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CN109979765B - Method for constructing asymmetric super capacitor based on sodium sulfite electrolyte - Google Patents

Method for constructing asymmetric super capacitor based on sodium sulfite electrolyte Download PDF

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CN109979765B
CN109979765B CN201711458361.0A CN201711458361A CN109979765B CN 109979765 B CN109979765 B CN 109979765B CN 201711458361 A CN201711458361 A CN 201711458361A CN 109979765 B CN109979765 B CN 109979765B
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electrolyte
sodium sulfite
positive electrode
cation exchange
exchange membrane
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夏晖
孙硕
翟腾
陈琪
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Nanjing University of Science and Technology
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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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • 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

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Abstract

本发明公开了一种基于亚硫酸钠电解液构建非对称超级电容器的方法。所述方法将正极材料与负极材料氧化铁用阳离子交换膜隔开，在正极部分滴入电解液，在负极滴入亚硫酸钠电解液，封装，制得MnO2//Fe2O3水系双电解液非对称超级电容器。本发明利用阳离子交换膜的阻隔阴离子传输的功能，成功限制亚硫酸根进入正极，从而避免了亚硫酸根的氧化过程。本发明构建的超级电容器具有非对称超级超级电容器的共性，具有高的功率密度、超长循环寿命，而且具有2.6V超宽的工作电位窗口。

Figure 201711458361

The invention discloses a method for constructing an asymmetric supercapacitor based on sodium sulfite electrolyte. In the method, the positive electrode material and the negative electrode material iron oxide are separated by a cation exchange membrane, the electrolyte is dropped into the positive electrode part, the sodium sulfite electrolyte solution is dropped into the negative electrode, and packaged to obtain a MnO 2 //Fe 2 O 3 aqueous dual electrolyte solution Asymmetric supercapacitors. The invention utilizes the function of blocking the transport of anions of the cation exchange membrane, and successfully restricts the sulfite radicals from entering the positive electrode, thereby avoiding the oxidation process of the sulfite radicals. The supercapacitor constructed by the invention has the commonality of asymmetric supercapacitors, has high power density, ultra-long cycle life, and has an ultra-wide working potential window of 2.6V.

Figure 201711458361

Description

Method for constructing asymmetric super capacitor based on sodium sulfite electrolyte
Technical Field
The invention relates to a method for constructing an asymmetric supercapacitor based on a sodium sulfite electrolyte, and belongs to the technical field of electrochemical energy storage.
Background
The super capacitor is a novel efficient secondary power supply between a battery and a traditional capacitor, and has the advantages of long cycle life, high power density, safety, environmental friendliness and the like. The power density of the battery is 10 to 100 times higher than that of the battery, and the battery can instantly release extra large current, so that the battery is very suitable for electric vehicles. For example, the super capacitor can be used as an electric vehicle together with high-energy batteries such as lithium secondary batteries, and the performance of the electric vehicle can be greatly improved by using the super capacitor under the working conditions of high-power output such as starting, climbing and accelerating. In addition, the super capacitor can also be widely applied to the fields of communication, industry and the like as a standby power supply and an independent power supply. Therefore, supercapacitors have been the focus of research.
The asymmetric super electric appliance mainly comprises electrodes, electrolyte, a diaphragm and a package, wherein the electrolyte is one of key factors influencing the super capacitor. Currently based on MnO2//Fe2O3Sodium sulfate electrolyte is commonly used in asymmetric super electrical appliances, but the currently reported work such as adv.funct.mater.2016,26, 3711-.
Because the sodium sulfite electrolyte can be used as a redox electrolyte, a pseudo capacitor can be additionally provided, and the sodium sulfite electrolyte has an ultra-wide potential window in a negative region according to the energy density formula of 1/2CV2Its energy density (E) is related to its operating potential window (V) and its capacity (C). However, sodium sulfite electrolyte can only be applied to symmetrical supercapacitors at present, and the maximum voltage window V can only reach 1.2V, so that the application of sodium sulfite is greatly limited.
Disclosure of Invention
The invention aims to break through the current situation that sodium sulfite can only be applied to a symmetrical super capacitor, apply sodium sulfite electrolyte to the asymmetrical super capacitor, overcome the defects of narrow potential window and low energy density of the symmetrical super capacitor, and construct a method for a water system double-electrolyte asymmetrical super capacitor with a 2.6V ultra-wide potential window, which has the characteristics of high capacity, excellent cycle life, 2.6V ultra-wide working potential window, high energy density, low cost, good safety performance and the like.
The technical scheme of the invention is as follows:
a method for constructing an asymmetric supercapacitor based on sodium sulfite electrolyte utilizes a cation exchange membrane to block sodium sulfite from entering a positive electrode to prepare a double-electrolyte asymmetric supercapacitor, and comprises the following specific steps:
separating positive electrode material and negative electrode material ferric oxide with cation exchange membrane, dripping electrolyte into positive electrode part, dripping sodium sulfite electrolyte into negative electrode part, and packaging to obtain MnO2//Fe2O3An aqueous double-electrolyte asymmetric supercapacitor.
The cathode material may be any conventionally used cathode material, and may be manganese oxide, ruthenium oxide, cobalt oxide, or the like.
Preferably, the negative electrode material is a composite material of iron oxide quantum dots and graphene, or nanorod iron oxide.
The electrolyte of the positive electrode part can be neutral, acidic or alkaline electrolyte, and specifically can be sodium sulfate, potassium hydroxide or dilute sulfuric acid electrolyte.
Preferably, the concentration of the sodium sulfite electrolyte is 0.2M-2M.
Preferably, the cation exchange membrane may be CMI 7000.
The supercapacitor stores energy by means of polarized electrolyte, and by applying electricity to the plates, the positive plates attract negative ions in the electrolyte, the negative plates attract positive ions, and two capacitive storage layers are formed, wherein the separated positive ions are near the negative plates, and the negative ions are near the positive plates.
Compared with the prior art, the invention has the following advantages:
(1) the sodium sulfite electrolyte is used as redox electrolyte, so that pseudo capacitance can be additionally provided, and the sodium sulfite electrolyte has an ultra-wide potential window in a negative region, so that the super capacitor with ultra-high energy density is constructed.
(2) The current situation that sodium sulfite can only be applied to the formed super capacitor is broken through, the advantage of a high-capacity high-potential window of sodium sulfite electrolyte is successfully utilized, the assembled asymmetric super capacitor can normally work at 2.6V, and the method has important significance for the development of the high-energy-density super capacitor.
(3) The double-electrolyte asymmetric supercapacitor is suitable for different anode and cathode electrolytes, can maximize the utilization rate of anode and cathode materials, and has an important promotion effect on the development of the double-electrolyte asymmetric supercapacitor.
Drawings
FIG. 1 is a cyclic voltammogram based on the different potentials of sodium sulfite and sodium sulfate electrolytes of example 1.
Fig. 2 is a 2.6V charge-discharge curve for the sodium sulfite and sodium sulfate based electrolyte of example 1.
Fig. 3 is a cycle life graph of an asymmetric supercapacitor device based on an iron oxide cathode and a manganese oxide anode.
Fig. 4 is a schematic structural diagram of an asymmetric supercapacitor device based on iron oxide cathode and manganese oxide anode.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples:
examples cation exchange membranes used were commercially available under the model CMI 7000.
Example 1
The first step of preparing manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth.
The second step is that: preparing iron oxide quantum dots: 0.5g of ferric nitrate and 0.05g of functional graphene are stirred in 30ml of alcohol solution until the mixture is dry, and then the mixture is decomposed into a compound of an iron oxide quantum dot and the graphene at 200 ℃.
The third step: assembling the water system double-electrolyte asymmetric supercapacitor: and sealing and fixing the cation exchange membrane and the negative electrode by using an aluminum-plastic membrane and a sealant, and dripping sodium sulfite electrolyte into the negative electrode part from the reserved opening. Then manganese oxide is fixed on the other side of the cation exchange membrane, three sides of the cation exchange membrane are sealed with the aluminum plastic membrane by using a sealant, sodium sulfate electrolyte is dripped, and finally the device is assembled by hot-press sealing.
Through tests, fig. 1 is a cyclic voltammetry curve based on different potentials of sodium sulfite and sodium sulfate electrolytes, and it can be seen that the device can normally operate at 2.6V. Fig. 2 shows the normal charge-discharge curve of the device at 2.6V, which indicates that the device can work normally at 2.6V. FIG. 3 is a cycle life diagram of the device, and it can be seen that the capacity of the asymmetric supercapacitor based on sodium sulfite can still reach 105F/g at a high scan speed, and the capacity retention rate reaches 93.2% after 2000 cycles. Fig. 4 is a photomicrograph of the device and a schematic view of the structure.
Example 2
The first step of preparing manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth.
The second step is that: preparing the nanorod iron oxide: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in water, transferring the solution to a hydrothermal kettle, putting carbon cloth into the hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 10 hours, and annealing the solution at 400 ℃ for 1 hour in the air to successfully prepare the iron oxide nanorod.
The third step: assembling the water system double-electrolyte asymmetric supercapacitor: and sealing and fixing the cation exchange membrane and the negative electrode by using an aluminum-plastic membrane and a sealant, and dripping sodium sulfite electrolyte into the negative electrode part from the reserved opening. Then manganese oxide is fixed on the other side of the cation exchange membrane, three sides of the cation exchange membrane are sealed with the aluminum plastic membrane by using a sealant, sodium sulfate electrolyte is dripped, and finally the device is assembled by hot-press sealing.
Through tests, the device can operate normally at 2.6V, and the electrode 3 material is flexible, so that the device can be applied to flexible electronic devices.
Example 3
The first step of preparing manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth.
The second step is that: preparing iron oxide quantum dots: 0.5g of ferric nitrate and 0.05g of functional graphene are stirred in 30ml of alcohol solution until the mixture is dry, and then the mixture is decomposed into a compound of an iron oxide quantum dot and the graphene at 200 ℃.
The third step: assembling the water system double-electrolyte asymmetric supercapacitor: and sealing and fixing the cation exchange membrane and the negative electrode by using an aluminum-plastic membrane and a sealant, and dripping sodium sulfite electrolyte into the negative electrode part from the reserved opening. Then manganese oxide is fixed on the other side of the cation exchange membrane, three sides of the cation exchange membrane are sealed with the aluminum plastic membrane by using a sealant, sodium hydroxide electrolyte is dripped, and finally the device is assembled by hot-press sealing.
Example 4
The first step of preparing manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth.
The second step is that: preparing iron oxide quantum dots: 0.5g of ferric nitrate and 0.05g of functional graphene are stirred in 30ml of alcohol solution until the mixture is dry, and then the mixture is decomposed into a compound of an iron oxide quantum dot and the graphene at 200 ℃.
The third step: assembling the water system double-electrolyte asymmetric supercapacitor: and sealing and fixing the cation exchange membrane and the negative electrode by using an aluminum-plastic membrane and a sealant, and dripping sodium sulfite electrolyte into the negative electrode part from the reserved opening. Then manganese oxide is fixed on the other side of the cation exchange membrane, three sides of the cation exchange membrane are sealed with the aluminum plastic membrane by using a sealant, dilute sulfuric acid electrolyte is dripped, and finally the device is assembled by hot-press sealing.

Claims (4)

1.基于亚硫酸钠电解液构建非对称超级电容器的方法，其特征在于，具体步骤如下：1. the method for building asymmetric supercapacitor based on sodium sulfite electrolyte, is characterized in that, concrete steps are as follows: 将正极材料与负极材料用阳离子交换膜隔开，在正极部分滴入电解液，在负极部分滴入亚硫酸钠电解液，封装，制得水系双电解液非对称超级电容器；所述的正极材料选自氧化锰、氧化钌或氧化钴；所述的负极材料选自氧化铁量子点与石墨烯的复合材料，或纳米棒氧化铁；所述的正极部分的电解液选自硫酸钠，氢氧化钾或稀硫酸电解液。The positive electrode material and the negative electrode material are separated by a cation exchange membrane, an electrolyte solution is dropped into the positive electrode part, and a sodium sulfite electrolyte solution is dropped into the negative electrode part, and packaged to obtain an aqueous dual electrolyte asymmetric supercapacitor; the positive electrode material is selected from the group consisting of: Manganese oxide, ruthenium oxide or cobalt oxide; the negative electrode material is selected from the composite material of iron oxide quantum dots and graphene, or nanorod iron oxide; the electrolyte of the positive electrode part is selected from sodium sulfate, potassium hydroxide or Dilute sulfuric acid electrolyte. 2.根据权利要求1所述的方法，其特征在于，所述的亚硫酸钠电解液的浓度为0.2M-2M。2. method according to claim 1 is characterized in that, the concentration of described sodium sulfite electrolyte is 0.2M-2M. 3.根据权利要求1所述的方法，其特征在于，所述的阳离子交换膜为CMI7000。3. The method according to claim 1, wherein the cation exchange membrane is CMI7000. 4.根据权利要求1至3任一所述的方法制得的基于亚硫酸钠电解液的非对称超级电容器。4. The asymmetric supercapacitor based on sodium sulfite electrolyte obtained by the method according to any one of claims 1 to 3.
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