CN110233062B - 二维Co3O4NSs/ACC@RGO复合电极材料的制备方法 - Google Patents
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Abstract
本发明公开了一种二维Co3O4NSs/ACC@RGO复合电极材料的制备方法，用于解决现有电极材料的制备方法实用性差的技术问题。技术方案是将清洗并干燥后的碳布、石墨与硝酸钠混合后逐滴加入浓硫酸，再依次加入KMnO4和蒸馏水，再将H2O2添加到混合物溶液中，加入水合肼并加热，将碳布进行洗涤、真空干燥得到还原石墨烯包覆碳布。采用电化学工作站进行电化学沉积。将沉积后的碳布进行洗涤、干燥、退火后获得Co3O4NSs/ACC@RGO复合电极材料。经测试，由本发明方法制备的Co3O4NSs/ACC@RGO复合电极材料用做正极在1Ag‑1下显示出845Fg‑1的高比电容，实用性好。
Description
技术领域
本发明涉及一种电极材料的制备方法，特别涉及一种二维Co3O4NSs/ACC@RGO 复合电极材料的制备方法。
背景技术
超级电容器也称电化学电容器，是介于传统电容器和蓄电池之间的一种新型储能器件，具有优良的可逆充放电性能和大容量储能性能。其优点有：功率密度高、循环寿命长、充电速度快、能够瞬时大电流放电、绿色无污染，具有很广阔的应用前景。目前，超级电容器的缺点在于其能量密度有限。导致超级电容器能量密度低的主要原因是：在相应的电压窗口下，电化学稳定电位窗口窄、比电容小。众所周知，电极材料对超级电容器的电压窗口、比电容和能量密度至关重要。
在电极材料方面，氧化物赝电容具有很大潜力。钴氧化物(CO3O4)作为一种典型的氧化物赝电容材料，由于其具有较高的理论比电容，制备成本低等优点而得到了广泛的研究。
文献“Xia X H,Tu J P,Mai Y J,et al.Self-supported hydrothermalsynthesized hollow Co3O4nanowire arrays with high supercapacitor capacitance[J].Journal of Materials Chemistry,2011,21.”公开了一种空心Co3O4纳米线的制备技术，该方法是在基底上沉积CO3O4薄膜，并在流动氩气中高温处理。将Co(NO3)2和硝酸钠溶解在氨水和水中，在空气中搅拌，直到粉红色逐渐变黑。将溶液转移瓶子，固定基板薄膜侧朝下，将密封瓶注入氧气并在烘箱中加热。随后，清洗并退火得到空心Co3O4纳米线。
但在该方法中，CO3O4基超级电容器的电极材料仍然局限于低能量密度 (10～50Wh/kg)。在此基础上，研制了一种具有高稳定电压窗(2.2V)的高活性二维 CO3O4电极材料和水电解质。吸附在电极材料表面的阳离子(Li+，CO2+)增加了H+和O2-吸附的物理屏障。因此，在这两个电极上，氧和氢的释放过电位增加，大大超过了水的热力学稳定极限。此外，还发现在循环测试过程中，电极材料的分解会导致电容和能量密度的降低。为了克服这一缺点，首次提出了在2M Li2SO4电解质中预先加入二价钴离子以平衡CO3O4电极溶解引起的变化的新策略。它不仅抑制了CO3O4电极材料的溶解，而且有利于提高比电容，实现超高能量密度、安全性和循环稳定性。
发明内容
为了克服现有电极材料的制备方法实用性差的不足，本发明提供一种二维Co3O4NSs/ACC@RGO复合电极材料的制备方法。该方法将清洗并干燥后的碳布、石墨与硝酸钠混合后逐滴加入浓硫酸并搅拌，缓慢加入KMnO4并搅拌，加入蒸馏水搅拌，再逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。最后向溶液中加入水合肼并加热，将碳布进行洗涤、真空干燥得到还原石墨烯包覆碳布(ACC@RGO)。采用电化学工作站用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，Co(NO3)2 6H2O作为电解质进行电化学沉积。将沉积后的碳布进行洗涤、干燥、退火后获得Co3O4NSs/ACC@RGO复合电极材料。经测试，由本发明方法制备的复合电极材料用做正极在1Ag-1下显示出845Fg-1的高比电容，该正极组装的超级电容器在水系电解质中显示出2.2V的高电压窗口，功率密度为1100W Kg-1时具有99WhKg-1的超高能量密度和10000次循环后的容量保持率为168％的超长循环寿命，实用性好。
本发明解决其技术问题所采用的技术方案：一种二维Co3O4NSs/ACC@RGO复合电极材料的制备方法，其特点是包括以下步骤：
步骤一、用乙醇和蒸馏水在超声波条件下预先清洗碳布10～30min，之后在60～90℃下真空干燥5～8小时。然后将石墨片、碳布和硝酸钠按照质量比为1:40:41加入烧杯中，然后逐滴加入50～80ml浓度98％浓硫酸并在-5℃～-8℃下搅拌，搅拌时间为 20～60min。
步骤二、将质量为碳布质量的5～8倍KMnO4缓慢加入上述混合溶液中在冰浴中剧烈搅拌1～3h，再转移到油浴中在20～50℃搅拌1～3h，然后将溶液与100～150ml 蒸馏水缓慢混合在冰浴中搅拌1～3h，再将混合溶液在80～98℃油浴中搅拌20～60min。最后逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。
步骤三、添加2～5ml浓度为96.3mmol的水合肼，将溶液在100～130℃油浴中在水冷冷凝器的冷凝作用下加热20～30h。将碳布进行去离子水洗涤3～5次，之后在 60～80℃下真空干燥8～12h后得到ACC@RGO。
步骤四、采用电化学工作站在-0.8～-1.0V的电位下，使用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，浓度为0.01～10mol L-1的Co(NO3)2 6H2O作为电解质进行电化学沉积，电沉积的时间为600～3600s。
步骤五、将沉积后的碳布用去离子水洗涤，再在60～90℃下在空气中干燥8～12h，最后在350～400℃下退火1～4h，获得Co3O4NSs/ACC@RGO复合电极材料。
本发明的有益效果是：该方法将清洗并干燥后的碳布、石墨与硝酸钠混合后逐滴加入浓硫酸并搅拌，缓慢加入KMnO4并搅拌，加入蒸馏水搅拌，再逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。最后向溶液中加入水合肼并加热，将碳布进行洗涤、真空干燥得到还原石墨烯包覆碳布(ACC@RGO)。采用电化学工作站用 ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，Co(NO3)2 6H2O 作为电解质进行电化学沉积。将沉积后的碳布进行洗涤、干燥、退火后获得 Co3O4NSs/ACC@RGO复合电极材料。经测试，由本发明方法制备的复合电极材料用做正极在1Ag-1下显示出845Fg-1的高比电容，该正极组装的超级电容器在水系电解质中显示出2.2V的高电压窗口，功率密度为1100W Kg-1时具有99WhKg-1的超高能量密度和10000次循环后的容量保持率为168％的超长循环寿命，实用性好。
下面结合附图和具体实施方式对本发明作详细说明。
附图说明
图1是本发明方法实施例1制备的Co3O4/ACC@RGO样品的XRD图谱。
图2是本发明方法实施例1使用原始的CO3O4中Co 2P的XPS光谱。
图3是本发明方法实施例2制备的Co3O4/ACC@RGO样品的SEM图像。
图4是本发明方法实施例2制备的二维Co3O4纳米片样品的TEM图像和相应的 SAED图像。
图5是本发明方法实施例3制备的二维CO3O4纳米片的AFM厚度测量图像。
图6是本发明方法实施例1制备的CO3O4/ACC@RGO电极在三电极测试系统中 1-10mVs-1的不同扫描速率下的CV曲线。
图7是使用本发明方法实施例2制备的电极组装的水系非对称超级电容器的GCD曲线。
图8是使用本发明方法实施例3制备的电极组装的水系非对称超级电容器在5A g-1时的循环性能曲线。
具体实施方式
以下实施例参照图1-8。
实施例1：
(1)用乙醇和蒸馏水在超声波条件下预先清洗碳布30min，之后在60℃下真空干燥5小时。然后将石墨片、碳布和硝酸钠按照质量比为1:40:41加入烧杯中，然后逐滴加入50ml浓度98％浓硫酸并在-5℃下搅拌，搅拌时间为20min。
(2)将质量为碳布质量的5倍KMnO4缓慢加入上述混合溶液中在冰浴中剧烈搅拌1h，再转移到油浴中在20℃搅拌1h，然后将溶液与100ml蒸馏水缓慢混合在冰浴中搅拌1h，再将混合溶液在80℃油浴中搅拌20min。最后逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。
(3)添加2ml浓度为96.3mmol的水合肼，将溶液在100℃油浴中在水冷冷凝器的冷凝作用下加热20h。最后，将碳布进行去离子水洗涤3次，之后在60℃下真空干燥8h得到ACC@RGO。
(4)采用电化学工作站在(与SCE相比)-0.8V的电位下，使用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，浓度为10mol L-1的Co(NO3)2 6H2O作为电解质进行电化学沉积，电沉积的时间为600s。
(5)将沉积后的碳布用去离子水洗涤，再在60℃下在空气中干燥8h，最后在350℃下退火2h，获得Co3O4NSs/ACC@RGO复合电极材料。
从图1中可以看出二维CO3O4纳米片具有Fd-3m(227)空间群的立方结构，晶格参数
非常接近立方的CO3O4 
从图2中可以看出C和CO3O4在CO3O4/ACC@RGO中共存。
从图6中可以看出装置在三电极工作电压窗口为1.2V，远高于碱性电解质中的工作电压窗口0.5V。
实施例2：
(1)用乙醇和蒸馏水在超声波条件下预先清洗碳布10min，之后在90℃下真空干燥8小时。然后将石墨片、碳布和硝酸钠按照质量比为1:40:41加入烧杯中，然后逐滴加入80ml浓度98％浓硫酸并在-8℃下搅拌，搅拌时间为60min。
(2)将质量为碳布质量的8倍KMnO4缓慢加入上述混合溶液中在冰浴中剧烈搅拌3h，再转移到油浴中在50℃搅拌3h，然后将溶液与150ml蒸馏水缓慢混合在冰浴中搅拌3h，再将混合溶液在98℃油浴中搅拌60min。最后逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。
(3)然后添加5ml浓度为96.3mmol的水合肼，将溶液在130℃油浴中在水冷冷凝器的冷凝作用下加热30h。最后，将碳布进行去离子水洗涤5次，之后在80℃下真空干燥12h得到ACC@RGO。
(4)采用电化学工作站在(与SCE相比)-1.0V的电位下，使用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，浓度为0.1mol L-1的Co(NO3)2 6H2O作为电解质进行电化学沉积，电沉积的时间为2500s。
(5)将沉积后的碳布用去离子水洗涤，再在90℃下在空气中干燥12h，最后在 400℃下退火4h，获得Co3O4NSs/ACC@RGO复合电极材料。
从图7中可以看出装置的工作电压窗口为2.2V，远高于碱性电解质中的工作电压窗口。从图中还可以看出在电流密度为1Ag-1的情况下，使用公式计算得出的比电容为87.4Fg-1。当电流密度达到10Ag-1时，比电容仍保持63Fg-1，表明其可逆性好、比容量高。
实施例3：
(1)用乙醇和蒸馏水在超声波条件下预先清洗碳布20min，之后在70℃下真空干燥6小时。然后将石墨片、碳布和硝酸钠按照质量比为1:40:41加入烧杯中，然后逐滴加入60ml浓度98％浓硫酸并在-6℃下搅拌，搅拌时间为40min。
(2)将质量为碳布质量的6倍KMnO4缓慢加入上述混合溶液中在冰浴中剧烈搅拌2h，再转移到油浴中在40℃搅拌2h，然后将溶液与120ml蒸馏水缓慢混合在冰浴中搅拌2h，再将混合溶液在90℃油浴中搅拌30min。最后逐滴将H2O2添加到混合物溶液中，直到溶液变得澄清。
(3)然后添加3ml浓度为96.3mmol的水合肼，将溶液在120℃油浴中在水冷冷凝器的冷凝作用下加热24h。最后，将碳布进行去离子水洗涤4次，之后在70℃下真空干燥10h得到ACC@RGO。
(4)采用电化学工作站在(与SCE相比)-0.9V的电位下，使用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，浓度为0.01mol L-1的Co(NO3)2 6H2O作为电解质进行电化学沉积，电沉积的时间为3600s。
(5)将沉积后的碳布用去离子水洗涤，再在80℃下在空气中干燥10h，最后在 380℃下退火3h，获得Co3O4NSs/ACC@RGO复合电极材料。
从图5中可以看出Co3O4纳米片的厚度为2.16nm。
从图8中可以看出装置经过10000次循环后的容量保持率为168％，具有超长循环寿命。
Claims (1)
1.一种二维Co3O4NSs/ACC@RGO复合电极材料的制备方法，其特征在于包括以下步骤：
步骤一、用乙醇和蒸馏水在超声波条件下预先清洗碳布10～30min，之后在60～90℃下真空干燥5～8小时；然后将石墨片、碳布和硝酸钠按照质量比为1:40:41加入烧杯中，然后逐滴加入50～80ml浓度98％浓硫酸并在-5℃～-8℃下搅拌，搅拌时间为20～60min；
步骤二、将质量为碳布质量的5～8倍KMnO4缓慢加入上述混合溶液中在冰浴中剧烈搅拌1～3h，再转移到油浴中在20～50℃搅拌1～3h，然后将溶液与100～150ml蒸馏水缓慢混合在冰浴中搅拌1～3h，再将混合溶液在80～98℃油浴中搅拌20～60min；最后逐滴将H2O2添加到混合溶液中，直到溶液变得澄清；
步骤三、添加2～5ml浓度为96.3mmol的水合肼，将溶液在100～130℃油浴中在水冷冷凝器的冷凝作用下加热20～30h；将碳布进行去离子水洗涤3～5次，之后在60～80℃下真空干燥8～12h后得到ACC@RGO；
步骤四、采用电化学工作站在-0.8～-1.0V的电位下，使用ACC@RGO作为工作电极，铂板作为反电极，甘汞电极作为参考电极，浓度为0.01～10mol L-1的Co(NO3)26H2O作为电解质进行电化学沉积，电沉积的时间为600～3600s；
步骤五、将沉积后的碳布用去离子水洗涤，再在60～90℃下在空气中干燥8～12h，最后在350～400℃下退火1～4h，获得Co3O4NSs/ACC@RGO复合电极材料复合电极材料用做正极在1Ag-1下显示出845Fg-1的高比电容，该正极组装的超级电容器在水系电解质中显示出2.2V的高电压窗口，功率密度为1100W Kg-1时具有99WhKg-1的超高能量密度和10000次循环后的容量保持率为168％的超长循环寿命。
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