CN116514733A - 共价有机框架材料、配体和在钙钛矿太阳能电池中的应用 - Google Patents
共价有机框架材料、配体和在钙钛矿太阳能电池中的应用 Download PDFInfo
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- CN116514733A CN116514733A CN202310712375.XA CN202310712375A CN116514733A CN 116514733 A CN116514733 A CN 116514733A CN 202310712375 A CN202310712375 A CN 202310712375A CN 116514733 A CN116514733 A CN 116514733A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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Abstract
共价有机框架材料、配体和在钙钛矿太阳能电池中的应用。本发明属于钙钛矿太阳能电池领域。本发明的共价有机框架材料COF‑ET30是一类新型的多孔有机纳米材料,将COF‑ET30加入钙钛矿太阳能电池的钙钛矿层,制备相应的钙钛矿太阳能电池,相比传统材料,其有序的框架和较强的π‑π相互作用,能够促进电荷的分离和运输,减少电荷复合,降低钙钛矿层的缺陷浓度,在钙钛矿太阳能电池领域中展示出了优异的应用前景。
Description
技术领域
本发明属于钙钛矿太阳能电池领域,具体涉及一种共价有机框架材料、配体和在钙钛矿太阳能电池中的应用。
背景技术
太阳能电池的研发是人类社会应对能源危机、解决环境问题和寻求可持续发展的重要对策。目前太阳能电池的主力军为硅太阳能电池,他们具有效率高、稳定性好、产业链完整、使用寿命长等优势。不过,缺点也比较显著。不仅电池的原材料提取过程污染严重、能耗高;而且产线昂贵,最具代表的高效率HIT太阳能电池的一条产线价值过亿元;为了让太阳能电池的制备更加容易、高效且经济,科学界和工业界正在研制新的太阳能电池,其中钙钛矿太阳能电池(Perovskite solar cells, PSCs)就是备受关注的后起之秀。
钙钛矿太阳能电池是指采用有机-无机复合金属卤化钙钛矿材料为光敏剂的一类新型固态薄膜太阳能电池。自问世以来,获得了广泛关注,并在2013年被《Science》评为年度十大科学突破之一。与其他种类的太阳能电池相比,钙钛矿电池具备原料丰富、制备成本低、光电转换效率(PCE)高等优势,是目前最具产业前景的新型薄膜太阳能电池。但值得注意的是,钙钛矿结构在湿度较高的环境下晶格易被破坏,从而导致材料分解。因此,迫切需要找到一种同时满足高PCE和优良电池稳定性的方法。
发明内容
为了克服现有技术的不足,本发明提供了一种共价有机框架材料、配体和在钙钛矿太阳能电池中的应用。
本发明的目的是通过如下技术方案来完成的:
本发明的目的之一在于提供一种共价有机框架材料配体,所述配体具有以下结构:
。
本发明的目的之二在于提供一种基于上述配体的共价有机框架材料,所述共价有机框架材料具有如下结构单元:
。
本发明的目的之三在于提供一种上述共价有机框架材料在钙钛矿太阳能电池领域中的应用。
本发明与现有技术相比具有的显著效果:
本发明的共价有机框架材料COF-ET30是一类新型的多孔有机纳米材料,将COF-ET30加入钙钛矿太阳能电池的钙钛矿层,制备相应的钙钛矿太阳能电池,相比传统材料,其有序的框架和较强的π-π相互作用,能够促进电荷的分离和运输,减少电荷复合,降低钙钛矿层的缺陷浓度,在钙钛矿太阳能电池领域中展示出了优异的应用前景。
附图说明
图1为本发明的共价有机框架材料COF-ET30的制备路线图;
图2为本发明实施例中中间体的核磁氢谱图;
图3为本发明实施例中中间体的核磁碳谱图;
图4为本发明实施例中中间体的质谱图;
图5为本发明实施例中配体的核磁氢谱图;
图6为本发明实施例中配体的核磁碳谱图;
图7为本发明实施例中配体的质谱图;
图8为本发明实施例中共价有机框架材料COF-ET30的质谱图;
图9为本发明实施例制得的共价有机框架材料COF-ET30的红外表征;
图10为本发明应用例中钙钛矿太阳能电池的J-V曲线;
图11为本发明应用例中钙钛矿太阳能电池的湿度稳定性测试图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器,未经特殊说明,均为本领域常规材料、试剂、方法和仪器,本领域技术人员均可通过商业渠道获得。
下述实施例中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形,意在覆盖非排它性的包括。例如,包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素,而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
本发明所述“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
下述实施例中所用5-氨基-2-溴-4-氟苯甲酸(CAS:1340460-29-8)、苯并[1,2-B:3,4-B':5,6-B']三噻吩-2,5,8-三醛(CAS:2243590-42-1)均从上海皓鸿生物医药科技有限公司直接采购获得。元素分析所用仪器为德国ElementarUNICUBE元素分析仪。
实施例:
共价有机框架材料COF-ET30的合成路线如说明书附图1所示,具体的制备方法按以下步骤进行:
第一步、中间体的合成:
将2毫升N-甲基吡咯烷酮、576毫克异丙醇、碳酸钠(159毫克, 1.5毫摩尔)和醋酸钯(1毫克, 0.006毫摩尔)依次加入到Pyrex管中,在25℃下搅拌5分钟,得到均匀的混合溶液。随后加入5-氨基-2-溴-4-氟苯甲酸(351毫克, 1.5毫摩尔)和2毫升N-甲基吡咯烷酮的混合溶液,混合均匀后加热至140℃,然后加入亚铁氰化钾(634毫克, 0.6毫摩尔),继续在140℃下搅拌5小时。反应结束后,过滤,对粗品用体积比为10:1的二氯甲烷/乙酸乙酯的混合溶剂作为洗脱剂进行硅胶柱层析,得中间体。
氢谱:1H NMR (400 MHz, CDCl3):δ7.64 (d, 1 H), 7.40 (d, 1 H), 4.59 (s, 2H).
碳谱:13C NMR (100 MHz, CDCl3):δ178.84, 152.77, 150.26, 137.76, 137.57,129.22, 129.19, 121.09, 120.89, 117.80, 117.76, 117.67, 117.58, 99.03, 98.95.
质谱表征结果:ESI(m/z):[M+H]+calcd. for C8H5FN2O2, 180.03;found,180.95.
元素分析测试结果:Calcd. for C8H5FN2O2C, 53.34; H, 2.80; N, 15.55; O,17.76. Found: C, 53.65; H, 2.74; N, 15.49; O, 17.77.
根据以上分析数据可知,获得的中间体结构为:
。
第二步、配体的合成:
将中间体(1.5克, 13.08毫摩尔)加入到圆底烧瓶中,在-15℃条件下滴加三氟甲磺酸(4.3毫升, 44.4毫摩尔),随后氮气换气三次,升温至25℃搅拌24小时。反应结束后,向反应体系中加入20毫升冰水,随后用2摩尔每升的氢氧化钠溶液将反应体系的pH值调至7,过滤后滤饼用蒸馏水反复淋洗,并在真空下干燥,即得到配体。
氢谱:1H NMR (400 MHz, CDCl3):δ7.65 (d, 3 H), 7.11 (d, 3 H), 4.59 (s, 6H).
碳谱:13C NMR (100 MHz, CDCl3):δ169.59, 169.56, 169.35, 153.64, 151.12,136.61, 136.41, 128.03, 127.95, 124.70, 124.67, 119.91, 119.83, 119.73,119.53.
质谱表征结果:ESI(m/z):[M+H]+calcd. for C24H15F3N6O6, 540.10;found,541.03.
元素分析测试结果:Calcd. for C24H15F3N6O6C, 53.34; H, 2.80; N, 15.55; O,17.76. Found: C, 53.47; H, 2.81; N, 15.35; O, 17.70.
根据以上分析数据可知,获得的配体结构为:
。
第三步、共价有机框架材料COF-ET30的制备:
向pyrex管中加入配体(80毫克, 0.23毫摩尔)、苯并[1,2-B:3,4-B':5,6-B']三噻吩-2,5,8-三醛(49毫克, 0.23毫摩尔)、2.8毫升叔丁醇/邻二氯苯(v/v, 1:1)、0.2毫升6摩尔每升的醋酸水溶液,氮气置换3次,之后密封,在120℃下反应3天。反应结束后,过滤,固体依次用四氢呋喃和甲醇冲洗,最后在100℃下真空干燥12小时,得到共价有机框架材料,记为COF-ET30。
质谱表征结果:TOF-MS(m/z):[M+H]+calcd. for C132H96F9N15O18S9, 2638.44;found, 2639.26.
元素分析测试结果:Calcd. for C132H96F9N15O18S9C, 60.06; H, 3.67; N, 7.96;O, 10.91. Found: C,59.89; H, 3.61; N, 9.83; O, 10.95.
根据以上分析数据可知,获得的共价有机框架材料COF-ET30结构为:
。
对本发明实施例得到的共价有机框架材料COF-ET30进行红外表征:
测试仪器为IRAffinity-1傅里叶变换红外光谱仪,KBr压片,测试结果如说明书附图9所示。
由说明书附图9可知,在共价有机框架材料COF-ET30的红外图谱中,其中配体上原有的-NH2(3300 cm-1)振动消失,出现了新的键连-C=N(1628 cm-1),这也证明了共价有机框架材料COF-ET30的构建成功。
应用例:
基于本发明上述实施例得到的共价有机框架材料COF-ET30的钙钛矿太阳能电池的制备方法如下:
步骤(1)导电玻璃的制备:
用锌粉和3摩尔/升的盐酸蚀刻掺氟氧化锡(FTO)玻璃,然后依次用丙酮、异丙醇清洗腐蚀后的FTO导电玻璃片数次,最后浸入去离子水中超声10分钟。
步骤(2)电子传输层的制备:
在两个5毫升溶剂瓶中分别加入2.5毫升异丙醇,并在两瓶内分别滴加350微升的异丙醇钛和35微升3摩尔每升的盐酸,在搅拌条件下,将装有盐酸的溶剂瓶中的溶液滴加至含有异丙醇钛的溶剂瓶中,在室温下搅拌30分钟,即可得到致密层溶液。在3000 rpm转速下,将致密层溶液旋涂到FTO基底上,在70℃烘箱内烘10分钟后转移至马弗炉内,在500℃下煅烧30分钟。然后将二氧化钛浆料按照1:7的质量比在无水乙醇中稀释并搅拌均匀。再将上述浆料稀释液滴加到致密层基底上,以4000 rpm的速度旋涂45秒,再将旋涂好介孔层的基底至于马弗炉内,升温至500℃并在此温度下煅烧30分钟,最终制备得到电子传输层。
步骤(3)钙钛矿层的制备:
将碘化铅溶解在体积比为9:1的N,N-二甲基甲酰胺和二甲基亚砜混合溶液中,形成均匀的1.5毫摩每升的碘化铅溶液。为了掺入共价有机框架材料COF-ET30,将1毫克COF-ET30溶解在2毫升N,N-二甲基甲酰胺中,得到COF-ET30溶液,随后,将0.4微升COF-ET30溶液加入到0.2毫升碘化铅溶液中,再将该溶液以1500 rpm的转速在基底上旋涂30秒,随后70℃下退火60秒,在电子传输层表面形成碘化铅薄膜。将90毫升碘甲脒(FAI)、6.39毫克甲胺碘(MAI)和9毫克甲胺盐酸盐(MACl)溶解在1毫升异丙醇(IPA)中,随后以2000 rpm的速度旋涂在冷却后的碘化铅薄膜上。然后在150℃下退火15分钟。最后,将4.98毫克碘化苯乙胺(PEAI)溶解在1毫升IPA溶液中,形成PEAI溶液,随后以5000 rpm的转速旋涂30秒,得到钙钛矿层。上述过程是在一个充满氮气的手套箱中进行的。
步骤(4)空穴传输层的制备:
将72.3毫克2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(Spiro-OMeTAD),35微升双三氟甲烷磺酰亚胺锂溶液(LiTFSI),30微升4-叔丁基吡啶(TBP)和10毫升三(2-(1H-吡唑-1-基)-4-叔丁基吡啶)钴(III)三[双(三氟甲烷)磺酰亚胺](FK209 Co(III) TFSI salt)溶解在1毫升氯苯中,搅拌均匀。将上述溶液在3000 rpm下旋涂30秒,形成空穴传输层。
步骤(5)金属电极的制备:
将上述玻璃片放入蒸镀机,蒸镀80纳米厚的金电极。
为了检测共价有机框架材料COF-ET30对钙钛矿太阳能电池性能的影响,以钙钛矿层未掺入COF-ET30的钙钛矿太阳能电池作为空白对照,并对电池进行下述表征。
采用太阳模拟器(Newport, Oriel Class A, 91195A)和数字源表(Keithley2400)对钙钛矿太阳能电池进行测试。说明书附图10显示了含和不含COF-ET30的钙钛矿太阳能电池在AM 1.5 G,100 mW cm-2标准太阳模拟器下的电流密度-电压(J-V)曲线,可见,空白对照组的不含COF-ET30钙钛矿太阳能电池的转换效率(PCE)为21.52%,短路电流密度(J SC)为24.85 mA/cm2,开路电压(V OC)为1.13 V,填充因子(FF)为76.63%。而本发明上述应用例加入COF-ET30的钙钛矿太阳能电池,J SC为26.35 mA/cm2,V OC为1.17 V、 FF为86.67%、 PCE为26.72%。可见COF-ET30的加入,增强了界面电荷转移,减少了电荷复合,从而增强了转换效率,表明COF-ET30在钙钛矿太阳能电池中具有良好的应用前景。
此外,将上述应用例引入COF-ET30的钙钛矿太阳能电池储存在黑暗条件下(约等于60%的相对湿度)的盒子中200小时,以测试其湿度稳定性。测试结果如说明书附图11所示,随着时间的推移,其转换效率仍然稳定在26.2%左右,这表明,该电池具有良好的湿度稳定性。
以上所述,仅为本发明较佳的具体实施方式,这些具体实施方式都是基于本发明整体构思下的不同实现方式,而且本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (3)
1.一种共价有机框架材料配体,其特征在于,它具有以下结构:
。
2.基于权利要求1所述的配体的共价有机框架材料,其特征在于,它具有如下结构单元:
。
3.权利要求2所述的共价有机框架材料的应用,其特征在于,它应用于钙钛矿太阳能电池领域。
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