CN108962617B - Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere - Google Patents
Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere Download PDFInfo
- Publication number
- CN108962617B CN108962617B CN201810777465.6A CN201810777465A CN108962617B CN 108962617 B CN108962617 B CN 108962617B CN 201810777465 A CN201810777465 A CN 201810777465A CN 108962617 B CN108962617 B CN 108962617B
- Authority
- CN
- China
- Prior art keywords
- self
- cobalt
- graded
- assembled
- tetroxide
- 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
- 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 title claims abstract description 48
- 239000004005 microsphere Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- 239000010941 cobalt Substances 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000007772 electrode material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims abstract description 4
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000005476 size effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000002309 gasification Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
-
- 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)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开一种自组装四氧化三钴分级微球的制备方法及其应用,该制备方法如下:将钴盐、聚乙烯醇分散于乙二醇与去离子水混合溶液中,利用水热法得到氢氧化钴前驱体,再经高温退火处理,最终获得由二维纳米片自组装形成具有分级结构的四氧化三钴微球;所得四氧化三钴分级微球具体应用于超级电容器电极材料,且比电容保持率达70%以上。本发明利用聚乙烯醇的热解气化性质,在四氧化三钴结构中产生大量中空微孔,提高其孔隙率和比表面积,增加活性位点,且制备的四氧化三钴微球兼具微纳米尺寸效应和分级特性,有效避免因尺寸过小而引起的团聚问题,提高其电化学性能。
The invention discloses a preparation method and application of self-assembled tricobalt tetroxide graded microspheres. The preparation method is as follows: dispersing cobalt salt and polyvinyl alcohol in a mixed solution of ethylene glycol and deionized water, and using a hydrothermal method to obtain hydroxide The cobalt precursor is then subjected to high temperature annealing treatment to finally obtain cobalt tetroxide microspheres with a hierarchical structure formed by self-assembly of two-dimensional nanosheets; the obtained cobalt tetroxide graded microspheres are specifically used in supercapacitor electrode materials, and the specific capacitance retention rate is more than 70% . The invention utilizes the pyrolysis and gasification properties of polyvinyl alcohol to generate a large number of hollow micropores in the cobalt tetroxide structure, improve its porosity and specific surface area, and increase active sites, and the prepared cobalt tetroxide microspheres have both micro-nano size effect and classification It can effectively avoid the agglomeration problem caused by too small size and improve its electrochemical performance.
Description
技术领域technical field
本发明属于超级电容器电极材料技术领域,具体涉及一种自组装四氧化三钴分级微球的制备方法及其应用。The invention belongs to the technical field of supercapacitor electrode materials, and in particular relates to a preparation method and application of self-assembled tricobalt tetroxide graded microspheres.
背景技术Background technique
超级电容器也叫电化学电容器,是一种可直接储存电荷的二次储能器件,相比于传统的静电电容器和二次电池,其功率密度更高、循环更长、充电时间更短、能源效率更高,在移动电子产业、新能源储能系统、纯电动汽车等方面有着广泛的应用前景。Supercapacitors, also known as electrochemical capacitors, are secondary energy storage devices that can directly store charges. Compared with traditional electrostatic capacitors and secondary batteries, they have higher power density, longer cycles, shorter charging times, and higher energy efficiency. It has higher efficiency and has broad application prospects in the mobile electronics industry, new energy energy storage systems, and pure electric vehicles.
超级电容器中起到决定性作用的是电极材料,根据电极材料工作原理的不同,可分为两大类:一类是以炭基材料为代表的双电层电极材料,另一类是以过渡金属化合物或导电聚合物为基础的赝电容电极材料。赝电容材料,不仅包括双电层电荷存储,也包含电解液离子在材料表面发生氧化还原反应而存储的电荷,因此可以将容量提高一到两个数量级,从而大大提高比容量和能量密度,成为研究人员关注的焦点。目前研究的赝电容类材料主要是有:二氧化钌、氧化锰、氧化钒、氧化镍、四氧化三钴等,其中四氧化三钴由于价格低廉、自然资源丰富且具有优异的电子存储能力和极高的理论不容量(高达3500F/g)等优点,被认为是具有极高研究潜质的材料之一。Electrode materials play a decisive role in supercapacitors. According to the different working principles of electrode materials, they can be divided into two categories: one is electric double layer electrode materials represented by carbon-based materials, and the other is transition metal materials. Compound or conductive polymer-based pseudocapacitive electrode materials. Pseudocapacitive materials include not only the electric double layer charge storage, but also the charge stored by the redox reaction of electrolyte ions on the surface of the material, so the capacity can be increased by one to two orders of magnitude, thereby greatly improving the specific capacity and energy density. focus of researchers. The pseudocapacitor materials currently studied are: ruthenium dioxide, manganese oxide, vanadium oxide, nickel oxide, cobalt tetroxide, etc. Among them, cobalt tetroxide has excellent electronic storage capacity and extremely high theoretical capacity due to its low price and abundant natural resources. (up to 3500F/g) and other advantages, it is considered to be one of the materials with extremely high research potential.
近年来,具有各种微观结构、特殊形貌的四氧化三钴已经被成功制备,如中国专利CN103011306B授权了一种制备纳米级立方体状四氧化三钴的方法,中国专利CN104787806B授权了一种玫瑰花状纳米四氧化三钴及其制备方法,中国专利CN103247777B授权了锂离子电池用四氧化三钴多壳层空心球负极材料及其制备方法,中国专利CN103979616B授权了一种花环状四氧化三钴的制备方法,等等。目前,还未见有关于四氧化三钴纳米片自组装成分级微球的相关报道。In recent years, cobalt tetroxide with various microstructures and special morphologies has been successfully prepared. For example, Chinese patent CN103011306B authorizes a method for preparing nano-cube-shaped cobalt tetroxide, and Chinese patent CN104787806B authorizes a rose-shaped nano-cobalt tetroxide and its Preparation method, Chinese patent CN103247777B authorizes the lithium ion battery with cobalt tetroxide multi-shell hollow sphere negative electrode material and its preparation method, Chinese patent CN103979616B authorizes the preparation method of a rose-shaped tricobalt tetroxide, and so on. At present, there is no relevant report on the self-assembly of cobalt tetroxide nanosheets into graded microspheres.
发明内容SUMMARY OF THE INVENTION
本发明的目的是制备出一种具有微纳米尺寸效应和分级结构的四氧化三钴;本发明的另一目的是提供该材料作为超级电容器电极材料的应用,由该材料制成的超级电容器电极具有良好的电化学性能、较高的比电容和稳定的循环特性。为实现上述目的,本发明提供一种自组装四氧化三钴分级微球的制备方法及其应用。The purpose of the present invention is to prepare a kind of cobalt tetroxide with micro-nano size effect and hierarchical structure; another purpose of the present invention is to provide the application of this material as a supercapacitor electrode material, and the supercapacitor electrode made of this material has good electrochemical performance, high specific capacitance and stable cycling characteristics. In order to achieve the above purpose, the present invention provides a preparation method and application of self-assembled tricobalt tetroxide graded microspheres.
本发明的技术方案概述如下:The technical scheme of the present invention is summarized as follows:
一种自组装四氧化三钴分级微球的制备方法,将钴盐、聚乙烯醇分散于乙二醇与去离子水混合溶液中,利用水热法得到氢氧化钴前驱体,再经高温退火处理,最终获得由二维纳米片自组装形成具有分级结构的四氧化三钴微球,该制备方法具体包括以下步骤:A preparation method of self-assembled tricobalt tetroxide graded microspheres, the cobalt salt and polyvinyl alcohol are dispersed in a mixed solution of ethylene glycol and deionized water, a cobalt hydroxide precursor is obtained by a hydrothermal method, and then subjected to high temperature annealing treatment, and finally To obtain cobalt tetroxide microspheres with hierarchical structure formed by self-assembly of two-dimensional nanosheets, the preparation method specifically includes the following steps:
(1)按5:1-1:5的体积比混合乙二醇与去离子水,再向15-50mL混合溶液加入1-4mmol二价无机钴盐,再加入0.01-0.5g聚乙烯醇,在室温下搅拌0.5-1h;(1) Mix ethylene glycol and deionized water in a volume ratio of 5:1-1:5, then add 1-4 mmol of divalent inorganic cobalt salt to 15-50 mL of mixed solution, and then add 0.01-0.5 g of polyvinyl alcohol, Stir at room temperature for 0.5-1 h;
(2)将上述混合溶液转移至聚四氟乙烯内衬反应釜中,在150-200℃下,水热反应6-24h;(2) Transfer the above mixed solution to a polytetrafluoroethylene-lined reaction kettle, and perform a hydrothermal reaction at 150-200° C. for 6-24 hours;
(3)待反应产物自然冷却至室温,离心、洗涤后,在60℃下,将所得沉淀物干燥12h,再以1-10℃/min的升温速率加热至350-600℃,恒温煅烧2-4h,制得所述自组装四氧化三钴分级微球。(3) After the reaction product was naturally cooled to room temperature, centrifuged and washed, the obtained precipitate was dried at 60°C for 12h, then heated to 350-600°C at a heating rate of 1-10°C/min, and calcined at a constant temperature for 2- 4h, the self-assembled tricobalt tetroxide graded microspheres were prepared.
优选的是,所述二价无机钴盐为醋酸钴、硝酸钴、硫酸钴、氯化钴中的一种。Preferably, the divalent inorganic cobalt salt is one of cobalt acetate, cobalt nitrate, cobalt sulfate, and cobalt chloride.
优选的是,所述洗涤的操作过程:用去离子水洗涤分离出的沉淀物5-8次。Preferably, the operation process of the washing is as follows: washing the separated precipitate with deionized water for 5-8 times.
本发明还提供上述一种自组装四氧化三钴分级微球的应用,该自组装四氧化三钴分级微球具体应用于超级电容器电极材料,且电极材料的比电容保持率高达70%以上。The invention also provides the application of the above-mentioned self-assembled tricobalt tetroxide graded microspheres. The self-assembled tricobalt tetroxide graded microspheres are specifically applied to supercapacitor electrode materials, and the specific capacitance retention rate of the electrode materials is as high as 70% or more.
优选的是,所述超级电容器电极材料的制备过程如下:Preferably, the preparation process of the supercapacitor electrode material is as follows:
(1)按(7-8):(1-2):1的质量比混合四氧化三钴、导电剂和粘结剂,并加入N-甲基吡咯烷酮中,超声分散后,制得浆料;(1) mix cobalt tetroxide, conductive agent and binder according to the mass ratio of (7-8):(1-2):1, and add in N-methylpyrrolidone, after ultrasonic dispersion, make slurry;
(2)将浆料均匀涂布在基底上,在80-120℃下,真空干燥12-24h后,以10-20MPa的压力进行压片处理。(2) The slurry is uniformly coated on the substrate, and after vacuum drying at 80-120° C. for 12-24 hours, the tableting treatment is performed at a pressure of 10-20 MPa.
优选的是,所述导电剂为乙炔黑、石墨、Super P中的一种。Preferably, the conductive agent is one of acetylene black, graphite and Super P.
优选的是,所述粘结剂为PVDF、PTFE中的一种。Preferably, the binder is one of PVDF and PTFE.
优选的是,所述基底为泡沫镍、铜箔、铝箔、碳纸中的一种。本发明的有益效果:Preferably, the substrate is one of foamed nickel, copper foil, aluminum foil, and carbon paper. Beneficial effects of the present invention:
(1)本发明首次以聚乙烯醇作为合成四氧化三钴的结构导向剂,利用聚乙烯醇的热解气化性质,生成大量内部中空的四氧化三钴分级结构,中空孔道的设计提高了四氧化三钴的孔隙率和比表面积,增加活性位点,使四氧化三钴具有优良的电化学特性;(1) The present invention uses polyvinyl alcohol as a structure-directing agent for synthesizing cobalt tetroxide for the first time, and utilizes the pyrolysis and gasification properties of polyvinyl alcohol to generate a large number of internal hollow hierarchical structures of cobalt tetroxide, and the design of hollow channels improves the porosity and ratio of cobalt tetroxide. Surface area, increase active sites, so that cobalt tetroxide has excellent electrochemical properties;
(2)本发明采用一步水热法,不添加任何模板剂、表面活性剂,实验操作简单、反应条件温和、重复性好;(2) the present invention adopts a one-step hydrothermal method, without adding any template agent or surfactant, the experimental operation is simple, the reaction conditions are mild, and the repeatability is good;
(3)本发明是在水热条件下,通过形成的纳米片自组装成具有分级结构的微球;(3) the present invention is to self-assemble into microspheres with a hierarchical structure through the formed nanosheets under hydrothermal conditions;
(4)本发明制备的四氧化三钴微球具有微纳米尺寸效应,同时形成的分级结构能有效避免因尺寸过小而造成团聚问题,有利于在储能领域的应用;(4) The cobalt tetroxide microspheres prepared by the present invention have a micro-nano size effect, and the hierarchical structure formed at the same time can effectively avoid the problem of agglomeration caused by too small size, which is beneficial to the application in the field of energy storage;
(5)本发明的材料制成的超级电容器电极具有良好的电化学性能、较高的比电容和稳定的循环特性。(5) The supercapacitor electrode made of the material of the present invention has good electrochemical performance, high specific capacitance and stable cycle characteristics.
附图说明Description of drawings
图1为实施例1所制得产物的X射线衍射谱图(XRD);Fig. 1 is the X-ray diffraction pattern (XRD) of the prepared product of Example 1;
图2为实施例1所制得产物的扫描电镜图(SEM);Fig. 2 is the scanning electron microscope (SEM) of the prepared product of embodiment 1;
图3为实施例1所制得产物作为超级电容器电极材料,在6mol/L的KOH电解液中扫面速度为10mV/s的循环伏安曲线图;Fig. 3 is the cyclic voltammetry curve of the product obtained in Example 1 as a supercapacitor electrode material, and the sweep speed is 10mV/s in 6mol/L KOH electrolyte;
图4为实施例1所述的超级电容器电极材料在不同电流密度下的6mol/LKOH电解液中的恒电流放电曲线图;Fig. 4 is the galvanostatic discharge curve diagram of the supercapacitor electrode material described in Example 1 in 6mol/LKOH electrolyte under different current densities;
图5为实施例1所制得四氧化三钴分级微球在不同电流密度下的比电容图。FIG. 5 is a specific capacitance diagram of tricobalt tetroxide graded microspheres prepared in Example 1 under different current densities.
具体实施方式Detailed ways
下面结合具体实施例和附图对本发明做进一步的详细阐述,以令本领域技术人员参照说明书文字能够据以实施。The present invention will be further described in detail below with reference to specific embodiments and accompanying drawings, so that those skilled in the art can implement the invention with reference to the description.
实施例1Example 1
称取0.5g乙酸钴、0.02gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤5次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 24 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water for 5 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 400 °C tube furnace for 2 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例2Example 2
称取0.5g乙酸钴、0.05gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤6次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.05g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 24 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water for 6 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 400 °C tube furnace for 2 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例3Example 3
称取0.5g乙酸钴、0.02gPVA溶于25ml去离子水中搅拌30min,量取5ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤6次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 25ml of deionized water and stir for 30min, measure 5ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 24 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water for 6 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 400 °C tube furnace for 2 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例4Example 4
称取0.5g乙酸钴、0.02gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度150℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤7次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 150°C for 24h, naturally cooled to room temperature, the reaction product was centrifuged and washed with deionized water for 7 times, then dried at 60°C for 12h, and then the reaction product was calcined in a 400°C tube furnace for 2h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例5Example 5
称取0.5g乙酸钴、0.02gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热12h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤7次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 12 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water 7 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 400 °C tube furnace for 2 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例6Example 6
称取0.5g乙酸钴、0.02gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤8次,然后在60℃下干燥12h,再将反应产物在600℃管式炉中煅烧2h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 24 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water for 8 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 600 °C tube furnace for 2 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
实施例7Example 7
称取0.5g乙酸钴、0.02gPVA溶于15ml去离子水中搅拌30min,量取15ml乙二醇加入上述溶液中再搅拌30min,将上述混合溶液转移至带有聚四氟乙烯内衬的反应釜中,在烘箱温度180℃下加热24h,自然冷却至室温,将反应产物离心分离并用去离子水洗涤8次,然后在60℃下干燥12h,再将反应产物在400℃管式炉中煅烧4h,即得到最终所需四氧化三钴产物。Weigh 0.5g of cobalt acetate, 0.02g of PVA, dissolve in 15ml of deionized water and stir for 30min, measure 15ml of ethylene glycol and add it to the above solution and stir for 30min, transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining , heated at an oven temperature of 180 °C for 24 h, cooled to room temperature naturally, the reaction product was centrifuged and washed with deionized water for 8 times, then dried at 60 °C for 12 h, and then the reaction product was calcined in a 400 °C tube furnace for 4 h, That is, the final desired cobalt tetroxide product is obtained.
将上述得到的四氧化三钴与导电剂乙炔黑和粘结剂PVDF按质量比8:1:1混合,均匀分散于N-甲基吡咯烷酮(NMP)中形成浆料,将浆料均匀涂在泡沫镍基底上,在干燥箱中80℃干燥24h,之后进行压片处理,压力设置为10MPa。The above-obtained cobalt tetroxide is mixed with conductive agent acetylene black and binder PVDF in a mass ratio of 8:1:1, uniformly dispersed in N-methylpyrrolidone (NMP) to form a slurry, and the slurry is uniformly coated on the foam nickel base. After drying in a drying oven at 80 °C for 24 h, the tableting treatment was performed, and the pressure was set to 10 MPa.
对实施例1制出的自组装四氧化三钴分级微球进行表征和电化学性能测试以证实本发明的有益效果。The self-assembled tricobalt tetroxide graded microspheres prepared in Example 1 were characterized and electrochemical performance tested to confirm the beneficial effects of the present invention.
图1为实施例1所制得产物的XRD谱图,谱图中的衍射峰与标准选项卡JCPDS 42-1467完全一致为典型的尖晶石结构四氧化三钴特征衍射峰,且无其它杂质特征峰出现。Figure 1 is the XRD spectrum of the product prepared in Example 1. The diffraction peaks in the spectrum are completely consistent with the standard tab JCPDS 42-1467, which are typical spinel structure cobalt tetroxide characteristic diffraction peaks, and no other impurity characteristic peaks appear. .
图2为实施例1所制得产物的SEM图,由图可知,该具有分级结构的微球是由纳米片有规则的组装而构成,且微球内部贯穿中空孔道,粒径大小在5-20μm。Fig. 2 is the SEM image of the product obtained in Example 1. As can be seen from the figure, the microspheres with a hierarchical structure are composed of nanosheets regularly assembled, and the interior of the microspheres runs through hollow channels, and the particle size is between 5- 20μm.
图3为实施例1所制得产物作为超级电容器电极材料,在6mol/L的KOH电解液中扫面速度为10mV/s的循环伏安曲线图,可以看出,曲线图中还原峰的峰电流达20mA,氧化峰的峰电流为-15mA,即以该四氧化三钴产物作为电极材料,具有明显的氧化还原过程,是典型的赝电容反应机理。Fig. 3 is the cyclic voltammetry curve of the product obtained in Example 1 as a supercapacitor electrode material with a sweep rate of 10mV/s in 6mol/L KOH electrolyte. It can be seen that the peak of the reduction peak in the curve The current reaches 20mA, and the peak current of the oxidation peak is -15mA, that is, the tricobalt tetroxide product is used as the electrode material, which has an obvious redox process, which is a typical pseudocapacitive reaction mechanism.
图4为实施例1所述的超级电容器电极材料在6mol/L的KOH电解液中,电势窗口范围在0-0.54V,不同电流密度下的恒电流放电曲线图。由图可知,当电流密度为1A/g时,电极的比电容达到265.9F/g,说明该材料具有做超级电容器的潜能。FIG. 4 is a galvanostatic discharge curve diagram of the supercapacitor electrode material described in Example 1 in a 6 mol/L KOH electrolyte, a potential window range of 0-0.54 V, and different current densities. It can be seen from the figure that when the current density is 1A/g, the specific capacitance of the electrode reaches 265.9F/g, indicating that the material has the potential to be used as a supercapacitor.
图5为实施例1所制得四氧化三钴分级微球在不同电流密度下的比电容图。从图中可知,在电流密度分别为1A/g、2A/g、3A/g、4A/g、5A/g、7A/g、10A/g时,比电容分别为265.9F/g、259.2F/g、251.1F/g、244.4F/g、235F/g、223.3F/g、207F/g,当电流密度从1A/g增大到10A/g时,本发明所制备出超级电容器电极材料比电容保持率高达78%。FIG. 5 is a specific capacitance diagram of tricobalt tetroxide graded microspheres prepared in Example 1 under different current densities. It can be seen from the figure that when the current densities are 1A/g, 2A/g, 3A/g, 4A/g, 5A/g, 7A/g, and 10A/g, the specific capacitances are 265.9F/g and 259.2F, respectively. /g, 251.1F/g, 244.4F/g, 235F/g, 223.3F/g, 207F/g, when the current density increases from 1A/g to 10A/g, the supercapacitor electrode material prepared by the present invention The specific capacitance retention rate is as high as 78%.
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。Although the embodiment of the present invention has been disclosed as above, it is not limited to the application listed in the description and the embodiment, and it can be applied to various fields suitable for the present invention. For those skilled in the art, it can be easily Therefore, the invention is not limited to the specific details without departing from the general concept defined by the appended claims and the scope of equivalents.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810777465.6A CN108962617B (en) | 2018-07-16 | 2018-07-16 | Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810777465.6A CN108962617B (en) | 2018-07-16 | 2018-07-16 | Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108962617A CN108962617A (en) | 2018-12-07 |
CN108962617B true CN108962617B (en) | 2020-02-14 |
Family
ID=64481166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810777465.6A Active CN108962617B (en) | 2018-07-16 | 2018-07-16 | Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108962617B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109817964B (en) * | 2019-03-06 | 2019-12-03 | 浙江工业大学 | A kind of preparation method of CoSn alloy composite negative pole material |
CN111704175A (en) * | 2020-05-28 | 2020-09-25 | 兰州大学 | A preparation method of cobalt tetroxide microspheres assembled from hexagonal sheets |
CN112023926B (en) * | 2020-08-05 | 2022-02-18 | 兰州大学 | Electro-catalytic hydrogen evolution material and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101200308A (en) * | 2007-11-09 | 2008-06-18 | 浙江华友钴镍材料有限公司 | Preparation method of cobaltosic oxide for electric battery |
CN102531070A (en) * | 2011-12-30 | 2012-07-04 | 郑州轻工业学院 | Co3O4 nanometer material for supercapacitor and preparation method thereof |
CN103586460A (en) * | 2013-11-11 | 2014-02-19 | 山东大学 | Magnetic porous cobalt hollow ball electromagnetic wave absorption material, preparation method and application thereof |
CN103771544A (en) * | 2014-02-22 | 2014-05-07 | 吉林大学 | Preparation method of hollow cobaltosic oxide microsphere |
CN104795253A (en) * | 2015-04-17 | 2015-07-22 | 天津大学 | Preparation method of hollow cobaltosic oxide microball materials and application for manufacturing electrodes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009011658A1 (en) * | 2007-07-18 | 2009-01-22 | Nanyang Technological University | Hollow porous microspheres |
CN102190332B (en) * | 2011-04-01 | 2013-03-13 | 山东大学 | Electromagnetic wave absorbing material of monodisperse nanometer ferriferrous oxide hollow ball, its preparation method and application |
CN107973333B (en) * | 2016-10-25 | 2020-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite metal oxide with hollow sea urchin-like structure, its preparation method and application |
-
2018
- 2018-07-16 CN CN201810777465.6A patent/CN108962617B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101200308A (en) * | 2007-11-09 | 2008-06-18 | 浙江华友钴镍材料有限公司 | Preparation method of cobaltosic oxide for electric battery |
CN102531070A (en) * | 2011-12-30 | 2012-07-04 | 郑州轻工业学院 | Co3O4 nanometer material for supercapacitor and preparation method thereof |
CN103586460A (en) * | 2013-11-11 | 2014-02-19 | 山东大学 | Magnetic porous cobalt hollow ball electromagnetic wave absorption material, preparation method and application thereof |
CN103771544A (en) * | 2014-02-22 | 2014-05-07 | 吉林大学 | Preparation method of hollow cobaltosic oxide microsphere |
CN104795253A (en) * | 2015-04-17 | 2015-07-22 | 天津大学 | Preparation method of hollow cobaltosic oxide microball materials and application for manufacturing electrodes |
Non-Patent Citations (2)
Title |
---|
"Construct 3D porous hollow Co3O4 micro-sphere: A potential oxidizer of nano-energetic materials with superior reactivity";Jun Wang等;《Applied Surface Science》;20180220;第442卷;摘要、实验部分、结果与讨论部分 * |
"Role of PVA in synthesis of nano Co3O4-decorated graphene oxide";Surekha S. Jogdand等;《Polymers Advanced Technologies》;20150611;第26卷;第1114-1122页 * |
Also Published As
Publication number | Publication date |
---|---|
CN108962617A (en) | 2018-12-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104299797B (en) | One kind is based on NiCo2S4And its water system asymmetrical type ultracapacitor of composite | |
CN103594254B (en) | The preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material | |
CN112670093B (en) | A porous Co3O4@Ni-MOF core-shell nanosheet array material and its preparation method and application | |
CN109616331B (en) | A core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
CN109741966B (en) | Ni6MnO8@ carbon nanotube composite material and preparation method and application thereof | |
CN108773859B (en) | A kind of vulcanized nanomaterial and its preparation method and application | |
CN108658119B (en) | Method and application for preparing copper sulfide nanosheets and their composites by low temperature vulcanization technology | |
CN106449179A (en) | Method of assembling MOF/nitrogen-doped active carbon asymmetric supercapacitor device | |
CN109411238B (en) | A kind of layered double hydroxide composite electrode material and preparation method and use thereof | |
CN106847547A (en) | Three-dimensional tubulose molybdenum bisuphide/polypyrrole composite electrode material for super capacitor and its preparation | |
CN105810456B (en) | A kind of activated graphene/needle-like nickel hydroxide nano composite and preparation method thereof | |
CN104176783A (en) | Preparation method and application method for nitrogen-carbon-material-coated manganese dioxide nanowire | |
CN108962617B (en) | Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere | |
CN107910199A (en) | A kind of super capacitor anode material with fake capacitance characteristic and preparation method thereof | |
CN108598394A (en) | Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application | |
CN113745009B (en) | Preparation method of binary nanocomposite Co3S4/NiCo2S4 and its application in supercapacitor electrode | |
CN106449136B (en) | Alpha-nickel hydroxide cobalt electrode material and the preparation method and application thereof | |
CN112490017A (en) | Preparation method and application of NiCo-LDH nano material | |
CN112044372A (en) | Hollow titanium dioxide @ carbon composite microsphere and preparation method thereof | |
CN106449138A (en) | Carbon-coated cobalt molybdate network nanosheet array material, preparation method and application | |
CN106847539A (en) | A kind of composite of the carbon coating cobalt molybdic acid hydridization manganese dioxide heterojunction structure of ultracapacitor | |
CN110491684B (en) | Acicular flower cobalt-nickel double metal hydroxide composite material and its preparation method and application | |
CN108281620A (en) | A kind of preparation method of anode material of lithium-ion battery titanium dioxide | |
CN108597899B (en) | NiSe2-Ni2O3 nanocomposite material for supercapacitor and preparation method thereof | |
CN107316749B (en) | Co3O4@CoWO4The preparation method and applications of nano-wire array Core-shell structure material |
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 |