CN108417649A - 一种氧化锡基太阳能电池纳米材料的制备方法及应用 - Google Patents
一种氧化锡基太阳能电池纳米材料的制备方法及应用 Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011858 nanopowder Substances 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 12
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910003092 TiS2 Inorganic materials 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 3
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- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
本发明公开了一种氧化锡基太阳能电池纳米材料的制备方法及应用,包括二氧化锡、二硫化锡和二硫化钛,各组成成分的摩尔比:SnO2:SnS2:TiS2=x:y:z,其中,1.5≤x≤2.5,0.2≤y≤0.6,0.1≤z≤0.25。本发明还提供了氧化锡基太阳能电池纳米材料的制备方法及应用。本发明的纳米粉体材料,在中性环境中降解带色有机物可以循环利用5次及以上,其光催化性能几乎不变;但在酸性环境中光催化性能的稳定性变差。本发明的纳米粉体材料光电转化较高,制备原材料来源广泛,廉价易得,制备方法简单,成本低;纳米粉体易于压片成型,满足太阳能窗口材料的加工要求。
Description
技术领域
本发明属于新能源材料技术领域,涉及一种氧化锡基太阳能电池纳米材料的制备方法及应用。
背景技术
能源是人类社会存在和发展的物质基础。煤炭、石油、天然气等不可再生化石能源的枯竭和环境的日益恶化已经成为人类生存与发展的重大障碍。因此,绿色能源的开发利用迫在眉睫。太阳能是人类取之不尽的绿色能源,太阳能电池材料是人类利用太阳能的主要方式。太阳能电池材料的工作原理是,太阳光照在太阳能电池材料表面时,部分太阳光被吸收,使具有足够能量的光子能够在材料中将电子从价带中激发以致产生电子-空穴对,界面层附近的电子和空穴在复合前,通过空间电荷的电场作用被相互分离,在半导体P-N结电场的作用下,N型半导体的空穴往P型区移动,P型区中的电子往N型区移动,接通电路后就形成电流。界面层(电池面积)越大,界面层吸收的光能越多,在界面层产生的电子-空穴对越多,在太阳能电池中形成的电流也越大,太阳能的利用效率就越高。
现阶段可做太阳能电池材料的有单晶Si、多晶Si、非晶Si、GaAs、InP、GaAlAs、CuInS2、CdS、CdTe等,多晶硅和单晶硅的光电转换效率分别在12%和15%左右,但其制作成本很高,而且单晶硅与多晶硅太阳能电池材料只适合于强光环境,弱光条件下几无发电,同时生产过程存在严重污染,质量要求高(Si纯度99.999%),使用寿命一般也只有20年左右;非晶硅制作工艺尽管简单,硅材料消耗少、电耗低,在弱光下也能发电,但光电转换效率只有10%左右,且性能随时间延长而出现逐渐衰减。GaAs是III-V族元素二元化合的黑灰色半导体材料,能在空气中稳定存在,不为非氧化性的酸侵蚀,其电子迁移率高、介电常数小,能引入深能级杂质、电子有效质量小,能带结构特殊而具有特殊的光电传输特性,在通讯领域得到广泛应用,但砷化镓材料的成本昂贵而且有毒。陈鸣波等采用低压金属有机化学气相沉积法制备的三元化合物GaInP2及其叠层(GaInP2/GaAs)太阳能电池的光电转换效率也只有23.82%。CuInS2是一种重要的IB-IIIA-VIA族三元化合物,以其作为太阳能电池的光吸收层,其光吸收系数为105cm-1,是当前一种较理想的太阳能电池材料,且禁带宽度对温度的变化也不敏感,对太阳光的利用率也不到15%,离理论效率(28-32%)差距很大。现阶段国内外有很多通过掺杂的方法来提高CuInS2的光电转化效率的报道,如Zribi等报道的Sn掺杂CuInS2薄膜,John等报道的Na掺杂可提高CuInS2薄膜的光电特性;等等。但由于CuInS2的能带宽度已经接近最佳太阳能电池材料所需的禁带宽度,元素掺杂在一定程度上改变了CuInS2材料的能带宽度,但引入掺杂元素增加了相应的工艺环节和晶体缺陷形成几率。到目前为止还没有看到由于元素掺杂而显著提高CuInS2薄膜太阳能电池性能的报道。因此,通过金属与非金属元素的单掺杂来提高CuInS2电池光电性能的空间不大。Klenk等采用气相沉积法制备的CuInS2光伏材料,发现Cu的过量会产生CuS的偏析及其复合能带,可增强吸光范围和吸光强度,有利光电转换效率的提高,提高的幅度很少。现行采用真空溅射技术制备的四元化合物CuInGaSe(简称CIGS),是三元化合物CIS通过掺入适量的Ga替代部分In而成的混溶晶体,是目前商用薄膜太阳能电池中居世界最高水平,其光电转化效率也不到30%,与太阳能光电转换率的卡诺上限值可达95%相比,还有很大发展空间。我国虽有非常丰富铜、铟、镓、硒矿床资源,发展CIGS薄膜太阳能电池有得天独厚的天然优势,但其相对高昂的成本难以普惠广大民众。在多元化合物太阳能电池材料中,大多数局限于二元化合物及少量的三元化合物,四元以上化合物的光电性能几乎未见报道。但是,多元化合物太阳能电池材料是今后发展的主要方向。随着科学技术的进步与社会经济的高速发展,世界环境污染问题日趋严重,特别是工业有机废水的污染尤为严重。光催化处理污水技术是目前有机物污水处理中最有效的方法之一。其基本原理就是利用光生电子与空穴所衍生的高能物种氧化还原有机物,使其矿化或转变为无毒无害物质。如采用硫改性的氧化铈半导体材料光催化处置甲基橙;采用二氧化钛及其改性或与其它金属氧化物或硫化物复合的半导体材料光催化处理工业废水,等等;但这些光催化剂的光量子效率均不高,存在处置时间长,日处置量较小,难以工业化等缺陷。
发明内容
本发明的目的在于克服现阶段太阳能电池材料制备技术存在的缺陷和光电转换效率不高等问题,提供一种廉价易得、光电转化效率高、生产成本低、无毒无污染、加工方便、可再生利用、能对紫外-可见光具有全响应范围的氧化锡基太阳能电池纳米材料的制备方法及应用,利用高浓度阴离子表面活性剂对半导体金属硫化物和半导体金属氧化物、及其非金属改性的半导体复合物的微结构调控,实施太阳能电池纳米材料的生产,获得高效的太阳能光电转换材料与高效处理工业污水的光催化剂。
本发明利用所得纳米粉体材料将含有带色基团的有机物在太阳光的辐射下将有机物进行分解,矿化为无毒无害小分子物质;
本发明利用所得纳米粉体材料,可对太阳光进行光电转化,并具有较高的光电转化效率。
本发明的特征是以阴离子表面活性剂苯磺酸钠与手性α-氨基酸为模板,采用固相合成方法制备出一种具有等差能隙梯度的xSnO2.ySnS2.zTiS2复合型太阳能纳米粉体材料,其能隙宽度△Eg=1.55~1.85eV,能隙梯度d=△Eg=1.4eV。
其技术方案如下:
一种氧化锡基太阳能电池纳米材料,包括二氧化锡、二硫化锡和二硫化钛,二硫化锡和二硫化钛较均匀地分布在复合材料中,各组成成分的摩尔比:SnO2:SnS2:TiS2=x:y:z,其中,1.5≤x≤2.5,0.2≤y≤0.6,0.1≤z≤0.25;氧化锡、二硫化锡和二硫化钛分别对太阳光的紫外光、较高能量的可见光及较低能量的可见光均有较强的吸收,这为太阳能的高效利用提供了理论依据。
优选地,SnO2:SnS2:TiS2=x:y:z=(1.8~2.2):(0.25~0.45):(0.1~0.2);其中S的价态中大部分(75.4~95.5%)是-2;有少量(4.5~14.6%)为+4和+6的硫存在。
进一步,所述二氧化锡、二硫化锡以及二硫化钛的微晶尺寸均在6-15nm之间,颗粒尺寸在20-50nm。
一种本发明所述的氧化锡基太阳能电池纳米材料的制备方法,包括以下步骤:按一定摩尔比分别称取五水四氯化锡、钛酸四丁酯、九水硫化钠三种反应物,以及按等摩尔比称取模板剂苯磺酸钠与手性α-氨基酸,模板剂的用量为三种反应物总质量的8%~12%称取。将上述五种物质在研钵中混合研磨20~30min,得到褐黑色糊状物质,静止2-4h后置于烘箱中,于120-150℃下反应90-120min,使未反应的物质能充分反应;将产物冷却到室温后取出研细、去离子水浸泡、搅拌,然后抽滤洗涤6次以上,将所得的滤饼在100-110℃烘干后移入坩埚,在马弗炉中于450-550℃焙烧5h,自然冷却到室温取出,获得氧化锡基太阳能纳米粉体材料。测定其光电转化效率,可达28.82%;将其应用于带色有机物的分解,效果显著,通常20-60min内将带色有机物分解。
本发明所述氧化锡基太阳能电池纳米材料在光催化降解带色有机物过程中的应用。
进一步,将本发明的纳米粉体材料进一步研磨粉碎,移入光催化反应仪中,加入带色有机物污水(如甲基橙、亚甲基蓝等),常温常压下光照反应即可。
再进一步,纳米粉体材料和污水用量比为1:1000g/L,光照波长370-800nm,光照时间为20-60min。
本发明的有益效果:
本发明的纳米粉体材料,在中性环境中降解带色有机物可以循环利用5次及以上,其光催化性能几乎不变;但在酸性环境中光催化性能的稳定性变差。
本发明的纳米粉体材料光电转化较高,制备原材料来源广泛,廉价易得,制备方法简单,成本低;纳米粉体易于压片成型,满足太阳能窗口材料的加工要求。
具体实施方式
下面结合具体实施方式对本发明的技术方案作进一步详细地说明。
以不同用量的苯磺酸钠和手性α-氨基酸为模板,五水四氯化锡、钛酸四丁酯、九水硫化钠三种反应物为本发明的纳米粉体材料制备的前驱物,在确定的研磨时间20min、静置时间240min、反应温度120℃、反应时间120min、焙烧温度500℃的前提下,不同配比的模板剂用量与不同反应前驱物配比的工艺条件下,所得本发明的纳米粉体材料的光电转换效率、以及在相同的纳米粉体用量与带色有机污染物的降解液用量比为1g/L,光降解时间为40min,光催化性能如表1所示:
表1实施案例
本发明氧化锡基太阳能电池纳米材料中的三种化合物的能带间隙宽度分别为3.5、2.1、0.7eV,呈等差数列,其公差d=△Eg=1.4eV,其能隙宽度△Eg=1.55~1.85eV。构建成晶体材料内部的不同电势电场,有利于不同波长太阳光激发的载流子的加速分离,减少不同能量载流子的复合、堙没,提高光电转换效率。复合纳米粉体材料的粒径大小与纳米粒子的隧道效应紧密相关,微晶尺寸与光电转换效率呈正相关性。晶体中的缺陷浓度有利于电荷的转移而产生的界面极化场,有利于光生载流子的分离,在不同内电场的加速分离下,提高光电子的迁移速率,导致光电转换效率的提高。晶体内部具有局部微区手性结构。
以上所述,仅为本发明较佳的具体实施方式,本发明的保护范围不限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可显而易见地得到的技术方案的简单变化或等效替换均落入本发明的保护范围内。
Claims (7)
1.一种氧化锡基太阳能电池纳米材料,其特征在于,包括二氧化锡、二硫化锡和二硫化钛,各组成成分的摩尔比:SnO2:SnS2:TiS2=x:y:z,其中,1.5≤x≤2.5,0.2≤y≤0.6,0.1≤z≤0.25。
2.根据权利要求1所述的氧化锡基太阳能电池纳米材料,其特征在于,SnO2:SnS2:TiS2=x:y:z=(1.8~2.2):(0.25~0.45):(0.1~0.2);其中S的价态中75.4~95.5%是-2;4.5~14.6%为+4和+6。
3.根据权利要求1所述的氧化锡基太阳能电池纳米材料,其特征在于,所述二氧化锡、二硫化锡以及二硫化钛的微晶尺寸均在6-15nm之间,颗粒尺寸在20-50nm。
4.一种权利要求1所述的氧化锡基太阳能电池纳米材料的制备方法,其特征在于,包括以下步骤:按一定摩尔比分别称取五水四氯化锡、钛酸四丁酯、九水硫化钠三种反应物,以及按等摩尔比称取模板剂苯磺酸钠与手性α-氨基酸,模板剂的用量为三种反应物总质量的8%~12%称取;将上述五种物质在研钵中混合研磨20~30min,得到褐黑色糊状物质,静止2-4h后置于烘箱中,于120-150℃下反应90-120min,使未反应的物质能充分反应;将产物冷却到室温后取出研细、去离子水浸泡、搅拌,然后抽滤洗涤6次以上,将所得的滤饼在100-110℃烘干后移入坩埚,在马弗炉中于450-550℃焙烧5h,自然冷却到室温取出,获得氧化锡基太阳能纳米粉体材料。
5.权利要求1所述氧化锡基太阳能电池纳米材料在光催化降解带色有机物过程中的应用。
6.根据权利要求5所述氧化锡基太阳能电池纳米材料在光催化降解带色有机物过程中的应用,其特征在于,将权利要求1的纳米粉体材料进一步研磨粉碎,移入光催化反应仪中,加入带色有机物污水,常温常压下光照反应。
7.根据权利要求6所述所述氧化锡基太阳能电池纳米材料在光催化降解带色有机物过程中的应用,其特征在于,纳米粉体材料和污水用量比为1:1000g/L,光照波长370-800nm,光照时间为20-60min。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110504362A (zh) * | 2019-07-17 | 2019-11-26 | 浙江浙能技术研究院有限公司 | 一种SnO2电子选择传输层的改性方法 |
CN110911508A (zh) * | 2019-11-29 | 2020-03-24 | 湖南文理学院 | 一种新型的紫外-可见全波段吸收材料其制备方法及应用 |
CN111732121A (zh) * | 2020-07-13 | 2020-10-02 | 济南大学 | 一种CuInS2@CuCo-CeO2复合纳米探针及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1460544A (zh) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | 纳米ZnO-SnO2复合氧化物光催化剂的制备方法 |
CN101182032A (zh) * | 2007-11-15 | 2008-05-21 | 电子科技大学 | 一种二氧化锡/氧化硅纳米复合材料的制备方法 |
US9376332B2 (en) * | 2013-03-15 | 2016-06-28 | Nitto Denko Corporation | Multivalence photocatalytic semiconductor elements |
CN107337233A (zh) * | 2017-06-05 | 2017-11-10 | 陕西科技大学 | 一种一步硫化法合成二氧化钛与二硫化钛复合材料的方法 |
-
2018
- 2018-02-07 CN CN201810124783.2A patent/CN108417649B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1460544A (zh) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | 纳米ZnO-SnO2复合氧化物光催化剂的制备方法 |
CN101182032A (zh) * | 2007-11-15 | 2008-05-21 | 电子科技大学 | 一种二氧化锡/氧化硅纳米复合材料的制备方法 |
US9376332B2 (en) * | 2013-03-15 | 2016-06-28 | Nitto Denko Corporation | Multivalence photocatalytic semiconductor elements |
CN107337233A (zh) * | 2017-06-05 | 2017-11-10 | 陕西科技大学 | 一种一步硫化法合成二氧化钛与二硫化钛复合材料的方法 |
Non-Patent Citations (1)
Title |
---|
贺仲兵等: "《硫掺杂氧化锡纳米材料的固相合成及其可见光降解百草枯》", 《无机化学学报》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110504362A (zh) * | 2019-07-17 | 2019-11-26 | 浙江浙能技术研究院有限公司 | 一种SnO2电子选择传输层的改性方法 |
CN110504362B (zh) * | 2019-07-17 | 2023-06-16 | 浙江浙能技术研究院有限公司 | 一种SnO2电子选择传输层的改性方法 |
CN110911508A (zh) * | 2019-11-29 | 2020-03-24 | 湖南文理学院 | 一种新型的紫外-可见全波段吸收材料其制备方法及应用 |
CN110911508B (zh) * | 2019-11-29 | 2021-08-13 | 湖南文理学院 | 一种新型的紫外-可见全波段吸收材料其制备方法及应用 |
CN111732121A (zh) * | 2020-07-13 | 2020-10-02 | 济南大学 | 一种CuInS2@CuCo-CeO2复合纳米探针及其制备方法 |
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