CN100359613C

CN100359613C - Method for making metal oxide/carbon electrochemical capacitor and electrode

Info

Publication number: CN100359613C
Application number: CNB2003101077089A
Authority: CN
Inventors: 张宝宏; 黄世斌; 丛文博; 杨滨昌
Original assignee: HARBIN ENGINEERING UNIVERSITY SANJIN HIGH AND NEW TECHNOLOGY Co Ltd
Current assignee: HARBIN ENGINEERING UNIVERSITY SANJIN HIGH AND NEW TECHNOLOGY Co Ltd; Harbin Engineering University
Priority date: 2003-11-18
Filing date: 2003-11-18
Publication date: 2008-01-02
Anticipated expiration: 2023-11-18
Also published as: CN1545114A

Abstract

The present invention belongs to manufacture methods of a metal oxide / carbon electrochemical capacitor and an electrode. Monolithic capacitors are arranged and installed in a casing according to anodes, membranes and cathodes. The anode of the first mode of the present invention is formed in a mode that manganese dioxide, graphite, lead oxide, activated carbon and adhesive are mixed to a scale, and ethanol is added into the mixture which is prepared to paste form to be coated on porous conducting materials. The anode of the second mode is formed in mode that only the manganese dioxide is changed to silver oxide, the graphite is changed to acetylene black, and other components and the manufacture method are the same to that of the anode of the first mode. The cathodes are formed in a mode that the activated carbon, the graphite and the adhesive are mixed proportionally, the ethanol is added into the mixture which is prepared into paste form to be coated on the porous conducting materials. The present invention has the advantages of large capacitance and long charging and discharging cycle lives, and heavy current discharge can be done, etc. The present invention can be extensively used on electrical equipment in the fields of mobile communication, information technologies, mechanical industry, electric automobiles, aerospace, national defense, etc. to be used as an auxiliary power supply.

Description

The manufacture method of the electrode of metal oxide/carbon electrochemical capacitor

Technical field

The invention belongs to the metal oxide/mixed type electrochemical capacitor of material with carbon element composition and the manufacture method of electrode.

Background technology

Electrochemical capacitor is called electric chemical super capacitor (Electrochemical Supercapacitors) or ultracapacitor (Supercapacitors or Ultracapacitors) again, and it is based on the energy-storage travelling wave tube of the electrochemical process of electrode/solution interface.The capacity of electrochemical capacitor is 20-200 a times of traditional capacitor capacity, can reach faraday's level even thousand faraday's levels.It has the big and high advantage of rechargeable battery energy density of conventional capacitor power density concurrently, is considered to a kind of efficient, practical novel energy.

Electrochemical capacitor can be divided into two types according to energy storage mechanism.One class is based on the double electric layer capacitor of electric double layer principle in interface between high-ratio surface material with carbon element and solution, the another kind of underpotential deposition on two dimension or three-dimensional material surface or the pseudo capacitance device of oxidation-reduction process of being based on.The capacitance size of double electric layer capacitor is relevant with the size of electrode potential and specific area, thereby can improve electric double layer capacitance by the specific area that improves electrode potential and increase electrode.Yet the method by simple increasing specific surface area has certain limitation.Because in increasing specific surface area, micropore quantity on the material with carbon element increases, and micropore size is unfavorable for improving electric double layer capacitance when very little, and the active group that increases carbon surface can increase substantially capacitance.For example Smlipka utilizes specific area only to be 2m ²The carbon fiber of/g is made electrode material, and behind activation generation active group, specific capacitance of single electrode can reach 200F/g.The pseudo capacitance device mainly uses metal oxide to make electrode, mainly is electrode material with the ruthenic oxide.Because ruthenic oxide costs an arm and a leg, for reduce cost the researcher all at the metal oxide of exploring other to replace ruthenic oxide.MnO wherein ₂Be a kind of preferably electrode material of low price, capacitive property, but since manganese dioxide in oxidation-reduction process, variation of valence easily takes place and makes variation on the manganese dioxide recurring structure make the chemical property decay in the manganese of+4 valencys.As seen " the nanometer α-MnO that delivers by authors such as Xia Xi of " Journal of Inorganic Materials " the 5th phase in October, 2000 ₂Preparation and performance study thereof " literary composition.

Summary of the invention

The present invention improves the ratio electric capacity of manganese dioxide by add alpha-oxidation lead at the positive pole of electrochemical capacitor as stabilizer, and capacitance is improved more than 60%, and unipolar electric capacity is reached more than the 600F/g.

The present invention is by anodal, negative pole and the barrier film that is used to isolate positive and negative electrode constitutes, and all is assemblied in the housing.This invention positive pole is by manganese dioxide, graphite, beta oxidation lead, active carbon and porous conductive material are made, its manufacture method is with manganese dioxide, graphite, beta oxidation lead, active carbon mixes by a certain percentage with bonding agent, its proportioning makes the mass percent of beta oxidation lead and manganese dioxide between 0.5-10%, add ethanol furnishing paste then, be applied to by designing requirement and made (dimensions of porous conductive material is decided by the capacitance size of designing requirement) on the porous conductive material of given size, through being cold-pressed into certain thickness thin slice, positive pole is promptly made in oven dry under 80 ℃ state again.

The negative pole that the positive pole of this invention is prepared is made by active carbon, graphite and porous conductive material, its manufacture method is identical with the method for making positive pole, promptly taking by weighing active carbon, graphite and bonding agent respectively mixes by a certain percentage, making the mass ratio of active carbon in negative pole is 90%, add ethanol furnishing paste then, be applied to by designing requirement and made on the porous conductive material with anodal corresponding dimensions, through being cold-pressed into certain thickness thin slice, under 80 ℃ of states, dry, promptly make negative pole.

The plumbous nanometer alpha-oxidation lead that adopts of the beta oxidation of in positive pole, using as stabilizer, barrier film adopts poromerics; Sequence arrangement by positive pole, barrier film, negative pole during assembling is assemblied in the housing of capacitor, encapsulates after adding electrolyte, and the binding post that picks out positive and negative electrode in the capping of housing is assembled into the monomer electrochemical capacitor.As required voltage and capacity in the use can adopt the monomer electrochemical capacitor of varying number to connect and be connected in parallel.

So the present invention can be widely used in fields such as mobile communication, information technology, mechanical industry, electric automobile, Aero-Space, national defence, for example: auxiliary power power supplys such as the startup of electric automobile, the accessory power supply of computer, electric welding machine, photoflash lamp, compact electronic device etc.

Description of drawings

The structural representation of Fig. 1 metal oxide/carbon electrochemical capacitor

Fig. 2 contains the MnO of 2% β-PbO ₂Electrode and the MnO that does not have interpolation β-PbO ₂The constant current charge-discharge curve chart of electrode

Fig. 3 contains the MnO of β-PbO ₂Electrode is at 7molL ^-1Cyclic voltammogram among the KOH

Embodiment

Example 1. takes by weighing manganese dioxide, beta oxidation lead, graphite, active carbon and bonding agent respectively by 65: 5: 5: 20: 5 mass ratio mixes, add ethanol furnishing paste, be applied on the porous conductive material 80 ℃ of oven dry, pressure at 20MPa depresses to thin slice, makes positive pole [1]; Take by weighing active carbon, graphite and bonding agent respectively and mix, add ethanol furnishing paste, be applied on the porous conductive material,, depress to thin slice, make negative pole [2] at the pressure of 20MPa 80 ℃ of oven dry by 90: 5: 5 mass ratio.Make barrier film [3] with microporous polypropylene film.Sequence arrangement by anodal [1], barrier film [3], negative pole [2] in the capacitor casing of packing into [4], adds 7molL ^-1KOH solution after encapsulate.In housing [4] capping, pick out the binding post of positive and negative electrode [1,2], be assembled into monolithic capacitor.

Bonding agent is the mixture of carboxymethyl cellulose and polytetrafluoroethylene in the prescription, and mass ratio is 1: 1.

The metal oxide that provides this invention through test is a manganese dioxide, in anodal [1], add the constant current charge and discharge curve chart 2 of beta oxidation lead as its positive pole of electrochemical capacitor [1] of stabilizer, represent with solid line among the figure, simultaneously provide the anodal constant current charge and discharge curve that the manganese dioxide that does not under equal conditions add stabilizer beta oxidation lead is the electrochemical capacitor of metal oxide with dashed line form in Fig. 2, both compare capacitor anode [1] charge and discharge performances of being added with beta oxidation lead as can be seen are far better from Fig. 2; Provide cyclic voltammetry curve Fig. 3 of this invention electrochemical capacitor simultaneously.

So can being widely used in doing on the electric equipment in fields such as mobile communication, information technology, mechanical industry, electric automobile, Aero-Space, national defence accessory power supply, the present invention uses.

Claims

1. the manufacture method of the electrode of a metal oxide/carbon electrochemical capacitor, the monomer whose capacitor is by being contained in the housing [4] and through positive pole [1] and negative pole [2] formation that barrier film [3] separates, it is characterized in that positive pole [1] is made up of manganese dioxide, graphite, beta oxidation lead, active carbon and porous conductive material; Negative pole [2] is made up of active carbon, graphite and porous conductive material.

2. the manufacture method of the electrode of metal oxide/carbon electrochemical capacitor according to claim 1; The manufacture method that it is characterized in that its positive pole [1], manganese dioxide, beta oxidation lead, graphite, active carbon and bonding agent are mixed by certain mass ratio, making the plumbous mass percent with manganese dioxide of beta oxidation is 0.5-10%, add ethanol furnishing paste then, be applied on the porous conductive material, under 80 ℃ of states, dry, be pressed into thin slice through colding pressing.

3. the manufacture method of the electrode of metal oxide/carbon electrochemical capacitor according to claim 1, the manufacture method that it is characterized in that its negative pole [2] is that active carbon, graphite and bonding agent are mixed by certain mass ratio, making the mass percent of active carbon in negative pole [2] is 90%, adding ethanol furnishing paste then is applied on the porous conductive material, under 80 ℃ of states, dry, be pressed into thin slice through colding pressing.