CN108011089B - 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 - Google Patents
一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 Download PDFInfo
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- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明涉及一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,属于无机材料领域。其制备方法具体过程如下:(1)将钴盐水溶液与石墨烯水溶液按一定比例混合,在惰性气体及室温条件下搅拌一定时间;(2)加入强碱水溶液,反应一定时间;(3)撤掉惰性气体,加入强氧化剂,陈化一定时间;(4)陈化结束后所得悬浊液经过滤、洗涤、干燥,得到一种六元环状羟基氧化钴/石墨烯纳米复合材料。本发明具有工艺流程简单、反应条件温和、易大规模制备等优点,所得产品形貌可控,且羟基氧化钴在石墨烯表面均匀分散,有望在超级电容器、锂离子电池及催化等领域得到应用。
Description
技术领域
本发明属于无机材料领域,具体涉及一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。
技术背景
随着经济社会的快速发展,当今世界对于能源存储设备的要求越来越高,因此制备高性能的锂离子电池和电化学电容器、提高能源的有效利用率和储存效率就成了急需解决的问题。其中电极材料是储能设备性能优劣的关键。钴酸锂因具有放电电压高、充放电电压平稳、比能量高等优点,是目前锂离子电池最为常用的电极材料。钴氧化物(氧化钴、四氧化三钴、羟基氧化钴、氢氧化亚钴)作为生产钴酸锂的常见钴源之一,其结构与性质对钴酸锂的电化学性能具有明显影响。因此,开发高性能的钴氧化物纳米材料及制备工艺具有广阔的应用前景。
钴氧化物理论容量非常高,但是其导电性差、充放电过程中体积变化大等缺点在一定程度上限制了其应用。为提高钴氧化物的电化学性能,本文制备了六元环状羟基氧化钴/石墨烯纳米复合材料。石墨烯作为一种新型的碳材料,它具有二维平面单原子层结构,可以使金属氧化物纳米颗粒成核或镶嵌于其表面或侧面,其超高的比表面积以及良好的电子传输性等独特性质,使其成为了一种优异的复合材料添加剂。石墨烯作为载体或包覆材料能有效的改善羟基氧化钴的导电性及循环稳定性,羟基氧化钴也能在一定程度上阻止石墨烯的折叠、团聚,这种纳米复合材料兼具了石墨烯和羟基氧化钴的优势,提高了其在超级电容器及锂离子电池储能中的电化学性能。
研究发现,纳米材料的粒度、粒度分布及形貌对其性能及应用具有显著影响。纳米材料的可控制备,即尺寸与形貌的可控制备是相关领域研究人员追求的目标。从公开发表的论文与专利来看,相对于氢氧化亚钴及四氧化三钴,关于羟基氧化钴的研究较少,其制备工艺还处于初级阶段。专利CN201310375503.2公开了一种纳米级羟基氧化钴的合成工艺,但是所得羟基氧化钴无规则形貌,粒度分布较宽。专利CN201210016504.3在制备得到CoOOH后,还需在喷雾干燥器中进行造粒,增加设备,过程复杂。目前还未有关于六元环状羟基氧化钴/石墨烯纳米复合材料及制备方法的报道。本发明首次提供了一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。本发明具有工艺流程简单,过程能耗低,产品形貌和粒径可控,批次间重复性好,易大规模生产等优点,所得六元环状羟基氧化钴/石墨烯纳米复合材料有望在锂离子电池、超级电容器、催化等领域得到应用。
发明内容
本发明的目的在于提供一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。
为实现上述目的,本发明采用的技术方案如下:
一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其具体步骤为:
(1)分别配制钴盐和石墨烯水溶液,所述钴盐水溶液中钴离子(Co2+)摩尔浓度为0.001-0.1mol/L,所述石墨烯水溶液中石墨烯质量浓度为0.1-2mg/mL;
(2)将钴盐水溶液和石墨烯水溶液混合均匀,在氮气或惰性气体中,室温条件下搅拌0.5-5h;
(3)加入强碱水溶液,于30-80℃反应0.5-5h,所述强碱水溶液中氢氧根离子(OH-)摩尔浓度为0.01-1.0mol/L;
(4)撤掉氮气或惰性气体,加入强氧化剂,继续陈化0.5-5h;所述强氧化剂在最终反应液中的质量分数为2%-10%;
(5)陈化结束后,所得悬浊液经过滤、洗涤、干燥,得到六元环状羟基氧化钴/石墨烯纳米复合材料。
所述钴盐为硫酸钴、氯化钴、硝酸钴、醋酸钴中的一种或两种以上。
所述钴盐水溶液中钴离子(Co2+)与石墨烯水溶液中石墨烯的质量比为1:5-5:1。
所述强碱水溶液中的强碱为氢氧化锂、氢氧化钠、氢氧化钾中的一种或两种以上。
所述步骤(3)中以2.5-20mL/min的流速加入强碱水溶液。
所述钴盐水溶液中钴离子(Co2+)与强碱水溶液中氢氧根离子(OH-)的摩尔比为1:5-1:40。
所述强氧化剂为双氧水(质量分数为25%-28%)、次氯酸钠中的一种或两种。
与现有技术相比,本发明具有以下优点:
(1)首次合成了纳米级六元环状羟基氧化钴/石墨烯复合材料,这种独特的材料有望在锂离子电池、超级电容器、催化领域等取得应用;
(2)产品形貌及粒度可控、制备方法具有过程能耗低、工艺流程简单、易大规模生产等优点。
附图说明
图1为本发明实施例1产品的SEM图。
图2为本发明实施例2产品的SEM图。
图3为本发明实施例2产品的XRD图。
图4为本发明实施例3产品的SEM图。
具体实施方式
以下实施例用于说明本发明。
实施例1
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25mL,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL,以5mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应1h;(3)撤掉N2,加入质量分数为28%的双氧水10ml,陈化2h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,其SEM图见图1,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例2
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25mL,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL,以5mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应2h;(3)撤掉N2,加入质量分数为28%的双氧水10ml,陈化3.5h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,其SEM图见图2,其XRD图见图3,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例3
(1)配置浓度为0.05mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25ml,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL,以5mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应1h;(3)撤掉N2,加入质量分数为28%的双氧水10ml,陈化2h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,其SEM图见图4,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例4
(1)配置浓度为0.0125mol/L的氯化钴水溶液和1mg/mL的石墨烯水溶液各100mL,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.25mol/L的氢氧化钠水溶液200mL,以10mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应2h;(3)撤掉N2,加入质量分数为28%的双氧水40ml,陈化2h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例5
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各100mL,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.5mol/L的氢氧化钠水溶液200mL,以5mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应2h;(3)撤掉N2,加入质量分数为28%的双氧水40ml,陈化2h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例6
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各100mL,混合均匀,转移至三口烧瓶中,三口烧瓶内提前通入氮气,室温下机械搅拌4h;(2)配制浓度为0.25mol/L的氢氧化钠水溶液200mL,以5mL/min的流速打入三口烧瓶中,在50℃及搅拌条件下反应2h;(3)撤掉N2,加入质量分数为28%的双氧水20ml,陈化2h;(4)陈化结束后,所得悬浊液经过滤、洗涤、干燥,制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
Claims (6)
1.一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:其具体步骤为:
(1)分别配制钴盐和石墨烯水溶液,所述钴盐水溶液中钴离子Co2+摩尔浓度为0.001-0.1 mol/L,所述石墨烯水溶液中石墨烯质量浓度为0.1-2 mg/mL;
(2)将钴盐水溶液和石墨烯水溶液混合均匀,在氮气或惰性气体中,室温条件下搅拌0.5-5 h;
(3)加入强碱水溶液,于30-80 ℃反应0.5-5 h,所述强碱水溶液中氢氧根离子(OH-)摩尔浓度为0.01-1.0 mol/L;所述钴盐水溶液中钴离子Co2+与强碱水溶液中氢氧根离子(OH-)的摩尔比为1:5-1:40;
(4)撤掉氮气或惰性气体,加入强氧化剂,继续陈化0.5-5 h;所述强氧化剂在最终反应液中的质量分数为2%-10%;
(5)陈化结束后,所得悬浊液经过滤、洗涤、干燥,得到六元环状羟基氧化钴/石墨烯纳米复合材料。
2.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:所述钴盐为硫酸钴、氯化钴、硝酸钴或醋酸钴中的一种或两种以上。
3.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:所述钴盐水溶液中钴离子Co2+与石墨烯水溶液中石墨烯的质量比为1:5-5:1。
4.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:所述强碱水溶液中的强碱为氢氧化锂、氢氧化钠或氢氧化钾中的一种或两种以上。
5.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:以2.5-20 mL/min的流速加入强碱水溶液。
6.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法,其特征在于:所述强氧化剂为次氯酸钠或质量分数为25%-28%的双氧水中的一种或两种。
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