WO2023207813A1 - Preparation method for multi-stage nanosheet array nico2o4/rgo/nf and application as electrode - Google Patents

Preparation method for multi-stage nanosheet array nico2o4/rgo/nf and application as electrode Download PDF

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WO2023207813A1
WO2023207813A1 PCT/CN2023/089953 CN2023089953W WO2023207813A1 WO 2023207813 A1 WO2023207813 A1 WO 2023207813A1 CN 2023089953 W CN2023089953 W CN 2023089953W WO 2023207813 A1 WO2023207813 A1 WO 2023207813A1
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rgo
nico
nanosheet array
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preparation
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曲美玥
栗顺
姜大威
王冬冬
张清扬
姜名勇
李师航
赵泽熙
刘天舒
徐�明
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一汽奔腾轿车有限公司
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    • 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
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • step 3 In a nitrogen atmosphere with a nitrogen flow rate of 100 mL/min, heat the nickel cobalt oxide precursor/rGO/nickel foam obtained in step 2) to 220-380°C at 2°C/min, and calcine for 2.2-3h to obtain Honeycomb nanosheet array nickel cobalt oxide/rGO/nickel foam is NiCo 2 O 4 /rGO/NF.
  • Figure 3 is the CV curve of NiCo 2 O 4 /rGO and NiCo 2 O 4 /rGO/NF in 1M KOH and 0.5M methanol;
  • NiCo 2 O 4 /rGO and NiCo 2 O 4 /rGO/NF were subjected to methanol electrooxidation test.
  • the CV curve shows that at 0.6V, NiCo 2 O 4 /rGO/NF electrode has a current density as high as 176Ag-1, which is 2 times the current density of NiCo 2 O 4 /rGO electrode (88Ag -1 ).
  • the current density of NiCo 2 O 4 /rGO/NF The current density is still as high as 152Ag -1 .
  • the current density can be restored to 172Ag -1 , which is 97% of the initial value. As shown in Figure 4, this phenomenon shows that the current density of the secondary material is reduced. Due to methanol consumption.

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  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a preparation method for a multi-stage nanosheet array NiCo2O4/rGO/NF. Nickel cobaltate NiCo2O4 is compounded with high-conductivity graphene, and is further grown on a foamed nickel substrate to prepare a NiCo2O4 hybrid having a special morphology, and then a three-dimensional multi-stage nanosheet array NiCo2O4/rGO/NF is constructed. A nanosheet array is directly grown on an NF substrate, which increases the exposure of active sites, and is more beneficial to the transmission of electrons or particles. The multi-stage nanosheet array NiCo2O4/rGO/NF is applied as an electrode. An active material is directly grown on the foamed nickel substrate, thereby reducing a contact resistance between the active material and a current collector. Nanosheets have porous structures, and a large number of open pore channels are formed between the interconnected nanosheets, which is more beneficial to the permeation of electrolyte ions.

Description

多级纳米片阵列NiCo2O4/rGO/NF制备方法与作电极应用Preparation method of multi-level nanosheet array NiCo2O4/rGO/NF and its application as electrode 技术领域Technical field
本发明涉及多级结构材料技术领域，特别涉及一种多级纳米片阵列NiCo2O4/rGO/NF制备方法与作电极应用。The invention relates to the technical field of multi-level structural materials, and in particular to a preparation method and electrode application of a multi-level nanosheet array NiCo 2 O 4 /rGO/NF.
背景技术Background technique
超级电容器因其对环境无污染、高功率密度、快速的充放电过程等优点，受到研究者们的广泛关注，电极材料是影响其性能的关键因素，RuO2等贵金属作为电极材料，受限于其昂贵的成本和自身毒性。直接甲醇燃料电池DMFCs，是通过甲醇与空气或氧气反应转化为电能的储能装置，具有燃料便宜、易于储存、理论比能量高，近乎零污染排放等优点，是理想动力源之一。但是一些诸如催化剂易中毒、高成本以及甲醇阳极渗透等问题制约了其发展，甲醇在阳极不完全氧化时会产生HCHO、CH3COOH以及一些类CO化合物等中间产物，这种反应的中间产物会被电极表面吸附，从而导致催化剂中毒。因此，提升甲醇燃料电池DMFCs的关键在于要减少或避免反应中间产物CO化合物的形成和吸附。Supercapacitors have attracted widespread attention from researchers because of their environmentally friendly advantages, such as high power density and fast charging and discharging processes. Electrode materials are the key factors affecting their performance. As electrode materials, precious metals such as RuO 2 are limited by Its high cost and own toxicity. Direct methanol fuel cells (DMFCs) are energy storage devices that convert methanol into electrical energy through the reaction of methanol with air or oxygen. It has the advantages of cheap fuel, easy storage, high theoretical specific energy, and near-zero pollution emissions. It is one of the ideal power sources. However, some problems such as easy poisoning of the catalyst, high cost, and anode penetration of methanol have restricted its development. When methanol is incompletely oxidized at the anode, intermediate products such as HCHO, CH 3 COOH, and some CO-like compounds will be produced. The intermediate products of this reaction will Adsorbed by the electrode surface, causing catalyst poisoning. Therefore, the key to improving DMFCs in methanol fuel cells is to reduce or avoid the formation and adsorption of CO compounds as reaction intermediate products.
钴酸镍NiCo2O4是一种尖晶石结构的过渡金属氧化物，将其与具有高导电性的石墨烯复合，并将其进一步生长在泡沫镍基质上制备具有特殊形貌的NiCo2O4杂化物,由于其结构中存在Co3+/Co2+和Ni3+/Ni2+两种氧化还原电对，因而具有比单一氧化镍、氧化钴更高的电化学性能，然而，单一的复合氧化物钴酸镍的循环稳定性差限制了其应用。Nickel cobalt oxide NiCo 2 O 4 is a transition metal oxide with a spinel structure. It is compounded with graphene with high conductivity and further grown on a nickel foam matrix to prepare NiCo 2 with a special morphology. O 4 hybrid, due to the existence of two redox couples, Co 3+ /Co 2+ and Ni 3+ /Ni 2+ , has higher electrochemical performance than single nickel oxide and cobalt oxide. However, The poor cycling stability of the single composite oxide nickel cobalt oxide limits its application.
在传统电极制备过程中，电极材料常因涂覆不均匀而影响电化学活性，同时，加入的粘接剂不可避免地会降低电极的效率。目前，常用的制备石墨烯/泡沫镍方法多采用气相沉积法CVD，但CVD法对设备要求较高，且操作繁琐，不利于节约资源。 In the traditional electrode preparation process, the electrochemical activity of electrode materials is often affected by uneven coating. At the same time, the added binder will inevitably reduce the efficiency of the electrode. At present, the commonly used method for preparing graphene/nickel foam mostly uses the vapor deposition method CVD. However, the CVD method has high equipment requirements and is cumbersome to operate, which is not conducive to saving resources.
发明内容Contents of the invention
本发明针对现有技术中存在的问题，构思了一种多级纳米片阵列NiCo2O4/rGO/NF制备方法与作电极应用，钴酸镍NiCo2O4与具有高导电性石墨烯复合，并将其进一步生长在泡沫镍基质上制备具有特殊形貌的NiCo2O4杂化物，构建三维纳米结构电极。In view of the problems existing in the prior art, the present invention conceived a multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method and electrode application, in which nickel cobalt oxide NiCo 2 O 4 is composited with highly conductive graphene , and further grown it on a nickel foam matrix to prepare a NiCo 2 O 4 hybrid with special morphology to construct a three-dimensional nanostructure electrode.
实现本发明的技术方案之一：多级纳米片阵列NiCo2O4/rGO/NF制备方法，其特征是，包括以下步骤：One of the technical solutions to realize the present invention: a multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method, which is characterized by including the following steps:
1)在去离子水中,加入氧化石墨凝胶，超声分散16-20min后，得到氧化石墨悬浮液，继续加入柠檬酸，超声12min，并倒入高压釜中，在所述盛有氧化石墨悬浮液的高压釜中，加入预处理的泡沫镍，再氧化石墨悬浮液中，完全浸没所述预处理的泡沫镍，在115-120℃下，水热反应6-6.5h，水热反应结束后，自然冷却至室温，用去离子水洗涤所得产物后，冷冻干燥2.5-3h后，得到GO/NF；1) Add graphite oxide gel to deionized water, and disperse it with ultrasonic for 16-20 minutes to obtain a graphite oxide suspension. Continue to add citric acid, ultrasonic for 12 minutes, and pour it into an autoclave. The graphite oxide suspension is filled with In the autoclave, add the pretreated nickel foam, re-oxidize the graphite suspension, completely immerse the pretreated nickel foam, and perform a hydrothermal reaction at 115-120°C for 6-6.5h. After the hydrothermal reaction is completed, Cool to room temperature naturally, wash the product with deionized water, and freeze-dry it for 2.5-3 hours to obtain GO/NF;
2)在盛有110-140mL去离子水的四口烧瓶中，置于步骤1)得到所述的GO/NF后，加入10-25mg柠檬酸，在持续搅拌条件下，以0.8-1.5ml/min速度滴加NaOH碱液，控制所述四口烧瓶中溶液pH＝10±0.1，稳定6-9min，将六水合硝酸镍、六水合硝酸钴溶于去离子水中，形成混合盐溶液，同时以0.8-1.5mL/min速度滴加混合盐溶液和碱液，使溶液pH值稳定在10±0.1；待混合盐溶液滴加完毕，将所得含有GO/NF的浆液转移至Teflon反应釜中，在85-95℃下，晶化5-7h，反应结束后，自然冷却至室温，用去离子水洗涤所得产物后，冷冻干燥2.5-3h，得到钴酸镍前体/rGO/泡沫镍；2) In a four-necked flask containing 110-140mL of deionized water, place it in step 1) to obtain the GO/NF, add 10-25mg of citric acid, and add 0.8-1.5ml/ Add NaOH alkali solution dropwise at min speed, control the pH of the solution in the four-necked flask to 10±0.1, and stabilize it for 6-9 minutes. Dissolve nickel nitrate hexahydrate and cobalt nitrate hexahydrate in deionized water to form a mixed salt solution. Add the mixed salt solution and alkali solution dropwise at a speed of 0.8-1.5mL/min to stabilize the pH value of the solution at 10±0.1; after the dropwise addition of the mixed salt solution is completed, transfer the obtained slurry containing GO/NF to the Teflon reactor. Crystallize at 85-95°C for 5-7 hours. After the reaction is completed, cool to room temperature naturally. After washing the product with deionized water, freeze-dry it for 2.5-3 hours to obtain nickel cobalt oxide precursor/rGO/nickel foam;
3)在氮气气氛中，氮气流速100mL/min，将步骤2)得到所述的钴酸镍前体/rGO/泡沫镍以2℃/min升温至220-380℃，煅烧2.2-3h后，得到蜂巢状纳米片阵列钴酸镍/rGO/泡沫镍，即为NiCo2O4/rGO/NF。 3) In a nitrogen atmosphere with a nitrogen flow rate of 100 mL/min, heat the nickel cobalt oxide precursor/rGO/nickel foam obtained in step 2) to 220-380°C at 2°C/min, and calcine for 2.2-3h to obtain Honeycomb nanosheet array nickel cobalt oxide/rGO/nickel foam is NiCo 2 O 4 /rGO/NF.
进一步，步骤1)中所述氧化石墨悬浮液的浓度范围为1-2mg/mL；氧化石墨与柠檬酸的质量比为2:1，超声功率为310W。Further, the concentration range of the graphite oxide suspension described in step 1) is 1-2 mg/mL; the mass ratio of graphite oxide to citric acid is 2:1, and the ultrasonic power is 310W.
进一步，步骤1)中所述的高压釜的衬里为聚四氟乙烯Teflon。Further, the lining of the autoclave described in step 1) is polytetrafluoroethylene Teflon.
进一步，步骤2)中配制所述的混合盐溶液中镍离子和钴离子的摩尔比为1:2；镍离子和钴离子的摩尔之和范围为10-15mmol。Further, the molar ratio of nickel ions and cobalt ions in the mixed salt solution prepared in step 2) is 1:2; the molar sum of nickel ions and cobalt ions ranges from 10 to 15 mmol.
进一步，步骤2)中配制所述的NaOH碱液浓度为0.2-0.25mol/L。Further, the concentration of the NaOH alkali solution prepared in step 2) is 0.2-0.25 mol/L.
进一步，步骤2)中所述的柠檬酸的质量范围为10-20mg。Further, the mass range of the citric acid described in step 2) is 10-20 mg.
实现本发明的技术方案之二：多级纳米片阵列NiCo2O4/rGO/NF作为电极应用，其特征是，用多级纳米片阵列NiCo2O4/rGO/NF作为甲醇燃料电池和超级电容器的电极阳极。The second technical solution for realizing the present invention: multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode, which is characterized in that the multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as a methanol fuel cell and super The electrode anode of the capacitor.
本发明多级纳米片阵列NiCo2O4/rGO/NF制备方法与作电极应用的有益效果体现在：The beneficial effects of the multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method and electrode application of the present invention are reflected in:
1、一种多级纳米片阵列NiCo2O4/rGO/NF制备方法，通过使用柠檬酸作为络合剂和分散剂，适度焙烧合成了rGO泡沫镍基质原位生长的三维纳米片阵列多级结构复合物钴酸镍/石墨烯/泡沫镍，一方面，在NF基底上直接生长纳米片阵列，增加了活性位点的暴露，更有利于电子或粒子传输，另一方，面这种杂化材料避免了制备过程中使用粘接剂，省略了繁琐的传统电极制备过程，制备方法操作简便、易于控制、成本低廉；1. A multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method. By using citric acid as a complexing agent and dispersant, moderate roasting synthesizes a multi-level three-dimensional nanosheet array grown in situ on a rGO foam nickel matrix. The structural composite nickel cobaltate/graphene/nickel foam, on the one hand, directly grows the nanosheet array on the NF substrate, which increases the exposure of active sites and is more conducive to electron or particle transmission. On the other hand, this hybridization The material avoids the use of adhesives in the preparation process and omits the cumbersome traditional electrode preparation process. The preparation method is simple to operate, easy to control, and low in cost;
2、一种多级纳米片阵列NiCo2O4/rGO/NF作为电极应用，在1M KOH和0.5MCH3OH电解液中，作为电极在0.6V时，具有高达176Ag-1的电流密度，在经过1000次循环后，电流密度仍然高达152Ag-1，由于活性材料直接生长在泡沫镍基底上，降低了活性材料与集流体之间的接触电阻，减少了死体积的存在，同时，纳米片具有多孔结构，互连的纳米片之间形成大量的开放性孔道，有利于电解质离 子的渗透；2. A multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode. In 1M KOH and 0.5MCH 3 OH electrolyte, as an electrode, it has a current density of up to 176Ag -1 at 0.6V. After 1000 cycles, the current density is still as high as 152Ag -1 . Since the active material grows directly on the nickel foam substrate, the contact resistance between the active material and the current collector is reduced, and the existence of dead volume is reduced. At the same time, the nanosheets have Porous structure, a large number of open pores formed between interconnected nanosheets, which is conducive to electrolyte dissociation penetration of the child;
3、一种多级纳米片阵列NiCo2O4/rGO/NF作为电极应用，将其作为超级电容器电极材料，此电极在1Ag-1的电流密度下比电容高达2580Fg-1，在高达20Ag-1的电流密度下，比电容可达2102Fg-1。3. A multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode and used as a supercapacitor electrode material. The specific capacitance of this electrode is as high as 2580Fg -1 at a current density of 1Ag -1 and as high as 20Ag - At a current density of 1 , the specific capacitance can reach 2102Fg -1 .
附图说明Description of drawings
图1是在实施例1中，经多级纳米片阵列NiCo2O4/rGO/NF制备方法，得到的NiCo2O4/rGO的HRTEM照片；Figure 1 is an HRTEM photo of NiCo 2 O 4 /rGO obtained through the multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method in Example 1;
图2是在实施例1中，经多级纳米片阵列NiCo2O4/rGO/NF制备方法，得到的NiCo2O4/rGO/NF的的HRTEM照片；Figure 2 is an HRTEM photograph of NiCo 2 O 4 /rGO/NF obtained through the multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method in Example 1;
图3是在1M KOH和0.5M甲醇中，NiCo2O4/rGO和NiCo2O4/rGO/NF的CV曲线；Figure 3 is the CV curve of NiCo 2 O 4 /rGO and NiCo 2 O 4 /rGO/NF in 1M KOH and 0.5M methanol;
图4是在1M KOH和0.5M甲醇中，NiCo2O4/rGO/NF经过1000次循环后的CV曲线；Figure 4 is the CV curve of NiCo 2 O 4 /rGO/NF after 1000 cycles in 1M KOH and 0.5M methanol;
图5是在1M KOH和0.5M甲醇中，是NiCo2O4/rGO/NF的I-T曲线图；Figure 5 is the IT curve of NiCo 2 O 4 /rGO/NF in 1M KOH and 0.5M methanol;
图6是在2M KOH电解液中，NiCo2O4/rGO/NF 5Ag-1循环5000次恒电流充放电图。Figure 6 is a galvanostatic charge and discharge diagram of NiCo 2 O 4 /rGO/NF 5Ag -1 in 2M KOH electrolyte after 5000 cycles.
具体实施方式Detailed ways
以下结合附图1—6和具体实施例对本发明作进一步详细说明，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。The present invention will be further described in detail below with reference to the accompanying drawings 1-6 and specific embodiments. The specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention.
实施例1：Example 1:
NiCo2O4/rGO的制备：Preparation of NiCo 2 O 4 /rGO:
采用改进的Hummers法制备氧化石墨烯GO凝胶，将其进一步进行超声得到氧化石墨烯悬浮液，加入柠檬酸，此时与GO相互作用的柠檬酸中的羧基官能团去质子化解离为带负电的羧酸根离子；在搅拌条件下，缓慢滴加混合金属盐溶液和碱液，此时，与GO相互作用的带负电的柠檬酸根离子依靠静电吸引力和配位作用快速捕获溶液中游离的金属阳离子，离心干燥后进一步煅烧后，生成NiCo2O4/rGO，如附图1所示； An improved Hummers method is used to prepare graphene oxide GO gel, which is further ultrasonic to obtain a graphene oxide suspension, and citric acid is added. At this time, the carboxyl functional groups in the citric acid that interact with GO are deprotonated and dissociated into negatively charged ones. Carboxylate ions; under stirring conditions, slowly drop the mixed metal salt solution and alkali solution. At this time, the negatively charged citrate ions interacting with GO rely on electrostatic attraction and coordination to quickly capture the free metal cations in the solution. , after centrifugal drying and further calcination, NiCo 2 O 4 /rGO is generated, as shown in Figure 1;
NiCo2O4/rGO/NF制备：NiCo 2 O 4 /rGO/NF preparation:
将经过预处理的NF放入含有柠檬酸的石墨烯悬浮液中，转移至Teflon反应釜，水热法得到GO/NF之后，通过一步水相柠檬酸助液相和后焙烧处理进一步在GO/NF表面上生长纳米片阵列NiCo2O4/rGO/NF，对NiCo2O4/rGO/NF进行表征，如附图2所示，产物是由是由超薄钴酸镍纳米片以近乎垂直方向均匀生长在泡沫镍表面，形成了较为规整的纳米片阵列。The pretreated NF is put into a graphene suspension containing citric acid and transferred to a Teflon reactor. After the GO/NF is obtained by hydrothermal method, the GO/NF is further processed through a one-step aqueous citric acid assisted liquid phase and post-baking treatment. The nanosheet array NiCo 2 O 4 /rGO/NF is grown on the surface of NF, and the NiCo 2 O 4 /rGO/NF is characterized. As shown in Figure 2, the product is made of ultra-thin nickel cobalt oxide nanosheets with nearly vertical It grows uniformly on the surface of nickel foam, forming a relatively regular array of nanosheets.
实施例2：Example 2:
用多级纳米片阵列NiCo2O4/rGO/NF作为甲醇燃料电池和超级电容器的电极阳极。Multilevel nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode anode for methanol fuel cells and supercapacitors.
多级纳米片阵列NiCo2O4/rGO/NF的电化学表征Electrochemical characterization of multi-level nanosheet array NiCo 2 O 4 /rGO/NF
1)采用传统的三电极体系，对NiCo2O4/rGO/NF电极进行电化学性能测试，剪取1cm×1cm的NiCo2O4/rGO/NF作为工作电极，活性材料的负载量为0.5mg/cm2，饱和甘汞电极SCE作为参比电极，铂片作为对电极，电解质溶液为2M KOH溶液和1M KOH及0.5M甲醇。1) Use a traditional three-electrode system to test the electrochemical performance of the NiCo 2 O 4 /rGO/NF electrode. Cut a 1cm × 1cm piece of NiCo 2 O 4 /rGO/NF as the working electrode. The loading of the active material is 0.5 mg/cm 2 , saturated calomel electrode SCE was used as the reference electrode, platinum sheet was used as the counter electrode, and the electrolyte solution was 2M KOH solution, 1M KOH and 0.5M methanol.
2)如附图3所示，在1M KOH和0.5M甲醇中，NiCo2O4/rGO和NiCo2O4/rGO/NF进行甲醇电氧化测试，CV曲线表明在0.6V时，NiCo2O4/rGO/NF电极具有高达176Ag-1的电流密度，是NiCo2O4/rGO电极电流密度(88Ag-1)的2倍，在经过1000次循环后，NiCo2O4/rGO/NF的电流密度仍高达152Ag-1，在更换新的电解液后，电流密度可恢复至172Ag-1，为初始值的97％，如附图4所示，这一现象说明次材料电流密度的降低是由于甲醇的消耗导致。2) As shown in Figure 3, in 1M KOH and 0.5M methanol, NiCo 2 O 4 /rGO and NiCo 2 O 4 /rGO/NF were subjected to methanol electrooxidation test. The CV curve shows that at 0.6V, NiCo 2 O 4 /rGO/NF electrode has a current density as high as 176Ag-1, which is 2 times the current density of NiCo 2 O 4 /rGO electrode (88Ag -1 ). After 1000 cycles, the current density of NiCo 2 O 4 /rGO/NF The current density is still as high as 152Ag -1 . After replacing the new electrolyte, the current density can be restored to 172Ag -1 , which is 97% of the initial value. As shown in Figure 4, this phenomenon shows that the current density of the secondary material is reduced. Due to methanol consumption.
由于在制备电极的过程中，未加入粘接剂，活性物质直接生长在导电基质上进一步增强了电极电极电导率，加快了离子/电子在电极和电极/电解质界面上的传递，通过计时电流法在0.6V下连续测量1800s，如附图5所示，在前30s内存在电流衰减，但在此后的一段时间，其表现出高稳定性，电流密度可高达156Ag-1，为初始电流密度的84％，表明电极对反应中间体具有良好的耐受性，充分说明其用作直接甲醇燃料电池的电极具有优异的倍率性和循环稳定性。 Since no binder is added during the preparation of the electrode, the active material grows directly on the conductive matrix, which further enhances the conductivity of the electrode and accelerates the transfer of ions/electrons at the electrode and electrode/electrolyte interface. Through chronoamperometry, Continuous measurement for 1800s at 0.6V, as shown in Figure 5, there is current decay in the first 30s, but after a period of time, it shows high stability, the current density can be as high as 156Ag -1 , which is the initial current density 84%, indicating that the electrode has good tolerance to reaction intermediates, fully demonstrating that its use as an electrode for direct methanol fuel cells has excellent rate performance and cycle stability.
(3)如附图6所示，在2MKOH中，NiCo2O4/rGO/NF电极的恒电流充放电曲线，在5Ag-1的高电流密度下，经过5000次恒电流充放电之后，比电容仍为初始电容的78％，达1828Fg-1，表明多级纳米片阵列NiCo2O4/rGO/NF电极具有优异的循环稳定性。(3) As shown in Figure 6, in 2MKOH, the galvanostatic charge and discharge curve of NiCo 2 O 4 /rGO/NF electrode, at a high current density of 5Ag -1 , after 5000 times of galvanostatic charge and discharge, is better than The capacitance is still 78% of the initial capacitance, reaching 1828Fg -1 , indicating that the multi-level nanosheet array NiCo 2 O 4 /rGO/NF electrode has excellent cycling stability.
(4)多级纳米片阵列NiCo2O4/rGO/NF电极具有比NiCo2O4/rGO电极更优异的电化学性能，其原因是多级纳米片阵列NiCo2O4/rGO/NF相比于传统电极，NiCo2O4纳米片阵列直接生长在由石墨烯均匀包裹的泡沫镍基底上，可以降低活性材料与集流体之间的接触电阻，进而减少死体积的存在；多级纳米片阵列NiCo2O4/rGO/NF具有多孔结构，互连的纳米片之间可以形成大量的开放性孔道，更有利于电解质离子的渗透；多级纳米片阵列NiCo2O4/rGO/NF的钴和镍具有多种价态，价态间的转换可以为反应提供多个反应活性位点，促进高比电容的产生。(4) The multi-level nanosheet array NiCo 2 O 4 /rGO/NF electrode has better electrochemical performance than the NiCo 2 O 4 /rGO electrode. The reason is that the multi-level nanosheet array NiCo 2 O 4 /rGO/NF phase Compared with traditional electrodes, the NiCo 2 O 4 nanosheet array is directly grown on a nickel foam substrate evenly wrapped by graphene, which can reduce the contact resistance between the active material and the current collector, thereby reducing the existence of dead volume; multi-level nanosheets The array NiCo 2 O 4 /rGO/NF has a porous structure, and a large number of open channels can be formed between the interconnected nanosheets, which is more conducive to the penetration of electrolyte ions; the multi-level nanosheet array NiCo 2 O 4 /rGO/NF Cobalt and nickel have multiple valence states. The conversion between valence states can provide multiple reactive sites for reactions and promote the production of high specific capacitance.
以上所述仅是本发明的优选方式，应当指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应该视为本发明的保护范围。 The above are only preferred modes of the present invention. It should be noted that those skilled in the art can also make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications can It should also be regarded as the protection scope of the present invention.

Claims (7)

  1. 多级纳米片阵列NiCo2O4/rGO/NF制备方法，其特征是，包括以下步骤：A multi-level nanosheet array NiCo 2 O 4 /rGO/NF preparation method is characterized by including the following steps:
    1)在去离子水中,加入氧化石墨凝胶，超声分散16-20min后，得到氧化石墨悬浮液，继续加入柠檬酸，超声12min，并倒入高压釜中，在所述盛有氧化石墨悬浮液的高压釜中，加入预处理的泡沫镍，再氧化石墨悬浮液中，完全浸没所述预处理的泡沫镍，在115-120℃下，水热反应6-6.5h，水热反应结束后，自然冷却至室温，用去离子水洗涤所得产物后，冷冻干燥2.5-3h后，得到GO/NF；1) Add graphite oxide gel to deionized water, and disperse it with ultrasonic for 16-20 minutes to obtain a graphite oxide suspension. Continue to add citric acid, ultrasonic for 12 minutes, and pour it into an autoclave. The graphite oxide suspension is filled with In the autoclave, add the pretreated nickel foam, re-oxidize the graphite suspension, completely immerse the pretreated nickel foam, and perform a hydrothermal reaction at 115-120°C for 6-6.5h. After the hydrothermal reaction is completed, Cool to room temperature naturally, wash the product with deionized water, and freeze-dry it for 2.5-3 hours to obtain GO/NF;
    2)在盛有110-140mL去离子水的四口烧瓶中，置于步骤1)得到所述的GO/NF后，加入10-25mg柠檬酸，在持续搅拌条件下，以0.8-1.5ml/min速度滴加NaOH碱液，控制所述四口烧瓶中溶液pH＝10±0.1，稳定6-9min，将六水合硝酸镍、六水合硝酸钴溶于去离子水中，形成混合盐溶液，同时以0.8-1.5mL/min速度滴加混合盐溶液和碱液，使溶液pH值稳定在10±0.1；待混合盐溶液滴加完毕，将所得含有GO/NF的浆液转移至Teflon反应釜中，在85-95℃下，晶化5-7h，反应结束后，自然冷却至室温，用去离子水洗涤所得产物后，冷冻干燥2.5-3h，得到钴酸镍前体/rGO/泡沫镍；2) In a four-necked flask containing 110-140mL of deionized water, place it in step 1) to obtain the GO/NF, add 10-25mg of citric acid, and add 0.8-1.5ml/ Add NaOH alkali solution dropwise at min speed, control the pH of the solution in the four-necked flask to 10±0.1, and stabilize it for 6-9 minutes. Dissolve nickel nitrate hexahydrate and cobalt nitrate hexahydrate in deionized water to form a mixed salt solution. Add the mixed salt solution and alkali solution dropwise at a speed of 0.8-1.5mL/min to stabilize the pH value of the solution at 10±0.1; after the dropwise addition of the mixed salt solution is completed, transfer the obtained slurry containing GO/NF to the Teflon reactor. Crystallize at 85-95°C for 5-7 hours. After the reaction is completed, cool to room temperature naturally. After washing the product with deionized water, freeze-dry it for 2.5-3 hours to obtain nickel cobalt oxide precursor/rGO/nickel foam;
    3)在氮气气氛中，氮气流速100mL/min，将步骤2)得到所述的钴酸镍前体/rGO/泡沫镍以2℃/min升温至220-380℃，煅烧2.2-3h后，得到蜂巢状纳米片阵列钴酸镍/rGO/泡沫镍，即为NiCo2O4/rGO/NF。3) In a nitrogen atmosphere with a nitrogen flow rate of 100 mL/min, heat the nickel cobalt oxide precursor/rGO/nickel foam obtained in step 2) to 220-380°C at 2°C/min, and calcine for 2.2-3h to obtain Honeycomb nanosheet array nickel cobalt oxide/rGO/nickel foam is NiCo 2 O 4 /rGO/NF.
  2. 根据权利要求1所述的多级纳米片阵列NiCo2O4/rGO/NF及其制备方法，其特征是：步骤1)中所述氧化石墨悬浮液的浓度范围为1-2mg/mL；氧化石墨与柠檬酸的质量比为2:1，超声功率为310W。The multi-level nanosheet array NiCo 2 O 4 /rGO/NF and its preparation method according to claim 1, characterized in that: the concentration range of the oxidized graphite suspension in step 1) is 1-2 mg/mL; oxidation The mass ratio of graphite to citric acid is 2:1, and the ultrasonic power is 310W.
  3. 根据权利要求1所述的多级纳米片阵列NiCo2O4/rGO/NF及其制备方法，其特征是：步骤1)中所述的高压釜的衬里为聚四氟乙烯Teflon。The multi-level nanosheet array NiCo 2 O 4 /rGO/NF and its preparation method according to claim 1, characterized in that: the lining of the autoclave in step 1) is polytetrafluoroethylene Teflon.
  4. 根据权利要求1所述的多级纳米片阵列NiCo2O4/rGO/NF及其制备方法，其特 征是：步骤2)中配制所述的混合盐溶液中镍离子和钴离子的摩尔比为1:2；镍离子和钴离子的摩尔之和范围为10-15mmol。The multi-level nanosheet array NiCo 2 O 4 /rGO/NF and its preparation method according to claim 1, which is particularly The characteristic is: the molar ratio of nickel ions and cobalt ions in the mixed salt solution prepared in step 2) is 1:2; the molar sum of nickel ions and cobalt ions ranges from 10 to 15 mmol.
  5. 根据权利要求1所述的多级纳米片阵列NiCo2O4/rGO/NF及其制备方法，其特征：步骤2)中配制所述的NaOH碱液浓度为0.2-0.25mol/L。The multi-level nanosheet array NiCo 2 O 4 /rGO/NF and its preparation method according to claim 1, characterized in that the concentration of the NaOH alkali solution prepared in step 2) is 0.2-0.25 mol/L.
  6. 根据权利要求1所述的多级纳米片阵列NiCo2O4/rGO/NF及其制备方法，其特征在于：步骤2)中所述的柠檬酸的质量范围为10-20mg。The multi-level nanosheet array NiCo 2 O 4 /rGO/NF and its preparation method according to claim 1, characterized in that: the mass range of the citric acid described in step 2) is 10-20 mg.
  7. 多级纳米片阵列NiCo2O4/rGO/NF作为电极应用，其特征是，用多级纳米片阵列NiCo2O4/rGO/NF作为甲醇燃料电池和超级电容器的电极。 The multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode. The characteristic is that the multi-level nanosheet array NiCo 2 O 4 /rGO/NF is used as an electrode for methanol fuel cells and supercapacitors.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129401A (en) * 2016-06-29 2016-11-16 北京化工大学 A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof
CN107591251A (en) * 2017-07-14 2018-01-16 电子科技大学 A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof
CN110189922A (en) * 2019-06-07 2019-08-30 北京化工大学 Honeycomb nano-chip arrays cobalt acid nickel/rGO/ nickel foam and preparation method
CN113019376A (en) * 2021-03-18 2021-06-25 北京化工大学 Copper-based composite catalyst for growing graphene modified foam nickel substrate and preparation method thereof
CN115083798A (en) * 2022-04-29 2022-09-20 一汽奔腾轿车有限公司 Multistage nanosheet array NiCo 2 O 4 Preparation method of/rGO/NF and application of/rGO/NF as electrode

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104773764B (en) * 2015-03-30 2016-08-24 北京化工大学 A kind of preparation method of three-dimensional flower-shaped cobalt acid nickel nano film mesoporous microsphere

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129401A (en) * 2016-06-29 2016-11-16 北京化工大学 A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof
CN107591251A (en) * 2017-07-14 2018-01-16 电子科技大学 A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof
CN110189922A (en) * 2019-06-07 2019-08-30 北京化工大学 Honeycomb nano-chip arrays cobalt acid nickel/rGO/ nickel foam and preparation method
CN113019376A (en) * 2021-03-18 2021-06-25 北京化工大学 Copper-based composite catalyst for growing graphene modified foam nickel substrate and preparation method thereof
CN115083798A (en) * 2022-04-29 2022-09-20 一汽奔腾轿车有限公司 Multistage nanosheet array NiCo 2 O 4 Preparation method of/rGO/NF and application of/rGO/NF as electrode

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