CN113502106B - 一种VO2/SiO2气凝胶复合薄膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种VO2/SiO2气凝胶复合薄膜的制备方法,属于新材料及节能环保领域。本发明以M相VO2粉体和SiO2气凝胶粉体为原料,通过球磨混合分散法获得VO2/SiO2气凝胶复合粉体分散液,然后与成膜液和成膜助剂混合,通过涂覆工艺获得VO2/SiO2气凝胶复合薄膜。该复合薄膜具有高的可见光透过率和太阳光调制能力,因此,在建筑玻璃节能和智能调光玻璃领域具有广泛的应用前景。
Description
技术领域
本发明涉及一种VO2/SiO2气凝胶复合薄膜及其制备方法,属于新材料及节能环保领域。
背景技术
目前,建筑物的能源消耗和节能问题已受到社会各界越来越多的关注,而窗口是建筑物与外界能量交换的主要通道,因此窗口节能在建筑物节能中起着关键作用。二氧化钒(VO2)在68℃具有可逆的绝缘体-金属结构转变,其相变过程中伴随着光学、电学性能的急剧变化,相变前为半导体态,对红外光呈现为高透过特性;相变后为金属态,对红外光呈现为高遮蔽特性。由于太阳辐射的总能量中98%的能量集中于红外光与可见光波段,其中的大多数能量都集中在红外波段,因此,基于VO2热致变色特点制备的智能调光玻璃,可以利用二氧化钒的相变特性实现对室内温度的智能调控,从而达到建筑节能效果。
当前,基于VO2材料制备的智能调光薄膜仍然需要在以下问题方面给予改进和提高:进一步降低VO2相变温度、提高薄膜可见光透过率和太阳光调制能力等。研究表明,通过对VO2进行钨(W)、钼(Mo)等元素掺杂,可以有效降低其相变温度。但是,利用元素掺杂降低VO2的相变温度的同时,也往往会导致可见光透过率降低和太阳光调节能力降低等问题,这成为二氧化钒基智能窗口研究中的瓶颈之一。
发明内容
针对VO2薄膜目前存在的可见光透过率和太阳光调制能力低的问题,本发明旨在提供一种简单方便的VO2/SiO2复合薄膜的制备方法,以M相VO2粉体和常压干燥制备的SiO2气凝胶粉体为原料,通过简单的球磨混合分散法,获得VO2/SiO2气凝胶分散液,再与一定量的成膜剂、溶剂混合,通过涂覆法获得VO2/SiO2气凝胶复合薄膜。
本发明致力于解决VO2薄膜可见光透过率和太阳光调制能力低的问题,采用简单的球磨混合分散法制备涂膜浆料,通过涂覆工艺制备VO2/SiO2气凝胶复合薄膜,本发明所述VO2/SiO2气凝胶复合薄膜同时具有高的可见光透过率和太阳光调制能力,因此,在建筑玻璃节能和智能调光玻璃领域具有广泛的应用前景,且所述粉体及薄膜制备方法具有工艺简单、成本低廉且普适性高等优点。
一种VO2/SiO2气凝胶复合薄膜的制备方法,以M相VO2粉体和SiO2气凝胶粉体为原料,通过简单的球磨混合、分散和涂覆工艺制备获得;所述制备方法包括下述步骤:
(1)分别称取一定量的VO2粉体和SiO2气凝胶粉体,加入一定量的溶剂Ⅰ和磨球,在一定的转速下球磨一段时间后,获得VO2/SiO2气凝胶复合粉体分散液;
所述VO2/SiO2气凝胶复合粉体分散液中VO2粉体和SiO2气凝胶粉体的浓度为0.005~5g/mL,优选为0.01~2g/mL;所述VO2粉体和SiO2气凝胶粉体的质量比为0.1~10:1,优选VO2粉体和SiO2气凝胶粉体的质量比为0.3~8:1;
(2)将VO2/SiO2气凝胶复合粉体分散液与一定量的成膜液混合,搅拌均匀后获得涂膜液,通过涂覆法将涂膜液均匀涂覆在基体表面,最终获得VO2/SiO2气凝胶复合薄膜;
所述VO2/SiO2气凝胶复合粉体分散液与成膜液的体积比为1:2~10;
其中,所述VO2粉体(粒径10~800nm左右)为晶体结构为M相的VO2粉体,所述M相VO2粉体可以为无掺杂的纯相VO2粉体,也可以是掺杂有Zn、W、Mo、F、Mg等金属和非金属元素的元素掺杂VO2(MxVO2,M为Zn、W、Mo、Mg、F等能够通过掺杂降低VO2相变温度的元素,M掺杂量为0.2~20at%)粉体,上述VO2粉体可以通过水热/溶剂热和后热处理法制备获得,也可以直接通过固相反应法获得。
所述SiO2气凝胶粉体为一种直接通过常压干燥工艺获得的具有高孔容积和比表面积的SiO2气凝胶粉体或由常压干燥工艺获得的具有高孔容积和比表面积的SiO2气凝胶块体通过破碎获得,所述SiO2气凝胶粉体的比表面积为500~1000m2/g,孔容积为1.0~6.0m2/g,平均孔直径为3~20nm。
上述技术方案中,;所述VO2粉体和SiO2气凝胶粉体与磨球的质量比为1:20~500,优选1:50~350。
上述技术方案中,所述溶剂Ⅰ为无水乙醇、甲苯、二甲苯、乙二醇甲醚、乙二醇乙醚、乙二醇丁醚、丙酮、二甲基甲酰胺、二甲基乙酰胺、醋酸丁酯、醋酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃中的一种或几种。
上述技术方案中,所述磨球的直径为0.1mm~5mm,球磨机转速为300~1500转/min,球磨时间为10min~3h。
上述技术方案中,所述磨球为氧化锆磨球。
上述技术方案中,所述VO2/SiO2气凝胶复合粉体分散液具有以下特点:VO2/SiO2气凝胶复合粉体分散液经溶剂蒸发干燥后所得到的VO2/SiO2气凝胶复合粉体的比表面积为200~600m2/g,孔体积为0.3~1.5cm3/g,平均孔直径2~10nm。
上述技术方案中,所述成膜液为含有一定量的成膜基质和溶剂Ⅱ的溶液或预聚体,所述成膜基质为聚氨酯、聚乙烯醇缩丁醛、聚甲基丙烯酸甲酯(PMMA)、丙烯酸乳液和醇酸树脂中的一种或几种,所述溶剂为甲苯、无水乙醇、二甲基甲酰胺(DMF)、二甲基乙酰胺、N-甲基吡咯烷酮(NMP)、二甲基亚砜、乙酸乙酯中的一种,所述成膜基质与溶剂Ⅱ的重量百分比为5~50wt%。
上述技术方案中,所述涂覆法为辊涂法、浸渍提拉法、刮涂法等中的一种。
上述技术方案中,所述基体为透明无机或有机基体,优选为普通玻璃、有机玻璃或PET薄膜。
上述技术方案中,涂膜厚度为1~30μm。
本发明所述VO2/SiO2气凝胶复合薄膜,VO2/SiO2气凝胶复合薄膜同时具有较高的可见光透过率和太阳光调制能力,当复合薄膜中所述VO2为元素掺杂VO2时,由于VO2的相变温度降低,复合薄膜同时具有较低相变温度、高可见光透过率和高太阳光调制能力特点。
本发明的有益效果为:本发明提供一种VO2/SiO2气凝胶复合薄膜及其简便的制备方法,该方法以M相VO2粉体和常压干燥工艺制备的SiO2气凝胶粉体为原料,通过球磨混合分散法获得VO2/SiO2气凝胶复合粉体分散液,然后与恰当的成膜液和成膜助剂混合,通过涂覆工艺获得VO2/SiO2气凝胶复合薄膜,所述球磨混合分散过程中SiO2气凝胶通过球磨使孔径变小(球磨过程中大孔破碎,小孔保留)并均匀分散于VO2粒子周围,能够有效阻止VO2粒子的团聚,起到一种促进VO2粒子均匀分散的作用;而且,由于SiO2气凝胶多孔结构和小孔径特点使SiO2气凝胶具有明显的增透作用,因而,本发明所述VO2/SiO2气凝胶复合薄膜因VO2的热致变色和SiO2气凝胶的增透协同作用而呈现出同时具有较高的可见光透过率和太阳光调制能力。当所述VO2为元素掺杂VO2粉体时(相变温度低于68℃),所述VO2/SiO2气凝胶复合薄膜具有较高的可见光透过率和太阳光调制能力,具有更大的实际应用价值和广阔的应用前景。
附图说明
图1为实施例1对应的VO2/SiO2气凝胶复合薄膜样品在高低温下的光谱透过率曲线图。
图2为实施例2对应的VO2/SiO2气凝胶复合薄膜样品在高低温下的光谱透过率曲线图。
图3为实施例3对应的VO2/SiO2气凝胶复合薄膜样品在高低温下的光谱透过率曲线图。
图4为对比例1对应的VO2/SiO2气凝胶复合薄膜样品在高低温下的光谱透过率曲线图。
图5为对比例2对应的VO2/SiO2气凝胶复合薄膜样品在高低温下的光谱透过率曲线图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
下述实施例中所述试验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
下述实施例中,如无特殊说明,对制得的VO2/SiO2气凝胶复合薄膜样品性能参数的测定中:
(1)使用波长范围为300~2500nm的Lambda750分光光度计对VO2/SiO2气凝胶复合薄膜样品的热致变色性能进行监测,通过一个小型加热装置对涂膜玻璃样品进行加热,分别测试涂膜玻璃在20℃和90℃下的透过光谱。为了评估复合薄膜热致变色能力,积分可见光透过率Tlum(380nm≤λ≤780nm)和整个太阳光透过率Tsol(300nm≤λ≤2500nm),分别由方程式(1)和(2)计算得出:
式中,T(λ)表示特定波长λ处的透过率,表示人眼视觉的标准发光效率函数,表示空气质量1.5(对应于高于地平线37°的太阳)的太阳辐照度光谱。相变前后可见光透过率变化ΔTlum和太阳光调制能力ΔTsol分别由下面公式得出:
ΔTlum=Tlum(90℃)-Tlum(20℃) (3)
ΔTsol=Tsol(90℃)-Tsol(20℃) (4)
实施例1
分别称取0.2gVO2粉体(粒径200~500nm)和0.2g的SiO2气凝胶(比表面积为647m2/g,孔容积为5.3cm3/g,平均孔径为15.4nm),将其放入内含10mLN,N-二甲基甲酰胺(DMF)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在转速为600r/min球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-DMF溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片(2cm×4cm)表面,最终获得VO2/SiO2气凝胶复合薄膜。
研究表明,上述方法所制备的VO2/SiO2气凝胶复合薄膜在20℃下可见光透过率为41.8%,加热到90℃时可见光透过率为40.2%,平均可见光透过率为41%,太阳光调制能力为12.9%。
实施例2
分别称取0.2gVO2粉体(粒径200~500nm)和0.4g的SiO2气凝胶(比表面积为647m2/g,孔容积为5.3cm3/g,平均孔径为15.4nm),将其放入内含10mLDMF(N,N-二甲基甲酰胺)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在转速为600r/min球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-DMF溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片(2cm×4cm)表面,最终获得VO2/SiO2气凝胶复合薄膜。
研究表明,上述方法所制备的VO2/SiO2气凝胶复合薄膜在20℃下可见光透过率为38.8%,加热到90℃时可见光透过率为43.4%,平均可见光透过率为41%,太阳光调制能力为14.0%。
实施例3
分别称取0.2gMg掺杂VO2(2at%Mg-VO2)粉体(粒径200~500nm)和0.2g的SiO2气凝胶(比表面积为647m2/g,孔容积为5.3cm3/g,平均孔径为15.4nm),将其放入内含10mLDMF(N,N-二甲基甲酰胺)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在转速为600r/min球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-NMP溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片(2cm×4cm)表面,最终获得VO2/SiO2气凝胶复合薄膜。
研究表明,上述方法所制备的Mg-VO2/SiO2气凝胶复合薄膜在20℃下可见光透过率为45.7%,加热到90℃时可见光透过率为49.0%,平均可见光透过率为47.4%,太阳光调制能力为13.7%。
实施例4
分别称取0.2gZn掺杂VO2(2at%Zn-VO2)粉体(粒径200~500nm)和0.2g的SiO2气凝胶(比表面积为647m2/g,孔容积为5.3cm3/g,平均孔径为15.4nm),将其放入内含10mLDMF(N,N-二甲基甲酰胺)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在转速为600r/min球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-DMF溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片(2cm×4cm)表面,最终获得VO2/SiO2气凝胶复合薄膜。
研究表明,上述方法所制备的Zn-VO2/SiO2气凝胶复合薄膜在20℃下可见光透过率为48.6%,加热到90℃时可见光透过率为47.4%,太阳光调制能力为21.0%。
对比例1
称取0.2gVO2粉体(粒径200~500nm),将其放入内含10mLDMF(N,N-二甲基甲酰胺)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在转速为600r/min球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-DMF溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片(2cm×4cm)表面,最终获得VO2薄膜。
研究表明,上述方法所制备的VO2薄膜在20℃下可见光透过率为39.0%,加热到90℃时可见光透过率为41.1%,平均可见光透过率为40.1%,太阳光调制能力为6.4%。
对比例2
分别称取0.2gVO2粉体和0.2g的普通SiO2粉体(粒径5μm左右),将其放入内含10mLDMF(N,N-二甲基甲酰胺)和60g直径1mm的氧化锆磨球的玛瑙球磨罐中,在600r/min转速下球磨30min;抽取3mL球磨混合液与12mL的25wt%PMMA-DMF溶液(PMMA的DMF溶液)搅拌20min,以获得涂膜液,通过锟涂法将涂膜液均匀涂覆在玻璃基片表面,最终获得VO2/SiO2复合薄膜。
研究表明,上述方法所制备的VO2/SiO2复合薄膜在20℃下可见光透过率为40.1%,加热到90℃时可见光透过率为41.7%,平均可见光透过率为40.9%,太阳光调制能力为5.2%。
Claims (10)
1.一种VO2/SiO2气凝胶复合薄膜的制备方法,其特征在于,包括如下步骤:
(1)将VO2粉体和SiO2气凝胶粉体与溶剂Ⅰ进行球磨,获得VO2/SiO2气凝胶复合粉体分散液;
所述VO2/SiO2气凝胶复合粉体分散液中VO2粉体和SiO2气凝胶粉体的浓度为0.005~5g/mL,所述VO2粉体和SiO2气凝胶粉体的质量比为0.1~10:1;
(2)将VO2/SiO2气凝胶复合粉体分散液与成膜液混合,搅拌均匀后获得涂膜液,通过涂覆法将涂膜液均匀涂覆在基体表面,最终获得VO2/SiO2气凝胶复合薄膜;
所述VO2/SiO2气凝胶复合粉体分散液与成膜液的体积比为1:2~10;
所述VO2粉体为晶体结构为M相的VO2粉体;
所述VO2粉体的粒径10~800nm;所述SiO2气凝胶粉体的比表面积为500~1000m2/g,孔容积为1.0~6.0m2/g,平均孔直径为3~20nm。
2.根据权利要求1所述的制备方法,其特征在于,所述M相VO2粉体为无掺杂的纯相VO2粉体,或掺杂有Zn、W、Mo、F、Mg的VO2粉体,掺杂量为0.2~20at%。
3.根据权利要求1所述的制备方法,其特征在于,所述溶剂Ⅰ为无水乙醇、甲苯、二甲苯、乙二醇甲醚、乙二醇乙醚、乙二醇丁醚、丙酮、二甲基甲酰胺、二甲基乙酰胺、醋酸丁酯、醋酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃中的一种或几种。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述VO2粉体和SiO2气凝胶粉体与磨球的质量比为1:20~500,磨球的直径为0.1mm~5mm。
5.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,球磨的转速为300~1500转/min,球磨的时间为10min~3h。
6.根据权利要求1或4所述的制备方法,其特征在于,步骤(1)中,磨球为氧化锆磨球。
7.根据权利要求1所述的制备方法,其特征在于,所述成膜液为成膜基质和溶剂Ⅱ的溶液或预聚体,所述成膜基质为聚氨酯、聚乙烯醇缩丁醛、聚甲基丙烯酸甲酯、丙烯酸乳液和醇酸树脂中的一种或几种,所述溶剂Ⅱ为甲苯、无水乙醇、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、乙酸乙酯中的一种,所述成膜基质与溶剂Ⅱ的重量百分比为5~50wt%。
8.根据权利要求1所述的制备方法,其特征在于,所述涂覆法为辊涂法、浸渍提拉法、刮涂法中的一种;所述基体为透明无机或有机基体。
9.根据权利要求8所述的制备方法,其特征在于,所述基体为普通玻璃、有机玻璃或PET薄膜。
10.权利要求1-9中任意一项所述的制备方法制得的VO2/SiO2气凝胶复合薄膜。
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WO2020242314A1 (en) * | 2019-05-29 | 2020-12-03 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Thermochromic materials |
CN112919820A (zh) * | 2021-01-21 | 2021-06-08 | 大连工业大学 | 一种Zn掺杂VO2粉体及利用该粉体制备复合薄膜的方法 |
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