CN109360745B - 一种石墨烯复合电极的制备方法 - Google Patents
一种石墨烯复合电极的制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯复合电极的制备方法,涉及电极制备技术领域。本发明制备方法包括:柔性石墨的改性、负载、分散、石墨烯预处理、制备;本发明在制作电极片的过程中避免了石墨烯片层之间的团聚问题,提高材料的双电层容量,同时改性柔性石墨和石墨烯复合后的电极具备较强的耐腐蚀性,实用性较好,多次使用后其灵敏性依旧很高。
Description
技术领域:
本发明涉及电极制备技术领域,具体涉及一种石墨烯复合电极的制备方法。
背景技术:
石墨烯材料,由于其独特的结构和光电性质受到了人们广泛的重视。单层石墨由于其大的比表面积,优良的导电、导热性能和低的热膨胀系数而被认为是理想的材料。如:1,高强度,杨氏摩尔量,(1,100GPa),断裂强度:(125GPa);2,高热导率,(5,000W/mK);3,高导电性、载流子传输率,(200,000cm2/V*s);4,高的比表面积,(理论计算值:2,630m2/g)。尤其是其高导电性质,大的比表面性质和其单分子层二维的纳米尺度的结构性质,可在超级电容器和锂离子电池中用作电极材料。到目前为止,所知道的制备石墨烯的方法有多种,如:(1)微机械剥离法。这种方法只能产生数量极为有限石墨烯片,可作为基础研究;(2)超高真空石墨烯外延生长法。这种方法的高成本以及小圆片的结构限制了其应用;(3)化学气相沉积法(CVD)。此方法可以满足规模化制备高质量石墨烯的要求,但成本较高,工艺复杂。(4)溶剂剥离法。此方法缺点是产率很低,限制它的商业应用;(5)氧化-还原法。
以上方法均是采用制备的石墨烯粉末经过混料、涂布、辊压、切片等工艺做成电极片,在石墨烯的制备和制成极片的过程中总是存在石墨烯材料的团聚的问题,进而做成电池后影响电池的能量密度,石墨烯材料的实际能量密度远远小于其理论值。
发明内容:
本发明所要解决的技术问题在于克服现有技术的不足,提供一种石墨烯复合电极的制备方法。
本发明所要解决的技术问题采用以下的技术方案来实现:
一种石墨烯复合电极的制备方法,包括以下步骤:
(1)柔性石墨的改性:将柔性石墨加入到去离子水中,回流搅拌10-30min,然后加入钛酸酯偶联剂和链增长剂,继续回流搅拌0.5-2h;
(2)负载:向步骤1中溶液加入硫酸镍,回流搅拌0.5-4h,降温至70-75℃加入蓖麻油和活性助剂,继续搅拌20-40min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散1-2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将石墨烯分散于40-80℃的浓硝酸中,搅拌4-6h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1-2h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡30-60min,然后再在所述氧化石墨烯分散液中浸泡1-5min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡30-500次,且在每种分散液中浸泡时间为1-5min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于500~1000℃高温反应1-5h,冷却后,得到石墨烯复合电极片。
所述柔性石墨、钛酸酯偶联剂、链增长剂、石墨烯的质量比为20-30:6-8:0.2-0.3:20-30。
所述硫酸镍、蓖麻油、活性助剂的质量比为6-8:1-2:1-3。
所述活性助剂的制备方法为:将肌氨酸加入到去离子水中,40℃搅拌10min,然后添加山梨糖醇和钛酸四乙酯,加热至回流状态保温搅拌0.5-4h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
所述肌氨酸、山梨糖醇、钛酸四乙酯的质量比为10-15:15-20:0.1。
柔性石墨作为一种新型功能性碳素材料,是由天然石墨鳞片经插层、水洗、干燥、高温膨化得到的一种疏松多孔的蠕虫状物质。柔性石墨除了具备天然石墨本身的耐冷热、耐腐蚀、自润滑等优良性能以外,还具有天然石墨所没有的柔软、压缩回弹性、吸附性、生态环境协调性、生物相容性、耐辐射性等特性。
镍能在碱性条件下催化糖类、氨基酸、多肽、糖苷类和醇类等物质的电催化氧化,具备较高的电催化活性。将镍盐负载在柔性石墨上,可以提高柔性石墨的电化学活性,使其对电流有较强的反应信号;同时改性后的柔性石墨可以将石墨烯吸附在其表面和片层中,使得石墨烯自身难以团聚,减少了石墨烯因自身聚集而造成的能量损耗。
本发明的有益效果是:本发明在制作电极片的过程中避免了石墨烯片层之间的团聚问题,提高材料的双电层容量,同时改性柔性石墨和石墨烯复合后的电极具备较强的耐腐蚀性,实用性较好,多次使用后其灵敏性依旧很高。
具体实施方式:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例1
复合电极的制备:
(1)柔性石墨的改性:将20g柔性石墨加入到去离子水中,回流搅拌30min,然后加入6g钛酸酯偶联剂和0.2g链增长剂,继续回流搅拌2h;
(2)负载:向步骤1中溶液加入6g硫酸镍,回流搅拌2h,降温至70℃加入1g蓖麻油和1.5g活性助剂,继续搅拌30min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将25g石墨烯分散于50℃的浓硝酸中,搅拌4h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡50min,然后再在所述氧化石墨烯分散液中浸泡3min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡200次,且在每种分散液中浸泡时间为4min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于700℃高温反应4h,冷却后,得到石墨烯复合电极片。
活性助剂的制备:将12g肌氨酸加入到去离子水中,40℃搅拌10min,然后添加16g山梨糖醇和0.1g钛酸四乙酯,加热至回流状态保温搅拌4h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
实施例2
复合电极的制备:
(1)柔性石墨的改性:将24g柔性石墨加入到去离子水中,回流搅拌30min,然后加入7g钛酸酯偶联剂和0.2g链增长剂,继续回流搅拌2h;
(2)负载:向步骤1中溶液加入6g硫酸镍,回流搅拌2h,降温至70℃加入1g蓖麻油和1.8g活性助剂,继续搅拌30min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将26g石墨烯分散于50℃的浓硝酸中,搅拌4h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡50min,然后再在所述氧化石墨烯分散液中浸泡3min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡200次,且在每种分散液中浸泡时间为4min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于700℃高温反应4h,冷却后,得到石墨烯复合电极片
活性助剂的制备:将12g肌氨酸加入到去离子水中,40℃搅拌10min,然后添加16g山梨糖醇和0.1g钛酸四乙酯,加热至回流状态保温搅拌4h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例1
复合电极的制备:
(1)柔性石墨的改性:将20g柔性石墨加入到去离子水中,回流搅拌30min,继续回流搅拌2h;
(2)负载:向步骤1中溶液加入6g硫酸镍,回流搅拌2h,降温至70℃加入1g蓖麻油和1.5g活性助剂,继续搅拌30min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将25g石墨烯分散于50℃的浓硝酸中,搅拌4h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡50min,然后再在所述氧化石墨烯分散液中浸泡3min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡200次,且在每种分散液中浸泡时间为4min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于700℃高温反应4h,冷却后,得到石墨烯复合电极片。
活性助剂的制备:将12g肌氨酸加入到去离子水中,40℃搅拌10min,然后添加16g山梨糖醇和0.1g钛酸四乙酯,加热至回流状态保温搅拌4h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例2
复合电极的制备:
(1)柔性石墨的改性:将20g柔性石墨加入到去离子水中,回流搅拌30min,然后加入6g钛酸酯偶联剂和0.2g链增长剂,继续回流搅拌2h;
(2)负载:向步骤1中溶液加入6g硫酸镍,回流搅拌2h,降温至70℃加入1.5g活性助剂,继续搅拌30min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将25g石墨烯分散于50℃的浓硝酸中,搅拌4h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡50min,然后再在所述氧化石墨烯分散液中浸泡3min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡200次,且在每种分散液中浸泡时间为4min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于700℃高温反应4h,冷却后,得到石墨烯复合电极片。
活性助剂的制备:将12g肌氨酸加入到去离子水中,40℃搅拌10min,然后添加16g山梨糖醇和0.1g钛酸四乙酯,加热至回流状态保温搅拌4h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
对照例3
复合电极的制备:
(1)柔性石墨的改性:将20g柔性石墨加入到去离子水中,回流搅拌30min,然后加入6g钛酸酯偶联剂和0.2g链增长剂,继续回流搅拌2h;
(2)负载:向步骤1中溶液加入6g硫酸镍,回流搅拌2h,降温至70℃加入1g蓖麻油,继续搅拌30min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散2h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将25g石墨烯分散于50℃的浓硝酸中,搅拌4h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将石墨烯加入到无水乙醇中,超声分散1h,得到石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡50min,然后再在所述氧化石墨烯分散液中浸泡3min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡200次,且在每种分散液中浸泡时间为4min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于700℃高温反应4h,冷却后,得到石墨烯复合电极片。
实施例1-2制备的电极检测准确性高,重复性好,多次使用后灵敏度依旧很高,对照例1-3制备的电极重复性较弱,多次使用后灵敏度有所下降。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种石墨烯复合电极的制备方法,其特征在于,包括以下步骤:
(1)柔性石墨的改性:将柔性石墨加入到去离子水中,回流搅拌10-30 min,然后加入钛酸酯偶联剂和链增长剂,继续回流搅拌0.5-2 h;
(2)负载:向步骤1中溶液加入硫酸镍,回流搅拌0.5-4 h,降温至70-75℃加入蓖麻油和活性助剂,继续搅拌20-40 min,趁热过滤,固体用去离子水洗去杂质,50℃真空干燥至恒重;
(3)分散:将步骤2中固体加入到无水乙醇中,超声分散1-2 h,得到改性柔性石墨分散液;
(4)石墨烯预处理:将石墨烯分散于40-80℃的浓硝酸中,搅拌4-6 h,过滤产物用去离子水洗涤,干燥,得氧化石墨烯;再将氧化石墨烯加入到无水乙醇中,超声分散1-2 h,得到氧化石墨烯分散液;
(5)制备:将集流体在改性柔性石墨分散液中浸泡30-60min,然后再在所述氧化石墨烯分散液中浸泡1-5min;接着再在改性柔性石墨分散液和氧化石墨烯分散液中交替浸泡 30-500次,且在每种分散液中浸泡时间为1-5min,干燥后即得到复合电极;将所述复合电极在惰性气体保护下,于500~1000℃高温反应1-5h,冷却后,得到石墨烯复合电极片。
2. 根据权利要求1所述的石墨烯复合电极的制备方法,其特征在于:所述柔性石墨、钛酸酯偶联剂、链增长剂、石墨烯的质量比为20-30 :6-8 :0.2-0.3 :20-30。
3. 根据权利要求1所述的石墨烯复合电极的制备方法,其特征在于:所述硫酸镍、蓖麻油、活性助剂的质量比为6-8 :1-2 :1-3。
4. 根据权利要求1所述的石墨烯复合电极的制备方法,其特征在于,所述活性助剂的制备方法为:将肌氨酸加入到去离子水中,40℃搅拌10 min,然后添加山梨糖醇和钛酸四乙酯,加热至回流状态保温搅拌0.5-4 h,过滤,所得固体用去离子水洗去杂质,50℃真空干燥至恒重。
5. 根据权利要求4所述的石墨烯复合电极的制备方法,其特征在于:所述肌氨酸、山梨糖醇、钛酸四乙酯的质量比为10-15 :15-20 :0.1。
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