WO2018184182A1 - Electrode manufacturing method for supercapacitor - Google Patents

Electrode manufacturing method for supercapacitor Download PDF

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Publication number
WO2018184182A1
WO2018184182A1 PCT/CN2017/079650 CN2017079650W WO2018184182A1 WO 2018184182 A1 WO2018184182 A1 WO 2018184182A1 CN 2017079650 W CN2017079650 W CN 2017079650W WO 2018184182 A1 WO2018184182 A1 WO 2018184182A1
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Prior art keywords
supercapacitor
preparing
electrode
supercapacitor electrode
solution
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PCT/CN2017/079650
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French (fr)
Chinese (zh)
Inventor
钟玲珑
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深圳市佩成科技有限责任公司
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Priority to PCT/CN2017/079650 priority Critical patent/WO2018184182A1/en
Publication of WO2018184182A1 publication Critical patent/WO2018184182A1/en

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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
    • H01G11/22—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
    • H01G11/24—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
    • H01G11/84—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

Definitions

  • the present invention relates to a method for preparing a supercapacitor electrode, and belongs to the field of nanomaterial preparation.
  • Iron oxide nanomaterials are widely used in catalysts, energy storage and conversion equipment, magnetic materials, water pollution treatment, gas sensitive materials, pigments, etc. due to their excellent properties.
  • the supercapacitor has the advantages of high power density, fast charge and discharge speed, good cycle stability and long life. As a new type of energy storage device, it has attracted more and more attention.
  • this paper mainly attempts to synthesize a variety of iron oxide nanomaterials, such as one-dimensional nanostructures, hollow structures, polyhedral structures, and other X-based synthetic methods.
  • Modern analytical testing techniques such as ray diffraction (XRD), scanning electron microscopy (S EM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and specific surface tester (BET) characterize the microstructure of materials. Appearance and structure, respectively, using the prepared iron oxide nanomaterials as supercapacitor and lithium ion battery electrode materials, assembled into test devices, using cyclic voltammetry, AC impedance, constant current charge and discharge test methods to study the electrochemical properties of the material, I got good test results.
  • XRD ray diffraction
  • S EM scanning electron microscopy
  • FE-SEM field emission scanning electron microscopy
  • TEM transmission electron microscopy
  • BET specific surface tester
  • the supercapacitor As a new type of energy storage device, the supercapacitor has the advantages of high output power, short charging time, wide operating temperature range, long service life, safety and no pollution, and is expected to become a new green power source in this century.
  • commonly used materials for supercapacitor electrodes include carbon materials, metal oxide materials, conductive polymer materials, etc., but these materials have inherent problems, resulting in a relatively low specific capacity of the electrode material, which is bound to be a capacitor. The overall performance has a big impact.
  • the object of the present invention is to overcome the deficiencies of materials prepared by conventional preparation methods, and to provide a super electric Method for preparing a container electrode.
  • the present invention adopts the following technical solutions:
  • the present invention provides a method for preparing a supercapacitor electrode, comprising the following steps:
  • Step one synthesizing iron oxide, respectively dissolving Fe(N0 3 ) 3 , 9H 2 0 and KOH in deionized water; after stirring, transferring the mixed solution to a reaction in a dry box; centrifuging the obtained precipitate, repeating Washing; drying the precipitate in vacuo to obtain a yellow-green product as oc-FeOOH; heating the product and then cooling it naturally, finally obtaining a red product of ot-Fe 2 0 3 ;
  • Step two respectively, using the synthesized ot-FeOOH and ot-Fe 2 0 3 nanomaterials as electrode actives, selecting a conductive agent and a binder, adding the ethanol solvent in proportion, and ultrasonically dispersing to obtain a uniform suspension;
  • Step 3 the suspension obtained in the second step is applied to the pre-washed foamed nickel electrode, placed in a vacuum drying oven, and taken out after a certain period of time;
  • Step 4 The solvent and moisture are removed and compacted to bring the powder into close contact with the foamed nickel electrode to form a supercapacitor electrode.
  • the foregoing step one specifically includes:
  • Step 1.1 Fe(N0 3 ) 3-9H 2 0 and KOH are dissolved in deionized water;
  • Step 1.2 the KOH solution is added dropwise to the stirred Fe(NO 3 ) 3 ⁇ 9 ⁇ 20 solution;
  • Step 1.3 adding deionized water to the mixed solution, after stirring, transferring the mixed solution into the reaction kettle;
  • Step 1.4 the reaction vessel containing the solution is reacted in a dry box
  • Step 1.5 after the reaction is completed, the reaction vessel is naturally cooled to room temperature, and the obtained precipitate is centrifuged, and washed repeatedly with anhydrous ethanol and distilled water to remove the unreacted reagent;
  • Step 1.6 the washed precipitate is vacuum dried to obtain a yellow-green product is ot-FeOOH;
  • Step 1.7 the product was then placed in a muffle furnace, warmed to 350 ° C, and then naturally cooled to room temperature, finally resulting in a dry, loose red product of oc-Fe 2 0 3 .
  • the reaction vessel containing the solution is reacted in a drying oven at 100 ° C for 6 hours.
  • the conductive agent is conductive carbon black
  • the binder is polytetrafluoroethylene, according to the mass ratio. It is a 75:15:10 ratio electrode active, conductive agent and binder.
  • the above step 3 is specifically: applying a suspension of 50 ⁇ l to the pre-washed foamed nickel electrode with a micro-injector, placing it in a vacuum oven at 80 ° C, and taking it out after 10 h.
  • the above step 4 is specifically to remove the solvent and moisture, and compacted under a pressure of 10 MPa to make the powder contact with the foamed nickel electrode.
  • the method for preparing a supercapacitor electrode provided by the invention has the advantages of high crystallinity, excellent crystallinity and regularity of crystal structure arrangement, and has good conductivity by experiments.
  • FIG. 1 is a schematic diagram of an X-ray diffraction (XRD) pattern of an ot-FeOOH nanorod prepared in accordance with the present invention.
  • XRD X-ray diffraction
  • the present invention provides a method for preparing a supercapacitor electrode.
  • the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • the method for preparing a supercapacitor electrode provided by this embodiment specifically includes the following steps:
  • the washed precipitate was vacuum dried at 60 ° C for 8 h to obtain a yellow-green product of ot-FeOOH.
  • the product was then placed in a muffle furnace, warmed to 350 ° C for 3 hours, and then naturally cooled to room temperature, finally resulting in a dry, loose red product of oc-Fe 2 0 3 .
  • the synthesized ot-FeOOH and ot-Fe 2 0 3 nanomaterials are used as electrode active materials, conductive carbon black is used as conductive agent, and polytetrafluoroethylene (PTFE) is used as binder, in proportion (mass ratio of 75) :15:10)
  • PTFE polytetrafluoroethylene
  • a saturated calomel electrode is used as a reference electrode
  • a foamed nickel electrode is used as a counter electrode
  • a foamed nickel electrode with an active material is used as a working electrode, and is carried out in a 1 mol-L-i KOH electrolyte. test.
  • the crystal structure of the ot-FeOOH nanorod material synthesized by hydrothermal method was characterized and analyzed by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • the XRD pattern of the product is shown in Fig. 1.
  • most of the diffraction peaks correspond well to the data reported in the standard spectrum JCPDS 00-029-0713, indicating that the obtained product is the orthorhombic a-FeOOH.
  • the strongest diffraction peak on the (110) plane indicates that the material has the largest diffraction orientation in the (110) direction.
  • the diffraction peaks have been marked in the spectrum, and the crystal planes corresponding to the respective peaks are shown in the figure.
  • SEM Scanning electron microscopy
  • the method for preparing a supercapacitor electrode provided by the invention has the advantages of high crystallinity, excellent crystallinity and regularity of crystal structure arrangement, and has good conductivity by experiments.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

An electrode manufacturing method for a supercapacitor, the method comprising: synthesizing iron oxide, employing synthesized α-FeOOH and α-Fe2O3 nano-materials as an electrode active material, selecting a conductive agent and binder to acquire a suspension, coating the suspension on a washed and cleaned nickel foam electrode, removing the solvent and water, and performing compaction to enable contact tightness between the powder material and the nickel foam electrode to form an electrode of a supercapacitor. The electrode manufacturing method of a supercapacitor is employed to manufacture supercapacitor electrodes that have superior crystallinity, excellent crystal properties, and regularity of a crystal structure arrangement, and are proven to have superior conductivity by experiments.

Description

发明名称：超级电容器电极制备方法  Title of Invention: Method for preparing supercapacitor electrode
技术领域  Technical field
[0001] 本发明涉及一种超级电容器电极制备方法， 属于纳米材料制备领域。  [0001] The present invention relates to a method for preparing a supercapacitor electrode, and belongs to the field of nanomaterial preparation.
背景技术  Background technique
[0002] 氧化铁纳米材料由于其优良的性能被广泛应用于催化剂、 能量储存与转化设备 、 磁性材料、 水污染处理、 气敏材料、 颜料等方面。 而超级电容器具有功率密 度高、 充放电速度快、 循环稳定性好、 寿命长等优点， 作为一种新型的储能装 置日益受到大家的关注。 本文是在氧化铁纳米材料研究现状的基础上， 主要尝 试采用液相沉淀法等合成手段， 可控制备合成了多种氧化铁纳米材料， 如一维 纳米结构、 中空结构、 多面体结构， 利用 X-射线衍射 (XRD)、 扫描电子显微镜 (S EM)、 场发射扫描电子显微镜 (FE-SEM)、 透射电子显微镜 （TEM) 、 比表面测 试仪 （BET) 等现代分析测试技术表征了材料的微观形貌和结构， 分别以制得的 氧化铁纳米材料作为超级电容器和锂离子电池电极材料， 组装成测试器件， 使 用循环伏安、 交流阻抗、 恒电流充放电测试方法研究了材料的电化学性能， 得 到了良好的测试结果。  [0002] Iron oxide nanomaterials are widely used in catalysts, energy storage and conversion equipment, magnetic materials, water pollution treatment, gas sensitive materials, pigments, etc. due to their excellent properties. The supercapacitor has the advantages of high power density, fast charge and discharge speed, good cycle stability and long life. As a new type of energy storage device, it has attracted more and more attention. Based on the research status of iron oxide nanomaterials, this paper mainly attempts to synthesize a variety of iron oxide nanomaterials, such as one-dimensional nanostructures, hollow structures, polyhedral structures, and other X-based synthetic methods. Modern analytical testing techniques such as ray diffraction (XRD), scanning electron microscopy (S EM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and specific surface tester (BET) characterize the microstructure of materials. Appearance and structure, respectively, using the prepared iron oxide nanomaterials as supercapacitor and lithium ion battery electrode materials, assembled into test devices, using cyclic voltammetry, AC impedance, constant current charge and discharge test methods to study the electrochemical properties of the material, I got good test results.
技术问题  technical problem
[0003] 作为一种新型储能装置， 超级电容器具有输出功率高、 充电吋间短、 工作温度 范围宽、 使用寿命长、 安全且无污染等优点， 有望成为本世纪新型的绿色电源 。 目前常用的用于超级电容器电极材料的包括碳材料、 金属氧化物材料、 导电 聚合物材料等， 但这些材料由于固有的一些问题， 导致制备出的电极材料比容 量相对较低， 这势必对电容器的整体性能有很大的影响。  [0003] As a new type of energy storage device, the supercapacitor has the advantages of high output power, short charging time, wide operating temperature range, long service life, safety and no pollution, and is expected to become a new green power source in this century. At present, commonly used materials for supercapacitor electrodes include carbon materials, metal oxide materials, conductive polymer materials, etc., but these materials have inherent problems, resulting in a relatively low specific capacity of the electrode material, which is bound to be a capacitor. The overall performance has a big impact.
问题的解决方案  Problem solution
技术解决方案  Technical solution
[0004] 鉴于上述现有技术的不足之处， 本发明的目的在于提供一种超级电容器电极制 备方法。  In view of the above deficiencies of the prior art, it is an object of the present invention to provide a method for preparing a supercapacitor electrode.
[0005] 本发明的目的是为了克服传统制备方法制备的材料的不足， 提供了一种超级电 容器电极制备方法。 为了达到上述目的， 本发明采取了以下技术方案： [0005] The object of the present invention is to overcome the deficiencies of materials prepared by conventional preparation methods, and to provide a super electric Method for preparing a container electrode. In order to achieve the above object, the present invention adopts the following technical solutions:
[0006] 本发明提供了一种超级电容器电极制备方法， 包括以下步骤：  The present invention provides a method for preparing a supercapacitor electrode, comprising the following steps:
[0007] 步骤一、 合成氧化铁， 分别将 Fe(N0 3) 3，9H 20和 KOH溶解在去离子水中； 搅 拌后， 将混合溶液转移在干燥箱中反应； 把所得沉淀离心出来， 反复洗涤； 将 沉淀真空干燥， 得到黄绿色的产物为 oc-FeOOH; 将产物升温然后自然冷却， 最 后得到红色产物为 ot-Fe 20 3； [0007] Step one, synthesizing iron oxide, respectively dissolving Fe(N0 3 ) 3 , 9H 2 0 and KOH in deionized water; after stirring, transferring the mixed solution to a reaction in a dry box; centrifuging the obtained precipitate, repeating Washing; drying the precipitate in vacuo to obtain a yellow-green product as oc-FeOOH; heating the product and then cooling it naturally, finally obtaining a red product of ot-Fe 2 0 3 ;
[0008] 步骤二、 分别以合成的 ot-FeOOH和 ot-Fe 20 3纳米材料为电极活性物， 选择导电 剂和粘结剂， 按比例加入乙醇溶剂后超声分散得到均一的悬浮液； [0008] Step two, respectively, using the synthesized ot-FeOOH and ot-Fe 2 0 3 nanomaterials as electrode actives, selecting a conductive agent and a binder, adding the ethanol solvent in proportion, and ultrasonically dispersing to obtain a uniform suspension;
[0009] 步骤三、 将步骤二得到的悬浮液涂在预先洗净的泡沫镍电极上， 放入真空干燥 箱中， 一定吋间后取出； [0009] Step 3, the suspension obtained in the second step is applied to the pre-washed foamed nickel electrode, placed in a vacuum drying oven, and taken out after a certain period of time;
[0010] 步骤四、 除去溶剂和水分， 并压实， 使粉料与泡沫镍电极接触紧密， 形成超级 电容器电极。  [0010] Step 4. The solvent and moisture are removed and compacted to bring the powder into close contact with the foamed nickel electrode to form a supercapacitor electrode.
[0011] 优选的， 上述步骤一具体包括：  [0011] Preferably, the foregoing step one specifically includes:
[0012] 步骤 1.1、 分别将 Fe(N0 3) 3-9H 20和 KOH溶解在去离子水中； [0012] Step 1.1, respectively, Fe(N0 3 ) 3-9H 2 0 and KOH are dissolved in deionized water;
[0013] 步骤 1.2、 将 KOH溶液滴加入搅拌中的 Fe(NO 3) 3·9Η 20溶液中； [0013] Step 1.2, the KOH solution is added dropwise to the stirred Fe(NO 3 ) 3 ·9Η 20 solution;
[0014] 步骤 1.3、 加去离子水到混合溶液中， 搅拌后， 将混合溶液转移到反应釜内； [0014] Step 1.3, adding deionized water to the mixed solution, after stirring, transferring the mixed solution into the reaction kettle;
[0015] 步骤 1.4、 盛有溶液的反应釜在干燥箱中反应； [0015] Step 1.4, the reaction vessel containing the solution is reacted in a dry box;
[0016] 步骤 1.5、 反应结束后待反应釜自然冷却到室温， 把所得沉淀离心出来， 用无水 乙醇和蒸馏水反复洗涤， 以除去未反应完的试剂；  [0016] Step 1.5, after the reaction is completed, the reaction vessel is naturally cooled to room temperature, and the obtained precipitate is centrifuged, and washed repeatedly with anhydrous ethanol and distilled water to remove the unreacted reagent;
[0017] 步骤 1.6、 将洗好的沉淀真空干燥， 得到黄绿色的产物为 ot-FeOOH;  [0017] Step 1.6, the washed precipitate is vacuum dried to obtain a yellow-green product is ot-FeOOH;
[0018] 步骤 1.7、 将产物然后放入马弗炉， 升温至 350°C保持， 然后自然冷却到室温， 最后得到干燥松散的红色产物为 oc-Fe 20 3。 [0018] Step 1.7, the product was then placed in a muffle furnace, warmed to 350 ° C, and then naturally cooled to room temperature, finally resulting in a dry, loose red product of oc-Fe 2 0 3 .
[0019] 优选的， 上述步骤 1.1中分别将 0.01mol Fe(NO 3) 3.9H
Figure imgf000004_0001
KOH [0019] Preferably, 0.01 mol of Fe(NO 3 ) 3 .9H is respectively used in the above step 1.1.
Figure imgf000004_0001
KOH
溶解在 10ml去离子水中。  Dissolved in 10 ml of deionized water.
[0020] 优选的， 上述步骤 1.3中加 20ml去离子水到混合溶液中， 搅拌 10分钟后， 将混 合溶液转移到 50ml的反应釜内。 [0020] Preferably, 20 ml of deionized water is added to the mixed solution in the above step 1.3, and after stirring for 10 minutes, the mixed solution is transferred to a 50 ml reaction vessel.
[0021] 优选的， 上述步骤 1.4中在盛有溶液的反应釜在 100°C的干燥箱中反应 6小吋。 [0021] Preferably, in the above step 1.4, the reaction vessel containing the solution is reacted in a drying oven at 100 ° C for 6 hours.
[0022] 优选的， 上述步骤二中导电剂为导电炭黑， 粘结剂为聚四氟乙烯， 按照质量比 为 75: 15: 10配比电极活性物、 导电剂和粘结剂。 [0022] Preferably, in the above step 2, the conductive agent is conductive carbon black, and the binder is polytetrafluoroethylene, according to the mass ratio. It is a 75:15:10 ratio electrode active, conductive agent and binder.
[0023] 优选的， 上述步骤三具体为用微量进样器将 50μ1的悬浮液涂在预先洗净的泡沫 镍电极上， 放入 80°C的真空干燥箱中， 10 h后取出。 [0023] Preferably, the above step 3 is specifically: applying a suspension of 50 μl to the pre-washed foamed nickel electrode with a micro-injector, placing it in a vacuum oven at 80 ° C, and taking it out after 10 h.
[0024] 优选的， 上述步骤四具体为除去溶剂和水分， 并于 10 MPa的压力下压实， 使粉 料与泡沫镍电极接触紧密。 [0024] Preferably, the above step 4 is specifically to remove the solvent and moisture, and compacted under a pressure of 10 MPa to make the powder contact with the foamed nickel electrode.
发明的有益效果  Advantageous effects of the invention
有益效果  Beneficial effect
[0025] 本发明提供的超级电容器电极制备方法， 制备出的超级电容器电极具有较高的 结晶度， 具有出色的结晶性和晶体结构排列的规整性， 通过实验证明， 具有很 好的导电性。  [0025] The method for preparing a supercapacitor electrode provided by the invention has the advantages of high crystallinity, excellent crystallinity and regularity of crystal structure arrangement, and has good conductivity by experiments.
对附图的简要说明  Brief description of the drawing
附图说明  DRAWINGS
[0026] 图 1为本发明制备的 ot-FeOOH纳米棒的 X射线衍射 （XRD) 图谱示意图。  1 is a schematic diagram of an X-ray diffraction (XRD) pattern of an ot-FeOOH nanorod prepared in accordance with the present invention.
本发明的实施方式 Embodiments of the invention
[0027] 本发明提供一种超级电容器电极制备方法， 为使本发明的目的、 技术方案及效 果更加清楚、 明确， 以下参照附图并举实施例对本发明进一步详细说明。 应当 理解， 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 provides a method for preparing a supercapacitor electrode. The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0028] 本实施例提供的超级电容器电极制备方法， 具体包括以下步骤： [0028] The method for preparing a supercapacitor electrode provided by this embodiment specifically includes the following steps:
[0029] 水热合成氧化铁， 首先分别将 O.Olmol Fe(NO 3) 3·9Η 20和 0.04mol KOH [0029] Hydrothermal synthesis of iron oxide, firstly O.Olmol Fe(NO 3 ) 3 ·9Η 2 0 and 0.04 mol KOH, respectively
溶解在 10ml去离子水中。 然后将 KOH溶液滴加入搅拌中的 Fe(NO 3) 3·9Η 20溶液 中。 加 20ml去离子水到混合溶液中， 搅拌 10分钟后， 将混合溶液转移到 50ml的 反应釜内。 盛有溶液的反应釜在 100°C的干燥箱中反应 6小吋。 反应结束后待反 应釜自然冷却到室温， 把所得沉淀离心出来， 用无水乙醇和蒸馏水反复洗涤， 以除去未反应完的试剂。 将洗好的沉淀在 60°C下真空干燥 8h， 得到黄绿色的产 物为 ot-FeOOH。 将产物然后放入马弗炉， 升温至 350°C保持 3小吋， 然后自然冷 却到室温， 最后得到干燥松散的红色产物为 oc-Fe 20 3。 [0030] 分别以合成的 ot-FeOOH和 ot-Fe 20 3纳米材料为电极活性物， 导电炭黑为导电剂 ， 聚四氟乙烯 (PTFE) 为粘结剂， 按比例 （质量比为 75:15:10) 加入乙醇溶剂后 超声分散得到均一的悬浮液。 用微量进样器将 50μ1的悬浮液涂在预先洗净的泡沫 镍电极上， 放入 80°C的真空干燥箱中， 10 h后取出。 除去溶剂和水分， 并于 10 MPa的压力下压实， 使粉料与泡沫镍电极接触紧密。 后在 lmol/L的 KOH溶液中 浸泡活化 10小吋， 测试。 本实施例的三电极体系中， 以饱和甘汞电极为参比电 极、 泡沫镍电极为对电极、 带活性材料的泡沫镍电极为工作电极， 在 l mol-L -i 的 KOH电解液中进行测试。 Dissolved in 10 ml of deionized water. The KOH solution was then added dropwise to the stirred Fe(NO 3 ) 3 ·9Η 20 solution. 20 ml of deionized water was added to the mixed solution, and after stirring for 10 minutes, the mixed solution was transferred to a 50 ml reaction vessel. The reaction vessel containing the solution was reacted in a drying oven at 100 ° C for 6 hours. After the completion of the reaction, the reaction vessel was naturally cooled to room temperature, and the resulting precipitate was centrifuged, and washed repeatedly with absolute ethanol and distilled water to remove unreacted reagent. The washed precipitate was vacuum dried at 60 ° C for 8 h to obtain a yellow-green product of ot-FeOOH. The product was then placed in a muffle furnace, warmed to 350 ° C for 3 hours, and then naturally cooled to room temperature, finally resulting in a dry, loose red product of oc-Fe 2 0 3 . [0030] respectively, the synthesized ot-FeOOH and ot-Fe 2 0 3 nanomaterials are used as electrode active materials, conductive carbon black is used as conductive agent, and polytetrafluoroethylene (PTFE) is used as binder, in proportion (mass ratio of 75) :15:10) Ultrasonic dispersion after addition of ethanol solvent gave a uniform suspension. A 50 μl suspension was applied to the pre-washed foamed nickel electrode using a micro-injector, placed in a vacuum oven at 80 ° C, and removed 10 hours later. The solvent and moisture were removed and compacted at a pressure of 10 MPa to bring the powder into contact with the foamed nickel electrode. After 10 min of immersion in a 1 mol/L KOH solution, the test was carried out. In the three-electrode system of the present embodiment, a saturated calomel electrode is used as a reference electrode, a foamed nickel electrode is used as a counter electrode, and a foamed nickel electrode with an active material is used as a working electrode, and is carried out in a 1 mol-L-i KOH electrolyte. test.
[0031] 用 X射线衍射 （XRD) 对通过水热方法合成的 ot-FeOOH纳米棒材料的晶体结构 进行了表征和分析， 如图 1为产物的 XRD图谱。 从图中可以看到， 大部分的衍射 峰都可以很好的与标准谱图 JCPDS 00-029-0713报道的数据相对应， 表明所得到 的产物是正交晶系 a-FeOOH。 在 （110) 面有最强的衍射峰， 表明材料在 （110 ) 方向有最大的衍射取向。 其衍射峰已在谱图中标出， 各个峰值所对应的晶面 如图中所示。  [0031] The crystal structure of the ot-FeOOH nanorod material synthesized by hydrothermal method was characterized and analyzed by X-ray diffraction (XRD). The XRD pattern of the product is shown in Fig. 1. As can be seen from the figure, most of the diffraction peaks correspond well to the data reported in the standard spectrum JCPDS 00-029-0713, indicating that the obtained product is the orthorhombic a-FeOOH. The strongest diffraction peak on the (110) plane indicates that the material has the largest diffraction orientation in the (110) direction. The diffraction peaks have been marked in the spectrum, and the crystal planes corresponding to the respective peaks are shown in the figure.
[0032] 运用扫描电镜 （SEM) 对所制备的 ot-FeOOH纳米材料进行了形貌和微结构的分 析， 可以得到样品尺寸和外形相对均一， 有轻微团聚现象， 外形均为纳米线状 ， 所制备的粉体是由纳米棒组成， 其尺寸长轴约为 320-680nm， 短轴约为 20-80n m。 加入 PVP后， 产物分散更好， 但形貌不再是均一的纳米棒， 出现些许片状结 构， 尺寸没有变化太多。  [0032] Scanning electron microscopy (SEM) was used to analyze the morphology and microstructure of the prepared ot-FeOOH nanomaterials. The sample size and shape were relatively uniform, with slight agglomeration and nanowire shape. The prepared powder is composed of nanorods having a major axis of about 320-680 nm and a minor axis of about 20-80 nm. After the addition of PVP, the product disperses better, but the morphology is no longer a uniform nanorod, and there are some flaky structures, and the size does not change much.
[0033] 样品的透射电镜图进一步证实了其微观结构。 在低倍数下， 证实了通过水热方 法合成的 ot-FeOOH确实是有纳米棒组成的， 从较大的放大倍数下可以得到， 纳 米棒内部为实心。 通过测量两列晶格纹的晶面间距分别为 0.249nm和 0.247nm， 分别对应着 （111) 和 （101) 面， 结果再一次证明了 XRD的分析结果。  [0033] The transmission electron micrograph of the sample further confirmed its microstructure. At low magnification, it was confirmed that the ot-FeOOH synthesized by the hydrothermal method is indeed composed of nanorods, which can be obtained from a large magnification, and the inside of the nanorod is solid. By measuring the interplanar spacing of the two columns of lattice patterns, they are 0.249 nm and 0.247 nm, respectively corresponding to the (111) and (101) planes. The results again prove the XRD analysis results.
[0034]  [0034]
[0035] 本发明提供的超级电容器电极制备方法， 制备出的超级电容器电极具有较高的 结晶度， 具有出色的结晶性和晶体结构排列的规整性， 通过实验证明， 具有很 好的导电性。  [0035] The method for preparing a supercapacitor electrode provided by the invention has the advantages of high crystallinity, excellent crystallinity and regularity of crystal structure arrangement, and has good conductivity by experiments.
[0036] 可以理解的是， 对本领域普通技术人员来说， 可以根据本发明的技术方案及其 发明构思加以等同替换或改变， 而所有这些改变或替换都应属于本发明所附的 权利要求的保护范围。 [0036] It is to be understood that those skilled in the art can make equivalent substitutions or changes to the inventions and the inventions of the present invention. All such changes or substitutions are intended to fall within the scope of the appended claims.

Claims

权利要求书 Claim
[权利要求 1] 一种超级电容器电极制备方法， 其特征在于： 所述制备方法包括以下 步骤：  [Claim 1] A method for preparing a supercapacitor electrode, characterized in that the preparation method comprises the following steps:
步骤一、 合成氧化铁， 分别将 Fe(N0 3) 3，9H 20和 KOH溶解在去离子 水中； 搅拌后， 将混合溶液转移在干燥箱中反应； 把所得沉淀离心出 来， 反复洗涤； 将沉淀真空干燥， 得到黄绿色的产物为 oc-FeOOH ; 将 产物升温然后自然冷却， 最后得到红色产物为 oc-Fe 20 3； Step 1. Synthesize iron oxide, dissolve Fe(N0 3 ) 3 , 9H 2 0 and KOH in deionized water respectively; after stirring, transfer the mixed solution to a reaction in a dry box; centrifuge the resulting precipitate and wash it repeatedly; The precipitate was vacuum dried to obtain a yellow-green product as oc-FeOOH; the product was warmed and then naturally cooled, and finally the red product was obtained as oc-Fe 2 0 3 ;
步骤二、 分别以合成的 ot-FeOOH和 ot-Fe 20 3纳米材料为电极活性物， 选择导电剂和粘结剂， 按比例加入乙醇溶剂后超声分散得到均一的悬 浮液； Step 2: using the synthesized ot-FeOOH and ot-Fe 2 0 3 nanomaterials as electrode active materials, selecting a conductive agent and a binder, adding the ethanol solvent in proportion, and ultrasonically dispersing to obtain a uniform suspension;
步骤三、 将步骤二得到的悬浮液涂在预先洗净的泡沫镍电极上， 放入 真空干燥箱中， 一定吋间后取出；  Step 3: The suspension obtained in the second step is applied to the pre-washed foamed nickel electrode, placed in a vacuum drying oven, and taken out after a certain period of time;
步骤四、 除去溶剂和水分， 并压实， 使粉料与泡沫镍电极接触紧密， 形成超级电容器电极。  Step 4, removing the solvent and moisture, and compacting, so that the powder is in close contact with the foamed nickel electrode to form a supercapacitor electrode.
[权利要求 2] 如权利要求 1所述的超级电容器电极制备方法， 其特征在于： 所述步 骤一具体包括：  [Claim 2] The method for preparing a supercapacitor electrode according to claim 1, wherein: the step one specifically includes:
步骤 1.1、 分别将 Fe(N0 3) 3-9H 20和 K0H溶解在去离子水中； 步骤 1.2、 将 K0H溶液滴加入搅拌中的 Fe(N0 3) 3·9Η 20溶液中； 步骤 1.3、 加去离子水到混合溶液中， 搅拌后， 将混合溶液转移到反 应釜内； Step 1.1: Dissolve Fe(N0 3 ) 3-9H 2 0 and K0H in deionized water respectively; Step 1.2, add the K0H solution to the stirred Fe(N0 3 ) 3 ·9Η 20 solution; Step 1.3 Add deionized water to the mixed solution, and after stirring, transfer the mixed solution to the reaction vessel;
步骤 1.4、 盛有溶液的反应釜在干燥箱中反应；  Step 1.4: The reaction vessel containing the solution is reacted in a dry box;
步骤 1.5、 反应结束后待反应釜自然冷却到室温， 把所得沉淀离心出 来， 用无水乙醇和蒸馏水反复洗涤， 以除去未反应完的试剂； 步骤 1.6、 将洗好的沉淀真空干燥， 得到黄绿色的产物为 oc-FeOOH ; 步骤 1.7、 将产物然后放入马弗炉， 升温至 350°C保持， 然后自然冷却 到室温， 最后得到干燥松散的红色产物为 oc-Fe 20 3。 Step 1.5: After the reaction is completed, the reaction vessel is naturally cooled to room temperature, and the obtained precipitate is centrifuged, and washed repeatedly with absolute ethanol and distilled water to remove the unreacted reagent; Step 1.6, the washed precipitate is vacuum dried to obtain yellow The green product is oc-FeOOH; Step 1.7, the product is then placed in a muffle furnace, warmed to 350 ° C, and then naturally cooled to room temperature, finally resulting in a dry, loose red product of oc-Fe 2 0 3 .
[权利要求 3] 如权利要求 2所述的超级电容器电极制备方法， 其特征在于： 所述步 骤 1.1中分别将 O.Olmol Fe(NO 3) 3·9Η 20和 0.04mol KOH溶解在 10ml去 离子水中。 [Claim 3] The method for preparing a supercapacitor electrode according to claim 2, wherein: in the step 1.1, 0.1 mol of Fe(NO 3 ) 3 ·9Η 2 0 and 0.04 mol of KOH are respectively dissolved in 10 ml. Ionic water.
[权利要求 4] 如权利要求 2所述的超级电容器电极制备方法， 其特征在于： 所述步 骤 1.3中加 20ml去离子水到混合溶液中， 搅拌 10分钟后， 将混合溶液 转移到 50ml的反应釜内。  [Claim 4] The method for preparing a supercapacitor electrode according to claim 2, wherein: in step 1.3, 20 ml of deionized water is added to the mixed solution, and after stirring for 10 minutes, the mixed solution is transferred to a reaction of 50 ml. Inside the kettle.
[权利要求 5] 如权利要求 2所述的超级电容器电极制备方法， 其特征在于： 所述步 骤 1.4中在盛有溶液的反应釜在 100°C的干燥箱中反应 6小吋。 [Claim 5] The method for preparing a supercapacitor electrode according to claim 2, wherein in the step 1.4, the reaction vessel containing the solution is reacted in a drying oven at 100 ° C for 6 hours.
[权利要求 6] 如权利要求 1所述的超级电容器电极制备方法， 其特征在于： 所述步 骤二中导电剂为导电炭黑， 粘结剂为聚四氟乙烯， 按照质量比为 75:1[Claim 6] The method for preparing a supercapacitor electrode according to claim 1, wherein: in the second step, the conductive agent is conductive carbon black, and the binder is polytetrafluoroethylene, and the mass ratio is 75:1.
5:10配比电极活性物、 导电剂和粘结剂。 5:10 ratio electrode active, conductive agent and binder.
[权利要求 7] 如权利要求 1所述的超级电容器电极制备方法， 其特征在于： 所述步 骤三具体为用微量进样器将 50μ1的悬浮液涂在预先洗净的泡沫镍电极 上， 放入 80°C的真空干燥箱中， 10 h后取出。 [Claim 7] The method for preparing a supercapacitor electrode according to claim 1, wherein the step 3 is specifically: applying a suspension of 50 μl to the pre-washed foamed nickel electrode with a micro-injector, and placing In a vacuum oven at 80 ° C, remove it after 10 h.
[权利要求 8] 如权利要求 1所述的超级电容器电极制备方法， 其特征在于： 所述步 骤四具体为除去溶剂和水分， 并于 10 MPa的压力下压实， 使粉料与 泡沫镍电极接触紧密。 [Claim 8] The method for preparing a supercapacitor electrode according to claim 1, wherein: the step 4 is specifically removing solvent and moisture, and compacting at a pressure of 10 MPa to make a powder and a foamed nickel electrode. Close contact.
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