CN108011089B - 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 - Google Patents
一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 Download PDFInfo
- Publication number
- CN108011089B CN108011089B CN201711239700.6A CN201711239700A CN108011089B CN 108011089 B CN108011089 B CN 108011089B CN 201711239700 A CN201711239700 A CN 201711239700A CN 108011089 B CN108011089 B CN 108011089B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- graphene
- aqueous solution
- cobalt oxyhydroxide
- oxyhydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- -1 cobalt oxyhydroxide Chemical compound 0.000 title claims abstract description 38
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- 230000032683 aging Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 7
- 238000005086 pumping Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- 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 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/24—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，属于无机材料领域。其制备方法具体过程如下：(1)将钴盐水溶液与石墨烯水溶液按一定比例混合，在惰性气体及室温条件下搅拌一定时间；(2)加入强碱水溶液，反应一定时间；(3)撤掉惰性气体，加入强氧化剂，陈化一定时间；(4)陈化结束后所得悬浊液经过滤、洗涤、干燥，得到一种六元环状羟基氧化钴/石墨烯纳米复合材料。本发明具有工艺流程简单、反应条件温和、易大规模制备等优点，所得产品形貌可控，且羟基氧化钴在石墨烯表面均匀分散，有望在超级电容器、锂离子电池及催化等领域得到应用。
Description
技术领域
本发明属于无机材料领域，具体涉及一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。
技术背景
随着经济社会的快速发展，当今世界对于能源存储设备的要求越来越高，因此制备高性能的锂离子电池和电化学电容器、提高能源的有效利用率和储存效率就成了急需解决的问题。其中电极材料是储能设备性能优劣的关键。钴酸锂因具有放电电压高、充放电电压平稳、比能量高等优点，是目前锂离子电池最为常用的电极材料。钴氧化物(氧化钴、四氧化三钴、羟基氧化钴、氢氧化亚钴)作为生产钴酸锂的常见钴源之一，其结构与性质对钴酸锂的电化学性能具有明显影响。因此，开发高性能的钴氧化物纳米材料及制备工艺具有广阔的应用前景。
钴氧化物理论容量非常高，但是其导电性差、充放电过程中体积变化大等缺点在一定程度上限制了其应用。为提高钴氧化物的电化学性能，本文制备了六元环状羟基氧化钴/石墨烯纳米复合材料。石墨烯作为一种新型的碳材料，它具有二维平面单原子层结构，可以使金属氧化物纳米颗粒成核或镶嵌于其表面或侧面，其超高的比表面积以及良好的电子传输性等独特性质，使其成为了一种优异的复合材料添加剂。石墨烯作为载体或包覆材料能有效的改善羟基氧化钴的导电性及循环稳定性，羟基氧化钴也能在一定程度上阻止石墨烯的折叠、团聚，这种纳米复合材料兼具了石墨烯和羟基氧化钴的优势，提高了其在超级电容器及锂离子电池储能中的电化学性能。
研究发现，纳米材料的粒度、粒度分布及形貌对其性能及应用具有显著影响。纳米材料的可控制备，即尺寸与形貌的可控制备是相关领域研究人员追求的目标。从公开发表的论文与专利来看，相对于氢氧化亚钴及四氧化三钴，关于羟基氧化钴的研究较少，其制备工艺还处于初级阶段。专利CN201310375503.2公开了一种纳米级羟基氧化钴的合成工艺，但是所得羟基氧化钴无规则形貌，粒度分布较宽。专利CN201210016504.3在制备得到CoOOH后，还需在喷雾干燥器中进行造粒，增加设备，过程复杂。目前还未有关于六元环状羟基氧化钴/石墨烯纳米复合材料及制备方法的报道。本发明首次提供了一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。本发明具有工艺流程简单，过程能耗低，产品形貌和粒径可控，批次间重复性好，易大规模生产等优点，所得六元环状羟基氧化钴/石墨烯纳米复合材料有望在锂离子电池、超级电容器、催化等领域得到应用。
发明内容
本发明的目的在于提供一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法。
为实现上述目的，本发明采用的技术方案如下：
一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其具体步骤为：
(1)分别配制钴盐和石墨烯水溶液，所述钴盐水溶液中钴离子(Co2+)摩尔浓度为0.001-0.1mol/L，所述石墨烯水溶液中石墨烯质量浓度为0.1-2mg/mL；
(2)将钴盐水溶液和石墨烯水溶液混合均匀，在氮气或惰性气体中，室温条件下搅拌0.5-5h；
(3)加入强碱水溶液，于30-80℃反应0.5-5h，所述强碱水溶液中氢氧根离子(OH-)摩尔浓度为0.01-1.0mol/L；
(4)撤掉氮气或惰性气体，加入强氧化剂，继续陈化0.5-5h；所述强氧化剂在最终反应液中的质量分数为2％-10％；
(5)陈化结束后，所得悬浊液经过滤、洗涤、干燥，得到六元环状羟基氧化钴/石墨烯纳米复合材料。
所述钴盐为硫酸钴、氯化钴、硝酸钴、醋酸钴中的一种或两种以上。
所述钴盐水溶液中钴离子(Co2+)与石墨烯水溶液中石墨烯的质量比为1:5-5:1。
所述强碱水溶液中的强碱为氢氧化锂、氢氧化钠、氢氧化钾中的一种或两种以上。
所述步骤(3)中以2.5-20mL/min的流速加入强碱水溶液。
所述钴盐水溶液中钴离子(Co2+)与强碱水溶液中氢氧根离子(OH-)的摩尔比为1:5-1:40。
所述强氧化剂为双氧水(质量分数为25％-28％)、次氯酸钠中的一种或两种。
与现有技术相比，本发明具有以下优点：
(1)首次合成了纳米级六元环状羟基氧化钴/石墨烯复合材料，这种独特的材料有望在锂离子电池、超级电容器、催化领域等取得应用；
(2)产品形貌及粒度可控、制备方法具有过程能耗低、工艺流程简单、易大规模生产等优点。
附图说明
图1为本发明实施例1产品的SEM图。
图2为本发明实施例2产品的SEM图。
图3为本发明实施例2产品的XRD图。
图4为本发明实施例3产品的SEM图。
具体实施方式
以下实施例用于说明本发明。
实施例1
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25mL，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL，以5mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应1h；(3)撤掉N2，加入质量分数为28％的双氧水10ml，陈化2h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，其SEM图见图1，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例2
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25mL，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL，以5mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应2h；(3)撤掉N2，加入质量分数为28％的双氧水10ml，陈化3.5h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，其SEM图见图2，其XRD图见图3，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例3
(1)配置浓度为0.05mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各25ml，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.25mol/L的氢氧化钠水溶液50mL，以5mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应1h；(3)撤掉N2，加入质量分数为28％的双氧水10ml，陈化2h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，其SEM图见图4，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例4
(1)配置浓度为0.0125mol/L的氯化钴水溶液和1mg/mL的石墨烯水溶液各100mL，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.25mol/L的氢氧化钠水溶液200mL，以10mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应2h；(3)撤掉N2，加入质量分数为28％的双氧水40ml，陈化2h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例5
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各100mL，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.5mol/L的氢氧化钠水溶液200mL，以5mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应2h；(3)撤掉N2，加入质量分数为28％的双氧水40ml，陈化2h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
实施例6
(1)配置浓度为0.025mol/L的氯化钴水溶液和2mg/mL的石墨烯水溶液各100mL，混合均匀，转移至三口烧瓶中，三口烧瓶内提前通入氮气，室温下机械搅拌4h；(2)配制浓度为0.25mol/L的氢氧化钠水溶液200mL，以5mL/min的流速打入三口烧瓶中，在50℃及搅拌条件下反应2h；(3)撤掉N2，加入质量分数为28％的双氧水20ml，陈化2h；(4)陈化结束后，所得悬浊液经过滤、洗涤、干燥，制备得到六元环状羟基氧化钴/石墨烯纳米复合材料。
Claims (6)
1.一种六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：其具体步骤为：
（1）分别配制钴盐和石墨烯水溶液，所述钴盐水溶液中钴离子Co2+摩尔浓度为0.001-0.1 mol/L，所述石墨烯水溶液中石墨烯质量浓度为0.1-2 mg/mL；
（2）将钴盐水溶液和石墨烯水溶液混合均匀，在氮气或惰性气体中，室温条件下搅拌0.5-5 h；
（3）加入强碱水溶液，于30-80 ℃反应0.5-5 h，所述强碱水溶液中氢氧根离子（OH-）摩尔浓度为0.01-1.0 mol/L；所述钴盐水溶液中钴离子Co2+与强碱水溶液中氢氧根离子（OH-）的摩尔比为1:5-1:40；
（4）撤掉氮气或惰性气体，加入强氧化剂，继续陈化0.5-5 h；所述强氧化剂在最终反应液中的质量分数为2%-10%；
（5）陈化结束后，所得悬浊液经过滤、洗涤、干燥，得到六元环状羟基氧化钴/石墨烯纳米复合材料。
2.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：所述钴盐为硫酸钴、氯化钴、硝酸钴或醋酸钴中的一种或两种以上。
3.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：所述钴盐水溶液中钴离子Co2+与石墨烯水溶液中石墨烯的质量比为1:5-5:1。
4.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：所述强碱水溶液中的强碱为氢氧化锂、氢氧化钠或氢氧化钾中的一种或两种以上。
5.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：以2.5-20 mL/min的流速加入强碱水溶液。
6.根据权利要求1所述六元环状羟基氧化钴/石墨烯纳米复合材料的制备方法，其特征在于：所述强氧化剂为次氯酸钠或质量分数为25%-28%的双氧水中的一种或两种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711239700.6A CN108011089B (zh) | 2017-11-30 | 2017-11-30 | 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711239700.6A CN108011089B (zh) | 2017-11-30 | 2017-11-30 | 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108011089A CN108011089A (zh) | 2018-05-08 |
| CN108011089B true CN108011089B (zh) | 2020-08-07 |
Family
ID=62055420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711239700.6A Active CN108011089B (zh) | 2017-11-30 | 2017-11-30 | 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108011089B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466722A (zh) * | 2013-08-26 | 2013-12-25 | 无锡中经金属粉末有限公司 | 一种纳米级羟基氧化钴合成工艺 |
| CN105633382A (zh) * | 2016-03-16 | 2016-06-01 | 扬州大学 | 一氧化钴/石墨烯复合物锂离子电池负极材料的制备方法 |
| CN106549153A (zh) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | 一种空心六边形状羟基氧化钴纳米材料及其制备方法 |
-
2017
- 2017-11-30 CN CN201711239700.6A patent/CN108011089B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466722A (zh) * | 2013-08-26 | 2013-12-25 | 无锡中经金属粉末有限公司 | 一种纳米级羟基氧化钴合成工艺 |
| CN106549153A (zh) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | 一种空心六边形状羟基氧化钴纳米材料及其制备方法 |
| CN105633382A (zh) * | 2016-03-16 | 2016-06-01 | 扬州大学 | 一氧化钴/石墨烯复合物锂离子电池负极材料的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108011089A (zh) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | A review on the synthesis of CuCo2O4-based electrode materials and their applications in supercapacitors | |
| Tian et al. | Bio-template synthesized NiO/C hollow microspheres with enhanced Li-ion battery electrochemical performance | |
| Xia et al. | Solution synthesis of metal oxides for electrochemical energy storage applications | |
| CN107579241B (zh) | 一种三维帐篷型石墨烯-金属氧化物纳米复合材料的制备方法 | |
| CN107954483B (zh) | 一种α相氢氧化镍超薄纳米片及其制备方法 | |
| Xiao et al. | Balancing crystallinity and specific surface area of metal-organic framework derived nickel hydroxide for high-performance supercapacitor | |
| CN103318978B (zh) | 一种介孔钴酸镍纤维的制备方法及其应用 | |
| Ju et al. | Prussian blue analogue derived low-crystalline Mn2O3/Co3O4 as high-performance supercapacitor electrode | |
| CN111921529B (zh) | 镍钴金属有机骨架/镍钴金属氢氧化物异质材料的制备方法及应用 | |
| CN107611380B (zh) | 一种氧化镍/立体结构石墨烯复合材料的制备方法 | |
| CN110371936B (zh) | 一种层间距可调的钠离子电池用硒化铜纳米片阵列的制备方法及其应用 | |
| CN103840176B (zh) | 一种表面负载Au纳米颗粒的三维石墨烯基复合电极及其制备方法和应用 | |
| CN109742371B (zh) | 一种三维碳网络包覆Ni2P纳米颗粒复合材料的制备方法 | |
| Wei et al. | Hollow structures Prussian blue, its analogs, and their derivatives: Synthesis and electrochemical energy‐related applications | |
| CN111330620A (zh) | 插层型类石墨氮化碳复合材料、其制备方法及其应用 | |
| CN110745784A (zh) | 一种金属氧化物纳米颗粒及其制备方法和应用 | |
| CN111211312A (zh) | 一种锂-硫电池正极材料及其制备方法 | |
| CN111186827A (zh) | 一种高倍率磷酸铁锂微球的制备方法 | |
| CN108767261B (zh) | 一种三维微纳复合结构的石墨化碳材料、其制备方法及应用 | |
| CN104183827A (zh) | 一种磷酸铁锂纳米棒及其制备方法 | |
| Ren et al. | Electrospinning-derived functional carbon-based materials for energy conversion and storage | |
| CN113213535A (zh) | 一种可同时应用于正负极、结构可控的vs2微米花电极材料的制备方法 | |
| CN117352700A (zh) | 一种双原子掺杂碳材料包覆复合磷酸盐正极材料及其制备方法 | |
| CN107452955B (zh) | 一种具有中空结构的六棱柱状羟基氧化钴材料及其制备方法 | |
| CN108011089B (zh) | 一种六元环状羟基氧化钴/石墨烯纳米复合材料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |