CN101697323A - Electrochemically modified graphite electrode - Google Patents
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- CN101697323A CN101697323A CN200910229452A CN200910229452A CN101697323A CN 101697323 A CN101697323 A CN 101697323A CN 200910229452 A CN200910229452 A CN 200910229452A CN 200910229452 A CN200910229452 A CN 200910229452A CN 101697323 A CN101697323 A CN 101697323A
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Abstract
The invention discloses an electrochemically modified graphite electrode, which consists of a graphite body and an active layer, wherein the active layer is attached to the surface of the graphite body. The electrochemically modified graphite electrode is characterized in that: the active layer (2) is a product directly obtained in a way that the graphite body (1) is subjected to circular treatment between electrochemical oxidation and electrochemical reduction in water-based electrolyte solution with ionic conductivity. The electrochemically modified graphite electrode is used as an electrode material of an electrochemical capacitor, has high energy, high power density and high-speed charge and discharge performances, also has the advantages of high electric conductivity, low material cost, high stability, long service life, simple manufacture, low production cost and the like. In addition, the electrochemically modified graphite electrode of the invention can be widely applied to applicable electrochemical engineering and serves as the electrode material.
Description
Technical field
The present invention relates to a kind of electrochemically modified graphite electrode, belong to the Applied Electrochemistry technical field.
Background technology
Applied Electrochemistry is that relevant electrochemical principle is applied to the field relevant with actual production process, its task is diversified, wherein important has: the development and utilization of electrochemistry new forms of energy system, the metallic surface finish, electrochemical corrosion and protection, the exploitation of electrochemical sensor and electrolysis inorganic, organic compound are synthetic etc.Applied Electrochemistry industry be unable to do without electrode, and selection of electrode materials is very important.The dynamic index of the structural shape of the direction of electrode process and dynamics, electrode and electrolysis tank and electric groove life, maintenance cost and labour's consumption and technical process etc. all depends on the structure of electrode and used material to a great extent, especially when carrying out electrode type and electric groove structural design, all durability, conductivity, electro catalytic activity and the power consumption with electrode material has confidential relation, and the novel electrode material of constantly developing superior performance receives very big concern all the time.
Along with The development in society and economy, people more and more pay close attention to green energy resource and biological environment.Electrochemical capacitor (also being called ultracapacitor) comes into one's own day by day as a kind of novel energy-storing device.Compare with present widely used various energy storage devices, the electrochemical capacitor charge storage discharges and recharges speed and efficient and is better than again once or secondary cell far above physical capacitor.In addition, electrochemical capacitor also have environmentally safe, have extended cycle life, characteristics such as serviceability temperature wide ranges, fail safe height.The development of electrochemical capacitor and hydrogen car, hybrid vehicle and electric automobile is closely related, supplies with device and combines with fuel cell, lithium ion battery homenergic, can satisfy the instantaneous high power requirements under the conditions such as startup, climbing.
The development core of electrochemical capacitor technology is an electrode material.Electrochemical capacitor can be divided into two kinds according to energy storage mechanism: double electric layer capacitor and pseudo capacitance device.The electrochemical double-layer that double electric layer capacitor relies on electrode material and electrolyte interface to form comes stored charge, electrode material requires to have high-specific surface area, typical material be porous carbon material (for example, activated carbon), electrolyte is organic or water solution system, requires to adopt mostly in the practicality organic solution system in order to satisfy higher energy density; Yet the energy density of porous carbon material and power density be usually rapidly decay under the high current density condition, is difficult to satisfy the active demand to electrochemical capacitor high-energy/high power density such as electric automobile.The pseudo capacitance device relies on the quick redox reaction of electrode material in electrolyte and comes stored charge, and electrolyte is generally water solution system; Electrode material requires to have reversible, quick redox reaction, and typical material is transition group metallic oxide (for example, ruthenium oxide hydration) and conducting polymer (for example, polyaniline), and they can store more electric charge on unit are; Shortcomings such as yet there is the material cost height in they, and stability is poor, and useful life is short.
Crystal structure of graphite is complete, good stability, conductivity height, common conductive agent as electrochemical capacitor electrode.A kind of graphite is disclosed in U.S. Pat 2009059474A1 and US2009061312A1 as composite electrochemical capacitor electrode material of conductive network and preparation method thereof.In Chinese patent CN101009161A, disclose the electrochemical capacitor of a kind of high-ratio surface flaky graphite, showed the excellent electric double layer capacitance characteristic of the activated carbon of can comparing as electrode material.People's such as H.Y.Wang (Electrochem.Commun.10 (2008) 382) the graphite that studies show that can be used as the positive electrode of hybrid electrochemical capacitor.Yet the pseudo-capacitance characteristic of utilizing graphite electrode is not appeared in the newspapers so far as yet as the electrode of electrochemical capacitor.
As everyone knows, after material with carbon element process chemistry or electrochemical oxidation were handled, its surface can generate oxygen-content active group, thereby has had certain pseudo-capacitance characteristic.People such as Sullivan (J.Electrochem.Soc.147 (2000) 2636) have reported that glass-carbon electrode is through behind the electrochemical modification, has the pseudo-capacitance characteristic, can be used as the electrode material of electrochemical capacitor, but have shortcomings such as pseudo-capacitance amount glass-carbon electrode price height, electrochemical activation time low, that use is long.The pluses and minuses of comprehensive above-mentioned double electric layer capacitor and pseudo capacitance device electrode material, as can be seen, but to develop a kind of high-energy/high power density, low material cost, high stability, electrode material long-life and suitability for industrialized production be the key issue that electrochemical capacitor is badly in need of solving at present.
Summary of the invention
Deficiency at the prior art existence, technical problem to be solved by this invention is, a kind of electrochemically modified graphite electrode is provided, and it has characteristics such as high-energy and high power density, high conductivity, low material cost, high stability, long-life, and make simple and easy, production cost is low.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is, a kind of electrochemically modified graphite electrode, and it is made up of graphite body and active layer, on the surface of active layer attached to the graphite body; Wherein: the graphite body is the block that is made of graphite material; Active layer is directly by graphite body product through obtaining after electrochemical oxidation and the electrochemical reduction circular treatment in having the aqueous electrolyte solution of ionic conductivity.
Above-mentioned electrode, its described circular treatment between electrochemical oxidation and electrochemical reduction comprises that the graphite body is carried out the mode that constant potential is controlled or constant current is controlled to be handled.Wherein: the processing mode of the graphite body being carried out constant potential control is: in having the aqueous electrolyte solution of ionic conductivity, at first constant electrode potential carries out the anode electrochemical oxidation more than oxygen evolution potential, and then constant electrode potential carries out electrochemical cathode reduction below oxygen evolution potential operation repeats, and meets the demands until the thickness of the active layer that obtains.The processing mode of the graphite body being carried out constant current control is: at first constant current density is 1～300mA/cm
2Carry out the anode electrochemical oxidation, and then constant current density be-1～-300mA/cm
2The operation of carrying out electrochemical cathode reduction repeats, and meets the demands until the thickness of the active layer that obtains.
No matter be the electrochemical modification that adopts the constant potential control mode, still adopt the electrochemical modification of constant current control mode, they are the same on principle.Promptly when oxygen evolution reaction takes place, the graphite body is carried out the anode electrochemical oxidation, the graphite body surface can generate the porous peroxidating graphite of one deck when initial, because the peroxidating graphitic conductive is poor, causes anode current to develop to graphite body depth direction by porous peroxidating graphite linings.Therefore, single anode oxidation process can only form thick, porous peroxidating graphite linings.After anodic oxidation, the cathode reduction process that carries out below oxygen evolution potential can be reduced to graphite with peroxidating graphite linings 100%.Carry out the anode electrochemical oxidation afterwards again, anode current also can continue the graphite that oxidation has been reduced except acting on the graphite body, makes active layer grain refinement and contain more porous peroxidating graphite.The operation of anode electrochemical oxidation-electrochemical cathode reduction repeats, i.e. circulating treatment procedure, will help forming have certain thickness, coarse, porous, contain and enrich oxygen-content active functional group and the active layer crystallite laminated structure.In the present invention, the constant potential that the anode electrochemical oxidation is applied more just or constant current density big more, and the constant potential that applied of electrochemical cathode reduction is negative more or constant current density is big more, then the number of times of needed circular treatment and time are just few more.The present invention did not limit the number of times and the time of circular treatment, and whether the thickness conduct that mainly is based on by the control active layer reaches desired effects as criterion.
Above-mentioned electrode, its described electrochemical modification are to carry out at the aqueous electrolyte solution with ionic conductivity; Said aqueous electrolyte solution is that inorganic compound or organic compound are dissolved in the water and form, and preferentially is H
2SO
4Or HClO
4The aqueous solution.Suitable aqueous electrolyte solution requires to have very high ionic conductivity, requires to help forming efficiently active layer coarse, porous.H
2SO
4Or HClO
4Aqueous solution ionic conductivity height, anion a little less than anode absorption, thereby help forming at short notice active layer.
Above-mentioned electrode, in order to satisfy the requirement of higher working strength, its described active layer can further be directly by graphite body product through obtaining after electrochemical oxidation and electrochemical reduction circular treatment in having the aqueous electrolyte solution of ionic conductivity, pass through further mechanical compaction again, thereby attached on the graphite body surface of forming by native graphite or electrographite block materials.Because active layer is grown directly upon on the graphite body, therefore have extraordinary electrical contact performance, guaranteed to have very little internal resistance as electrochemical capacitor electrode, can obtain higher power output.
Above-mentioned electrode is on the part or all surfaces of its described active layer attached to the graphite body.That is to say that the distribution of active layer on the graphite body surface is local arbitrarily or whole, in order to satisfy the Structural Design Requirement of electrochemical capacitor.
Above-mentioned electrode, its described active layer are the crystallite sheet structural group one-tenth that is contained oxygen-content active functional group by the surface, and active layer is coarse, porous.The roughening of active layer and porous help obtaining more active surface area and electrolytical transmission; And the crystallite sheet structural group one-tenth of oxygen-content active functional group is contained on the surface, then because the redox reaction of a large amount of oxygen-content active functional groups that exist, make it have very high pseudo-capacitance characteristic, on unit are, can store more electric charge, thereby have higher specific energy density.
Above-mentioned electrode, the thickness of its described active layer are 1 micron～200 microns.Active layer is thick more, and capacitance is big more, and is can charge stored many more.Active layer thickness during less than 1 micron capacitance too little, practical value is little.Active layer thickness is during greater than 200 microns, and then active layer is peeled off easily, and electrode stability is poor.Therefore, active layer thickness be 1 micron～200 microns comparatively suitable.This thickness range is applied to electrochemical capacitor, makes it have higher specific power density.
Above-mentioned electrode, its described graphite body are thread, netted, sheet, column, spherical or erose graphite block body, and its hexagonal and rhomboidal crystal are than being any number.That is to say that shape and concrete crystal formation to the graphite bulk material do not have specific (special) requirements.
Electrochemically modified graphite electrode of the present invention is suitable as the electrode material of electrochemical capacitor, and it has characteristics such as high-energy and high power density, high conductivity, low material cost, high stability, long-life, and make simple and easy, production cost is low.Use as electrode material in the Applied Electrochemistry engineerings such as electrochemically modified graphite electrode of the present invention can also be widely used in that electrochemical hydrogen storage, electrochemical sensor, lithium ion battery, Ni-MH battery, fuel cell, water electrolysis, sewage disposal, organic substance electricity are synthetic, electrodialysis and electro-deposition.
Description of drawings
The present invention is described in more detail below in conjunction with specific embodiment and accompanying drawing thereof.
Fig. 1 is the structural representation of electrochemically modified graphite electrode embodiment of the present invention;
Fig. 2 is the stereoscan photograph (SEM) of electrochemically modified graphite electrode active layer of the present invention;
Fig. 3 is the x-ray photoelectron spectroscopy (XPS) of electrochemically modified graphite electrode (a) and electrochemically modified graphite electrode of the present invention (b) not;
Fig. 4 is electrochemically modified graphite electrode (a, 50mVs not
-1) and electrochemically modified graphite electrode (b, 3mVs
-1C, 5mVs
-1D, 10mVs
-1E, 20mVs
-1F, 50mVs
-1) cyclic voltammetry curve;
Fig. 5 is the charging and discharging curve of electrochemically modified graphite electrode.
Embodiment
The structure of electrochemically modified graphite electrode of the present invention as shown in Figure 1, it is made up of graphite body 1 and active layer 2, on the surface of active layer 2 attached to graphite body 1; The block materials that graphite body 1 is made up of native graphite or electrographite; Described active layer 2 be directly by graphite body 1 in having the aqueous electrolyte solution of ionic conductivity through after the circular treatment between electrochemical oxidation and the electrochemical reduction and the product that obtains, and on the surface attached to graphite body 1.Active layer 2 can pass through further mechanical compaction, and can be attached to the part on the graphite body surface or whole.Active layer 2 is to be become by the crystallite sheet structural group that oxygen-content active functional group is contained on the surface, and is coarse and porous, and its thickness is 1 micron～200 microns.Graphite body 1 is thread, netted, sheet, column, spherical or erose block materials, and its hexagonal and rhomboidal crystal are than being any number.Described aqueous electrolyte solution with ionic conductivity is that inorganic compound or organic compound are dissolved in the water and form, preferred H
2SO
4Or HClO
4The aqueous solution.Described circular treatment between electrochemical oxidation and electrochemical reduction comprises that the graphite body is carried out the mode that constant potential is controlled or constant current is controlled to be handled.Wherein: the processing mode of the graphite body being carried out constant potential control is: in having the aqueous electrolyte solution of ionic conductivity, at first constant electrode potential carries out the anode electrochemical oxidation more than oxygen evolution potential, and then constant electrode potential carries out electrochemical cathode reduction below oxygen evolution potential operation repeats, and meets the demands until the thickness of the active layer that obtains.The processing mode of the graphite body being carried out constant current control is: at first constant current density is 1～300mA/cm
2Carry out the anode electrochemical oxidation, and then constant current density be-1～-300mA/cm
2The operation of carrying out electrochemical cathode reduction repeats, and meets the demands until the thickness of the active layer that obtains.The present invention is further illustrated below by embodiment.
Embodiment 1:
This electrode is a graphite body 1 with electrographite sheet material, and elder generation is with a part (1cm of its end face
2) be exposed to 2M H
2SO
4In the aqueous solution, by the constant current pulse it is carried out circular treatment between electrochemical oxidation and the electrochemical reduction: at first constant anodic current density is 260mA/cm
2, anodized 200s; The constant cathode current density is-220mA/cm more afterwards
2, 120s is handled in cathodic reduction; The above-mentioned processing procedure that circulates 6 times is colded pressing through machinery at last again, obtains thickness and be 40 microns active layer 2.Handle by this electrochemical modification, its SEM picture as shown in Figure 2.Active layer 2 is to be become by many crystallite sheet structural group as can see from Figure 2, and is coarse and porous.Further by XPS the element on graphite body 1 and active layer 2 surfaces is formed and analyzed, the result as shown in Figure 3.As can see from Figure 3, than graphite body 1, the O1s/C1s peak relative intensity of crystallite sheet body structure surface increases considerably in the active layer 2 that the process electrochemical modification obtains, be that the O1s/C1s mol ratio improves greatly, show that active layer 2 is the crystallite sheet structural group one-tenth that is contained oxygen-content active functional group by the surface.
The graphite electrode of above-mentioned electrographite sheet material and process electrochemical modification is placed 2.3M H
2SO
4In the aqueous solution, adopt the three-electrode system of standard to carry out the electrochemical capacitor evaluating characteristics.Fig. 4 is the electrographite sheet material graphite electrode of not electrochemical modification and the cyclic voltammetry curve that passes through the graphite electrode of electrochemical modification.As can see from Figure 4, electrochemically modified graphite electrode does not have the clear redox peak, and showing does not have the pseudo-capacitance characteristic; And electrochemically modified graphite electrode is at 0.4V
Vs.SCENear a pair of wide and high redox peak has appearred, the redox reaction of its corresponding oxygen-content active functional group, and the shape of curve is along the diagonal symmetry, show that electrochemically modified graphite electrode has reversible, jumbo pseudo-capacitance characteristic, can be used as the electrode material of electrochemical capacitor.Fig. 5 is the charging and discharging curve of electrochemically modified graphite electrode.As can see from Figure 5, its charging and discharging curve feature is symmetrical, shows very excellent electrochemical capacitor characteristic once more.The capacitance of electrochemically modified graphite electrode can (i * dt)/dE calculates based on equation: C=.Capacitance under the 2mA charging or discharging current is 2.08Fcm
-2, the capacitance under the 100mA charging or discharging current is 1.70Fcm
-2, the capacitance conservation rate still can reach 82% under the situation of 50 times of charging current raisings.Volumetric capacitance amount under the 2mA charging or discharging current has reached 520Fcm
-3Here electrochemically modified graphite electrode not only is used for energy storage, also play the effect of collector, so the electrode material internal resistance reduces greatly.By up to ten thousand times cyclic polarization test, the capacitance conservation rate still can reach 80%, shows that it has the higher stable performance.
Embodiment 2:
The cylinder that this electrode is made with native graphite is a graphite body 1, its surface area 10cm
2, its integral body is exposed to 1M HClO
4In the aqueous solution, carry out circular treatment between electrochemical oxidation and the electrochemical reduction by the constant potential pulse: at first constant anode potential is 2.5V
Vs.SCE, anodized 500s; The constant cathode current potential is 0.2V more afterwards
Vs.SCE, cathodic reduction place 400s; The above-mentioned processing procedure that circulates at last 8 times has obtained thickness and is 180 microns active layer 2.Very similar among the microstructure characteristic of this active layer 2 and the embodiment 1 is not repeated at this.Above-mentioned graphite electrode through electrochemical modification is placed 2.3M H
2SO
4In the aqueous solution, adopt the three-electrode system of standard to carry out the electrochemical capacitor evaluating characteristics.Capacitance under the 2mA charging or discharging current is 9.2Fcm
-2, the capacitance under the 100mA charging or discharging current is 8.29Fcm
-2, the capacitance conservation rate still can reach 90% under the situation of 50 times of charging current raisings.Volumetric capacitance amount under the 2mA charging or discharging current has reached 511Fcm
-3
Embodiment 3:
This electrode is a graphite body 1 with the electrographite net, its surface area 3cm
2, its integral body is exposed in the 3M NaOH aqueous solution, carry out circular treatment between electrochemical oxidation and the electrochemical reduction by the constant potential pulse: at first constant anode potential is 1.0V
Vs.SCE, anodized 1000s; The constant cathode current potential is-1.0V more afterwards
Vs.SCE, cathodic reduction place 300s; The above-mentioned processing procedure that circulates at last 10 times has obtained thickness and is 100 microns active layer 2.Very similar among the microstructure characteristic of this active layer 2 and the embodiment 1 is not repeated at this.Above-mentioned graphite electrode through electrochemical modification is placed 2.3M H
2SO
4In the aqueous solution, adopt the three-electrode system of standard to carry out the electrochemical capacitor evaluating characteristics.Capacitance under the 2mA charging or discharging current is 3.8Fcm
-2, the capacitance under the 100mA charging or discharging current is 3.04Fcm
-2, the capacitance conservation rate still can reach 80% under the situation of 50 times of charging current raisings.Volumetric capacitance amount under the 2mA charging or discharging current has reached 380Fcm
-3
Embodiment 4:
This electrode is a graphite body 1 with manual inflation graphite, with its surface area 1cm
2Local surfaces be exposed in the 1M KCl aqueous solution, carry out circular treatment between electrochemical oxidation and the electrochemical reduction by the constant current pulse: at first constant anodic current density is 50mA/cm
2, anodic oxidation place 300s; The constant cathode current density is-50mA/cm more afterwards
2, 100s is handled in cathodic reduction; The above-mentioned processing procedure that circulates at last 3 times has obtained thickness and is 8 microns active layer 2.Very similar among the microstructure characteristic of this active layer 2 and the embodiment 1 is not repeated at this.Above-mentioned graphite electrode through electrochemical modification is placed 2.3M H
2SO
4In the aqueous solution, adopt the three-electrode system of standard to carry out the electrochemical capacitor evaluating characteristics.Capacitance under the 2mA charging or discharging current is 0.2Fcm
-2, the capacitance under the 100mA charging or discharging current is 0.16Fcm
-2, the capacitance conservation rate still can reach 80% under the situation of 50 times of charging current raisings.Volumetric capacitance amount under the 2mA charging or discharging current has reached 250Fcm
-3
Embodiment 5:
This electrode is a graphite body 1 with the native graphite fibrofelt, its surface area 10cm
2, its integral body is exposed in the 6M aqueous formic acid, carry out circular treatment between electrochemical oxidation and the electrochemical reduction by the constant current pulse: at first constant anodic current density is 5mA/cm
2, anodized 3600s; The constant cathode current density is-10mA/cm more afterwards
2, 1000s is handled in cathodic reduction; The above-mentioned processing procedure that circulates 4 times passes through mechanical hot pressing at last again, obtained thickness and be 5 microns active layer 2.Very similar among the microstructure characteristic of this active layer 2 and the embodiment 1 is not repeated at this.Above-mentioned graphite electrode through electrochemical modification is placed 2.3M H
2SO
4In the aqueous solution, adopt the three-electrode system of standard to carry out the electrochemical capacitor evaluating characteristics.Capacitance under the 2mA charging or discharging current is 0.1Fcm
-2, the capacitance under the 100mA charging or discharging current is 0.07Fcm
-2, capacitance conservation rate 70% under the situation of 50 times of charging current raisings.Volumetric capacitance amount under the 2mA charging or discharging current has reached 200Fcm
-3
The foregoing description result shows that the electrode material that electrochemically modified graphite electrode is used for electrochemical capacitor has high-energy, high power density and high speed charge-discharge performance.In addition, also have advantages such as high conductivity, low material cost, high stability, long-life, manufacturing is simple and easy and production cost is low.
The above; it only is preferred embodiment of the present invention; can not be understood that it is that the present invention is done any pro forma restriction; any one of ordinary skill in the art; in not breaking through the scope of technical scheme disclosed in this invention; the equivalence techniques displacement that the part that the innovative technology that utilizes the present invention to disclose has been done is changed or modified all drops in protection scope of the present invention.
Utilize of the present invention electrochemically modified graphite electrode to be used for electrochemical capacitor although only introduced here, can not be understood that it is that the present invention is done restriction in the following application.Utilize that electrochemically modified graphite electrode of the present invention can be widely used in also that electrochemical hydrogen storage, electrochemical sensor, lithium ion battery, Ni-MH battery, fuel cell, water electrolysis, sewage disposal, organic substance electricity are synthetic, use as electrode material in the Applied Electrochemistry engineerings such as electrodialysis and electro-deposition.
Claims (9)
1. electrochemically modified graphite electrode, it is made of graphite body, active layer, and described graphite body is made up of the graphite block body material, and active layer is attached on the graphite body surface; It is characterized in that: described active layer (2) is directly by graphite body (1) product through obtaining after the circular treatment between electrochemical oxidation and the electrochemical reduction in having the aqueous electrolyte solution of ionic conductivity.
2. electrochemically modified graphite electrode according to claim 1 is characterized in that: described circular treatment between electrochemical oxidation and electrochemical reduction, and it comprises:
In having the aqueous electrolyte solution of ionic conductivity, at first more than oxygen evolution potential, graphite body (1) is carried out the anode electrochemical oxidation with electrode potential is constant, and then below oxygen evolution potential, graphite body (1) is carried out electrochemical cathode reduction with electrode potential is constant, repeat operation, meet the demands until the active layer that obtains (2) thickness; Perhaps
In having the aqueous electrolyte solution of ionic conductivity, at first constant current density is 1～300mA/cm
2Graphite body (1) is carried out the anode electrochemical oxidation, and then constant current density is-1-300mA/cm
2Graphite body (1) is carried out electrochemical cathode reduction, repeat operation, meet the demands until the thickness of the active layer that obtains (2).
3. electrochemically modified graphite electrode according to claim 2 is characterized in that: described aqueous electrolyte solution with ionic conductivity is to be dissolved in the electrolyte solution that forms in the water by inorganic compound or organic compound.
4. electrochemically modified graphite electrode according to claim 3 is characterized in that: described aqueous electrolyte solution is H
2SO
4Or HClO
4The aqueous solution.
5. electrochemically modified graphite electrode according to claim 4 is characterized in that: described graphite body (1) is made up of native graphite or electrographite block materials; And to carrying out mechanical compaction attached to the lip-deep active layer of graphite body (1) (2).
6. electrochemically modified graphite electrode according to claim 5 is characterized in that: on the part or all of surface of described active layer (2) attached to graphite body (1).
7. electrochemically modified graphite electrode according to claim 1 is characterized in that: the crystallite sheet structural group that described active layer (2) contains oxygen-content active functional group by the surface becomes its coarse, porous.
8. electrochemically modified graphite electrode according to claim 7 is characterized in that: the thickness of described active layer (2) is 1 micron～200 microns.
9. electrochemically modified graphite electrode according to claim 5 is characterized in that: described graphite body (1) is thread, netted, sheet, column, spherical or irregularly shaped graphite block body material, and its hexagonal and rhomboidal crystal are than being any number.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894683A (en) * | 2010-06-24 | 2010-11-24 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| US9683314B2 (en) | 2013-02-19 | 2017-06-20 | Ocean University Of China | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| US20170346069A1 (en) * | 2015-02-20 | 2017-11-30 | Kaneka Corporation | Graphite film, laminate film, method for producing same, and electrode material |
| CN117535684A (en) * | 2024-01-09 | 2024-02-09 | 天津大学 | Electrode assembly of electrolytic cell, electrolytic cell device for producing hydrogen peroxide and application thereof |
-
2009
- 2009-10-26 CN CN200910229452A patent/CN101697323A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894683A (en) * | 2010-06-24 | 2010-11-24 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| CN101894683B (en) * | 2010-06-24 | 2012-06-13 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| US9683314B2 (en) | 2013-02-19 | 2017-06-20 | Ocean University Of China | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| US20170346069A1 (en) * | 2015-02-20 | 2017-11-30 | Kaneka Corporation | Graphite film, laminate film, method for producing same, and electrode material |
| US10535863B2 (en) * | 2015-02-20 | 2020-01-14 | Kaneka Corporation | Graphite film, laminate film, method for producing same, and electrode material |
| CN117535684A (en) * | 2024-01-09 | 2024-02-09 | 天津大学 | Electrode assembly of electrolytic cell, electrolytic cell device for producing hydrogen peroxide and application thereof |
| CN117535684B (en) * | 2024-01-09 | 2024-04-19 | 天津大学 | Electrode assembly of electrolytic cell, electrolytic cell device for producing hydrogen peroxide and application thereof |
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Application publication date: 20100421 |