CN113788461A - 一种生物矿化的微反应器调控固态合成纳米材料及其储钾器件的应用 - Google Patents
一种生物矿化的微反应器调控固态合成纳米材料及其储钾器件的应用 Download PDFInfo
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Abstract
微型反应系统在纳米材料的液相或液‑气相中的合成取得了重要的进展，但在固态合成中研究甚少。本专利采用仿生矿化的方法，原位制备了一种新型的生物矿化的微反应器，其外部由介晶氯化钾外壳以及内部由卡拉胶胶体颗粒填充组成。得益于氯化钾良好的热稳定性和生物矿化结构的紧凑性，微反应器在高温固态合成TM（过渡金属）‑S‑Se纳米材料方面展现出良好的通用性。其中，所制备的MoSxSe2‑x/C纳米复合材料具有良好的均匀性、高产率和有毒气体排放少等优点，并具有优异的K+存储性能。封闭的反应体系不仅使得在空气中制备非氧化物纳米材料成为可能，大大减少了生产过程和成本。而且作为一种新的绿色合成技术，为工业生产中调控固态合成纳米材料打开了一扇新的大门。
Description
技术领域
本发明属于纳米材料合成领域，提供了一种空气中调控高温固态合成纳米材料的方法——生物矿化微反应器，以及在储钾器件中的应用。
背景技术
随着纳米技术的快速发展，许多新型的纳米材料已经被合成，其中多种材料表现出令人印象深刻的特性和诱人的应用前景。尽管在实验室合成的过程很好，但在大规模生产纳米材料时遇到一系列问题，这大大限制了其商业应用。其中一个问题是设备成本高，高压或释放有毒气体带来的安全风险。另一个问题是，纳米材料的高活性和严重团聚会大大降低规模化生产中结构和成分的可控性和均匀性，导致性能和功能的降低。因此，人们非常期待创新的方法来实现纳米材料的可控规模制备。
近年来，微型化反应系统在化学合成中获得了显著的地位。在这种方法中，化学反应从一个大的反应器转移到许多内部有微小通道或腔室的微反应器中，实现了产品的高产量、良好的均匀性和较少的能源消耗。不幸的是，尽管微反应器在合成各种纳米材料，如金属、氧化物、量子点和沸石方面有许多成功的报道，但这种微反应器只适用于液-液或液-气相合成，不适合工业生产中占主导地位的固态反应。因此，开发新的小型化反应系统用于纳米材料的固态合成具有非常重要的研究意义和广阔的应用前景。
本专利设计并制备了一种新型的微反应器，通过仿生矿化的方法进行纳米材料的高温固态合成。生物矿化的微反应器具有介晶特性的KCl外壳和生物分子内核，里面可以填充反应前驱体物质。得益于KCl外壳良好的热稳定性、保温性、刚度和机械强度，在微反应器中进行了TM（过渡金属）-S-Se三元体系的高温固态合成。其中所制备的MoSxSe2-x/C复合材料具有较高的均匀性以及优异的储钾性能。更重要的是，该微反应器提供的封闭的微反应环境不仅使得在空气中合成非氧化物纳米材料成为可能，而且也有利于在实验室研究和工业规模化生产中控制合成各种纳米材料。
发明内容
本发明所要解决的技术问题是用生物矿化的微反应器在空气中实现对固态合成纳米材料的调控，并且将其作为电极材料应用于钾离子混合电容器。为了解决上述的技术问题，本发明采用的技术方案是：将卡拉胶与适当比例的反应物前驱体溶解在热水中，加入一定量的氯化钾，之后进行冷冻干燥，此过程中会形成卡拉胶胶体，并进一步诱导氯化钾进行生物矿化过程，形成生物矿化的微反应器。在马弗炉中升温至指定温度并保持合适的时间进行高温固态反应。将反应后的产物进行多次水洗，经真空干燥后获得样品。最后将获得的样品用作电极材料，应用于高性能的钾离子混合电容器。
与现有技术相比，本发明的有益效果体现在：
(1) 生物矿化微反应器技术方法得益于其自身形成的独特的结构以及微反应环境，使得在空气中制备非氧化物纳米材料成为可能，这大大降低了反应条件，极大地缩小了制备成本；
(2) 适用于制备其他纳米复合材料，例如FeSxSe2-x，Co9SxSe8-x，SnSxSe1-x，CuSxSe1-x，展示了该技术较好的通用性；
(3) 制备的纳米复合材料具有良好的均匀分散性，应用电极材料展现出优异的电化学性能，为高性能器件的开发开辟了道路；
(4) 该技术工艺绿色环保，制备流程简易，成本低，通用性高，实用性强，便于推广应用。
附图说明
图1为实施例1-3制备的MoSxSe2-x/C复合材料的X射线衍射分析(XRD)谱图。
图2为实施例2制备的MoSxSe2-x/C复合材料水洗前的扫描电子显微镜(SEM)图及透射电子显微镜(TEM)图。
图3为制备的MoSxSe2-x/C复合材料的透射电子显微镜(TEM)图。
图4为实施例4-7制备的复合材料的X射线衍射分析 (XRD)谱图。
图5为实施例4-7制备的复合材料的扫描电子显微镜(SEM)图。
图6为本发明实施例2制备的MoSxSe2-x/C复合材料作为钾离子混合电容器电极，测得的能量-功率密度曲线。
图7为本发明实施例2制备的MoSxSe2-x/C复合材料组装成钾离子混合电容器，在5A g-1电流密度下测得的循环寿命，插图为该器件点亮的LED小灯泡。
具体实施方式
现参考以下具体实施例对本发明做出说明，但并非仅限于实施例。
实施例1
将2 g k-型卡拉胶，0.50 g (NH4)6Mo7O24·4H2O，0.50 g H2SeO3溶解在200 ml的去离子水中，加热至80 ℃至其完全溶解。然后在剧烈搅拌下加入20 g KCl。将样品放入-40℃冰箱中冷冻12 h，并且放入真空冷冻干燥机中干燥。之后放入马弗炉中在600 ℃加热10min，经过多次去离子水洗涤，在真空烘箱中干燥获取最终样品。将该纳米复合材料进行表征，表征结果如图1。如图1的XRD谱图所示，实施例1具有良好的结晶性，并且对应于MoSxSe2-x。
实施例2
本实施例的方法与实施例1基本相同，不同之处为：在实施例1的基础上，在马弗炉中600 ℃加热30 min。并将其进行表征，表征结果如图1-3。如图1的XRD谱图所示实施例2具有良好的结晶性，并且对应于MoSxSe2-x。图2的SEM图展示了生物矿化后的微反应器的基本形貌，内部由卡拉胶胶体颗粒及反应物填充，外部由介晶氯化钾外壳组成。该微反应器内部构成封闭的微反应环境，使得在空气中制备非氧化物成为可能。进一步通过TEM图证明了氯化钾的介晶性质。图3结果显示了MoSxSe2-x/C复合材料的均匀分布性。
实施例3
本实施例的方法与实施例1基本相同，不同之处为：在实施例1的基础上，在马弗炉中600 ℃加热60 min。并将其进行表征，表征结果如图1。
实施例4
本实施例的方法与实施例2基本相同，不同之处为：在实施例2的基础上，将0.50 g(NH4)6Mo7O24·4H2O替换为0.63 g FeCl3。并将其进行表征，表征结果如图4-5。如图4的XRD谱图所示实施例4具有良好的结晶性，并且对应于FeSxSe2-x。图5的SEM图展示了其基本形貌结构。
实施例5
本实施例的方法与实施例2基本相同，不同之处为：在实施例2的基础上，将0.50 g(NH4)6Mo7O24·4H2O替换为0.50 g CoCl2。并将其进行表征，表征结果如图4-5。如图4的XRD谱图所示实施例5具有良好的结晶性，并且对应于Co9SxSe8-x。图5的SEM图展示了其基本形貌结构。
实施例6
本实施例的方法与实施例2基本相同，不同之处为：在实施例2的基础上，将0.50 g(NH4)6Mo7O24·4H2O替换为1.00 g SnCl4。并将其进行表征，表征结果如图4-5。如图4的XRD谱图所示实施例6具有良好的结晶性，并且对应于SnSxSe1-x。图5的SEM图展示了其基本形貌结构。
实施例7
本实施例的方法与实施例2基本相同，不同之处为：在实施例2的基础上，将0.50 g(NH4)6Mo7O24·4H2O替换为0.52 g CuCl2。并将其进行表征，表征结果如图4-5。。如图4的XRD谱图所示实施例7具有良好的结晶性，并且对应于CuSxSe1-x。图5的SEM图展示了其基本形貌结构。实施例4-7展示了生物矿化微反应器在空气中制备非氧化物的良好的通用性。
应用例1
将实施例2制备的MoSxSe2-x/C纳米复合材料与导电乙炔黑，聚偏氟乙烯按照7:2:1的质量比加入到1-甲基-2-吡咯烷酮溶剂中研磨均匀，并涂覆在不锈钢片上制备成电极片。在氩气条件下的手套箱中与金属钾片组装成半电池。之后经过预钾处理，同活性碳电极组装成钾离子混合电容器。使用电化学工作站对其进行测试，结果如图6，图7所示。
从图6的钾离子混合电容器的能量-功率密度曲线中可以看出其具有优异的电化学性能。在498 W kg-1的功率密度下提供了108 Wh kg-1的高能量密度，具有较高的商用价值。此外，如图7所示，在5A g-1电流密度下循环20000圈依然具有87.1%的容量保持率，该器件具有优异的循环使用寿命。插图为钾离子混合电容器点亮的22个工作电压为3V的LED灯，表现出该器件具有较好的实用价值。
Claims (5)
1.一种生物矿化的微反应器调控固态合成纳米材料及其储钾器件的应用，其特征在于包含如下的步骤：(a) 前驱体选择：从原料成本以及可持续发展的方面考虑，选择来源广泛的海洋藻类提取物作为前驱体，通过电子显微镜确定其基本的微观形貌特征，探究其作为前驱体的基本特性，并且通过进一步的元素分析确定其中元素含量；(b) 纳米复合材料的制备：将海洋藻类前驱体，硒酸盐，钼酸盐溶解在热水中，并且加入氯化钾，经冷冻干燥后，在马弗炉中高温加热，最后，经过水洗去除杂质，最后放入真空烘箱中干燥获得样品；(c)纳米复合材料的调控：基于已合成的纳米复合材料，为了获取最优样品以及纳米复合材料合成的通用性，必须对其进行调控，在原有制备基础上，调节反应时间以及引入不同种类的金属盐；(d) 钾离子电容器的组装：将所制备的纳米复合材料同导电乙炔黑以及聚偏氟乙烯按比例加入到N-甲基吡咯烷酮中，经研磨混合成均匀的浆料，制备成电极片，在充满氩气的手套箱中组装成钾离子半电池，并且进一步通过预钾化，和活性碳正极匹配组装成钾离子混合电容器。
2.根据权利要求1所述的纳米材料的制备方法，其特征在于：在步骤a中，前驱体的选择可以为海洋藻类提取物卡拉胶，它取材广泛，造价低，绿色环保可再生，并且具有独特的生物结构以及丰富的硫酸酯基团，用作前驱体非常具有优势。
3.根据权利要求1所述的纳米材料的制备方法，其特征在于：在步骤b中，将2g k-型卡拉胶，0.50 g 钼酸铵，0.50 g亚硒酸溶解在200 ml的去离子水中，加热至80 ℃至其完全溶解，然后在剧烈搅拌下加入20 g 氯化钾，将样品放入-40 ℃冰箱中冷冻12 h，并且放入真空冷冻干燥机中干燥，之后放入马弗炉中，在600℃加热1 h，经过多次去离子水洗涤，在真空烘箱中干燥获取最终样品。
4.根据权利要求1所述的纳米材料的制备方法，其特征在于：在步骤c中，为了实现对碳纳米材料的调控，将马弗炉的温度控制在600 ℃，加热时间分别为10-60 min，此外，引入不同种类的金属盐，根据亚硒酸的使用量，分别加入与亚硒酸摩尔比为1：1的FeCl3, CoCl2,SnCl4 和CuCl2 金属盐。
5.根据权利要求1-4所述的采用微反应器法合成纳米材料的方法，其特征在于：所制备的MoSxSe2-x/C纳米复合材料具有较高的产率以及良好的均匀性，将其用作钾离子电极材料表现出优异的导电性以及出色的电容性能，进一步组装成的钾离子电容器可以提供较高的能量-功率密度以及出色的长循环寿命，本发明技术路线绿色环保，成本低，通用性高，实用性强。
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