CN108538634B - Water-system compound electrolyte and preparation method and application thereof - Google Patents

Water-system compound electrolyte and preparation method and application thereof Download PDF

Info

Publication number
CN108538634B
CN108538634B CN201810515376.4A CN201810515376A CN108538634B CN 108538634 B CN108538634 B CN 108538634B CN 201810515376 A CN201810515376 A CN 201810515376A CN 108538634 B CN108538634 B CN 108538634B
Authority
CN
China
Prior art keywords
electrolyte
super capacitor
activated carbon
application
compound electrolyte
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
Application number
CN201810515376.4A
Other languages
Chinese (zh)
Other versions
CN108538634A (en
Inventor
于运花
杨佳怡
丁晨峰
兰金叻
杨小平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201810515376.4A priority Critical patent/CN108538634B/en
Publication of CN108538634A publication Critical patent/CN108538634A/en
Application granted granted Critical
Publication of CN108538634B publication Critical patent/CN108538634B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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

Abstract

The invention relates to a water system compound electrolyte and a preparation method and application thereof, which solve the technical problem of low energy density of the conventional super capacitor, and take sodium sulfate as a basic electrolyte and a complex compound prepared by compounding copper chloride dihydrate providing metal ions and tetrabutylammonium bromide serving as a surfactant as an electrolyte additive. The invention also provides a preparation method and application thereof. The invention can be widely applied to the field of electrochemistry.

Description

Water-system compound electrolyte and preparation method and application thereof
Technical Field
The invention relates to the field of super capacitor electrolyte, in particular to a water system compound electrolyte and a preparation method and application thereof.
Background
The super capacitor is called electrochemical capacitor, and has two energy storage modes, namely double-layer capacitance energy storage and pseudo-capacitance energy storage. Unlike conventional lithium batteries, supercapacitors have the advantages of safety, stable long cycle performance, high power density, and the like, and thus have received increasing attention.
The advantages of the super capacitor promote the super capacitor to be well applied to the aspects of electric power, transportation, consumer electronics and the like, but the defects of the super capacitor are not ignored. At present, the energy storage mode of the water system super capacitor is double-layer energy storage, a porous carbon material is taken as an electrode material, sulfuric acid is taken as an electrolyte, however, the capacitance provided by the double-layer super capacitor is 150F g-1About 5-10Wh kg of energy density-1. Its relatively low energy density limits its application in many ways. The research on supercapacitors today is on how to increase their energy density. The currently common method is to research modified electrode materials, including atom-doped and composite metal oxides and conductive polymers, and to a great extent increase energy density by means of pseudo-capacitive energy storage, but the improvement of capacity by means of heteroatom doping is limited, and the modified electrode materials are manufacturedThe preparation process is complex, and the coulombic efficiency has a certain difference compared with the traditional carbon material.
Based on the above problems, we focused on the research of an aqueous electrolyte by changing the existing thinking, and the aqueous electrolyte comprises two parts of a solvent and a solute, and has the properties of high ionic conductivity, no toxicity, safety, low interfacial impedance, quick action on two electrodes and electronic compensation. The water system electrolyte has simple preparation process and obvious effect, but the water system electrolyte also has the problems at present, the voltage window is lower, the decomposition window of a common water system is about 1V, and the energy density is limited on the lifting height, and people improve the defect problem of the water system electrolyte by two methods, one is to add neutral electrolyte, according to Fic K, Lota G, Meller M, et al. novel insulation inter neutral electrolyte as electrically connected electrolyte high-voltage supercapacitors [ J].Energy&Environmental Science,2012, 5(2):5842-2MoO4,andKI:Synergistic effect and the improved capacitive performances for carbon-based supercapacitors[J]Journal of Power Sources,2017,341:448-2MoO4Compared with the traditional system, the KI compound electrolyte has 17.4 times of specific capacity and good circulation stability, so that the research on the water system electrolyte has important significance for the super capacitor.
Disclosure of Invention
The invention aims to overcome the defect of low energy density of the conventional super capacitor, and provides an aqueous compound electrolyte with easy energy storage, high energy density and high coulombic efficiency, a preparation method thereof and application thereof in the super capacitor.
Therefore, the invention provides a water system compound electrolyte, which takes sodium sulfate as a basic electrolyte and a complex compound prepared by compounding copper chloride dihydrate for providing metal ions and tetrabutylammonium bromide serving as a surfactant as an electrolyte additive.
The invention also provides a preparation method of the water system compound electrolyte, which comprises the following steps:
(1) preparing a sodium sulfate neutral salt solution: adding sodium sulfate into deionized water to prepare a sodium sulfate neutral salt solution with the concentration of 0.5-5mol/L, and placing a beaker filled with the sodium sulfate neutral salt solution on a magnetic stirrer at the stirring speed of 400r/min for 1-3 h; (2) preparing a metal salt solution: adding metal salt solid powder into the sodium sulfate neutral salt solution prepared in the step (1) to prepare a metal salt solution with the concentration of 0.005-5mol/L, and placing a beaker filled with the metal salt solution on a magnetic stirrer at the stirring speed of 400r/min for 1-3 h; (3) preparing a compound electrolyte: and (3) adding tetrabutylammonium bromide serving as a surfactant into the metal salt solution prepared in the step (2) to prepare a compound electrolyte with the surfactant concentration of 0.005-5mol/L, and placing a beaker filled with the compound electrolyte on a magnetic stirrer at the stirring speed of 400r/min for 1-3 h.
Preferably, the metal salt solid powder is copper chloride dihydrate.
Preferably, the reaction ambient temperature is 25 ℃.
Preferably, the reaction environment has a humidity of 26 RH%.
The invention also provides an application of the water system compound electrolyte in the super capacitor, which comprises the following steps:
a. uniformly stirring a commercial activated carbon material and 3.5 mass percent polyvinylidene fluoride (PVDF) which takes N-methyl pyrrolidone as a solvent into paste, taking a platinum sheet as a current collector, controlling the activated quality of activated carbon to be 1.5mg, and drying an activated carbon electrode plate in a vacuum oven at 120 ℃ for 12 hours; b. soaking the activated carbon electrode plate dried in the step a in the prepared compound electrolyte for 8 hours, and taking a cellulose diaphragm as a diaphragm to prepare a symmetrical super capacitor, wherein two poles of the symmetrical super capacitor are both activated carbon electrodes; c. and c, circularly testing the symmetrical super capacitor prepared in the step b by adopting a two-electrode testing method under the conditions of constant voltage and current, and calculating the unit capacitance value under the corresponding current density.
Preferably, in the step a, the mass fraction ratio of the commercialized activated carbon material to the polyvinylidene fluoride with the mass fraction of 3.5% and the N-methyl pyrrolidone as the solvent is 9: 1.
Preferably, the voltage range is 0.0-2V, and the current range is 0.2-20A/g.
The invention has the following advantages:
(1) the surfactant and the metal ions are added into the electrolyte of the super capacitor, and the surfactant plays a dual role, so that on one hand, the surface tension of a solid-liquid interface can be reduced, the interface impedance is reduced, more ions are promoted to be transferred to the interface, on the other hand, more metal ions can be bound, the metal ions are uniformly dispersed on the interface, the reaction activity is improved, and the complex can be further used for storing energy when being activated, so that the energy density of the super capacitor can be greatly improved, and the performance is good.
(2) Commercial activated carbon is used as an electrode material, a sodium sulfate aqueous solution is used as a solvent, and copper chloride dihydrate and a surfactant tetrabutylammonium bromide are added to serve as a compound electrolyte. The coordination between metal ions and the surfactant has an excellent effect, the surfactant can reduce the surface tension at the interface of the activated carbon and the electrolyte, more copper ions can be fixed on the interface through the coordination with the metal ions, and the complex can be activated to further store energy. Based on this new idea, we tried to get through Cu2+/Cu+The pseudo-capacitance reaction of the/Cu on the liquid-solid interface improves the energy density of the super capacitor and simultaneously leads the system to have high coulombic efficiency. In addition, with a neutral electrolyte of 1M Na2SO4(63.1F g-1) In contrast, the novel electrolyte is at 1A g-1Current density of 657.2F g-1The specific capacity and the existence of the surfactant are beneficial to stabilizing monovalent copper ions, and the deposition of a large amount of copper is effectively avoided to a certain extent.
(3) The preparation method has the advantages of simple and easy preparation process, low cost, easy application and wide application range, and has high practicability aiming at different electrode materials.
Drawings
FIG. 1 shows that the electrolytes of the present invention are Na, respectively2SO4,Na2SO4+TBAB,Na2SO4+CuCl2, Na2SO4+CuCl2Graph of the rate performance of the + TBAB solution.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as described in the claims.
Example 1
Adding sodium sulfate into deionized water to prepare a neutral electrolyte with the concentration of 0.5mol/L, placing the neutral electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h.
Adding a copper chloride dihydrate solution into the neutral electrolyte to prepare a metal salt solution with the concentration of 0.005mol/L, placing the metal salt solution on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h.
And continuously adding tetrabutylammonium bromide into the prepared solution to prepare a compound electrolyte with the concentration of 0.005mol/L, placing the compound electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h. Then, the electrochemical test is carried out by taking the activated carbon as an electrode material.
Example 2
Adding sodium sulfate into deionized water to prepare a neutral electrolyte with the concentration of 0.5mol/L, placing the neutral electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h.
Adding a copper chloride dihydrate solution into the neutral electrolyte to prepare a metal salt solution with the concentration of 0.5mol/L, placing the metal salt solution on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h.
And continuously adding tetrabutylammonium bromide into the prepared solution to prepare a compound electrolyte with the concentration of 0.025mol/L, placing the compound electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 1 h. Then, the electrochemical test is carried out by taking the activated carbon as an electrode material.
Example 3
Adding sodium sulfate into deionized water to prepare a neutral electrolyte with the concentration of 0.5mol/L, placing the neutral electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 2 h.
Adding a copper chloride dihydrate solution into the neutral electrolyte to prepare a metal salt solution with the concentration of 0.5mol/L, placing the metal salt solution on a magnetic stirrer at the speed of 400r/min, and stirring for 2 h.
And continuously adding tetrabutylammonium bromide into the prepared solution to prepare a compound electrolyte with the concentration of 0.1mol/L, placing the compound electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 2 hours. Then, the electrochemical test is carried out by taking the activated carbon as an electrode material.
Example 4
Adding sodium sulfate into deionized water to prepare neutral electrolyte with the concentration of 2.5mol/L, placing the neutral electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 2 h.
Adding a copper chloride dihydrate solution into the neutral electrolyte to prepare a metal salt solution with the concentration of 2.5mol/L, placing the metal salt solution on a magnetic stirrer at the speed of 400r/min, and stirring for 2 h.
And continuously adding tetrabutylammonium bromide into the prepared solution to prepare a compound electrolyte with the concentration of 2.5mol/L, placing the compound electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 2 hours. Then, the electrochemical test is carried out by taking the activated carbon as an electrode material.
Example 5
Adding sodium sulfate into deionized water to prepare a neutral electrolyte with the concentration of 5mol/L, placing the neutral electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 3 h.
Adding a copper chloride dihydrate solution into the neutral electrolyte to prepare a metal salt solution with the concentration of 5mol/L, placing the metal salt solution on a magnetic stirrer at the speed of 400r/min, and stirring for 3 h.
And continuously adding tetrabutylammonium bromide into the prepared solution to prepare a compound electrolyte with the concentration of 5mol/L, placing the compound electrolyte on a magnetic stirrer at the speed of 400r/min, and stirring for 3 hours. Then, the electrochemical test is carried out by taking the activated carbon as an electrode material.

Claims (3)

1. The application of the water system compound electrolyte in the super capacitor is characterized in that the water system compound electrolyte takes sodium sulfate as a basic electrolyte, and a complex compound prepared by compounding copper chloride dihydrate for providing metal ions and tetrabutylammonium bromide serving as a surfactant is taken as an electrolyte additive, and the method comprises the following steps:
a. uniformly stirring a commercial activated carbon material and 3.5 mass percent polyvinylidene fluoride (PVDF) which takes N-methyl pyrrolidone as a solvent into paste, taking a platinum sheet as a current collector, controlling the activated quality of activated carbon to be 1.5mg, and drying the activated carbon electrode sheet in a vacuum oven at 120 ℃ for 12 hours;
b. soaking the activated carbon electrode plate dried in the step a in the prepared compound electrolyte for 8 hours, and taking a cellulose diaphragm as a diaphragm to prepare a symmetrical super capacitor, wherein two poles of the symmetrical super capacitor are both activated carbon electrodes;
c. and c, circularly testing the symmetrical super capacitor prepared in the step b by adopting a two-electrode testing method under the conditions of constant voltage and current, and calculating the unit capacitance value under the corresponding current density.
2. The application of the water-system compound electrolyte in the super capacitor as claimed in claim 1, wherein in the step a, the mass fraction ratio of the commercialized activated carbon material to the polyvinylidene fluoride with the mass fraction of 3.5% and N-methyl pyrrolidone as the solvent is 9: 1.
3. The application of the water system compound electrolyte in the super capacitor as claimed in claim 1, wherein the voltage range is 0.0-2V, and the current range is 0.2-20A/g.
CN201810515376.4A 2018-05-25 2018-05-25 Water-system compound electrolyte and preparation method and application thereof Active CN108538634B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810515376.4A CN108538634B (en) 2018-05-25 2018-05-25 Water-system compound electrolyte and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810515376.4A CN108538634B (en) 2018-05-25 2018-05-25 Water-system compound electrolyte and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108538634A CN108538634A (en) 2018-09-14
CN108538634B true CN108538634B (en) 2020-04-28

Family

ID=63472728

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810515376.4A Active CN108538634B (en) 2018-05-25 2018-05-25 Water-system compound electrolyte and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108538634B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948318B (en) * 2021-09-27 2022-12-09 西安交通大学 High-pressure water system electrolyte and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100501888C (en) * 2005-09-08 2009-06-17 中国科学院山西煤炭化学研究所 Electrolyte for electrochemical capacitor and its preparing method
CN101546652B (en) * 2009-05-06 2011-11-30 北京科技大学 Method for improving electric capacity of anode of electrochemical capacitor of organic system
CN104335405B (en) * 2012-08-22 2017-02-22 日新电机株式会社 Energy storage battery
US9196425B2 (en) * 2013-09-04 2015-11-24 The Regents Of The University Of California High energy capacitors boosted by both catholyte and anolyte
CN106981371A (en) * 2016-01-15 2017-07-25 黄潮 A kind of water system electrolyte super capacitance cell

Also Published As

Publication number Publication date
CN108538634A (en) 2018-09-14

Similar Documents

Publication Publication Date Title
Zhang et al. High-performance hybrid supercapacitors enabled by protected lithium negative electrode and “water-in-salt” electrolyte
Lee et al. Manganese oxide electrochemical capacitor with potassium poly (acrylate) hydrogel electrolyte
CN105609720B (en) A kind of preparation method of NiPC@CNTs/S composites and application
JPH088147A (en) Electric capacitor
JP6859317B2 (en) Semi-solid flow Li / O2 battery
WO2017159803A1 (en) Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof
CN106024408A (en) Ruthenium oxide-copper sulfide composite material, application thereof and electrode plate for supercapacitor
CN104852064A (en) Organic-matter-halogen electrolyte and application thereof to flow battery
CN111146419B (en) Method for manufacturing long-life lead-acid battery cathode by using trace graphene oxide sheet
EP4088293A1 (en) Metal ion capacitor based on hard carbon as negative electrode and a mixture of activated carbon and sacrificial salt as the positive electrode
CN108538634B (en) Water-system compound electrolyte and preparation method and application thereof
CN109950060B (en) Super capacitor redox active electrolyte
JP4217775B2 (en) Ionic liquid
CN104269540A (en) Titanium dioxide/conducting polymer/sulfur three-element composite material and secondary cell
Makino et al. 4 V Aqueous hybrid supercapacitors based on dual electrolyte technologies
CN108492995B (en) Preparation method of high-voltage aqueous electrolyte lithium ion capacitor
Bu et al. Synchronous synthesis of electro-exfoliated/oxidized binder-free expanded graphite paper at low potential for solid-state capacitor
Yamagata et al. Charge-Discharge Behavior of Electric Double-Layer Capacitor with Alginate/Ionic Liquid Gel Electrolyte
CN104681281A (en) Composite electrode material having excellent rate performance and preparation method thereof
CN111415823B (en) Ni-Sn-S composite material and preparation method and application thereof
JP7288776B2 (en) Aqueous electrolyte for power storage device and power storage device containing this water-based electrolyte
Tang et al. and Shan Huk Department of Mechanical engineering, iowa State University, Ames, iowa, 50010, USA kCorresponding author email: shanhu@ iastate. edu
Egashira Capacitance Degradation in Hydrogel Electrolyte Containing Magnesium-ion Conducting Water-in-Salt Solution
CN115850721A (en) Low-temperature-resistant lead storage battery and preparation method of positive and negative electrode additive applied to battery
EP2909848A1 (en) Super hybrid capacitor

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