CN105702484A - 一种超级电容器电极材料NiO/介孔碳纳米球的制备方法 - Google Patents
一种超级电容器电极材料NiO/介孔碳纳米球的制备方法 Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 239000000377 silicon dioxide Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
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- 230000014759 maintenance of location Effects 0.000 description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种超级电容器电极材料NiO/介孔碳纳米球的制备方法。将氨水、水和乙醇混合,加入正硅酸乙酯,搅拌后制得SiO2溶胶;加入Ni(NO3)2·6H2O,搅拌10min,于100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,搅拌24h后,于100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;聚合物纳米球干燥后,在氮气气氛中,以2~10℃·min-1的升温速率从室温升温到700℃~900℃炭化,然后用NaOH溶液除去产物中的SiO2,得到NiO/介孔碳纳米球。本发明工艺简单,所得NiO/介孔碳纳米球作为超级电容器电极材料时,表现出较高的比容量和较好的循环稳定性。
Description
技术领域
本发明涉及一种超级电容器电极材料NiO/介孔碳纳米球的制备方法,属材料技术领域。
背景技术
超级电容器是一种介于电池与传统静电容器之间的新型储能器件,具有环境友好、循环寿命长等特点,在电动汽车电源和消费类电子产品等领域有着广阔而又重要的应用前景。多孔碳材料作为双电层电容器电极材料表现出良好的循环稳定性,但其比电容不高。而过渡金属氧化物(氧化镍、氧化锰等)作为法拉第赝电容器电极材料具有较高的比电容,但其循环稳定性能相对较差。多孔碳/过渡金属氧化物复合材料,由于兼具两者的优点,受到研究者的广泛关注。例如“一种介孔氧化镍/碳复合纳米材料及其制备方法”(中国发明专利,申请号:201410367910.3)以非离子表面活性剂作为模板剂、无机镍盐为镍源,通过溶剂蒸发诱导自组装的方法制备了可用于超级电容器电极材料的介孔氧化镍/碳复合纳米材料。“一种超级电容器电极材料碳包覆氧化镍NiO/C的制备方法”(中国发明专利,申请号:201310109686.3)将乙酸镍、尿素和聚乙烯吡咯烷酮溶解于乙醇和水中,进行水热反应,得到NiO材料,然后将NiO溶于葡萄糖溶液中,继续进行水热反应,制备得到NiO/C电极材料。碳微球/纳米球是一种球形结构的新型碳纳米材料,它具有形状规则、粒径可控等优点,在吸附、催化和储能等领域都有着广泛的应用。因此,将微球/纳米球与NiO进行复合,在高性能的超级电容器电极材料领域具有重要的应用前景。“一种氧化镍/碳小球复合材料的制备方法”(中国发明专利,申请号:201510190340.X)以有序介孔碳小球为载体,首先在NaOH溶液中进行回流处理,然后利用金属离子水解合成出氢氧化镍/碳小球,最后结合热处理,制得了氧化镍/碳小球复合材料。Liu等人通过乳液-水热-活化法制备了介孔碳微球,在介孔中引入硝酸镍,然后进行高温热解,制备了NiO/介孔碳微球复合材料,它作为超级电容器电极材料时具有良好的电化学性能(Nickel-DopedActivatedMesoporousCarbonMicrosphereswithPartiallyGraphiticStructureforSupercapacitors,EnergyFuels,2013,27,1168-1173.)。然而,这些NiO/碳球复合材料存在制备方法比较复杂等缺点。
发明内容
本发明的目的在于公开一种作为超级电容器电极材料的NiO/介孔碳纳米球的制备方法。用该方法制备的NiO/介孔碳纳米球电极材料,其制备工艺简单,具有比容量高,循环稳定性能好等优点。
为达到上述目的,本发明先将NiO与SiO2纳米复合得到NiO/SiO2纳米粒子,然后将NiO/SiO2纳米粒子均匀分散在间苯二酚/甲醛聚合物纳米球中,炭化后制得NiO被均匀包覆的NiO/介孔碳纳米球。NiO的赝电容可极大提高碳材料的比电容,而具有均匀介孔结构的碳骨架能够有效提高电极材料的循环稳定性能。
具体制备工艺是按如下步骤进行的:
按1:73:30:0.9~2.9体积份数量取氨水、水、乙醇和正硅酸乙酯。将氨水、水和乙醇混合均匀,加入正硅酸乙酯,搅拌0.5~1h后制得SiO2溶胶;加入Ni(NO3)2·6H2O,Ni(NO3)2·6H2O与正硅酸乙酯的质量比为0.05~0.1:1,搅拌10min,置于内衬聚四氟乙烯的不锈钢水热釜中100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,其中间苯二酚和甲醛溶液的质量比为1:1.15,并且间苯二酚和Ni(NO3)2·6H2O质量比为2.2~6.7:1。搅拌24h后,置于内衬聚四氟乙烯的不锈钢水热釜中100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以2~10℃·min-1的升温速率从室温升温到700℃~900℃炭化,然后再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,其中NaOH溶液与产物中的SiO2的质量比为12:1,得到NiO/介孔碳纳米球。
以上原料均为市售工业级产品。
分析测试结果表明,所得NiO/介孔碳纳米球大小均匀,分散性好,直径约300nm,比表面积600m2·g-1以上,平均孔径约7.5nm。
本发明具有如下优点:
1.本发明先将NiO与SiO2复合得到NiO/SiO2纳米粒子,然后再将NiO/SiO2纳米粒子均匀分散在间苯二酚/甲醛聚合物纳米球中,将NiO与SiO2纳米粒子复合可防止NiO在高温炭化过程中聚集及被碳材料还原,并有效防止NiO纳米粒子的团聚,使NiO被均匀包覆的NiO/介孔碳纳米球,因此,本发明产品性能好。
2.本发明中将NiO/SiO2纳米粒子均匀分散在间苯二酚/甲醛聚合物纳米球中,炭化后利用NaOH出去SiO2纳米粒子,赋予了NiO/介孔碳纳米球丰富的介孔结构,NiO的赝电容可极大提高碳材料的比电容,而具有均匀介孔结构的碳骨架能够有效提高电极材料的循环温度性能。
3.本发明通过一步法制备NiO/介孔碳纳米球,不需要制备好介孔碳纳米球后再引入镍源,再通过热处理的方法制备NiO/介孔碳纳米球,具有工艺简单的优点。
4.本发明制备的NiO/介孔碳纳米球大小均匀,分散性好,直径约300nm,比表面积600m2·g-1以上,平均孔径约7.5nm,NiO/介孔碳纳米球作为超级电容器电极材料时,经分析测试表明,在1.0Ag-1下充放电时,其比电容达300Fg-1以上,循环充放电5000次后的容量保持率在90%以上,表现出较高的比容量和较好的循环稳定性。
具体实施方式
实施例1
按1:73:30:0.9体积份数量取氨水、水、乙醇和正硅酸乙酯。将氨水、水和乙醇混合均匀,加入正硅酸乙酯,搅拌0.5h后制得SiO2溶胶;加入Ni(NO3)2·6H2O,Ni(NO3)2·6H2O与正硅酸乙酯的质量比为0.08:1,搅拌10min,于100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,其中间苯二酚和甲醛溶液的质量比为1:1.15,并且间苯二酚和Ni(NO3)2·6H2O质量比为6.7:1。搅拌24h后,于100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以3℃·min-1的升温速率从室温升温到700℃炭化,然后再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,其中NaOH溶液与产物中的SiO2的质量比为12:1,得到NiO/介孔碳纳米球。
实施例2
按1:73:30:1.3体积份数量取氨水、水、乙醇和正硅酸乙酯。将氨水、水和乙醇混合均匀,加入正硅酸乙酯,搅拌0.5h后制得SiO2溶胶;加入Ni(NO3)2·6H2O,其与正硅酸乙酯的质量比为0.1:1,搅拌10min,于100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,其中间苯二酚和甲醛溶液的质量比为1:1.15,间苯二酚和Ni(NO3)2·6H2O质量比为3.4:1。搅拌24h后,于100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以5℃·min-1的升温速率从室温升温到800℃炭化,然后再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,其中NaOH溶液与产物中的SiO2的质量比为12:1,得到NiO/介孔碳纳米球。
实施例3
按1:73:30:2.2体积份数量取氨水、水、乙醇和正硅酸乙酯。将氨水、水和乙醇混合均匀,加入正硅酸乙酯,搅拌50min后制得SiO2溶胶;加入Ni(NO3)2·6H2O,其与正硅酸乙酯的质量比为0.05:1,搅拌10min,于100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,其中间苯二酚和甲醛溶液的质量比为1:1.15,间苯二酚和Ni(NO3)2·6H2O质量比为4.5:1。搅拌24h后,于100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以8℃·min-1的升温速率从室温升温到850℃炭化,然后再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,其中NaOH溶液与产物中的SiO2的质量比为12:1,得到NiO/介孔碳纳米球。
实施例4
按1:73:30:2.9体积份数量取氨水、水、乙醇和正硅酸乙酯。将氨水、水和乙醇混合均匀,加入正硅酸乙酯,搅拌1h后制得SiO2溶胶;加入Ni(NO3)2·6H2O,其与正硅酸乙酯的质量比为0.075:1,搅拌10min,于100℃水热反应3h,制得NiO/SiO2纳米粒子;然后加入间苯二酚和甲醛溶液,其中间苯二酚和甲醛溶液的质量比为1:1.15,间苯二酚和Ni(NO3)2·6H2O质量比为2.2:1。搅拌24h后,于100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以10℃·min-1的升温速率从室温升温到900℃炭化,然后再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,其中NaOH溶液与产物中的SiO2的质量比为12:1,得到NiO/介孔碳纳米球。
分析测试结果表明,实施例1-4得到的NiO/介孔碳纳米球大小均匀,分散性好,直径约300nm,比表面积600m2·g-1以上,平均孔径约7.5nm。将实施例1-4得到的NiO/介孔碳纳米球与石墨和聚四氟乙烯(PTFE)按8:1:1质量比量取,研磨混合均匀后溶解在乙醇溶液中,超声振荡1h形成浆状物。将该浆状物均匀涂布在泡沫镍上,并在60℃干燥12h得到NiO/介孔碳纳米球超级电容器电极材料。以NiO/介孔碳纳米球为工作电极,泡沫镍为对电极,Hg/HgO电极为参比电极。用电化学工作站(CHI660D)在6mol·L-1的KOH电解液中,于25℃在电位窗口-1.0~0V测试NiO/介孔碳纳米球电极材料的比容量值和循环充放电性能。测试结果表明,所得NiO/介孔碳纳米球作为超级电容器电极材料,在1.0Ag-1下充放电时,比电容达300Fg-1以上,循环充放电5000次后的容量保持率在90%以上,表现出较高的比容量和较好的循环稳定性。
以上原料均为市售工业级产品。
上述水热反应是指:将反应物装入内衬聚四氟乙烯的不锈钢水热釜中进行水热处理反应。
Claims (1)
1.一种超级电容器电极材料NiO/介孔碳纳米球的制备方法,其特征在于:
先按体积份数量取氨水:水:乙醇:正硅酸乙酯=1:73:30:0.9~2.9,将氨水、水和乙醇混合均匀后加入正硅酸乙酯,搅拌0.5~1h,制得SiO2溶胶;然后加入Ni(NO3)2·6H2O,Ni(NO3)2·6H2O与正硅酸乙酯的质量比为0.05~0.1:1,搅拌10min,置于内衬聚四氟乙烯的不锈钢水热釜中100℃水热反应3h,制得NiO/SiO2纳米粒子;接着,按照质量比量取间苯二酚:甲醛溶液=1:1.15,并且满足间苯二酚:Ni(NO3)2·6H2O质量比为2.2~6.7:1,将间苯二酚和甲醛溶液加入到NiO/SiO2纳米粒子中,搅拌24h,再置于内衬聚四氟乙烯的不锈钢水热釜中100℃水热反应24h,制得含有NiO/SiO2纳米粒子的聚合物纳米球;最后,将所得聚合物纳米球干燥后,置于管式炉中,在氮气气氛中,以2~10℃·min-1的升温速率从室温升温到700℃~900℃炭化,再用浓度为3mol·L-1的NaOH溶液除去产物中的SiO2,得到NiO/介孔碳纳米球;
上述NaOH溶液的用量是产物中的SiO2质量的12倍;
上述原料均为市售工业级产品。
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