)礦(kuang)(kuang)電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)生(sheng)產(chan)過程中需要分別進(jin)行(xing)(xing)(xing) 3 次平(ping)行(xing)(xing)(xing)激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi)(P1-P3),并(bing)完成P4 的(de)(de)清(qing)邊(bian)。P1-P3 刻(ke)(ke)(ke)蝕(shi)環節的(de)(de)作用是(shi)切割電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)表面(mian),形成阻斷電(dian)(dian)(dian)(dian)(dian)流(liu)導(dao)通的(de)(de)單獨模塊,實現增大電(dian)(dian)(dian)(dian)(dian)壓和串聯電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)效果;P4 激(ji)(ji)光(guang)(guang)負責清(qing)邊(bian)以完成最(zui)后(hou)的(de)(de)封裝(zhuang)環節。每道激(ji)(ji)光(guang)(guang)具體作用如(ru)下所(suo)示:P1 激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi):在透(tou)明導(dao)電(dian)(dian)(dian)(dian)(dian)電(dian)(dian)(dian)(dian)(dian)極(ji) TCO 沉積(ji)后(hou),和電(dian)(dian)(dian)(dian)(dian)荷傳(chuan)輸(shu)層(ceng)(ceng)(ceng)沉積(ji)前(qian),進(jin)行(xing)(xing)(xing)激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi),以形成彼(bi)此獨立(li)的(de)(de)條形導(dao)電(dian)(dian)(dian)(dian)(dian)電(dian)(dian)(dian)(dian)(dian)極(ji);P2 激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi):在第二(er)電(dian)(dian)(dian)(dian)(dian)荷傳(chuan)輸(shu)層(ceng)(ceng)(ceng)沉積(ji)后(hou),底電(dian)(dian)(dian)(dian)(dian)極(ji)沉積(ji)之前(qian),進(jin)行(xing)(xing)(xing)激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi),去除HTL/鈣(gai)鈦(tai)礦(kuang)(kuang)層(ceng)(ceng)(ceng)/ETL,留下 TCO 層(ceng)(ceng)(ceng),形成一個(ge)空縫。進(jin)行(xing)(xing)(xing)底電(dian)(dian)(dian)(dian)(dian)極(ji)層(ceng)(ceng)(ceng)沉積(ji)時金屬會(hui)填滿這(zhe)個(ge)空縫,從而將一個(ge)電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)底電(dian)(dian)(dian)(dian)(dian)極(ji)與下一個(ge)電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)透(tou)明頂電(dian)(dian)(dian)(dian)(dian)極(ji)相連;P3 激(ji)(ji)光(guang)(guang)刻(ke)(ke)(ke)蝕(shi):去除相鄰電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)底電(dian)(dian)(dian)(dian)(dian)極(ji)/HTL(空穴層(ceng)(ceng)(ceng))/鈣(gai)鈦(tai)礦(kuang)(kuang)層(ceng)(ceng)(ceng)/ETL(電(dian)(dian)(dian)(dian)(dian)子層(ceng)(ceng)(ceng)),留下TCO 層(ceng)(ceng)(ceng),從而實現分離效果;P4 清(qing)邊(bian):去除薄膜的(de)(de)邊(bian)緣(yuan)區域,利(li)用激(ji)(ji)光(guang)(guang)劃(hua)線劃(hua)分出區域后(hou)進(jin)行(xing)(xing)(xing)清(qing)除。

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鈣(gai)鈦礦(kuang)(kuang)(kuang)電池(chi)的(de)鈣(gai)鈦礦(kuang)(kuang)(kuang)層制備(bei)(bei)(bei)是(shi)(shi)核心。目(mu)前大(da)面(mian)(mian)積(ji)鈣(gai)鈦礦(kuang)(kuang)(kuang)薄膜制備(bei)(bei)(bei)方法(fa)(fa)(fa)主要有:刮刀涂布(bu)(bu)法(fa)(fa)(fa)、狹縫(feng)涂布(bu)(bu)法(fa)(fa)(fa)、噴涂法(fa)(fa)(fa)、噴墨(mo)打(da)印法(fa)(fa)(fa)、軟(ruan)覆蓋沉(chen)(chen)積(ji)法(fa)(fa)(fa)、氣(qi)相沉(chen)(chen)積(ji)法(fa)(fa)(fa)。刮刀涂布(bu)(bu)法(fa)(fa)(fa)優點是(shi)(shi)可(ke)大(da)面(mian)(mian)積(ji)制備(bei)(bei)(bei),設(she)備(bei)(bei)(bei)要求(qiu)低(di)(di),維護(hu)簡(jian)單(dan),而缺點是(shi)(shi)材(cai)料利用(yong)(yong)率(lv)(lv)(lv)低(di)(di);狹縫(feng)涂布(bu)(bu)法(fa)(fa)(fa)優點是(shi)(shi)可(ke)大(da)面(mian)(mian)積(ji)制備(bei)(bei)(bei),可(ke)連續生產(chan),材(cai)料利用(yong)(yong)率(lv)(lv)(lv)高(gao),但對設(she)備(bei)(bei)(bei)精度要求(qiu)高(gao);噴涂法(fa)(fa)(fa)設(she)備(bei)(bei)(bei)成(cheng)本低(di)(di),但材(cai)料利用(yong)(yong)率(lv)(lv)(lv)低(di)(di),易造成(cheng)腔室(shi)污染(ran);噴墨(mo)打(da)印法(fa)(fa)(fa)可(ke)大(da)面(mian)(mian)積(ji)制備(bei)(bei)(bei),原料利用(yong)(yong)率(lv)(lv)(lv)高(gao),但生產(chan)效率(lv)(lv)(lv)較低(di)(di),噴墨(mo)頭的(de)維護(hu)與更換復雜;軟(ruan)覆蓋沉(chen)(chen)積(ji)法(fa)(fa)(fa)可(ke)大(da)面(mian)(mian)積(ji)制備(bei)(bei)(bei),但材(cai)料利用(yong)(yong)率(lv)(lv)(lv)低(di)(di),生產(chan)效率(lv)(lv)(lv)較低(di)(di);氣(qi)相沉(chen)(chen)積(ji)法(fa)(fa)(fa)可(ke)大(da)面(mian)(mian)積(ji)制備(bei)(bei)(bei),成(cheng)膜質量好(hao),但材(cai)料利用(yong)(yong)率(lv)(lv)(lv)低(di)(di),生產(chan)效率(lv)(lv)(lv)較低(di)(di)。

在制備空穴(xue)傳輸(shu)層、電子傳輸(shu)層時,常使(shi)用 PVD(物理氣相(xiang)沉(chen)積)的真空鍍膜工藝,具體可分為蒸鍍、磁控濺射和離子鍍(RPD)等。

PVD 蒸(zheng)鍍:依靠加(jia)熱(re)膜材使表面組(zu)分(fen)以原子(zi)團(tuan)或(huo)分(fen)子(zi)團(tuan)形式被蒸(zheng)發出來(lai),并沉降在基(ji)片表面形成薄(bo)膜。

磁控濺射:用高能等(deng)離子(zi)體轟擊靶材,并使(shi)表面組分以原子(zi)團或離子(zi)形式被濺射出來,并沉積在基(ji)片表面,經(jing)歷成(cheng)膜過程(cheng),最終形成(cheng)薄膜。

離子(zi)鍍(du):在(zai)真(zhen)空條件下,利用氣(qi)(qi)體放電使工作氣(qi)(qi)體或被蒸發(fa)(fa)物(wu)質(zhi)(膜材)部分離化,在(zai)工作氣(qi)(qi)體離子(zi)或被蒸發(fa)(fa)物(wu)質(zhi)的離子(zi)轟擊(ji)作用下,把(ba)蒸發(fa)(fa)物(wu)或其(qi)反應(ying)物(wu)沉積在(zai)被鍍(du)基片表面(mian)。

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三種(zhong) PVD 工藝(yi)各(ge)自特(te)點如下:蒸(zheng)鍍(du)(du)的成(cheng)膜(mo)速(su)率與成(cheng)膜(mo)純度(du)高,技(ji)(ji)術成(cheng)熟度(du)高,但(dan)薄(bo)(bo)膜(mo)附(fu)著力一般;磁控(kong)濺(jian)射膜(mo)厚可控(kong),重復性好,薄(bo)(bo)膜(mo)附(fu)著力強,技(ji)(ji)術成(cheng)熟,但(dan)薄(bo)(bo)膜(mo)中間厚兩邊薄(bo)(bo);離子鍍(du)(du)成(cheng)膜(mo)質量更高,但(dan)靶(ba)材利用率一般。

涂布(bu)工藝(yi)與(yu)鍍(du)膜工藝(yi)都是制(zhi)作鈣(gai)鈦(tai)礦(kuang)電(dian)池(chi)核心層(空(kong)穴傳輸(shu)層/鈣(gai)鈦(tai)礦(kuang)層/電(dian)子傳輸(shu)層)的主要工藝(yi),目前各層結構制(zhi)備方法選取(qu)上業界還沒有形成統一(yi)的共(gong)識,各種(zhong)路(lu)線均(jun)在嘗(chang)試(shi)。涂布(bu)與(yu) PVD 的主要區別有:涂布(bu)工藝(yi)為濕法工藝(yi),成本低廉且材料(liao)利用率高(gao),但膜厚(hou)均(jun)勻性(xing)較(jiao)差(cha);PVD 工藝(yi)為干法 ,設備昂貴,但成膜膜厚(hou)均(jun)勻性(xing)較(jiao)好。

3.3 部分鈣鈦礦設備廠商已具備整線交付能力

鈣鈦(tai)礦設(she)備(bei)(bei)(bei)端(duan)發展較(jiao)快,各工藝環節均有(you)國(guo)內(nei)本土(tu)公司布局,且部分企業(ye)已(yi)(yi)經(jing)擁有(you)整線設(she)備(bei)(bei)(bei)的(de)生(sheng)產能(neng)力。目前(qian)捷佳(jia)偉創與眾能(neng)光(guang)電(dian)具備(bei)(bei)(bei)整線設(she)備(bei)(bei)(bei)的(de)生(sheng)產能(neng)力,捷佳(jia)偉創設(she)備(bei)(bei)(bei)種類涵蓋 RPD、PVD、PAR、CVD、蒸發鍍膜(mo)及精密狹縫涂布、晶硅疊層印刷(shua)等;眾能(neng)光(guang)電(dian)已(yi)(yi)與國(guo)內(nei)大(da)型央國(guo)企、民營企業(ye)和(he)知名高校科研機(ji)構累計(ji)完(wan)成近200 個單體工藝設(she)備(bei)(bei)(bei)交(jiao)付(fu),產品包括涂布機(ji)、刮(gua)涂機(ji)、激光(guang)刻蝕(shi)機(ji)、PVD 和(he) ALD 等。

(本文僅供(gong)參考,不代表我們的任(ren)何投資建議(yi)。如需使用(yong)相關信息(xi),請參閱報告(gao)原文。)


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