CN106024419B - A kind of electrochemical capacitor and preparation method thereof - Google Patents

A kind of electrochemical capacitor and preparation method thereof Download PDF

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Publication number
CN106024419B
CN106024419B CN201610322571.6A CN201610322571A CN106024419B CN 106024419 B CN106024419 B CN 106024419B CN 201610322571 A CN201610322571 A CN 201610322571A CN 106024419 B CN106024419 B CN 106024419B
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electrochemical capacitor
preparation
black
carbon black
electrode slice
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CN106024419A (en
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崔贤长
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Nantong sitaibao Electronic Co., Ltd
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Quanzhou City Famous Industrial Design Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

A kind of electrochemical capacitor and preparation method thereof, belongs to technical field of energy material.Electrochemical capacitor, including carbon black, polyethylene glycol, silica solution, collector, electrolyte;Preparation method includes the following steps:Carbon black, polyethylene glycol are put into ball mill, ball milling, silica solution is added after ball milling, is sufficiently stirred, dried at 150 ~ 200 DEG C, in 15 ~ 32MPa lower sheeting, positive and negative anodes electrode slice is made, by electrode slice in 200 ~ 300 DEG C of 1 ~ 2h of heat preservation.Electrode slice outer surface is coated into collector, is put into container, under vacuum state, keeps 1 ~ 2h, be then placed in electrolyte impregnate 12 ~ for 24 hours, take out, diaphragm will be added among two electrodes, and obtain electrochemical capacitor.The electrochemical capacitor energy density of this method preparation is high, power density is big, long service life, use temperature range are wide, and preparation processing technology is simple, and raw material sources are extensive, is convenient for industrial application.

Description

A kind of electrochemical capacitor and preparation method thereof
Technical field
The invention belongs to technical field of energy material, in particular to a kind of electrochemical capacitor and preparation method thereof
Background technique
Electrochemical capacitor (electric capacitor, EC), compared with traditional capacitor, there is very high specific capacity, EC and battery, which are used in conjunction, can improve power-performance, and energy storage situation can be improved by being used in conjunction with capacitor.The EC of preparation can be used in and defend In the equipment such as star television receiver, remote controler, vehicle-mounted radio, camera, mobile phone, toy, fountain system.
That reports at present prepares electrochemical capacitor in the prior art, most using polytetrafluoroethylene (PTFE) as adhesive, with The binding force between electrode material granules is provided, during the preparation process, the dispersibility of polytetrafluoroethylene (PTFE) will affect pole strength, shadow Ring electrochemical capacitor performance.
There are also the xylene solutions of SBR styrene butadiene rubbers and acrylonitrile-butadiene rubber as adhesive, this kind of Adhesive directly overlays on active material, influences the surface area of active material, reduces capacitor capacitance.
Phenolic resin and epoxy resin also serve as adhesive, are pole strength and conductance using the advantages of this kind of adhesive Rate is all improved, but processing conditions is harsh, it is desirable that hot pressing heating in vacuum, and this kind of adhesive is mixed with active material and is not filled Point.
Meanwhile diaphragm is also a critical material for restricting capacitor development, the heat resistance and absorbency of conventional membrane are all It is not able to satisfy the challenging needs that market proposes membrane properties, higher heat resistance, homogeneity, chemical-resistant stability, absorbency Become the requirement of diaphragm of new generation.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of electrochemical capacitor and preparation method thereof, the electricity of this method preparation Chemical capacitor energy density is high, power density is big, long service life, use temperature range are wide, and preparation processing technology is simple, former Expect it is from a wealth of sources, be convenient for industrial application.
A kind of electrochemical capacitor of the invention, including carbon black, polyethylene glycol, silica solution, collector, electrolyte, diaphragm; Wherein, in mass ratio, polyethylene glycol:Carbon black=0.02~5%, silica solution:Carbon black=(1:20)~(1:10), the painting of collector It covers with a thickness of 4~5 μm.
Electrochemical capacitor of the invention, preparation method include the following steps:
Carbon black, polyethylene glycol are put into ball mill, ball milling, silica solution is added after ball milling, is sufficiently stirred, 150~200 Positive and negative anodes electrode slice is made, by electrode slice in 200~300 DEG C of 1~2h of heat preservation in 15~32MPa lower sheeting in DEG C drying, wherein In mass ratio, positive carbon black:Cathode carbon black=(3:2)~(1:1).
Electrode slice outer surface is coated into collector, is put into container, under vacuum state, 1~2h is kept, is then placed in electrolysis Impregnate 12 in liquid~for 24 hours, it takes out, diaphragm will be added among two electrodes, obtain electrochemical capacitor.
Wherein, one of the carbon black refers to furnace black, channel black, hot tearing is black, lamp black is black.
The black preferably acetylene carbon black of the hot tearing.
The mass fraction of silica is 8~12% in the silica solution.
The electrolyte is LB315 type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), wherein by volume, EC:DMC:DEC=1:1:1.
The diaphragm is to be radiated at PE membrane surface modification grafted propylene nitrile, methyl-prop by plasma irradiation or electron beam One of e pioic acid methyl ester, acrylic acid.
The conductive silver glue that the current collection extremely silver powder content is 75%.
The prior art is compared, the beneficial effects of the present invention are:
1. the present invention, as adhesive, is because silica solution has stronger caking property, in placement process using silica solution In gelatification can occur, partial size becomes larger under alkaline condition, number reduce, in acid condition, and have flocculation salt when, Ion is gathered into tridimensional network, this is all improved the strength and stability of capacitor.
2. the silica solution main component that the present invention uses for silica, has widened the use scope of capacitor, and silicon Colloidal sol safety and environmental protection, it is nontoxic, it is odorless.
3. using modified diaphragm, capacitor discharge performance improvement has better absorbency or liquid retention, capacitor Service life extends.
Specific embodiment
Embodiment 1
A kind of electrochemical capacitor, the silicon that the mass fraction including acetylene carbon black, polyethylene glycol, silica is 8% are molten Glue, LB315 type electrolyte, passes through the modified grafted methacrylic acid first of plasma irradiation at the conductive silver glue that silver powder content is 75% The PE film of ester;Wherein, in mass ratio, polyethylene glycol:Acetylene carbon black=0.5%, silica solution:Acetylene carbon black=1:10, silver powder contains Amount is 4 μm for the coating thickness of 75% conductive silver glue.Preparation method includes the following steps:By acetylene carbon black, polyethylene glycol It is put into ball mill, ball milling, the mass fraction that silica is added after ball milling is 8% silica solution, is sufficiently stirred, and is dried at 200 DEG C It is dry, in 32MPa lower sheeting, positive and negative anodes electrode slice is made, by electrode slice in 300 DEG C of heat preservation 2h, wherein in mass ratio, positive second Alkynes carbon black:Cathode acetylene carbon black=3:2.
The conductive silver glue for being 75% by electrode slice outer surface coating silver powder content, is put into container, under vacuum state, keeps 2h is then placed in electrolyte and impregnates for 24 hours, takes out, and, plus modified PE film, will obtain electrochemical capacitor among two electrodes Device.Wherein, electrolyte is LB315 type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate (EC), carbonic acid Dimethyl ester (DMC), diethyl carbonate (DEC), wherein by volume, EC:DMC:DEC=1:1:1.The charge and discharge under 1A electric current Testing 20,000 capacity retention ratios is 89%, capacitance 376F/g.
Embodiment 2
A kind of electrochemical capacitor, the mass fraction including furnace black, polyethylene glycol, silica be 12% silica solution, Silver powder content is 75% conductive silver glue, LB315 type electrolyte, passes through the PE film that electron beam irradiates modified grafted propylene acid;Its In, in mass ratio, polyethylene glycol:Furnace black=0.02%, silica solution:Furnace black=1:20, the conductive silver glue that silver powder content is 75% Coating thickness be 5 μm.Preparation method includes the following steps:Furnace black, polyethylene glycol are put into ball mill, ball milling, ball milling The mass fraction that silica is added afterwards is 8% silica solution, is sufficiently stirred, and is dried at 150 DEG C, in 15MPa lower sheeting, is made just Negative electricity pole piece, by electrode slice in 200 DEG C of heat preservation 1h, wherein in mass ratio, positive furnace black:Cathode furnace black=1:1.
The conductive silver glue for being 75% by electrode slice outer surface coating silver powder content, is put into container, under vacuum state, keeps 1h is then placed in electrolyte and impregnates 12h, takes out, and, plus modified PE film, will obtain electrochemical capacitor among two electrodes Device.Wherein, electrolyte is LB315 type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate (EC), carbonic acid Dimethyl ester (DMC), diethyl carbonate (DEC), wherein by volume, EC:DMC:DEC=1:1:1.The charge and discharge under 1A electric current Testing 20,000 capacity retention ratios is 89%, capacitance 308F/g.
Embodiment 3
A kind of electrochemical capacitor, the mass fraction including channel black, polyethylene glycol, silica be 12% silica solution, Silver powder content is 75% conductive silver glue, LB315 type electrolyte, passes through the PE film that electron beam irradiates modified grafted propylene nitrile;Its In, in mass ratio, polyethylene glycol:Channel black=0.02%, silica solution:Channel black=1:10, the conductive silver glue that silver powder content is 75% Coating thickness be 4 μm.Preparation method includes the following steps:Channel black, polyethylene glycol are put into ball mill, ball milling, ball milling The mass fraction that silica is added afterwards is 8% silica solution, is sufficiently stirred, and is dried at 180 DEG C, in 15MPa lower sheeting, is made just Negative electricity pole piece, by electrode slice in 250 DEG C of heat preservation 2h, wherein in mass ratio, positive channel black:Cathode channel black=3:2.
The conductive silver glue for being 75% by electrode slice outer surface coating silver powder content, is put into container, under vacuum state, keeps 2h is then placed in electrolyte and impregnates for 24 hours, takes out, and, plus modified PE film, will obtain electrochemical capacitor among two electrodes Device.Wherein, electrolyte is LB315 type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate (EC), carbonic acid Dimethyl ester (DMC), diethyl carbonate (DEC), wherein by volume, EC:DMC:DEC=1:1:1.The charge and discharge under 1A electric current Testing 20,000 capacity retention ratios is 89%, capacitance 354F/g.
Embodiment 4
A kind of electrochemical capacitor, polyethylene glycol black including lamp black, silica mass fraction be 8% silica solution, Silver powder content is 75% conductive silver glue, LB315 type electrolyte, passes through the modified grafted methacrylic acid methyl esters of plasma irradiation PE film;Wherein, in mass ratio, polyethylene glycol:Lamp black is black=and 5%, silica solution:Lamp black is black=and 1:20, silver powder content is 75% The coating thickness of conductive silver glue is 5 μm.Preparation method includes the following steps:Lamp black is black, polyethylene glycol is put into ball mill, Ball milling, the mass fraction that silica is added after ball milling is 8% silica solution, is sufficiently stirred, and is dried at 200 DEG C, is pushed in 32MPa Positive and negative anodes electrode slice is made, by electrode slice in 300 DEG C of heat preservation 2h, wherein in mass ratio, positive lamp black is black in piece:Cathode lamp black is black =3:2.
The conductive silver glue for being 75% by electrode slice outer surface coating silver powder content, is put into container, under vacuum state, keeps 1.5h is then placed in electrolyte and impregnates for 24 hours, takes out, and, plus modified PE film, will obtain electrochemical capacitor among two electrodes Device.Wherein, electrolyte is LB315 type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate (EC), carbonic acid Dimethyl ester (DMC), diethyl carbonate (DEC), wherein by volume, EC:DMC:DEC=1:1:1.The charge and discharge under 1A electric current Testing 20,000 capacity retention ratios is 89%, capacitance 323F/g.

Claims (7)

1. a kind of preparation method of electrochemical capacitor, which is characterized in that specifically comprise the following steps:
Carbon black, polyethylene glycol are put into ball mill, ball milling, silica solution is added after ball milling, is sufficiently stirred, dried at 150 ~ 200 DEG C It is dry, in 15 ~ 32MPa lower sheeting, positive and negative anodes electrode slice is made, by electrode slice in 200 ~ 300 DEG C of 1 ~ 2h of heat preservation, wherein press quality Than positive carbon black:Cathode carbon black=(3:2)~(1:1), polyethylene glycol:Carbon black=0.02 ~ 5%, silica solution:Carbon black=(1:20)~(1: 10);
Electrode slice outer surface is coated into collector, the coating thickness of collector is 4 ~ 5 μm, is put into container, under vacuum state, is protected Hold 1 ~ 2h, be then placed in electrolyte impregnate 12 ~ for 24 hours, take out, diaphragm will be added among two electrodes, obtain electrochemical capacitor Device.
2. the preparation method of electrochemical capacitor as described in claim 1, which is characterized in that the carbon black refers to furnace Black, channel black, one of hot tearing is black, lamp black is black.
3. the preparation method of electrochemical capacitor as claimed in claim 2, which is characterized in that the black hot tearing is acetylene charcoal It is black.
4. the preparation method of electrochemical capacitor as described in claim 1, which is characterized in that titanium dioxide in the silica solution The mass fraction of silicon is 8 ~ 12%.
5. the preparation method of electrochemical capacitor as described in claim 1, which is characterized in that the electrolyte is LB315 Type electrolyte, solute LiPF6Concentration is 1mol/L, and solvent is ethylene carbonate, dimethyl carbonate, diethyl carbonate, wherein is pressed Volume ratio, ethylene carbonate:Dimethyl carbonate:Diethyl carbonate=1:1:1.
6. the preparation method of electrochemical capacitor as described in claim 1, which is characterized in that the diaphragm be by it is equal from Son irradiation or electron beam are radiated at one of PE membrane surface modification grafted propylene nitrile, methyl methacrylate, acrylic acid.
7. the preparation method of electrochemical capacitor as described in claim 1, which is characterized in that the current collection extremely silver powder contains The conductive silver glue that amount is 75%.
CN201610322571.6A 2016-05-16 2016-05-16 A kind of electrochemical capacitor and preparation method thereof Active CN106024419B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101847513A (en) * 2010-02-26 2010-09-29 上海奥威科技开发有限公司 Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece
CN101899233A (en) * 2010-07-29 2010-12-01 上海翰博实业有限公司 Supercapacitor electrode corrosion-resistant conductive coating
CN105551821A (en) * 2015-12-16 2016-05-04 山东精工电子科技有限公司 Preparation method of super capacitor slurry

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101847513A (en) * 2010-02-26 2010-09-29 上海奥威科技开发有限公司 Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece
CN101899233A (en) * 2010-07-29 2010-12-01 上海翰博实业有限公司 Supercapacitor electrode corrosion-resistant conductive coating
CN105551821A (en) * 2015-12-16 2016-05-04 山东精工电子科技有限公司 Preparation method of super capacitor slurry

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