CN107236378A - 太阳能电池背板用涂料组合物及其太阳能电池背板 - Google Patents
太阳能电池背板用涂料组合物及其太阳能电池背板 Download PDFInfo
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- CN107236378A CN107236378A CN201710245918.6A CN201710245918A CN107236378A CN 107236378 A CN107236378 A CN 107236378A CN 201710245918 A CN201710245918 A CN 201710245918A CN 107236378 A CN107236378 A CN 107236378A
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Abstract
本发明提供了一种太阳能电池背板用涂料组合物及其太阳能电池背板，该涂料组合物包括如下组分：石墨烯类填料、树脂、二氧化钛、溶剂、固化剂和助剂，该太阳能电池背板的制备方法括如下步骤：将石墨烯类填料和PET切片混合均匀后，依次进行混炼、挤出、转鼓定型和双向拉伸，得到太阳能电池背板；将所述太阳能电池背板的表面处理出低温等离子体，利用前述的涂料组合物对太阳能电池背板的表面进行涂覆；进行烘干固化，得到产品。本发明采用石墨烯作为太阳能背板涂料的添加剂，使其产品具有机械性能好、耐紫外性好(耐老化，耐候性增强)、导热性好(散热快，耐高温，安全性高，提高了电池效率寿命等)等优点，使其在各种环境气候中都具有广泛的应用。
Description
技术领域
本发明涉及一种太阳能电池背板用涂料组合物及其太阳能电池背板，属于光伏技术领域。
背景技术
光伏发电是一种新能源，通过光伏效应可以将太阳能转变为电能，可作替代传统电能的绿色方案。光伏电池组件是由各种半导体元件组装而成，普遍采用玻璃、电池硅片、EVA、背板材料热压而成，因而必须加以保护以减少环境作用如湿气、氧气和紫外线带来的影响和破坏。因此，具有优良的电气绝缘性、层间粘结强度、耐候性、抗紫外性和阻湿性能的背板在光伏电池组件中发挥着重要的保护作用。
专利CN 104231701 A介绍了一种用于光伏组件的红外散热涂料及散热光伏组件背板的制备方法。通过在环氧或者酚醛树脂中加入炭黑来增加背板的散热性，降低光伏组件的工作温度，从而提高组件的输入功率，降低了光伏发电成本。但其所用树脂耐候性没有氟树脂强，炭黑导热率也远不如石墨烯。
专利CN 103740192 A公布了一种石墨烯改性的氟树脂涂料。石墨烯的加入增强了涂料的机械性能和耐腐蚀性，可用于建筑、炊具、航海等领域。因为其产品配方未考虑用于太阳能背板涂料，仍有很多不足，无法满足需求。
专利CN 103182823 A公布了一种太阳能电池背板及生产方法。利用改性聚氯乙烯来增加与PET层的粘附力。其工艺过于复杂。而通过石墨烯的掺杂，可以简单有效地改善涂层粘附力。
发明内容
针对现有技术中的缺陷，本发明的目的是提供一种太阳能电池背板用涂料组合物及其太阳能电池背板。
本发明是通过以下技术方案实现的：
第一方面，本发明提供了一种太阳能电池背板涂料组合物，其包括按重量份数计的如下组分：
作为优选方案，所述树脂选自氟碳树脂、聚氨酯、丙烯酸树脂、环氧树脂和有机硅树脂中的至少一种。
作为优选方案，所述溶剂选自乙酸丁酯、乙酸乙酯、丁酮中的一种或几种。
作为优选方案，所述固化剂选自异氰酸酯、多异氰酸酯、三聚氰胺、胺基树脂、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的一种或几种。
作为优选方案，所述助剂包括消泡剂和流平剂中的一种或两种。
作为优选方案，所述石墨烯类填料包括石墨烯和/或石墨烯改性产物。
第二方面，本发明提供了一种如前述的太阳能电池背板涂料组合物的制备方法，其特征在于，包括如下步骤：
将石墨烯类填料、树脂、二氧化钛和溶剂混合均匀后，进行超声处理；
加入固化剂和助剂，混合均匀即可。
第三方面，本发明提供了一种涂覆有前述的涂料组合物的太阳能电池背板的制备方法，其包括如下步骤：
将石墨烯类填料和PET切片混合均匀后，依次进行混炼、挤出、转鼓定型和双向拉伸，得到太阳能电池背板；
将所述太阳能电池背板的表面处理出低温等离子体，利用权利要求1所述的涂料组合物对太阳能电池背板的表面进行涂覆；
进行烘干固化，得到产品。
本发明中，PET基体的选择有PET/FC01 BK507，PET/CB608，PET/PT 811，PET/PTX279，PET/WB-8816，PET/A02 307，PET/7755，PET/A02 306，PET/A06 700，PET/A06 300等薄膜级别的PET。添加剂石墨烯的种类主要为氧化石墨烯，有机短链改性氧化石墨烯，有机长链改性氧化石墨烯，阻燃剂改性氧化石墨烯。其中有机短链改性剂的选择有SDS、SDBS、硅烷偶联剂，铝酸酯偶联剂，钛酸酯偶联剂等表面活性剂或者偶联剂。其中有机长链改性剂有聚阳离子表面活性剂，司盘，吐温等有机长链高分子表面活性剂。这些有机改性剂的加入一方面可以提高氧化石墨烯与PET基体相容性进而增加基体的机械性能，一方面有助于提高氧化石墨烯通过熔融复合在PET基体的分散性，进而在很低的添加量下便可以大幅度提高PET背底板的气体和水的阻隔性能，抗紫外性能以及隔热性能等综合性能。其中阻燃性改性剂的选择有多溴联苯醚(四溴联苯醚、五溴、六溴、八溴、十溴等)，Al(OH)3，有机磷等。这些改性剂加入的主要目的主要是为了增加PET基体的阻燃性能，进而宽化并延长太阳能电池的使用温度和寿命。
太阳能电池背板的制造原理为：首先规模化制备氧化石墨烯，再对氧化石墨烯表面和结构进行修饰和优化。然后将处理后的改性氧化石墨烯与PET切片通过高速混炼机预混均匀，在高能冲击作用下使得石墨烯均匀且充分地黏附在PET切片上，最后经过双螺杆熔融挤出，通过螺杆的剪切和挤压，石墨烯在被充分剥离的同时还可以使得PET分子很好的排列且缠绕在石墨烯片层上。
作为优选方案，所述石墨烯类填料包括石墨烯和/或石墨烯改性产物。
作为优选方案，所述石墨烯改性产物选自氧化石墨烯、偶联剂改性氧化石墨烯、氨基高分子改性氧化石墨烯、阳离子表面活性剂改性氧化石墨烯、溴代十二烷改性氧化石墨烯、溴代十六烷改性氧化石墨烯、溴代十八烷改性石墨烯、还原石墨烯中的至少一种。
作为优选方案，所述氧化石墨烯的制备方法为改进的Hummers法或改进的Hummers法，其中，改进的Hummers法为：调控硫酸和高锰酸钾的比例，在后期氧化过程中通过对氧化时间的进一步延长，从而省去前期的与氧化过程，大大节约了制备时间成本和原料成本。
作为优选方案，所述低温等离子体的处理方法是利用5～15kV/m2的高频高压电晕对太阳能电池背板的表面进行处理。
作为优选方案，所述涂覆的方式为喷涂或滚涂，所述喷涂的压力为0.1～0.3MPa。
作为优选方案，所述混炼的步骤中，是将石墨烯与树脂切片在高速混炼机中预混2～10min，控制高速混炼机的转速为8000～12000rpm；所述挤出的步骤中，控制螺杆的温度为260～290℃，进料机的转速为10～15rpm，主机的转速为20～30rpm；所述转鼓干燥的步骤中，控制干燥温度为100～180℃，转速为1～5rpm，真空度为20～50Pa；所述双向拉伸的步骤中，控制拉伸温度为80～90℃，拉伸倍数为3～4倍，冷却温度为30～50℃，慢辊辊速为20～100m/min，中辊辊速为30～250m/min，快辊辊速为30～450m/min。
与现有技术相比，本发明具有如下的有益效果：
1、采用石墨烯作为太阳能背板涂料的添加剂，使其产品具有机械性能好(强度大，耐磨性好，附着力强，不易分层)、耐紫外性好(耐老化，耐候性增强)、导热性好(散热快，耐高温，安全性高，提高了电池效率寿命等)等优点，使其在各种环境气候中都具有广泛的应用；
2、该树脂-石墨烯复合背地板材料在极低浓度石墨烯添加量下具有优良的气体/水阻隔性能(0.008-0.13g/m2*d)，隔热性能，抗紫外性能(UPF>110)，抗老化性能(黄变值△b在0.02-0.18/10d-350KW)，抗菌性能(抗菌率>96.8％)，此外还有出色的阻燃性(LOI>32)能以及稳定的绝缘性能(Rv:E9-E10)，解决了传统太阳能背底板材料性能的单一性，并且组装成太阳能电池不仅简化了太阳能电池背底板的组装工艺，而且大幅度提高了太阳能电池的使用寿命；
3、本发明较于同类型专利最大的不同在于通过对PET切片的石墨烯改性，从根源上满足了作为太阳能电池背底板PET基体所应该具有的热稳定性，自清洁性能，抗老化性能，气体/水阻阻隔性能，抗紫外性能，除此之外还拥有更加优异的机械强度。通过添加0.2wt.％的有机高分子改性氧化石墨烯后，其薄膜的拉伸断裂强度平均提高了65％，基膜在100℃高温蒸煮使断裂伸长率衰减至10％，蒸煮时间20h。在36℃，80％RH测试环境下，水蒸气透过率为0.008～0.13g/m2*d，相较于无添加石墨烯的PET薄膜提高了92％。复合基膜在紫外灯经250kWh/m2的能量照射后，黄变值△b在0.02～0.18，相较于无添加石墨烯的PET薄膜提高了88％。此外复合石墨烯的PET薄膜大肠杆菌和金黄色葡萄球菌的抗菌率达到了96％以上。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为改性氧化石墨烯的TEM照片；
图2为改性氧化石墨烯复合膜的紫外吸收谱；
图3为改性氧化石墨烯复合膜的抗菌效果展示。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯1份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份FEVE，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。改性石墨烯的制备方法为：将5g的氧化石墨分散在5L大烧杯中，超声分散40min，然后加热到35度机械搅拌下加入15g固含量的磷酸酯偶联剂溶液，加入10ml的乙酸，反向析出后抽滤干燥，反复洗涤致无改性剂残留时(每次用500ml去离子水进行少量多次洗涤，洗涤5次)，冷冻干燥即可。
本实施例制备的改性氧化石墨烯的TEM照片如图1所示，改性后的氧化石墨烯表面明显附着有很多小点，直接证明改性有机链分子与氧化石墨烯片强的作用力和充分的改性效果。
三、在经历过清理和电晕处理的PET板材表面辊涂上述涂料，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
本实施例制备的石墨烯-PET板材的紫外光透过测试图谱如图2所示，PET与改性氧化石墨烯复合后对紫外线有着极强的阻隔穿透效应，从而使得复合薄膜拥有极好的抗紫外性能。
抗菌测试结果如图3所示，PET与改性氧化石墨烯复合后对大肠杆菌有着极为出色的抗菌能力。
实施例2
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯0.1份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份FEVE，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。改性石墨烯的制备方法为：将5g的氧化石墨分散在5L大烧杯中，超声分散40min，然后加热到35度机械搅拌下加入15g固含量的铝酸酯偶联剂溶液，并加入10ml的乙酸，反向析出后抽滤干燥，反复洗涤致无改性剂残留时(每次用500ml去离子水进行少量多次洗涤，洗涤5次)，冷冻干燥即可。
三、在经历过清理和电晕处理的PET板材表面辊涂上述涂料，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
实施例3
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯0.01份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份FEVE，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。改性石墨烯的制备方法：将5g的氧化石墨分散在5L大烧杯中，超声分散40min，然后加热到35度机械搅拌下加入5g固含量的十八烷基溴化胺的溶液，反向析出后抽滤干燥，反复洗涤致无改性剂残留时(每次用500ml去离子水进行少量多次洗涤，洗涤5次)，冷冻干燥即可。
三、在经历过清理和电晕处理的PET板材表面喷涂上述涂料，压力0.2MPa，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
实施例4
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯1份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份PAA，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。改性石墨烯的制备方法为：将优选的5g的氧化石墨分散在5L大烧杯中，超声分散40min，然后加热到35度机械搅拌下加入15g固含量的钛酸酯偶联剂的溶液，加入10ml的乙酸，反向析出后抽滤干燥，反复洗涤致无改性剂残留时(每次用500ml去离子水进行少量多次洗涤，洗涤5次)，冷冻干燥即可。
三、在经历过清理和电晕处理的PET板材表面辊涂上述涂料，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
实施例5
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯0.1份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份PAA，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。
三、在经历过清理和电晕处理的PET板材表面辊涂上述涂料。经80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
实施例6
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机的容器中加入改性石墨烯0.01份，乙酸丁酯30份，充分搅拌30分钟，超声5分钟，至无大片可见石墨烯存在。然后加入30份PAA，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。改性石墨烯的制备方法为：将5g的氧化石墨分散在5L大烧杯中，超声分散40min，然后加热到35度机械搅拌下加入5g固含量的十八烷基二甲基氧化胺的溶液，反向析出后抽滤干燥，反复洗涤致无改性剂残留时(每次用500ml去离子水进行少量多次洗涤，洗涤5次)，冷冻干燥即可。
三、在经历过清理和电晕处理的PET板材表面喷涂上述涂料，压力0.2MPa。经80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的石墨烯增强型太阳能背板。
对比例1
本对比例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机溶剂的容器中加入30份乙酸丁酯，30份FEVE，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。
在经历过清理和电晕处理的PET板材表面辊涂上述涂料，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的对比太阳能背板。
对比例2
本实施例涉及一种太阳能电池背板用涂料组合物的制备：
一、按下列配方配料：
二、在耐有机溶剂的容器中加入30份乙酸丁酯，30份PAA，10份钛白粉，搅拌30分钟后过滤。最后，加入5份异氰酸酯，搅拌10分钟后，得到所需涂料。
在经历过清理和电晕处理的PET板材表面辊涂上述涂料，80℃干燥10分钟后，将涂层样放入熟化室内，50℃，3天，得到所需的对比太阳能背板。
对实施例中制得的光伏背板和对比例中制得的光伏背板进行性能检测，具体如表1所示：
表1
涂层附着力测试
依据标准GB/T9286-1998进行测试
QUV老化处理测试
依据标准GB/T 16422.3-2014,
水汽透过率测试
依据标准ASTM F1249-2006，在38℃/100％RH条件下进行。
如表1所示，本发明的光伏背板分别以氟树脂和丙烯酸树脂为涂层基体材料，以改性石墨烯为增强材料制得，其水汽阻隔率有明显提高。经过湿热老化后仍保持有良好的水汽阻隔性能。QUV老化处理证明改性石墨烯增强料有效的提高了光伏背板的耐紫外性能。
实施例7
本实施例涉及一种太阳能电池背板的制备，包括如下步骤：
1、规模化制备氧化石墨烯(优化Hummers法规模化制备氧化石墨，洗涤3～5次后在酸性条件下超声即可，简化了洗涤过程，大幅降低了污染程度并降低了成本)。
优化后的Hummers法制备氧化石墨烯的方法为：
1)460mL浓硫酸加入2L的烧杯中，冰浴温度为0℃；
2)石墨粉加入，待分散均匀后加入60g的KMnO4，期间温度保持10℃以下；
3)升高溶液温度至35℃，2h之后，再延长1.5h即可再加入920mL的蒸馏水(30mL等份加入保持温度低于50℃，即分批次加入，每批次加入30mL)，搅拌2h后，加入2.8L蒸馏水，再加入50mL左右的H2O2，冒泡完全溶液成亮黄色；
4)放置一天后，移除上清液至废液瓶，对剩余物多层沉降后再用10wt.％的盐酸洗涤，最后置换至pH大于1即可。
2、超声后的酸性氧化石墨烯分散液与改性剂(如硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、磷酸酯偶联剂，十二烷基二甲基氧化胺、十六烷基二甲基氧化胺、18烷基二甲基氧化胺、溴代十二烷、溴代十六烷、溴代十八烷、十八烷基溴化铵、有咪唑啉、吗啉胍类、三嗪类衍生物等)分子进行反应接枝，在酸性条件下均有利用催化上述改性剂在氧化石墨烯片上的接枝，一定温度和时间后抽滤并多次洗涤后冷冻干燥即可。
3、将干燥好的定量的改性氧化石墨烯与PET切片按照一定的比例(0.05～10wt.％)在预混机中高速混合2～15min，使得石墨烯完全黏附在PET切片上。
4、预混处理之后，将物料投入双螺杆混炼机中，双螺杆温区温度在260～290℃之间，进料速度在20～50g/min之间，螺杆速度在20～50rpm之间，挤出后经过冷却转鼓定型，最后双向拉伸成膜。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。
Claims (15)
1.一种太阳能电池背板涂料组合物，其特征在于，包括按重量份数计的如下组分：
2.如权利要求1所述的太阳能电池背板涂料组合物，其特征在于，所述树脂选自氟碳树脂、聚氨酯、丙烯酸树脂、环氧树脂和有机硅树脂中的至少一种。
3.如权利要求1所述的太阳能电池背板涂料组合物，其特征在于，所述溶剂选自乙酸丁酯、乙酸乙酯、丁酮中的一种或几种。
4.如权利要求1所述的太阳能电池背板涂料组合物，其特征在于，所述固化剂选自异氰酸酯、多异氰酸酯、三聚氰胺、胺基树脂、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体中的一种或几种。
5.如权利要求1所述的太阳能电池背板涂料组合物，其特征在于，所述助剂包括消泡剂和流平剂中的一种或两种。
6.如权利要求1所述的太阳能电池背板涂料组合物，其特征在于，所述石墨烯类填料包括石墨烯和/或石墨烯改性产物。
7.一种如权利要求1所述的太阳能电池背板涂料组合物的制备方法，其特征在于，包括如下步骤：
将石墨烯类填料、树脂、二氧化钛和溶剂混合均匀后，进行超声处理；
加入固化剂和助剂，混合均匀即可。
8.一种涂覆有权利要求1所述的涂料组合物的太阳能电池背板的制备方法，其特征在于，包括如下步骤：
将石墨烯类填料和PET切片混合均匀后，依次进行混炼、挤出、转鼓定型和双向拉伸，得到太阳能电池背板；
将所述太阳能电池背板的表面处理出低温等离子体，利用权利要求1所述的涂料组合物对太阳能电池背板的表面进行涂覆；
进行烘干固化，得到产品。
9.如权利要求8所述的太阳能电池背板的制备方法，其特征在于，所述石墨烯类填料为石墨烯或石墨烯改性产物。
10.如权利要求8所述的太阳能电池背板的制备方法，其特征在于，所述石墨烯改性产物选自氧化石墨烯、偶联剂改性氧化石墨烯、氨基高分子改性氧化石墨烯、阳离子表面活性剂改性氧化石墨烯、溴代十二烷改性氧化石墨烯、溴代十六烷改性氧化石墨烯、溴代十八烷改性石墨烯、还原石墨烯中的至少一种。
11.如权利要求8～10中任意一项所述的太阳能电池背板的制备方法，其特征在于，所述石墨烯类填料的添加量为PET切片重量的0.05～10％。
12.如权利要求11所述的太阳能电池背板的制备方法，其特征在于，所述氧化石墨烯的制备方法为Hummers法。
13.如权利要求8所述的太阳能电池背板的制备方法，其特征在于，所述低温等离子体的处理方法是利用5～15kV/m2的高频高压电晕对太阳能电池背板的表面进行处理。
14.如权利要求8所述的太阳能电池背板的制备方法，其特征在于，所述涂覆的方式为喷涂或滚涂，所述喷涂的压力为0.1～0.3MPa。
15.如权利要求8所述的太阳能电池背板的制备方法，其特征在于，所述混炼的步骤中，是将石墨烯与树脂切片在高速混炼机中预混2～10min，控制高速混炼机的转速为8000～12000rpm；所述挤出的步骤中，控制螺杆的温度为260～290℃，进料机的转速为10～15rpm，主机的转速为20～30rpm；所述转鼓干燥的步骤中，控制干燥温度为100～180℃，转速为1～5rpm，真空度为20～50Pa；所述双向拉伸的步骤中，控制拉伸温度为80～90℃，拉伸倍数为3～4倍，冷却温度为30～50℃，慢辊辊速为20～100m/min，中辊辊速为30～250m/min，快辊辊速为30～450m/min。
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| CN107652794A (zh) * | 2017-10-25 | 2018-02-02 | 佛山科学技术学院 | 一种石墨烯改性散热‑防腐氟碳功能涂料及其制备方法 |
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| CN108102539A (zh) * | 2018-01-09 | 2018-06-01 | 江阴振宏重型锻造有限公司 | 石墨烯防腐涂料及其制备方法以及涂覆风电主轴的方法 |
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| CN110105869A (zh) * | 2019-04-09 | 2019-08-09 | 广东墨睿科技有限公司 | 一种改性石墨烯散热涂料及其制备方法 |
| CN110183939A (zh) * | 2019-06-26 | 2019-08-30 | 陕西科技大学 | 一种石墨烯/环氧树脂防腐涂料的制备方法 |
| CN110712412A (zh) * | 2019-10-14 | 2020-01-21 | 合肥乐凯科技产业有限公司 | 一种耐候阻隔聚酯薄膜及其制造方法 |
| CN110655884A (zh) * | 2019-10-25 | 2020-01-07 | 江苏国胶新材料有限公司 | 一种纳米材料改性丙烯酸酯压敏胶及其制备方法 |
| CN111793414A (zh) * | 2020-07-10 | 2020-10-20 | 普罗旺斯科技（深圳）有限公司 | 一种抗菌散热涂层及其制备方法 |
| CN113527961A (zh) * | 2021-07-15 | 2021-10-22 | 南通强生光电科技有限公司 | 增强太阳能发电板输出功率的涂层的制备及其应用 |
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