鈣鈦礦太陽(yáng)能電池綜述

1、鈣鈦礦太陽(yáng)能電池Perovskite Solar Cell結(jié)構(gòu) 鈣鈦礦結(jié)構(gòu)旻一種具有ABX3島型的奇特結(jié)構(gòu)，呈觀出4富多彩的物理性質(zhì)包壽絕 緣體、鐵電.反鐵或、巨滋/龐城效應(yīng)，箸右的是形有超導(dǎo)電性這種ABX3型鈣 枚礦結(jié)構(gòu)以金屬Pb原子為八面體核心、鹵素Br原子為八而體頂兔、有機(jī)甲気基 團(tuán)住于面心立方晶格頂角住置，這種有機(jī)鹵化煬鈣鈦驢結(jié)構(gòu)的特點(diǎn)是： 1）鹵素入而體共頂點(diǎn)連摟，組成三維網(wǎng)絡(luò)，根煽Pauling的紀(jì)住多面體連接規(guī)則， 此科結(jié)構(gòu)比共核.共面連接穩(wěn)岌2）共頂連接使入面體網(wǎng)給之間的空陳比共枝、共面連接肘要大，允許較大尺寸富 子加入，即使產(chǎn)生大量晶體缺陷，戎者各組成富子的尺寸與幾何學(xué)要求有

2、較大出 入時(shí)，仍然能夠保持結(jié)構(gòu)穩(wěn)定；并有利于缺陷的擴(kuò)散遷移.林料結(jié)構(gòu) 以下為典型的鈣彼礦晶體結(jié)構(gòu)和與之匹配的壽效空入傳導(dǎo)妨料結(jié)構(gòu)典型電池結(jié)構(gòu)(b)V0( r NO. 7 « 16T4-16HC ?0J4FTOSSZt底（光入弟面）原理(a)金馬對(duì)歩極層空穴傳翔層(b)鈣鈦曠層一支掙層TQ激蜜層T(W>5»Cfiy發(fā)展?fàn)顩rsIf OWO 獰RrnCWS-y 1,L- oonoooho t 4 < J 4Celri >：ro» Wn KJAthCI SOCIO” YO從2009年至今.發(fā) 展十分迅速己有 接近20%的光電聘 化半。右田為領(lǐng)城 上的重大

3、進(jìn)茲。rjAMh<vMTV：HINNgde-rgqcKJr IM 53wtnjRoK2DU. PCB<t7>；kc n zrsmgxx-es:em«*wa “ a. L 2CrSWy»Ntvitxi <»i m m<“, 2n.i rcr上4?Ow LA. Tmi> L M*y20M. PE2H起漏 >12009年試制對(duì)，Akihiro Kojimalf次將CHjNHjPb和CHsNHfbBq制備成愛子點(diǎn) （9-10mmJ應(yīng)用到丈陽(yáng)能赳池中（DSSC丿，研屯了農(nóng)可見光范謝內(nèi)，該奏材料 紋化Tit）?太陽(yáng)色池的性能.獲得3.

4、8%的光削效率。JIAICIS，CUMMLMlAllUN5 訶小 34 WOrganometal Halide Perovskites as Visible-Light Sensitizers for PhotovoltaicCellsorganised on TiO： as n-lype semiconductors Solar energy was convened with an efliciency of 3.8經(jīng) on a ('H ,NH；Pbl rbased cell, while a high photo voltage of 0.96 V was obtained wi

5、th a ClhNIhPbBrvbascd cell.迅速發(fā)展到2011年，研兗者將實(shí)臉?lè)接噙M(jìn)行了改進(jìn)與優(yōu)化o制備的CH3NH3Pbl3l子點(diǎn)達(dá)到 23mm»電池效率堵加了 一倡達(dá)刊6.54%Ge thi"如59乜 2QII 3 <1058./nanoscafeCOMMUNICATIO N6.5% efficient perovskite quantum-dot-sensitized solar cell+Jew仝H、coh Iju. Ctmnu-R> id Lz Jbi-Wook Lee, Smus-Uuu i*ark und >a

6、ni-G>u Purk */9/>2"“崗）$，& fgT 2t（UIM）l! IO.l«W!clmliMf6n 但是由于部分全屬鹵化物在液志電鮮質(zhì)中發(fā)生涿鮮，彼大程度上降低了就池的総 災(zāi)性與使用壽命，這是該電丸的致命缺點(diǎn)。2012 年解決這一問(wèn)題，就旻將Spiro-OMeTAD作為有機(jī)空員傳輸材料應(yīng)用到鈣鈦礦赳池中, 換上這種材料后，鈣鈦礦電池穩(wěn)走性和工藝重復(fù)性大大堤富。Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell

7、with Efficiency Exceeding 9%Hui-Seen KimChar-Ryul Ire . Jsocg-Hycak Ini', Ki-Bran hx , Tlionwi AZxxjhP, Aricnna Madias/ Soo-Jin Vocr:. Rabir Humpfiry-Batcr, Jun HoEMidxid GratajT& NarrGyv Rack1k>,k 、J rt亦TJ1 1L 'J *1Xgsr9r，、 J * 亡% %r.u />T:堰f iFgMl2013 年 后來(lái)，隨著工藝不斯優(yōu)化，轉(zhuǎn)換效率僅約半年時(shí)間就濮增至

8、15%。Sequential deposition as a route to high-performance perovskite-sensitized solar cellsJulian B lischlo1*. Xarman Pclld1,2*. Soo Jin Vnoei1. Robin Humphry Baker1. Peng Gan1. Mohammad K Karccniddin1& MkWCiUd1利用序列沉積的方法制 備鈣鈦礦電池，改進(jìn)了 原有的一步制備法，獲 得了畝率達(dá)15%的有機(jī) 全厲鹵化場(chǎng)鈣鈦曠基太 陽(yáng)能電也2013 年用毛柏蒸發(fā)出制備了鈣伙礦平而異質(zhì)結(jié)電池，

9、擺脫了復(fù)雜的納未結(jié)構(gòu)，得到了畝 率翕達(dá)15.4%的麥件.Efficient planar heterojunction perovskite solar cells by vapour depositionMing/hen Mu1, Uldiad B Jirfiiwtnn1 h ilrniy J. Siialrh1SproOMelADFTO HQau500 rwnPorovrto JCompocs 叫AgPorovrto JFTO HQauSp-x> OMeiAD 今年最需轉(zhuǎn)化率己接近20%。Interface engineering of highly efficient perovs

10、kite solar cellslinajtping Zhou.1- Q> Clien； a> Gang 1J； Song Luo,1*2 Tze-bing Song,1-2 Ifoiji-Slwn« Duan,山 Zinio Huiig/ JinjCbi You? Yonheng Liu? 2 Yaii« YanM，Advancing perovskite solar cell technologies toward their theoretical power conversion efficiency (PCE) requires delicate co

11、ntrol over the carrier dynamics throughout the entire device By controlling the formation of the perovskite layer and careful choices of other materials. we suppressed carrier recombination in the absorber, facilitated carrier injection into the carrier transport layers and maintained good carrier e

12、xtraction at the electrodes. When measured via reverse bias scan, cell PCE is typically boosted to 16.6% on average, with the highest efficiency of *19.3% in a planar geometry without antireflective coating The fabrication of our perovskite solar cells was ton ducted in air and from solution at low

13、temperatures, which should simplify manufacturing of large-area perovskite devices that are inexpensive and perform at high levels.研究熱點(diǎn)和方向、鈣鈦礦極高吸光能力的撤觀機(jī)理 這科新型鈣鈦礦哌光材料的最犬優(yōu)的哌光糸數(shù)很丸，狹光能力此傳統(tǒng)染料 畜10信以上，到目當(dāng)為止其微觀機(jī)理都沒(méi)有走論。光生載流子的產(chǎn)生機(jī)理 觀有的理論解釋存農(nóng)兩種機(jī)理的爭(zhēng)論：激發(fā)電子空金對(duì)（自由電荷）機(jī)理和激發(fā)甑 子機(jī)理，協(xié)請(qǐng)曼光生栽流子的產(chǎn)生機(jī)理將對(duì)丸幡提富其轉(zhuǎn)換效卒至關(guān)重要；此卄， 疫有機(jī)金屬

14、鹵化場(chǎng)鈣鈦礦太陽(yáng)能電池中是否存衣由建迪煬，以及內(nèi)建電場(chǎng)如何以 如此低的能耗下驅(qū)動(dòng)栽源子輸運(yùn)和分離也是一個(gè)商待鮮決的問(wèn)題。、高效能量轉(zhuǎn)換的機(jī)理莊鈣鈦礦丈陽(yáng)能電池中，Gratzel等利用序列沉積方法制備了分歌質(zhì)TiO?納未骨 殺，將冇機(jī)金屬鹵化腸鈣鈦歹狹收層夾牲逢朗血極與空夬.傳輸屋之間，整個(gè)賽件 由空夬輸運(yùn)所主導(dǎo)；Sequential deposition as a route to highperformance perovskite -sensitized solar cells儀cnx比:Fd：vi *、g Jin Mtg'. Q.t>m15.ixw rvng Uiu:. M

15、uXxranudfc MS g “而Snaith等則利用包覆鈣鈦礦的Al2O3 介孔材料來(lái)代TiO2,荻得了優(yōu)于 15%的轉(zhuǎn)換效率，并且發(fā)觀屯子輸運(yùn)主導(dǎo)了整個(gè)轉(zhuǎn)換過(guò)程；因此，常要洙入硏丸其 中的機(jī)理與制約效率進(jìn)一步提咅的關(guān)綻因素。Sub-150 C processed meso-superstructured perovskite solar cells with enhaneed efficiencyKorrad lAiociechowski, MicNei Sa Uu gnx Le dens Antonio Abate and Henry J. Sailh*四、制備無(wú)鉛鈣鈦礦材料 觀衣的有

16、機(jī)金屬鹵化賜鈣彼歹材舛含有船元素，點(diǎn)餌際許多地方己彼列為桀止使 用的材舛，如何通過(guò)金屬元素槨代的方金找到同等丸更為轉(zhuǎn)換效率的無(wú)銘鈣鈦礦 吸收材料依然是一個(gè)桃戰(zhàn)。五、氧化物鈣鈦rtra能林料除了有機(jī)/無(wú)機(jī)復(fù)合鈣鈦礦材料以外，具備寓吸光性能的氧化賜鈣伙礦材料也引起 了丸量的關(guān)注：LETTERdoi:lO. X03&ruUir 1222Perovskite oxides for visible - light - absorbing ferroelectric and photovoltaic materialsIlya Grinberg D lnccnt West2. Maria Turr

17、et Gaoyang Gou David M. SleinS Liyan Wu2. Guannan <.henJ» Erii M. Gallo3.Andrew X. AkbahrV1, lter K. Davirx, Ifinathan I: Sj口niei*1 & Ancirrw M Rjppr 所以也她須研丸一些能帶合適.、唳光能力強(qiáng)的無(wú)機(jī)氣化楊鈣鈦礦財(cái)料亦高敗能量 轉(zhuǎn)換方面的潛能。穴、具有梯度能帶的鈣鈦礦吸光材料如果能紗通過(guò)元素眷代戎?jǐn)v雜的方法，制備出具有梯虞能帶的新型鈣儀礦吸光材 料，就可以制備類似于半導(dǎo)體多結(jié)太陽(yáng)能電池黑件(目首最富效率己經(jīng)超過(guò)40%), 以較

18、低的生尹成本丸鴨提升其轉(zhuǎn)換效率.Solar cell efficiency tables (version 44)Martin A. Green1 Keith Enwry2, Yosluhiro Hishikawa3, Wilhelm Warta*4 and Ewan D. Dunlop5Tabs IV.OPl 28 mu池 GFxrg;化朋uMer AS1M G 】733 曲碩 txm NJ 5前；育rc>0M%r。crt；I>'(；a«cs*CdtCf»E航c，0)IrenTy4 (surollesn Centre 血 le)Defplonco 心G

19、oAs291il3a OCbOb* L>11?冷&St WOO升“2綁IS£s>2r.«xl 2*1 00 g92GiSfe r；mArc ik tact. xn：3i：t 忍|ClOSOhin Mm)23.311.2*°0 0902 (np)15NRfl I3d4lMALIBU3心匕5 wis monoimci IrePi'CaAyHCflAjv44 4 - 2 Cn0 1652 <<W332HfG-KE i4?13)f Ek rre洛FZirpfc 3215U0OSGaHVGaAi GelrAiP/GelrAs3ft5&

20、#177;t 90702 320NREL i由OSOjHont ef s', spi! specVun (63Wdd陽(yáng)Si20“0"1975(0793血心刪U楓崢ZSyWhTTECH 02aJs* |Wj' «pte lircban369x18*1092 «jp>昭NREL劇切Amtrix 166)os'S IMg。羽2i21 72730.011SendsUWSW 2開r grc63 I&6)luminescent sub nodule7 11022如；20ESnn(9X»>tCN IVrer. GnAs c&

21、#171;<ls 57i七、新的電子/空兀傳導(dǎo)林料 觀衣使用的與有機(jī)會(huì)屬鹵化賜鈣伙礦狹光層柏広配的是冇機(jī)空矗傳輸材料Spiro OMeTAD,而其合成價(jià)格很高，目弟是畫金價(jià)格的五信以上。必須尋找更加有效. 穩(wěn)定且廉價(jià)的赳子/空夬傳輸材抖來(lái)提需鈣鈦礦衣陽(yáng)能電池的轉(zhuǎn)換效率。Cte Hs Jdi A ?C1d. 2<3505Yeccrved 刃th JxuyyNM Accepcea ：Oh :eorua-y 2034OOl. 10A swivel-cruciform thiophene based hole transporting material for efficient pero

22、vskite solar cells 十Thirumal Krishnjnxxjrlhy? Fu Kunwj；* Pablo P. Boix/ Hairong Li/ Teck Mir>y Koh嚴(yán) Wei L>n Leong.c Satvasheel Powsr? Andrew Grimsdale? Michael Gr5tzel° Nripan Mathev?5*3ec and Subodh G .Mhaisalkar*3A novel swivel-cruciform 33-bithiophene based hole-transporting material (

23、HTM) with a low lying highest occupied molecular orbital (HOMO) level was synthesized This new HTM (KTM3) in CHjNHjPbl, perovskite solar cells showed a higher (1.08 V) and fill factor (78 3%) compared to solar cells fabricated using the widely used spiro- OMeTAD八、進(jìn)一步提高器件穩(wěn)定性與壽命 盡管Gratzel等人發(fā)觀有機(jī)金屬鹵化楊鈣鈦

24、礦太陽(yáng)能電池在全日光輻照下速續(xù)使 用500小對(duì)后依然保持80%以上的轉(zhuǎn)換效率，是適今為止萼膜丈陽(yáng)能赳池中最穩(wěn) 走的，但商沽大憐孜進(jìn)才能實(shí)現(xiàn)工業(yè)化應(yīng)用。Long-term stability For long-term slability tests, the devices were sealed in argon using a 50-pm-diick hotmelting polymer and a microscope coverslip, and subjected to constant light soaking at approximately 100 mW cm 2. The

25、liglit source was an array of white light-eniillingdi(xles(LXA43-PVV51 KMXJK. Philips). During the testing, the devices were maintained at their niiixinmni power point using declronic control and ata temperature of about 45 (:. An automatic /- V measurement at different light intensities (0%, 1%, 10%, 50% and 100% the solar value) was made every 2 h.power p