CN107221448A - 一种超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球及其制备方法 - Google Patents
一种超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球及其制备方法 Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 56
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 29
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910018661 Ni(OH) Inorganic materials 0.000 title description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims abstract description 41
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 150000003926 acrylamides Chemical class 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OZTLSIFMYCDNHA-UHFFFAOYSA-I cerium(3+) nickel(2+) pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ni++].[Ce+3] OZTLSIFMYCDNHA-UHFFFAOYSA-I 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010295 mobile communication Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
本发明公开了一种超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球的制备方法。其特征在于，所述超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球由一步水热反应制备。将硫酸镍，硝酸铈铵，丙烯酰胺，六亚甲基四胺溶解于水得到混合溶液,记作溶液a；再将十六烷基三甲基溴化铵，苯胺溶于水中，滴加盐酸混合均匀，再滴加过硫酸铵溶液得到墨绿色溶液，记作溶液b；将溶液a与墨绿色溶液b混合，在内衬聚四氟乙烯的高压反应釜中进行水热反应。反应结束后，将所得产物离心洗涤并干燥，获得PANI/CeO2/Ni(OH)2多级微球。本发明所述制备方法操作简单，产物PANI/CeO2/Ni(OH)2多级微球分散性好，比表面积高，作为超级电容器电极材料具有很高的比电容和电化学循环稳定性。
Description
技术领域
本发明属于超级电容器电极材料领域，涉及一种PANI/CeO2/Ni(OH)2多级微球及其制备方法，具体地说，是涉及一种超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球及其制备方法。
背景技术
超级电容器是一种能够快速充放电、循环寿命长且功率密度高的新型储能装置，在移动通讯、电动汽车等方面具有广阔的应用前景，越来越受到科研工作者和产业界的重视。而电极材料对超级电容器的性能起到决定性作用，因此，高比电容活性物质的制备成为超级电容器中研究的重点。
目前，以氢氧化镍为代表的过渡金属氢氧化物(氧化物)，在超级电容器领域已被广泛应用于电极材料，由于其资源广泛、价格低廉、对环境无污染、电化学性能优越以及易于制备等特点，已经成为超级电容器电极材料的研究热点。最近，研究表明花状氢氧化镍微球由于其大的比表面积和高的表面缺陷，使其具有较好的电化学性能。但由于导电性能差而很难进一步发挥出很高的比电容量。研究发现,导电高分子材料也是极有应用前景的超级电容器的电极材料,其中聚苯胺(PANI)因其高电容、高导电性、低成本以及易于制备而最为引人注目。然而,PANI相对低的机械稳定性和循环寿命同样限制了它的应用。制备无机-有机杂合材料,利用其协同效应,是提高电极材料性能的有效途径。将过渡金属氢氧化物(氧化物)与导电聚合物PANI复合是一类非常重要的超级电容器材料。但由于PANI等导电聚合物的合成通常需要在酸性条件下制得，因此，需要预先合成PANI，再和其它无机材料混合，导致导电聚合物难以均匀分散，与无机材料的界面结合效果差，使其优异的电性能难以充分发挥出来。并且其制备方法较为复杂，耗时，制备条件苛刻。
基于上述原因，如何找到一种工艺相对简单、反应条件较温和，并能制备出有利于电子和电解质离子传输和扩散的PANI/CeO2/Ni(OH)2三元复合电极材料，则是本发明所要解决的主要问题。
发明内容
本发明针对现有制备聚苯胺与金属氧化物及氢氧化物复合电极材料步骤多，超级电容器复合电极材料难以均匀分散，聚苯胺与金属氧化物及氢氧化物界面结合不紧密从而影响其优异的电化学性能发挥的技术问题，提供一种高性能超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球的制备方法。该方法采用一步水热合成法，工艺简单，反应条件较温和，所制备出的 PANI/CeO2/Ni(OH)2多级微球比表面积大、微球孔径和PANI、CeO2在Ni(OH)2多级微球上的分散性容易控制，本发明采用以下技术方案予以实现：
一种高性能超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球及其制备方法，其特征在于，所述高性能超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球由一步水热反应制备，所述方法包括下述步骤：
1.称量0.1-0.5g硫酸镍(NiSO4·6H2O)，0.01-0.06g硝酸铈铵，0.01-0.05g丙烯酰胺，0.1-1.0g六亚甲基四胺(C6H12N4)分别加去离子水溶解，混合均匀，记作溶液a；
2.(2)称取0.01-0.05g十六烷基三甲基溴化铵(CTAB)，0.01-0.1g苯胺溶解于15ml去离子水中，滴加0.02-0.1ml盐酸后，搅拌混合均匀，再逐滴缓慢地加入5ml含有0.1-0.06g过硫酸铵的过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
3.将溶液a与墨绿色溶液b混合，转移至内衬聚四氟乙烯的反应釜中，在120-200℃反应1-12h。
4.反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀。
5.将步骤(4)中获得的沉淀物放入60-80℃真空干燥箱中干燥，得到最终产物PANI/CeO2/Ni(OH)2多级微球。
本发明的优点在于：在水溶液中进行一步反应，工艺简单，反应条件温和，制备成本低；所制备出的PANI/CeO2/Ni(OH)2多级微球比表面积大、微球孔径和PANI、CeO2在Ni(OH)2多级微球上的分散性容易控制。
附图说明
图1为实施例一所制备的PANI/CeO2/Ni(OH)2样品的XRD谱图。
图2为实施例一所制备的PANI/CeO2/Ni(OH)2样品的SEM照片
图3为实施例一所制备的PANI/CeO2/Ni(OH)2样品的氮气吸附等温线和孔径分布图。
图4为实施例一所制备的PANI/CeO2/Ni(OH)2样品的IR谱图。
图5为实施例一所制备的PANI/CeO2/Ni(OH)2样品作为超级电容器电极材料，在不同电流密度下的充放电性能。
图6为实施例一所制备的PANI/CeO2/Ni(OH)2样品作为超级电容器电极材料得到的充放电循环稳定性。
具体实施方式
下面结合附图和实施例对本发明进行详细说明：
实施例一：
1.称量0.156g硫酸镍(NiSO4·6H2O)，0.02g硝酸铈铵，0.03g丙烯酰胺，0.4g六亚甲基四胺(C6H12N4)加20ml去离子水溶解，混合均匀，记作溶液a；
2.再称取0.01g CTAB，0.015g苯胺溶解在15ml去离子水中，滴加0.05ml盐酸，搅拌至混合均匀，再逐滴缓慢地加入5ml的0.003g/ml过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
3.将溶液a与墨绿色溶液b混合，转移至内衬聚四氟乙烯的反应釜中，在180℃反应6h。
4.反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀。
5.将步骤(4)中获得的沉淀物放入70℃真空干燥箱中干燥，得到最终产物 PANI/CeO2/Ni(OH)2多级微球。
实施例二：
1.称量0.312g硫酸镍(NiSO4·6H2O)，0.04g硝酸铈铵，0.03g丙烯酰胺，0.8g六亚甲基四胺(C6H12N4)加20ml去离子水溶解，混合均匀，记作溶液a；
2.再称取0.01g CTAB，0.03g苯胺溶解在15ml去离子水中，滴加0.1ml盐酸，搅拌至混合均匀，再逐滴缓慢地加入5ml的0.003g/ml过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
3.将溶液a与墨绿色溶液b混合，转移至内衬聚四氟乙烯的反应釜中，在180℃反应3h。
4.反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀。
5.将步骤(4)中获得的沉淀物放入70℃真空干燥箱中干燥，得到最终产物 PANI/CeO2/Ni(OH)2多级微球。
实施例三：
1.称量0.312g硫酸镍(NiSO4·6H2O)，0.04g硝酸铈铵，0.03g丙烯酰胺，0.4g六亚甲基四胺(C6H12N4)加20ml去离子水溶解，混合均匀，记作溶液a；
2.再称取0.02g CTAB，0.015g苯胺溶解在15ml去离子水中，滴加0.05ml盐酸，搅拌至混合均匀，再逐滴缓慢地加入5ml的0.003g/ml过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
3.将溶液a与墨绿色溶液b混合，转移至内衬聚四氟乙烯的反应釜中，在150℃反应9h；
4.反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀；
5.将步骤(4)中获得的沉淀物放入60℃真空干燥箱中干燥，得到最终产物 PANI/CeO2/Ni(OH)2多级微球。
实施例四：
1.称量0.156g硫酸镍(NiSO4·6H2O)，0.03g硝酸铈铵，0.03g丙烯酰胺，0.6g六亚甲基四胺(C6H12N4)加20ml去离子水溶解，混合均匀，记作溶液a；
2.再称取0.03g CTAB，0.045g苯胺溶解在15ml去离子水中，滴加0.1ml盐酸，搅拌至混合均匀，再逐滴缓慢地加入5ml的0.003g/ml过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
3.将溶液a与墨绿色溶液b混合，转移至内衬聚四氟乙烯的反应釜中，在150℃反应9h。
4.反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀。
5.将步骤(4)中获得的沉淀物放入70℃真空干燥箱中干燥，得到最终产物 PANI/CeO2/Ni(OH)2多级微球。
样品的XRD谱图在日本理学公司的D-Max 2500/PC型X射线衍射仪上获得，图1为利用本发明实施例一所述方法制备的PANI/CeO2/Ni(OH)2多级微球的XRD谱图。由图可以看出，水热法合成的样品是PANI/CeO2/Ni(OH)2复合材料。
样品的形貌和微结构分析在JSM-6700F场发射扫描电子显微镜(SEM)上进行。图2为利用本发明实施例一所述方法制备的PANI/CeO2/Ni(OH)2多级微球的SEM照片。从图中的照片可以看出，所制备的样品是由纳米薄片片组装而成的单分散PANI/CeO2/Ni(OH)2多级微球，微球大小约8-10μm。
样品的比表面积和孔径分布是在美国麦克仪器公司ASAP2020M全自动比表面积及孔隙度吸附分析仪上得到的。图3为该样品的氮气吸附等温线和孔径分布图，求得BET比表面积为186.5m2/g，孔径分布在1.5～4.5nm之间，包含介孔和微孔两种结构。大的比表面积，有利于材料表面与电解液的充分接触，提供更多的活性位点，改善复合材料的电容性质。
图4为利用本发明实施例一所述方法制备的PANI/CeO2/Ni(OH)2多级微球的红外光谱图(IR)。从图中可以看出，复合材料的吸收峰中依然能够与聚苯胺的IR图谱特征吸收峰相匹配，结合产物的XRD图谱分析，表明实验合成的产物中含有聚苯胺。
实验结果表明，通过一步简单的水热反应，可以得到PANI/CeO2/Ni(OH)2多级微球，该微球比表面积高、孔径分布和PANI、CeO2在Ni(OH)2多级微球上的分散性容易控制。
图5为实施例一所制备的PANI/CeO2/Ni(OH)2样品作为超级电容器电极材料，在不同电流密度下的充放电性能。测试表明，本发明制备的PANI/CeO2/Ni(OH)2多级微球用作电极材料具有很高的比电容，在电流密度为1A·g-1时首次循环比电容为2870F·g-1。
图6为实施例一所制备的PANI/CeO2/Ni(OH)2样品作为超级电容器电极材料得到的充放电循环稳定性。在电流密度为1A·g-1时，连续充放电1000次后比电容仍然有2755F·g-1，容量保持率高达95.9％，远高于纯氢氧化镍的比电容保持率。较高的容量保持率表明复合材料有良好的储能特性，具有较高的实际应用价值。
上述实施例是本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，未背离本发明的原理与工艺过程下所作的其它任何改变、替代、简化等，均为等效的置换，都应包含在本发明的保护范围之内。
Claims (1)
1.一种超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球的制备方法。其特征在于，所述超级电容器电极材料PANI/CeO2/Ni(OH)2多级微球由一步水热反应制备，所述方法包括下述步骤：
(1)称量0.1-0.5g硫酸镍(NiSO4·6H2O)，0.01-0.06g硝酸铈铵，0.01-0.05g丙烯酰胺，0.1-1.0g六亚甲基四胺(C6H12N4)分别加去离子水溶解，搅拌混合均匀，记作溶液a；
(2)称取0.01-0.05g十六烷基三甲基溴化铵(CTAB)，0.01-0.1g苯胺溶解于15ml去离子水中，滴加0.02-0.1ml盐酸后，搅拌混合均匀，再逐滴缓慢地加入5ml含有0.1-0.06g过硫酸铵的过硫酸铵溶液，静置一段时间至溶液呈墨绿色，记作溶液b；
(3)将溶液a与溶液b混合，移至内衬聚四氟乙烯的50ml反应釜中，在120-200℃反应1-12h。
(4)反应结束后，取出反应釜冷却至室温，将沉淀分别用去离子水和无水乙醇分别离心洗涤三次，得到PANI/CeO2/Ni(OH)2沉淀。
(5)将步骤(4)中获得的沉淀物放入60-80℃真空干燥箱中干燥，得到最终产物PANI/CeO2/Ni(OH)2多级微球。
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