CN108083293A - 一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方的应用 - Google Patents
一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方的应用 Download PDFInfo
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910020598 Co Fe Inorganic materials 0.000 title claims abstract description 38
- 239000007772 electrode material Substances 0.000 title claims abstract description 12
- 229910002519 Co-Fe Inorganic materials 0.000 title claims description 35
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 28
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 239000001509 sodium citrate Substances 0.000 abstract description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 abstract description 11
- 150000001868 cobalt Chemical class 0.000 abstract description 10
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- 229940038773 trisodium citrate Drugs 0.000 abstract description 9
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- 238000007599 discharging Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 235000019263 trisodium citrate Nutrition 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
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- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本分案申请涉及一种高性能超级电容电极材料Co‑Fe类普鲁士蓝纳米立方的应用，属于电极材料制备技术领域。以无机钴盐和铁氰化钾为反应原料，以柠檬酸三钠为络合稳定剂，采用液相共沉淀反应法，通过控制铁氰化钾的用量及静置老化时间等反应条件，制备出分散性好和比表面积大的Co‑Fe类普鲁士蓝纳米立方材料，其尺寸大小约为300nm。采用本发明制备出的Co‑Fe类普鲁士蓝纳米立方材料，提高了电化学电容器的容量以及改善了电容器快速充放电和使用寿命等性能，在1mol/L硫酸钠溶液中电流为5A/g恒电流充放电时的电容值高达447F/g，并具有良好的倍率性能。
Description
本申请为申请号为2017105689300、申请日为2017年7月13日、发明名称“一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方及其制备方法和应用”的分案申请。
技术领域
本发明涉及一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方及其制备方法和应用，属于电极材料制备技术领域。
背景技术
普鲁士蓝是一种深蓝色的颜料，主要用于油漆、油墨、塑料等行业及文教用品的着色。由于在普鲁士蓝晶胞中，亚铁离子和铁离子分别占据两个不同的位置，而这两个位置上都可以用不同的其他过渡金属来替代，所以形成的类普鲁士蓝化合物的品种具有多样性。类普鲁士蓝化合物可以用于化学分析检测，医学等领域。由于类普鲁士蓝比表面积大，孔隙率高，离子嵌脱能力强，在用于碱金属离子电池的电极材料时，电化学性能表现优异。然而，类普鲁士蓝化合物被用于超级电容器的正极材料的研究较少。陈洁等【1】通过简单的化学共沉淀法获得普鲁士蓝衍生物，并应用于超级电容器材料，当电流为0.2A/g时，Ni2[Fe(CN)6]具有较高的比容量450F/g，但其倍率性能并不太理想。Co2[Fe(CN)6]也被合成，但其比容量和倍率性能都远低于Ni2[Fe(CN)6]。本发明以无机钴盐和铁氰化钾作为原料，以柠檬酸三钠为络合稳定剂，使用溶液共沉淀法可控制备Co-Fe类普鲁士蓝纳米立方材料，工艺过程简单，反应条件温和，产品成本低，适合规模化生产。
【1】陈洁，黄可龙，刘素琴，一种超级电容器电极材料及其制备，公开号101546650A。
发明内容
本发明的目的是提供一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方及其制备方法，该制备方法是以无机钴盐和铁氰化钾为反应原料，以柠檬酸三钠为络合稳定剂，采用液相共沉淀反应法，通过控制铁氰化钾的用量及静置老化时间等反应条件，制备出Co-Fe类普鲁士蓝纳米立方材料。利用该方法制备可以制备晶型稳定的Co-Fe类普鲁士蓝纳米立方，且所制备的Co-Fe类普鲁士蓝纳米立方具有高电容器性能。
本发明解决问题的技术方案是：一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方的制备方法，其步骤如下：
称取无机钴盐和络合稳定剂分别溶于去离子水中配制无机钴盐溶液和络合稳定剂溶液，将上述溶液混合，称取铁氰化钾溶于去离子水中配制成铁氰化钾溶液；在搅拌下，将铁氰化钾溶液缓慢滴加入混合溶液中；室温下，静置24小时，离心收集样品，使用去离子水洗涤多次，干燥即得到Co-Fe类普鲁士蓝纳米立方。
上述反应过程中，络合稳定剂溶液是将络合稳定剂加入到去离子水中配制成的溶液。
优选的，无机钴盐为氯化钴。
优选的，络合稳定剂为柠檬酸三钠。
优选的，所述铁氰化钾与无机钴盐的摩尔比为2:3～4:3，络合稳定剂与无机钴盐的摩尔比为5:3。
作为优选，所述铁氰化钾浓度为0.02mol/L，无机钴盐溶液浓度为0.03mol/L，络合稳定剂溶液浓度为0.05mol/L。
上述反应过程中，络合稳定剂的添加量过少，会导致Co-Fe类普鲁士蓝纳米立方严重聚集；络合稳定剂的添加量过多，Co-Fe类普鲁士蓝纳米立方不容易沉淀，导致产品收率降低。
本发明另一个目的请求保护采用上述方法制备的Co-Fe类普鲁士蓝纳米立方。所制备的Co-Fe类普鲁士蓝纳米立方的尺寸约为300nm。
本发明第三个目的请求保护上述方法制备的Co-Fe类普鲁士蓝纳米立方在制备电极上的应用。
一种电极，采用如下制备方法：将上述方法制备的Co-Fe类普鲁士蓝纳米立方、乙炔黑和聚四氟乙烯按质量比8:1:1混合，加入丙酮使三者充分混合，制成浆状，滚压成薄片并裁取5mg的薄片压在泡沫镍上制成电极片，然后在真空干燥箱中室温下真空干燥12h。
Co-Fe类普鲁士蓝纳米立方材料组装的电极表现出较佳的电化学电容器性能，在1mol/L硫酸钠溶液中电流密度为5A/g恒电流充放电时的电容值为380～450F/g。
与现有技术相比较，本发明的有益效果是：
本发明工艺过程简单，反应条件温和，常温下操作，不需要使用昂贵的表面活性剂和有机模板剂。原料来源丰富，方便，适合规模化生产。产品纳米立方约300nm，分散性好，比表面积大，采用本发明方法可制备出结晶性良好的Co-Fe类普鲁士蓝纳米立方材料。材料的多孔三维交联结构能够保证充分地与电解液接触，增加了反应表面积改善了固液界面上的离子扩散。Co-Fe类普鲁士蓝纳米立方材料提高了电化学电容器的容量，改善了电容器快速充放电和使用寿命等性能，在超级电容工业领域具有重要应用前景。
附图说明
本发明附图6幅，
图1是实施例1制备的Co-Fe类普鲁士蓝纳米立方的XRD图；
图2是实施例1制备的Co-Fe类普鲁士蓝纳米立方的SEM图；
图3是为添加柠檬酸三钠与不添加柠檬酸三钠的SEM对比图；(左-添加柠檬酸三钠，右-不添加柠檬酸三钠)；
图4是实施例1制备的Co-Fe类普鲁士蓝纳米立方组装的电极在1mol/L硫酸钠溶液中电流为5A/g时恒电流充放电曲线；
图5是实施例2制备的Co-Fe类普鲁士蓝纳米立方的SEM图；
图6是实施例2制备的Co-Fe类普鲁士蓝纳米立方组装的电极在1mol/L硫酸钠溶液中电流为5A/g时恒电流充放电曲线。
具体实施方式
下面通过附图和具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。
实施例1
称取0.143g六水合氯化钴(0.6mmol)和0.294g柠檬酸三钠(1mmol)溶于20mL去离子水中配制成氯化钴溶液，再称取0.132g铁氰化钾(0.4mmol)溶于去20mL离子水中配制成铁氰化钾溶液；在搅拌下，将铁氰化钾溶液缓慢滴加入氯化钴溶液中；室温下，静置老化24小时，离心收集样品，使用去离子水洗涤3次，于60°烘干。从图1，2可以看到尺寸约250nm的Co-Fe类普鲁士蓝纳米立方。
实施例1的对比例(无柠檬酸三钠)
称取0.143g六水合氯化钴(0.6mmol)溶于20mL去离子水中配制成氯化钴溶液，再称取0.132g铁氰化钾(0.4mmol)溶于去20mL离子水中配制成铁氰化钾溶液；在搅拌下，将铁氰化钾溶液缓慢滴加入氯化钴溶液中；室温下，静置老化24小时，离心收集样品，使用去离子水洗涤3次，于60°烘干。从图3为添加柠檬酸三钠与不添加柠檬酸三钠的电镜对比图。实施例1的应用例
将实施例1制得的Co-Fe类普鲁士蓝纳米立方、乙炔黑和聚四氟乙烯按质量比8:1:1混合，加入适量丙酮使三者充分混合，制成浆状，滚压成薄片并裁取5mg的薄片压在泡沫镍上制成电极片，然后在真空干燥箱中110℃下真空干燥12h。单电极测试采用Co-Fe类普鲁士蓝纳米立方材料为工作电极，饱和甘汞电极(SCE)为参比电极，金属铂片为辅助电极，电解液为1mol/L硫酸钠溶液。从图4可以测得Co-Fe类普鲁士蓝纳米立方电极在5A/g恒电流充放电时的电容值为447F/g。
实施例2
称取0.143g六水合氯化钴(0.6mmol)和0.294g柠檬酸三钠(1mmol)溶于20mL去离子水中配制成无机钴盐溶液，再称取0.132g铁氰化钾(0.8mmol)溶于去20mL离子水中配制成铁氰化钾溶液；在搅拌下，将铁氰化钾溶液缓慢滴加入无机钴盐溶液中；室温下，静置老化24小时，离心收集样品，使用去离子水洗涤3次，于60°烘干。从图5可以看到尺寸约300nm的Co-Fe类普鲁士蓝纳米立方。
实施例2的应用例
如按实施例2的应用例所述方法制备Co-Fe类普鲁士蓝纳米立方电极并进行性能测试。从图6，可以测得Co-Fe类普鲁士蓝纳米立方电极在1mol/L硫酸钠溶液中电流为5A/g恒电流充放电时的电容值为388F/g。
Claims (1)
1.一种高性能超级电容电极材料Co-Fe类普鲁士蓝纳米立方的应用，其特征在于，将Co-Fe类普鲁士蓝纳米立方、乙炔黑和聚四氟乙烯按质量比8:1:1混合，加入丙酮使三者充分混合，制成浆状，滚压成薄片并裁取5mg的薄片压在泡沫镍上制成电极片，然后在真空干燥箱中室温下真空干燥12h，制成工作电极，以饱和甘汞电极为参比电极，金属铂片为辅助电极，电解液为1mol/L硫酸钠溶液；
其中Co-Fe类普鲁士蓝纳米立方的制备方法为：称取六水合氯化钴0.6mmol和柠檬酸三钠1mmol溶于20mL去离子水中配制成氯化钴溶液，再称取铁氰化钾0.4mmol溶于去20mL离子水中配制成铁氰化钾溶液；在搅拌下，将铁氰化钾溶液缓慢滴加入氯化钴溶液中；室温下，静置老化24小时，离心收集样品，使用去离子水洗涤3次，于60°烘干。
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