CN101244820B - Activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor - Google Patents
Activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor Download PDFInfo
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- CN101244820B CN101244820B CN200810009983XA CN200810009983A CN101244820B CN 101244820 B CN101244820 B CN 101244820B CN 200810009983X A CN200810009983X A CN 200810009983XA CN 200810009983 A CN200810009983 A CN 200810009983A CN 101244820 B CN101244820 B CN 101244820B
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
The invention relates to an activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor. In activated carbon obtained by subjecting a carbonaceous material to an activation treatment, the overall content of alkali metals is set at 100 ppm or less, or the overall content of heavy metals is set at 20 ppm or less and the overall content of alkali metals is set at 200 ppm or less. In cases where such activated carbon is used as a raw material in electronic devices, the formation of dendrites by the reductive deposition of alkali metals or heavy metals tends not to occur, so that problems such as short-circuiting or the like tend not to arise, and a good rate of self-discharge retention is shown.
Description
The application be that July 3, application number in 2003 are 03818421.4 the applying date, denomination of invention divides an application for the patent application of " gac, its manufacture method, polarizability electrode and double-layer capacitor ".
Technical field
The present invention relates to gac, its manufacture method, polarizability electrode and double-layer capacitor.Gac of the present invention, except utilized its absorption property, the purposes such as washing, purification, recovery, gas storage, decolouring, also towards the electrical part of the low feature of the content that has made full use of basic metal and/or heavy metal, be particularly suitable as the electrode that secondary cell and double-layer capacitor are used.
Background technology
Gac is widely used in foodstuffs industry, chemical industry, medicine industry, other various industry, can list water purification particularly and make purposes, purifying air purposes, solvent recuperation purposes, stack desulfurization denitrogenation purposes, decolouring purposes, goes up purposes such as water treatment, water treatment down, the processing of dung urine, industry draining processing, purified sugar purposes, nuclear energy purposes (radiation material absorption), methane occlusion, hydrogen occlusion.These purposes are mainly to utilize the absorption property of gac, in addition, have also pointed to the gac as the sorbent material of absorption property excellence.
On the other hand, double-layer capacitor such as power supply, accessory power supply is gazed in support in recent years, is conceived to gac and extensively carries out with the exploitation of the performance of electrode as double-layer capacitor.The double-layer capacitor that gac is used as the polarizability electrode is because the electrostatic capacity excellence, therefore with person in electronics development, the also sharp increase of demand of electrical part electrode purposes etc.And, recently, except the miniaturization of existing storage backup power source etc., also carrying out the exploitation of the large vol goods that in accessory power supply such as motor, use etc.
Utilizing in the field of these gacs, field at related food, pharmaceuticals manufacturing, water purification, electron device, wish to obtain the gac of alkali-free metal or heavy metal, therefore the past is in the manufacture method of gac, carbonaceous material is carried out gas activation processing or reagent activation treatment, for example use alkali metal hydroxide as the activation auxiliary the alkali activation treatment after, in order to remove basic metal or heavy metal, generally use the process of strong acid washings such as hydrochloric acid, nitric acid, sulfuric acid from the activation treatment thing.
; as above-mentioned; situation about will use as the electrode materials of starting material, for example nonaqueous electrolytic solution secondary battery and the double-layer capacitor of electron device with the gac of strong acid washing; because the branch crystallization phenomenon due to the reduction of basic metal or heavy metal is separated out; cause faults such as short circuit; also because alkalimetal ion and heavy metal ion; there is problem because of self discharge electrostatic capacity conservation rate step-down (following will abbreviate the self discharge conservation rate as because of the electrostatic capacity conservation rate of self discharge) in easily self discharge.
Particularly use the situation of the alkali activation treatment of alkali metal hydroxide as the activation auxiliary, because alkali metal hydroxide is a strong oxidizing property, therefore when activation treatment, cause the corrosion of the heating furnace body of activation usefulness, in the activation treatment thing, sneak into heavy metal, promptly use the such activation treatment thing of hydrochloric acid and nitric acid washing, it is also very difficult to make the gac of having removed heavy metal fully, has this problem.When the gac that will sneak into heavy metal uses as the starting material of the polarizability electrode of electron device, for example double-layer capacitor, as described above, because the reduction of heavy metal is separated out, on the dividing plate of double-layer capacitor, form the heavy metal particles of branch crystallization, occur in the problem of boring a hole on the dividing plate etc., cause the fault of short circuit etc. sometimes.In addition, the basic metal that derives from the alkali metal hydroxide that uses as activator remains in the gac sometimes, when such gac is used as the starting material of the polarizability electrode of double-layer capacitor, also exist the electric leakage rheology big, charging efficiency reduces, the degenerate problem of (in other words, self discharge conservation rate step-down) of energy efficiency.
For example, proposed in the Te Kaiping 1-241811 communique with below the Fe 200ppm, below the Cr10ppm, below the Ni 10ppm, below the Na 200ppm, below the Cl 300ppm, the gac of ash content below 0.5% be as the double-layer capacitor of polarizability electrode, and record: metal ingredient is sneaked in the manufacturing process of gac, and the stripping of this metal ingredient becomes the reason of the long-term reliability reduction of double-layer capacitor., though the stripping of record metal ingredient becomes the reason that the long-term reliability of double-layer capacitor reduces,, how to suppress the not record of content of metal about in order to realize the double-layer capacitor of reliability.
In addition, open to disclose in the 2002-43190 communique the spy and can adopt the alkali activation method, the polarizability electrode active carbon of the double-layer capacitor of making by water, acid solution, alkaline solution washing after activation has been put down in writing by reducing the discharge of Ni amount decreasing., only lower the Ni amount and can not constitute double-layer capacitor with desired performance.
Therefore, the object of the invention is, be provided at when using as the starting material of electron device, branch crystallization phenomenon due to not taking place to separate out by the reduction of basic metal or heavy metal, be difficult for causing faults such as short circuit, also demonstrate high self discharge conservation rate, be fit to the gac of the purposes of relevant electron device.
Summary of the invention
The inventor finds, it is too much that above-mentioned the problems of the prior art result from the total content of the basic metal that contains in the gac and/or heavy metal, therefore for above-mentioned problem does not take place, it is effective that the total content of the basic metal of gac and/or heavy metal is adjusted into below the specific numerical value.In addition, the inventor finds, the too much reason of the total content of basic metal and/or heavy metal results from gac: with strong acid detergent active charcoal (perhaps activation treatment thing) time, will be with gac affinity height, the remaining heavy metal of the lower form with basic metal salinity and/or oxyhydroxide etc. of the solubleness of water (for example nickel hydroxide, copper hydroxide, zinc hydroxide etc.) is removed from gac be difficult, the more amount of basic metal and/or such heavy metal remains in the gac.In addition, the inventor finds: (i) by with carbonic acid the basic metal in the gac being formed carbonate, make the affinity reduction of basic metal and gac, improve water-solublely, can remove basic metal thus; (ii), make the affinity reduction of heavy metal and gac, improve water-solublely, can remove heavy metal thus by adopting alkaline matter that the heavy metal in the gac is formed coordination compound; (iii), can remove heavy metal by with the acidic aqueous solution washing activation treatment thing that contains oxygenant; Secondly, (iv), can remove basic metal (oxyhydroxide, carbonated etc.) during with hot wash effectively, in addition,, can remove basic metal (oxyhydroxide etc.) in excellent in efficiency ground by with hot salt acid elution with the situation ratio that washs the activation treatment thing with normal-temperature water.The inventor has finished the present invention based on these knowledge opinions.
That is, the 1st the invention provides a kind of gac, it is characterized in that, is activation treatment carbonaceous material and the gac that obtains, and alkali-metal total content is below the 100ppm.In addition, the 1st the invention provides a kind of manufacture method of gac, it is characterized in that, and the activation treatment carbonaceous material, the activation treatment thing liquid scrubbing that contains carbonic acid with obtaining obtains gac thus.
The 2nd the invention provides a kind of gac, it is characterized in that, is activation treatment carbonaceous material and the gac that obtains, and the total content of heavy metal is below the 20ppm.In addition, the 2nd the invention provides a kind of manufacture method of gac, it is characterized in that, and the activation treatment carbonaceous material, the activation treatment thing liquid scrubbing that contains alkaline matter with obtaining obtains gac thus.
The 3rd the invention provides a kind of gac, it is characterized in that, be that the carbonaceous material in the 2nd invention is specific for easy greying carbonaceous material, with activation treatment specific be the alkali activation treatment, improve the invention of invention effect more, be the easy greying carbonaceous material of alkali activation treatment and the gac that obtains, the total content of heavy metal is below the 20ppm, and alkali-metal content is below the 200ppm.In addition, the 3rd the invention provides a kind of manufacture method of gac, it is characterized in that, the easy greying carbonaceous material of alkali activation treatment washs the activation treatment thing that obtains with the acidic aqueous solution that contains oxygenant, obtain gac thus.In addition, the 3rd the present invention also provides a kind of manufacture method of gac, it is characterized in that, the easy greying carbonaceous material of alkali activation treatment, the activation treatment thing that obtains is washed in proper order with hot water, hot hydrochloric acid and water and by this, perhaps wash in proper order, perhaps wash in proper order, obtain gac thus with hot water, Soda Ash Light 99.2min., hot hydrochloric acid, ammoniacal liquor, hot hydrochloric acid and hot water and by this with hot water, Soda Ash Light 99.2min., hot hydrochloric acid, ammoniacal liquor and hot water and by this.
In addition, the 4th the invention provides by the the 1st, the 2nd and the 3rd gac of the present invention and tackiness agent and conductive material mix and polarizability electrode that is shaped and the double-layer capacitor that has used this polarizability electrode at least.
The simple declaration of accompanying drawing
Fig. 1 is the cross section sketch map of an example of expression double-layer capacitor of the present invention.
The preferred plan that carries out an invention
The 1st the present invention at first is described.
The 1st gac of the present invention is an activation treatment carbonaceous material and obtaining.At this, gac of the present invention, alkali-metal total content are below the 100ppm.This be because, when alkali-metal total content surpasses 100ppm, when gac is used as the starting material of electron device, cause the branch crystallization of separating out the metal that causes by reduction, cause faults such as short circuit, cause that the electrostatic capacity conservation rate of metal ion reduces.
In the 1st the present invention, the basic metal class as containing in gac lists lithium, sodium, potassium, caesium.Usually and since content many be sodium and/or potassium, the content of therefore controlling them becomes important.In addition, basic metal also has with the situation that metal alkali compound form exists in gac, but exists with forms such as oxide compound, oxyhydroxide, muriates usually.
Alkali metal content in the gac can be measured by atomic absorption analysis.
As the basic metal total content that makes the 1st gac of the present invention is method below the 100ppm, list:, but preferably list with repetitive scrubbings such as ion exchanged water and strongly acidic aqueous solutions: be suitable for described later, being the manufacture method of the gac of the present invention of feature with the liquid scrubbing that contains carbonic acid.
Raw material as the carbonaceous material that in the 1st the present invention, uses, if become the material of gac by carbonization and/or activation, then be not particularly limited, for example list synthetic raw materials such as natural materials such as mineral system, kapok, artificial silk, phenol, vinylformic acid, vinylon such as department of botany, peat, mud coal, brown coal, brown charcoal, bituminous coal, hard coal, coke, coal tar, coal-tar pitch, petroleum distillation residue, petroleum pitch such as fruit shells (charcoal) such as timber, sawdust, coconut husk, walnut shell, fruit and seed (charcoal), xylogen.
As activation treatment, do not limit applicable existing known gas activation facture and reagent activation treatment method especially.
More than the 1st of explanation the gac of the present invention adopts the 1st gac manufacture method of the present invention of following explanation and can more preferably make.
That is, the 1st gac manufacture method of the present invention is the activation treatment carbonaceous material, the activation treatment thing that obtains is used contained the liquid scrubbing (carbonic acid carrying out washing treatment) of carbonic acid, thereby obtain process of active carbon.By carbonic acid carrying out washing treatment activation treatment thing, wherein contained basic metal becomes water-soluble high alkaline carbonate, therefore can make the alkali metal component that remains in gac below 100ppm.
As " liquid that contains carbonic acid " that in the carbonic acid carrying out washing treatment, uses, preferred Soda Ash Light 99.2min..The concentration of carbonic acid does not limit especially in the Soda Ash Light 99.2min., normally 0.1 weight %-10 weight %.
In addition, the consumption of " liquid that contains carbonic acid " in the carbonic acid carrying out washing treatment is not restriction especially also, in practicality, with respect to activation treatment thing 1 weight part that will wash, be preferably the 1-100 weight part, when particularly considering operability, removal basic metal efficient, more preferably the 2-50 weight part is preferably the 5-20 weight part especially.
Temperature during the carbonic acid carrying out washing treatment is restriction especially, but when too high, the carbonate concentration in " liquid that contains carbonic acid " reduces, it is too low to remove basic metal efficient, cross alkali-metal removal efficient reduction on speed of response when hanging down, therefore be preferably 0-50 ℃, more preferably 0-45 ℃.
In addition, the number of times of the usefulness in the carbonic acid carrying out washing treatment " liquid that contains carbonic acid " washing activation treatment thing is restriction especially, but corresponding to remain on the gac the basic metal amount and as the alkali metal concn level of purpose, normally 1-3 time.
The not restriction especially of pressure of the usefulness in the carbonic acid carrying out washing treatment " liquid that contains carbonic acid " washing activation treatment thing, but be necessary on washing device, to be provided with special impressed pressure device when too high, therefore be preferably under the normal atmosphere～1MPa, more preferably under the normal atmosphere～pressure of 0.5MPa.
As described above, after (carbonic acid carrying out washing treatment) obtain gac with " liquid that contains carbonic acid " washing activation treatment thing, in order to remove the heavy metal (for example nickel, copper, zinc etc.) that trace contains in the gac as required, preferred further hydrochloric acid carrying out washing treatment.
The concentration of the hydrochloric acid that uses when the hydrochloric acid carrying out washing treatment is restriction especially not, so long as the concentration of general commercially available hydrochloric acid is promptly passable.Therefore, the concentration of the hydrochloric acid of use is preferably 0.01-37 weight %, particularly considers operability, security, and more preferably 0.1-30 weight % is preferably 0.5-25 weight % especially.
Implement the restriction especially of temperature of hydrochloric acid carrying out washing treatment, but hydrochloric acid is volatile when too high, often crosses when low that the removal efficient of heavy metal reduces, therefore be preferably 10-90 ℃, more preferably 20-90 ℃ scope.
In addition, the number of times of hydrochloric acid carrying out washing treatment is restriction especially, also depends on the basic metal amount that remains on the gac and as the alkali metal concn level of purpose, normally 1-3 time.
The hydrochloric acid carrying out washing treatment gac, preferably then carry out the water purification carrying out washing treatment with distilled water or ion exchanged water.Directly the water purification carrying out washing treatment is not carried out the hydrochloric acid carrying out washing treatment but is carried out the carbonic acid carrying out washing treatment and the gac that obtains yet.
The distilled water that uses when the water purification carrying out washing treatment or the amount of ion exchanged water be restriction especially not, detects less than till the chlorion but preferably wash.Specifically also depend on water purification mode of washing described later, be preferably the 1-10000 weight part with respect to gac 1 weight part usually, consider economy, operability 1-1000 weight part more preferably.
As the water purification mode of washing, list the mode of using the steel basin agitator treating, use strainer in decompression or add the mode that makes liquid communication and wash etc. of depressing.
Gac by obtaining, the gac that further hydrochloric acid carrying out washing treatment and/or water purification carrying out washing treatment is obtained as required with the liquid scrubbing that contains carbonic acid, dry under heating and/or decompression, become the gac of drying regime.
In the 1st gac manufacture method of the present invention, can as required before activation treatment, carry out the carbonizing treatment (for example handling) of ordinary method corresponding to the carbonaceous material kind 400-800 ℃ of destructive distillation.
In the 1st manufacture method of the present invention, the activation treatment carbonaceous material, but those treatment processs do not limit applicable existing known gas activation facture or reagent activation treatment method especially.
For example, as the gas activation facture, can list and to have used water vapour, carbonic acid gas, oxygen, propane burning vent gas, their activating treatment process of mixed gas etc., as reagent activation treatment method, can list the activating treatment process that has used reagent such as zinc chloride, calcium chloride, phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide.Particularly in the situation of using potassium hydroxide, sodium hydroxide as the common alkali activation treatment of reagent, the activation auxiliary uses alkali metal hydroxide, therefore easy residual alkali-metal tendency in gac is arranged, therefore when carrying out common alkali activation treatment, can preferably be suitable for the 1st manufacture method of the present invention.
The following describes the 2nd the present invention.
The 2nd gac of the present invention, the activation treatment carbonaceous material obtains, and is that the heavy metal total content is the following gac of 20ppm.This be because, when the heavy metal total content surpasses 20ppm, when gac is used as the starting material of electron device, generation is separated out the branch crystallization phenomenon that causes by the reduction of heavy metal, causes faults such as short circuit, and the self discharge conservation rate reduces, when for example when water purification is made, using in addition as sorbing material, in the water purification that obtains, though be denier, continuous stripping heavy metal.
In the 2nd the present invention, the heavy metal class as containing in gac lists nickel, copper, zinc, iron, silver etc.Wherein, what content was many usually is nickel, copper, zinc, iron, and the content of controlling them becomes important.Be controlled to especially preferably that nickel: 8ppm is following, copper: 1ppm following, zinc: 1ppm is following, iron: 0.3ppm is following, silver-colored: below the 0.1ppm.
Heavy metal content in the gac can be measured by inductively coupled plasma spectrometry analysis (ICP).
As the method for heavy metal total content below 20ppm that makes the 2nd gac of the present invention, list:, but preferably list with repetitive scrubbings such as ion exchanged water and strongly acidic aqueous solutions: be suitable for described later, being the manufacture method of the gac of the present invention of feature with the liquid scrubbing that contains alkaline matter.
As the raw material of the carbonaceous material that in the 2nd the present invention, uses, with in the 1st the present invention, illustrate identical.
As activation treatment, do not limit applicable existing known gas activation facture and reagent activation treatment method especially.
More than the 2nd of explanation the gac of the present invention adopts the 2nd gac manufacture method of the present invention of following explanation and can more preferably make.
That is, the 2nd gac manufacture method of the present invention is gas activation processing or reagent activation treatment carbonaceous material, and the activation treatment thing liquid scrubbing (alkaline washing processing) that contains alkaline matter with obtaining obtains process of active carbon thus.Handle the activation treatment thing by alkaline washing, wherein contained heavy metal becomes water-soluble high coordination compound, therefore can make the heavy metal that remains in gac below 20ppm.
" liquid that contains alkaline matter " as using in alkaline washing is handled lists: will preferred ammonia, organic amine, volatile salt or their the water-soluble aqueous solution such as mixture as alkaline matter.At this, as alkaline matter, from gac, to remove the viewpoint of the easness of alkaline matter, preferred ammonia, organic amine or their mixture.As organic amine, list methylamine, ethylamine, propyl group amine, dimethyl amine, diethylamide, dipropylamine, Trimethylamine, triethylamine etc.
In addition, the alkaline matter concentration in " liquid that contains alkaline matter " does not limit especially, normally 0.1 weight %-10 weight %.
In addition, the consumption of " liquid that contains alkaline matter " during alkaline washing is handled is not restriction especially also, in practicality, with respect to activation treatment thing 1 weight part that will wash, be preferably the 1-100 weight part, when particularly considering operability, removal basic metal efficient, more preferably the 2-50 weight part is preferably the 5-20 weight part especially.
Temperature when alkaline washing is handled is restriction especially, but alkaline matter crosses when low easily from " liquid that contains alkaline matter " volatilization that the removal efficient of heavy metal reduces on speed of response when too high, therefore is preferably 10-60 ℃, more preferably 20-50 ℃.
In addition, the restriction especially of number of times of usefulness " liquid that contains alkaline matter " the washing activation treatment thing during alkaline washing is handled, but corresponding to remain on the gac the heavy metal amount and as the heavy metal concentration level of purpose, normally 1-3 time.
The not restriction especially of pressure of usefulness " liquid that contains alkaline matter " the washing activation treatment thing during alkaline washing is handled, but be necessary on washing device, to be provided with special impressed pressure device when too high, therefore be preferably under the normal atmosphere～1MPa, more preferably under the normal atmosphere～pressure of 0.5MPa.
As described above, after usefulness " liquid that contains alkaline matter " washing activation treatment thing (alkaline washing processing) obtains gac,, preferably further use the salt acid elution in order to remove alkaline matter as required.
The concentration of the hydrochloric acid that uses when the hydrochloric acid carrying out washing treatment is restriction especially not, so long as the concentration of general commercially available hydrochloric acid is promptly passable.Therefore, the concentration of the hydrochloric acid of use is preferably 0.01-37 weight %, particularly considers operability, security, and more preferably 0.1-30 weight % is preferably 0.5-25 weight % especially.
Implement the restriction especially of temperature of hydrochloric acid carrying out washing treatment, but hydrochloric acid is volatile when too high, often crosses when low that the removal efficient of heavy metal reduces, therefore be preferably 10-90 ℃, more preferably 20-90 ℃ scope.
In addition, the number of times of hydrochloric acid carrying out washing treatment is restriction especially not, also depends on the kind and the concentration level that remain in the alkaline matter on the gac, normally 1-3 time.
The hydrochloric acid carrying out washing treatment gac, then preferably carry out the water purification carrying out washing treatment with distilled water or ion exchanged water.Directly the water purification carrying out washing treatment is not carried out the gac that the hydrochloric acid carrying out washing treatment obtains with regard to carrying out alkaline washing to handle yet.
The distilled water that uses when the water purification carrying out washing treatment or the amount of ion exchanged water be restriction especially not, detects less than till chlorion or the alkaline matter but preferably wash.Specifically also depend on water purification mode of washing described later, be preferably the 1-10000 weight part with respect to gac 1 weight part usually, consider economy, operability 1-1000 weight part more preferably.
As the water purification mode of washing, list the mode of using the steel basin agitator treating, use strainer in decompression or add the mode that makes liquid communication and wash etc. of depressing.
Gac by obtaining, the gac that further hydrochloric acid carrying out washing treatment and/or water purification carrying out washing treatment is obtained as required with the liquid scrubbing that contains alkaline matter, dry under heating and/or decompression, become the gac of drying regime.
In the 2nd gac manufacture method of the present invention, can as required before activation treatment, carry out the carbonizing treatment (for example handling) of ordinary method corresponding to the carbonaceous material kind 400-800 ℃ of destructive distillation.
The easy greying carbonaceous material of gas activation processing or reagent activation treatment in the 2nd manufacture method of the present invention, but those treatment processs do not limit gas activation facture among applicable the 1st the present invention or reagent activation treatment method especially.
For example, handle as gas activation, can list and to have used water vapour, carbonic acid gas, oxygen, propane burning vent gas, their activating treatment process of mixed gas etc., as the reagent activation treatment, can list the activating treatment process that has used reagent such as zinc chloride, calcium chloride, phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide.Particularly in the situation of using potassium hydroxide, sodium hydroxide as the common alkali activation treatment of reagent, the activation auxiliary uses alkali metal hydroxide, therefore easy residual alkali-metal tendency in gac is arranged, therefore when carrying out common alkali activation treatment, can preferably be suitable for the 2nd manufacture method of the present invention.
The following describes the 3rd the present invention.
The 3rd gac of the present invention, be that the carbonaceous material in the 2nd invention is specific for easy greying carbonaceous material, with activation treatment specific be the alkali activation treatment, be the gac that improves the invention effect more, be the easy greying carbonaceous material of alkali activation treatment and the gac that obtains.At this, the 3rd its heavy metal content of gac of the present invention is below the 20ppm.This be because, when heavy metal content surpassed 20ppm, when gac was used as the starting material of electron device, heavy metal was separated out in electron device, causes faults such as short circuit, the self discharge conservation rate reduces.In addition, in the 3rd gac of the present invention, alkali metal content is below the 200ppm further.This be because, when alkali metal content surpassed 200ppm, the electric leakage rheology was big, charging efficiency reduces, energy efficiency degenerates, self discharge conservation rate step-down.
In the 3rd gac of the present invention, the heavy metal class as containing in gac lists nickel, iron, zinc, tin, copper, silver etc.Wherein, usually content is many is nickel, iron and zinc at least a kind, and the content of controlling them becomes important.Be controlled to especially preferably that nickel: 8ppm is following, iron: 0.3ppm following, zinc: below the 0.3ppm.In addition, preferably control copper below 1ppm, preferred control silver is below 0.1ppm.
Heavy metal content in the gac as described above, can be measured by inductively coupled plasma spectrometry analysis (ICP).
In addition, in the 3rd the present invention, the basic metal class as containing in gac lists lithium, sodium, potassium, caesium.Usually and since content many be sodium and/or potassium, the content of therefore controlling them becomes important.In addition, basic metal also has with the situation that metal alkali compound form exists in gac, but exists with forms such as oxide compound, oxyhydroxide, muriate, carbonated usually.
Alkali metal content in the gac can be measured by atomic absorption analysis as described above.
In the 3rd gac of the present invention, the carbon component that more preferably adopts the hydrocarbon of the mixture etc. of benzene,toluene,xylene, mesitylene, these materials to extract is below the 0.2 weight %.When carbon component surpasses 0.2 weight %, become and cause that the gac pore stops up, electrostatic capacity reduces, the reason of weather resistance deterioration, not preferred.At this,, can example illustrate: with respect to gac 1 weight part, use hydrocarbon 5-50 weight part, after the mixing of the temperature more than the boiling point of hydrocarbon is stirred more than 1 hour, filter out gac, carry out these a series of operations of drying as extracting operation.The calculating of the carbon component that is extracted by hydrocarbon is undertaken by the weight of relatively extracting before and after the operation.The carbon component that is also preferably extracted by hydrocarbon in the 1st and the 2nd gac of the present invention is below the 0.2 weight %.
As the heavy metal total content that makes the 3rd gac of the present invention is method below the 20ppm, list:, but preferably list with repetitive scrubbings such as ion exchanged water and strongly acidic aqueous solutions: be suitable for described later, being the manufacture method of the gac of the present invention of feature with the acidic aqueous solution washing that contains oxygenant.Be below the 20ppm particularly as not only making the heavy metal content of the 3rd gac of the present invention, also making alkali metal content simultaneously is the following method of 200ppm, list with repetitive scrubbings such as ion exchanged water about room temperature and strongly acidic aqueous solutions, but preferably list: be suitable for described later, with the manufacture method that is the gac of the present invention of feature with hot water and hot salt acid elution at least.
As the carbonaceous material that in the 3rd the present invention, uses, listing the easy greying carbonaceous material that forms gac by activation, is the carbonaceous material of starting raw material with petroleum coke, petroleum pitch, synthetic mesophase asphalt phase, polyvinyl chloride, polyimide, polyacrylonitrile etc. for example.Wherein, can preferably use the mesophase pitch based carbon fiber.As the mesophase pitch based carbon fiber, consider from the aspect of excellent electric conductivity, preferably contain optical anisotropy this based carbon fiber that 50 volume % are above mutually, preferred 80 volume % are above.
At this, the mesophase pitch based carbon fiber is after synthetic mesophase asphalt phase, any a kind of material of deriving from the mesophase pitch of oil or coal are carried out melt-spinning, to carry out not melt processed, recarbonize handle and carbon fiber.The electrostatic capacity of the operability the when operability of consideration melt-spinning, productivity, activation, the gac that obtains is preferably used the synthetic mesophase asphalt phase.At this, not melt processed be for keep melt-spinning the state of pitch fibers form under activation (heating) processing and essential processing, normally with melt-spinning pitch fibers in the oxidizing atmospheres such as air that contain 1-20.9 weight % oxygen, be heated to processing about 100-350 ℃.With the carbonizing treatment that melt processed not continues, be by in inert gas atmosphere, heating not the melt processed thing with the not processing of melt processed thing carbonization.Heating temperature is crossed when low, because the carbon crystal structure is undeveloped, therefore becomes overactivation, and the low excessively tendency of density is arranged, and when too high, the crystallization of carbon fiber is excessive, is difficult to activate, and therefore is preferably 500-1000 ℃, more preferably 600-900 ℃.
In the 3rd the present invention, carbonaceous material is preferably pulverized the back and is used, but for as the activation auxiliary alkali metal hydroxide mix well, carry out alkali activation treatment described later effectively, greatly enhancing most of preferred use long axis direction is the following carbonaceous materials of 500 μ m, more preferably uses the following carbonaceous material of 200 μ m.The maximum length of long axis direction, for example electron micrograph of the crushed material of the carbonaceous material by observing random extraction and can confirming.Pulverizing can adopt known pulverizers such as conical breaker, double roll crusher, disk crusher, gyratory crusher, ball mill, centrifugal roller mill, ring roll mill, ball-bearing mill, three-roll mill to carry out.
As the alkali activation treatment among the 3rd the present invention, list and use the existing known alkali activation treatment of alkali metal hydroxide as the activation auxiliary.
More than Shuo Ming the 3rd gac of the present invention can adopt the 3rd gac manufacture method of the present invention of following explanation more preferably to make.
That is, the 3rd gac manufacture method of the present invention is the easy greying carbonaceous material of alkali activation treatment, the activation treatment thing that obtains is washed with the acidic aqueous solution that contains oxygenant, thereby obtain process of active carbon.By washing with the acidic aqueous solution that contains oxygenant, heavy metal contained in the activation treatment thing is transferred in the washings.Therefore can make the content of the heavy metal that remains in gac below 20ppm.Its reason is indeterminate, but by washing with the acidic aqueous solution that contains oxygenant, contained heavy metal becomes easily water-soluble ionic compound in the activation treatment thing, therefore is washed removal.
In the 3rd manufacture method of the present invention, at first the easy greying carbonaceous material of alkali activation treatment obtains the activation treatment thing.At this, the alkali activation treatment is that easy greying carbonaceous material is mixed by ordinary method with alkali metal hydroxide as the activation auxiliary, comes activatory by the mixture that obtains of heating under inert gas atmospheres such as nitrogen.
Alkali metal hydroxide as the activation auxiliary lists sodium hydroxide, potassium hydroxide, lithium hydroxide etc., wherein, in order to obtain showing the gac of big electrostatic capacity, preferably uses sodium hydroxide or potassium hydroxide.These materials can be used alone, but also also mix together.In addition, also can use with the form of the powder morphology or the dense thick aqueous solution.
About the consumption of alkali metal hydroxide with respect to easy greying carbonaceous material, when alkali metal hydroxide is very few, activation treatment is difficult to evenly and carries out fully, deviation takes place in character as the gac of purpose sometimes, served as on the contrary for a long time, not only uneconomical, also possible overactivity, though the tendency that has the electrostatic capacity of unit weight to increase, the electrostatic capacity that unit volume takes place reduces.Therefore, alkali metal hydroxide with respect to carbonaceous material 100 weight parts, is considered economy, operability, security with respect to the consumption of carbonaceous material, is preferably the 30-500 weight part, is preferably the 50-300 weight part especially.
About in order to activate the Heating temperature condition with the easy greying carbonaceous material of alkali metal hydroxide blended, when Heating temperature is crossed when low, activate insufficient, when too high, the gac that obtains carries out crystallization, when the electrode as double-layer capacitor uses, not only electrostatic capacity reduces, the danger that the basic metal that is produced by the alkali metal hydroxide that uses brings increases, and, even in activation furnace, use with the nickel that basic metal had high patience base material as pedestal, also encourage the grain boundary corrosion that the crystallization with base material (stove material) metal accompanies, heavy metal particles sneaking in gac enlarges markedly.Therefore, as for activatory Heating temperature (activation temperature), be preferably 400 ℃-1000 ℃, more preferably 450 ℃-900 ℃, the economy of heat is followed in consideration, is preferably 470 ℃-850 ℃ especially.
As the heat-up rate till activation temperature, consider the crystal boundary crystallization problem of aforesaid activating container, avoid rapid intensification, preferred 0.2 ℃-10 ℃/minute, more preferably 0.3-8 ℃/minute.
The hold-time of activation temperature, so long as fully being transmitted to the time of gac, heat do not limit, is generally 30 minutes especially-5 hours, consider when keeping, to carry out crystallization, preferred 45 minutes-4 hours.
The speed of cooling that begins from activation temperature is important in the crystal boundary crystallization meaning of avoiding activating body of heater.That is, sharply cooling encourages metallic crystalization, therefore is preferably 1-50 ℃/minute as speed of cooling, more preferably 1-30 ℃/minute.
Secondly, in the 3rd manufacture method of the present invention, will wash (oxygenant carrying out washing treatment) with " acidic aqueous solution that contains oxygenant " by the activation treatment thing that the easy greying carbonaceous material of alkali activation treatment obtains.By oxygenant carrying out washing treatment activation treatment thing, can remove from oxidized when using alkali metal hydroxide to carry out the alkali activation treatment and be subjected to the heavy metal that the body of heater of grain boundary corrosion is sneaked into from the activation treatment thing with producing effect.
Preferably before carrying out the oxygenant carrying out washing treatment, wash the activation treatment thing with warm water in advance.By this washing, can remove the alkali metal hydroxide that remains in the activation treatment thing, alkaline carbonate etc.That is, when carrying out the oxygenant carrying out washing treatment, by Warm Wash wash away may from the activation treatment thing remove can with the material of acidic aqueous solution reaction, can reduce the consumption of " acidic aqueous solution that contains oxygenant " thus.The temperature and the consumption of warm water do not limit, but are generally 30 ℃-90 ℃ temperature, are preferably the 3-50 weight part with respect to activation treatment thing 1 weight part, consider the volumetric efficiency of detersive efficiency, reactor, more preferably use the 5-45 weight part.
In the 3rd manufacture method of the present invention, oxygenant as being used for " containing the acidic aqueous solution of oxygenant " can list organo-peroxides such as organic peracids such as inorganic oxidizer such as hydrogen peroxide, persulfuric acid, peracetic acid, peroxyformic acid, t-butyl hydroperoxide.Wherein, consider the stability in acidic aqueous solution, obtaining property, security, to the influence of carbon material, most preferably hydrogen peroxide.
Oxidant concentration in like this " acidic aqueous solution that contains oxygenant ", 0.1-10 weight % preferably considers economy, to the influence of carbon material, is more preferably 0.2-5 weight %, especially preferably 0.5-2 weight %.
Acidic aqueous solution as " acidic aqueous solution that contains oxygenant " can use inorganic acid aqueous solutions such as aqueous solutions of organic acids such as formic acid, acetate, hydrochloric acid, sulfuric acid, nitric acid.Among these acid, from reducing the effect of remaining amount of metal, mineral acids such as preferred hydrochloric acid, sulfuric acid, nitric acid are considered acid group remaining in carbonaceous material, most preferably use hydrochloric acid.In addition, the concentration 0.1-5 equivalent preferably of acid is considered the removal of metal, to the influence of carbon material, is more preferably the 0.2-4 equivalent, considers economy, operability, especially preferably 0.5-3 equivalent.
As " acidic aqueous solution that contains oxygenant " consumption with respect to the activation treatment thing, activation treatment thing 1 weight part with respect to washing is preferably the 3-50 weight part, considers operability, economy, more preferably the 4-30 weight part is preferably the 5-20 weight part especially.
Wash temperature during the oxygenant carrying out washing treatment is restriction especially not, but when too high, not only cause peroxide breakdown as oxygenant, also can carry out the oxidation of carbonaceous material, serve as when hanging down, the tendency that has oxidant in effect to reduce, therefore the carbonate concentration that is preferably in " liquid that contains carbonic acid " reduces, remove basic metal efficient and reduce, therefore be preferably 0 ℃-50 ℃, more preferably 0 ℃-45 ℃.
The number of times of oxygenant carrying out washing treatment operation is restriction especially, also depends on the amount of metal that remains in the activation treatment thing and as the residual metal level level of the gac of purpose, but carries out 1-3 time scope mostly usually.
The not restriction especially of pressure of the usefulness in the oxygenant carrying out washing treatment " acidic aqueous solution that contains oxygenant " washing activation treatment thing, but need special device when too high, therefore be generally under the normal atmosphere～pressure of 1MPa, be preferably under the normal atmosphere～pressure of 0.5MPa.
By being implemented the oxide compound carrying out washing treatment, the activation treatment thing obtains gac, preferably the gac that further obtains with distilled water or ion-exchange water washing (water purification carrying out washing treatment).The distilled water that uses when the water purification carrying out washing treatment or the amount of ion exchanged water be restriction especially not, can wash till can not detecting chlorion.The mode that also depends on washing, but be preferably 1 weight part-10000 weight part with respect to gac 1 weight part usually, consider economy, operability, more preferably 1 weight part-1000 weight part.
As the water purification mode of washing, list the mode of using the steel basin agitator treating, use strainer in decompression or add the mode that makes liquid communication and wash etc. of depressing.
By the gac that obtains with " acidic aqueous solution that contains oxygenant " washing, the gac that further hydrochloric acid carrying out washing treatment and/or water purification carrying out washing treatment is obtained as required, dry under heating and/or decompression, become the gac of drying regime.
In addition, the 3rd the present invention, the total content of heavy metal is below the 20ppm as being fit to make not only, and alkali-metal total content is the manufacture method of the following gac of 200ppm, provide such manufacture method: the easy greying carbonaceous material of alkali activation treatment, 1. the activation treatment thing that obtains is washed in proper order with hot water, hot hydrochloric acid and water and by this, perhaps 2. wash in proper order with hot water, Soda Ash Light 99.2min., hot hydrochloric acid, ammoniacal liquor and hot water and by this, perhaps 3. wash in proper order, obtain gac thus with hot water, Soda Ash Light 99.2min., hot hydrochloric acid, ammoniacal liquor, hot hydrochloric acid and hot water and by this.
At this, alkali metal compounds such as alkali metal hydroxide, alkaline carbonate are to the solubleness of hot water, and the solubleness of comparison water especially improves.In addition, the reactivity that heavy metal is compared the hydrochloric acid about room temperature to the reactivity of hot hydrochloric acid especially improves, and therefore by with hot salt acid elution activation treatment thing, can easily make heavy metal contained in the activation treatment thing become easily water-soluble muriate.Therefore, by with the hot wash of activation treatment thing,, can make the content that remains in the heavy metal in the gac below 20ppm, and make alkali-metal content below 200ppm then with hot salt acid elution.In addition, in manufacture method of the present invention, because water and the hydrochloric acid can heated scrub used get final product, therefore in addition big change just can be with high yield rate manufacturing gac to existing alkali activation treatment facility.
In the above-mentioned order 1. in the 3rd manufacture method of the present invention, the activation treatment thing that will obtain by alkali activation treatment carbonaceous material is at first used hot wash (hot wash), with hot salt acid elution (hot salt acid elution), washes (water washing) then with water.At this, by hot wash, can excellent in efficiency ground remove the alkali metal hydroxide that remains in the activation treatment thing, alkaline carbonate etc.In addition, after the hot wash then in hot salt acid elution, can remove can with the material of acidic aqueous solution reaction, not only improve the effect of hot hydrochloric acid, can also reduce the consumption of acidic aqueous solution.The temperature and the consumption of hot water do not limit, but temperature is preferably 30 ℃-95 ℃, and more preferably 60 ℃-90 ℃, its consumption is preferably the 3-50 weight part with respect to activation treatment thing 1 weight part that should wash, consider the volumetric efficiency of detersive efficiency, reactor, more preferably use the 5-45 weight part.
Secondly with hot wash the activation treatment thing with hot salt acid elution.As concentration of hydrochloric acid, thereby cross when low owing to cause that the passive stateization of heavy metal can reduce removal efficient, handled gac is chlorinated when too high, therefore preferably at the 0.1-3 equivalent, more preferably implement in the normal scope of 0.5-2.5.In addition, use temperature as hot hydrochloric acid, cross the removal step-down of the heavy metal of partial oxidation when hanging down, also promote the passive stateization of the heavy metal of oxyhydroxide, carbonate form, the removal efficient of metal can reduce, and when too high, the hydrochloric acid volatilization is serious, not only the efficient of hydrochloric acid reduces, and it is big that the etching problem of the machine of use also becomes.Therefore, the use temperature of hot hydrochloric acid is preferably 60 ℃-90 ℃ scope.As the amount of hot hydrochloric acid, activation treatment thing 1 weight part with respect to washing is preferably the 3-50 weight part, considers operability, economy, and more preferably the 4-30 weight part is preferably the 5-20 weight part especially.
Next washes the activation treatment thing of having implemented hot wash and hot salt acid elution with water.Obtain gac in view of the above.Kish contained in the water that gac easily is used influences, and therefore preferably uses clean water such as ion exchanged water, distilled water, film permeate water as washing water.The amount of washing water is restriction especially not, can wash till can not detecting chlorion.The mode that also depends on washing, but be 1 weight part-10000 weight part with respect to gac 1 weight part usually, consider economy, operability, use in the scope of 1 weight part-1000 weight part to get final product.
As mode of washing, list the mode of using the steel basin agitator treating, use strainer in decompression or add the mode that makes liquid communication and wash etc. of depressing.
In the 3rd manufacture method of the present invention, the pressure when implementing hot wash, hot salt acid elution, water washing is restriction especially, but needs special device when too high, therefore is generally under the normal atmosphere～pressure of 1MPa, is preferably under the normal atmosphere～pressure of 0.5MPa.
In addition, in the above-mentioned order 2. in the 3rd manufacture method of the present invention, the activation treatment thing that will obtain by alkali activation treatment carbonaceous material, at first use hot wash (hot wash), wash (Soda Ash Light 99.2min. washing) with Soda Ash Light 99.2min., with hot salt acid elution (hot salt acid elution), with ammonia scrubbing (ammonia scrubbing), use hot wash (hot wash) then.With respect to the 1. different point of order is Soda Ash Light 99.2min. washing, ammonia scrubbing, last hot wash.At this, the Soda Ash Light 99.2min. washing operation is with the alkali-metal operation in the carbonate form removal activation treatment thing, can carry out in the same manner with situation about illustrating in the 1st manufacture method of the present invention.
In addition, the ammonia scrubbing operation is the operation of removing the heavy metal in the activation treatment thing with the ammino compound form, can carry out in the same manner with situation about illustrating in the 2nd manufacture method of the present invention.
Last hot wash operation can similarly be carried out with the 1. hot wash operation of order.
In addition, in the above-mentioned order 3. in the 3rd manufacture method of the present invention, the activation treatment thing that will obtain by alkali activation treatment carbonaceous material, at first use hot wash (hot wash), wash (Soda Ash Light 99.2min. washing) with Soda Ash Light 99.2min., with hot salt acid elution (hot salt acid elution), with ammonia scrubbing (ammonia scrubbing), use hot salt acid elution once more, use hot wash (hot wash) then.With respect to 2. the order different points be after ammonia scrubbing, carry out hot salt acid elution once more.
This hot salt acid elution with illustrated the same, by this washing operation, can remove the material that derives from ammonia (residue, metal complex) in the activation treatment thing.
The gac that adopts the 3rd manufacture method of the present invention of above explanation to obtain, dry under heating and/or decompression, become the gac of drying regime.
Above Shuo Ming the the 1st, the 2nd and the 3rd gac of the present invention, particularly useful as the material that is suitable for the polarizability electrode that double-layer capacitor uses.Therefore, the 4th the invention provides the the 1st, the 2nd or the 3rd gac of the present invention and tackiness agent and conductive material mix and polarizability electrode that is shaped and the double-layer capacitor that has used this polarizability electrode at least.
Below since the 4th polarizability electrode of the present invention explanation.
The 4th polarizability electrode of the present invention mixes conductive material such as tackiness agent such as polyvinylidene difluoride (PVDF), tetrafluoroethylene and carbon black at least and is shaped in the the 1st, the 2nd or the 3rd gac of the present invention.By the mixed conductivity material, can reduce electrode resistance, effective to the internal resistance that reduces the polarizability electrode in view of the above.
Make such when being suitable for polarizability electrode that double-layer capacitor uses, the applicable method of knowing usually.For example, conductive materials such as material that commercially available, polyvinylidene difluoride (PVDF), tetrafluoroethylene etc. are known as tackiness agent and carbon black add up to about percentum as required, after mediating attentively, put in the mould press molding.Or rolling, make sheet material, the shape that stamping-out becomes to need can be configured as electrode thus.In addition, also can on current collector, be coated with pug mill, make the coating electrode.When electrode forms, also can use organic compound such as pure and mild N-Methyl pyrrolidone and water equal solvent, dispersion agent, various additive as required.In addition, also can apply heat in the scope of not damaging the invention effect.
More than Shuo Ming polarizability electrode is useful as electrode shown in Fig. 1 (summary sectional view), the 4th double-layer capacitor of the present invention.Each integrant of the electrical condenser of pie graph 1, except using polarizability electrode of the present invention, can be made into the formation same with known double-layer capacitor, for example 1 and 2 expressions comprise the collector component of aluminium etc. among the figure, 3 and 4 expressions comprise the polarizability electrode of gac of the present invention, the dividing plate that 5 expressions are made of polypropylene non-woven fabric, the gasket that 6 expressions are made of polypropylene, polyethylene, polymeric amide, polyamidoimide, polybutene etc., the shell that 7 expressions constitute with base materials such as stainless steels.
In order to bring into play function as double-layer capacitor, be necessary to enclose electrolytic solution in shell 7, described electrolytic solution is to have dissolved known electrolyte solutions such as tetraethyl ammonium Tetrafluoroboric acid ester, tetramethyl-ammonium Tetrafluoroboric acid ester in amides equal solvents such as sulfoxide class, dimethyl formamides such as lactone such as nitriles such as carbonates such as ethylene carbonate, methylcarbonate, diethyl carbonate, Texacar PC, acetonitrile, gamma-butyrolactone, Alpha-Methyl-gamma-butyrolactone, dimethyl sulfoxide (DMSO).
The double-layer capacitor of formation shown in Figure 1 owing to used gac of the present invention, therefore demonstrates high self discharge conservation rate.
Embodiment
Be described more specifically the present invention by the following examples.
Use has the spinning jet of the nozzle slit of 1000 diameter 0.2mm in the seam of wide 2mm, with the residue decomposition of thermal treatment oil and the optical anisotropy pitch melt jet spinning of 285 ℃ of Mettler softening temperatures that obtains, carry out not melt processed and carbonizing treatment, made mesophase asphalt carbon fiber.
At the 300mL that thermometer and stirrer have been installed (milliliter) but glass split flask in to add the maximum length be ground into long axis direction be the mesophase pitch fiber 50g 20 μ m below and be broken into 95% potassium hydroxide 100g below the median size 1mm, with 200mL/ minute circulation nitrogen, stirred under 10rpm on one side on one side.But with oil bath this split flask of heating, 160 ℃ of heated and stirred of temperature were removed thermal source after 1 hour in system, Yi Bian the nitrogen 1 hour of circulating again Yi Bian stir, obtains the granulation thing.The granulation thing is the following size of 20mm.Then, this granulation thing was dewatered with 5 hours till 300 ℃ at the heat-up rate with 2 ℃/minute under the decompression of 1.5Torr.
With the dehydration that obtains granulation thing 24g put into 2 inches the horizontal nickel system reactor that thermometer has been installed, after atmosphere in the nitrogen displacement system, under the nitrogen gas stream that 100mL/ divides, be warmed up to 700 ℃ with 200 ℃/hour.After reaching 700 ℃, kept 1 hour, use 2 hours cool to room temperature thereafter.Make nitrogen circulation by the distilled water bubbler after 1 hour, put among the water 150mL.
After adopting decantation to remove supernatant liquid, add 150mL water again, stir.Adopt decantation to remove supernatant liquid, add Soda Ash Light 99.2min. (carbonate concentration 1 weight %) 100mL and stirring, adopt decantation to remove supernatant liquid at 10 ℃.After carrying out 2 these operations, add 1 equivalent salt sour water 200mL, the neutralization washing re-uses distilled water 3L and washs continuously, removes alkaline metal salt, and drying obtains gac 6.7g.
Comparative examples A 1
Except in embodiment A 1 with the Soda Ash Light 99.2min. washing, by repeating the same operation of other and embodiment A 1, obtain gac.
Except in embodiment A 1, having used carbonaceous material is ground into the resol carbide 50g below the 20 μ m,, obtains gac 5.9g by repeating the same operation of other and embodiment A 1.
Comparative examples A 2
Except in embodiment A 2 with the Soda Ash Light 99.2min. washing, by repeating the same operation of other and embodiment A 2, obtain gac.
(evaluation)
After the gac 100mg separately of the embodiment A 1-A2, the Comparative examples A 1-A2 that obtain then decomposed with perchloric acid 20mL wet type with nitric acid 200mL, use atomic absorption spectrum analysing arrangement (polarisation Zeeman atom extinction photometer Z-5300, (strain) Hitachi system) to measure remaining potassium, sodium metal ingredient.Table 1 is expressed the result who obtains.Also measured about other alkali metal composition (lithium, caesium), but content is below the limit of detection (1ppm).Therefore, the basic metal total content equals the total content of potassium and sodium in fact.
In addition, the gac separately of the embodiment A 1-A2, the Comparative examples A 1-A2 that obtain is ground into median size 5-20 μ m again, make Powdered Activated Carbon, having kneaded comprises the mixture of this Powdered Activated Carbon 80 weight %, conductive carbon 10 weight % and tetrafluoroethylene (teflon (registered trademark) 6J, Mitsui-chemical company of Du Pont) 10 weight %.The pug mill that obtains is configured as the sheet material of thickness 300 μ m by rolling system, use stamping-out device stamping-out to become the circle of diameter 2cm after, decompression 150 ℃ of dryings 4 hours, has been made flaky polarizability electrode down.
With the polarizability electrode that obtains in the glove box below the dew point-80 ℃ as shown in Figure 1 in Stainless Steel Case behind stacked in order collector component, polarizability electrode slice, polypropylene non-woven fabric, polarizability electrode slice, the collector component, make polarizability electrode dipping contain the polypropylene carbonate ester solution of 1 mole tetraethyl ammonium Tetrafluoroboric acid ester, the insulated enclosure pad of the polypropylene system of use, the loam cake and the filleting that cover Stainless Steel Case seal, and have made double-layer capacitor.
About the double-layer capacitor that obtains, use day to put motor system double-layer capacitor evaluating apparatus, at room temperature with average electrode surface area 2mA/cm
2Constant current charge is till final voltage 2.5V, and supplementary charging 30 minutes under low voltage when 2.5V is after supplementary charging finishes, with 2mA/cm
2Carry out constant current discharge, carry out 10 such charge and discharge cycles tests, obtain the initial electrostatic capacity with ordinary method by the discharge curve from 1.2V to 1.0V at that time.Table 1 is expressed the result who obtains.
About having obtained the double-layer capacitor of electrostatic capacity, at room temperature with average electrode surface area 2mA/cm
2Constant current charge till final voltage 2.5V, supplementary charging 30 minutes under low voltage when 2.5V, after charging finishes, the open placement after 50 hours, with 2mA/cm
2Carry out constant current discharge, obtained with ordinary method by the discharge curve from 1.2V to 1.0V at that time and place the back electrostatic capacity, this placement back electrostatic capacity is obtained self discharge conservation rate (%) divided by the initial electrostatic capacity of obtaining earlier.Table 1 is expressed the result who obtains.
Table 1
| Embodiment | Comparative example | |||
| A1 | A2 | A1 | A2 | |
| Na content (ppm) | 6 | 2 | 3 | 4 |
| K content (ppm) | 54 | 84 | 226 | 156 |
| Basic metal total content (ppm) | 60 | 86 | 229 | 160 |
| Initial electrostatic capacity (F/cc) | 28.5 | 17.0 | 28.3 | 17.1 |
| Place back electrostatic capacity (F/cc) | 27.9 | 16.8 | 25.1 | 15.3 |
| Self discharge conservation rate (%) | 97.8 | 98.8 | 88.0 | 89.4 |
Being known by table 1, is the double-layer capacitor that the gac of embodiment A 1 below the 100ppm and embodiment A 2 is made by the basic metal total content, and the self discharge conservation rate demonstrates and approaches 100% value, demonstrates excellent properties as double-layer capacitor.
On the other hand, surpass the double-layer capacitor that the gac of the Comparative examples A 1 of 100ppm and Comparative examples A 2 is made by the basic metal total content, self discharge conservation rate less than 90% is not sufficient performance as double-layer capacitor.
Use has the spinning jet of the nozzle slit of 1000 diameter 0.2mm in the seam of wide 2mm, with the residue decomposition of thermal treatment oil and the optical anisotropy pitch melt jet spinning of 285 ℃ of Mettler softening temperatures that obtains, carry out not melt processed and carbonizing treatment, made mesophase asphalt carbon fiber.
At the 300mL that thermometer and stirrer have been installed (milliliter) but glass split flask in to add the maximum length be ground into long axis direction be the mesophase pitch fiber 50g 20 μ m below and be broken into 95% potassium hydroxide 100g below the median size 1mm, with 200mL/ minute circulation nitrogen, stirred under 10rpm on one side on one side.But with oil bath this split flask of heating, 160 ℃ of heated and stirred of temperature were removed thermal source after 1 hour in system, Yi Bian the nitrogen 1 hour of circulating again Yi Bian stir, obtains the granulation thing.The granulation thing is the following size of 20mm.Then, this granulation thing was dewatered with 5 hours till 300 ℃ at the heat-up rate with 2 ℃/minute under the decompression of 1.5Torr.
With the dehydration that obtains granulation thing 24g put into 2 inches the horizontal nickel system reactor that thermometer has been installed, after atmosphere in the nitrogen displacement system, under the nitrogen gas stream that 100mL/ divides, be warmed up to 700 ℃ with 200 ℃/hour.After reaching 700 ℃, kept 1 hour, use 2 hours cool to room temperature thereafter.Make nitrogen circulation by the distilled water bubbler after 1 hour, put among the water 150mL.
After adopting decantation to remove supernatant liquid, add 150mL water again, stir.Adopt decantation to remove supernatant liquid, add 5% ammoniacal liquor 100mL and stirring, adopt decantation to remove supernatant liquid at 30 ℃.After carrying out 2 these operations, add 1 equivalent salt sour water 200mL, the neutralization washing re-uses distilled water 3L and washs continuously, removes salt, and drying obtains gac 6.4g.
Comparative example B1
Except in Embodiment B 1 not with ammonia scrubbing, by repeating the same operation of other and Embodiment B 1, obtain gac.
Except in Embodiment B 1, having used carbonaceous material is ground into the resol carbide 50g below the 20 μ m,, obtains gac 5.9g by repeating the same operation of other and Embodiment B 1.
Comparative example B2
Except in Embodiment B 2 not with ammonia scrubbing, by repeating the same operation of other and Embodiment B 2, obtain gac.
(evaluation)
After the gac 100mg separately of the Embodiment B 1-B2, the comparative example B1-B2 that obtain then decomposed with perchloric acid 20mL wet type with nitric acid 200mL, use inductively coupled plasma spectrometry analytical equipment (icp analysis device, IRIS AP, Japanese Thermo Electron corporate system) measured the remaining heavy metal content that comprises nickel, copper, zinc and iron.Table 2 is expressed the result who obtains.
In addition, the gac separately of the Embodiment B 1-B2, the comparative example B1-B2 that obtain is ground into median size 5-20 μ m again, make Powdered Activated Carbon, mediated the mixture that comprises this Powdered Activated Carbon 80 weight %, conductive carbon 10 weight % and tetrafluoroethylene (teflon (registered trademark) 6J, Mitsui-chemical company of Du Pont) 10 weight %.The kneaded material that obtains is configured as the sheet material of thickness 300 μ m by rolling system, use stamping-out device stamping-out to become the circle of diameter 2cm after, decompression 150 ℃ of dryings 4 hours, has been made flaky polarizability electrode down.
With the polarizability electrode that obtains in the glove box below the dew point-80 ℃ as shown in Figure 1 in Stainless Steel Case behind stacked in order collector component, polarizability electrode slice, polypropylene non-woven fabric, polarizability electrode slice, the collector component, make polarizability electrode dipping contain the polypropylene carbonate ester solution of 1 mole tetraethyl ammonium Tetrafluoroboric acid ester, the insulated enclosure pad of the polypropylene system of use, the loam cake and the filleting that cover Stainless Steel Case seal, and have made double-layer capacitor.
About the double-layer capacitor that obtains, use day to put motor system double-layer capacitor evaluating apparatus, at room temperature with average electrode surface area 2mA/cm
2Constant current charge is till final voltage 2.5V, and supplementary charging 30 minutes under low voltage when 2.5V is after supplementary charging finishes, with 2mA/cm
2Carry out constant current discharge, carry out 10 such charge and discharge cycles tests, obtain the initial electrostatic capacity with ordinary method by the discharge curve from 1.2V to 1.0V at that time.Table 2 is expressed the result who obtains.
About having obtained the double-layer capacitor of electrostatic capacity, at room temperature with average electrode surface area 2mA/cm
2Constant current charge till final voltage 2.5V, supplementary charging 30 minutes under low voltage when 2.5V, after charging finishes, the open placement after 50 hours, with 2mA/cm
2Carry out constant current discharge, obtained with ordinary method by the discharge curve from 1.2V to 1.0V at that time and place the back electrostatic capacity, this placement back electrostatic capacity is obtained self discharge conservation rate (%) divided by the initial electrostatic capacity of obtaining earlier.Table 2 is expressed the result who obtains.
Table 2
| Embodiment | Comparative example | |||
| B1 | B2 | B1 | B2 | |
| Ni content (ppm) | 6 | 27 | 4 | 31 |
| Cu content (ppm) | 0.1 | 0.3 | 1.1 | 1.04 |
| Zn content (ppm) | 0.05 | 0.07 | 0.09 | 0.12 |
| Fe content (ppm) | 0.12 | 0.18 | 0.41 | 0.47 |
| Heavy metal total content (ppm) | 8.5 | 4.9 | 30.1 | 33.2 |
| Initial electrostatic capacity (F/cc) | 33.2 | 31.5 | 23.5 | 23.4 |
| Place back electrostatic capacity (F/cc) | 30.4 | 27.7 | 22.1 | 18.4 |
| Self discharge conservation rate (%) | 97.4 | 91.1 | 87.9 | 78.6 |
Being known by table 2, is the double-layer capacitor that the gac of Embodiment B 1 below the 20ppm and Embodiment B 2 is made by total metal content, and the self discharge conservation rate demonstrates the value 90% or more, demonstrates the performance of excellence as double-layer capacitor.
On the other hand, surpass the double-layer capacitor that the gac of the comparative example B1 of 20ppm and comparative example B2 is made by the heavy metal total content, self discharge conservation rate less than 90% does not possess as the sufficient performance of double-layer capacitor.
Use has the spinning jet of the nozzle slit of 1000 diameter 0.2mm in the seam of wide 2mm, with the residue decomposition of thermal treatment oil and the optical anisotropy pitch melt jet spinning of 285 ℃ of Mettler softening temperatures that obtains, carry out not melt processed and carbonizing treatment, made mesophase asphalt carbon fiber.
The mesophase asphalt carbon fiber that obtains is ground into 0.02mm, in the crushed material 100g that obtains, adds 95% potassium hydroxide 200g and mix, mixture is packed in the nickel system reaction tubes of 4 inches of diameters that nitrogen ingress pipe and waste pipe have been installed.This reaction tubes is placed in the Heat Emission Pipe in Cylindrical Furnace, and on one side with 100 milliliters (mL)/minute circulation nitrogen, one side is warmed up to 700 ℃ with 3.3 ℃/minute heat-up rate, keeps 1 hour in this temperature.Thereafter, the speed cool to room temperature with 5 ℃/minute obtains the activation treatment thing.
The activation treatment thing that obtains is filled in the pressure filter of diameter 3cm, uses 60 ℃ of 2 liters of ion exchanged waters (L), under the pressure of 0.2MPa, wash.Then, use the 1 equivalent hydrochloric acid 2L that contains 1 weight % hydrogen peroxide, under 40 ℃ of temperature, pressure 0.2MPa, wash.Use the 4L ion exchanged water, 60 ℃ of temperature, pressure 0.2MPa washing down obtains gac.With the gac that obtains 100 ℃ of heating 3 hours, then heating 8 hours under the pressure of 0.1MPa, drying under reduced pressure obtains the gac of drying regime thus.
As the acidic aqueous solution that will use, use the 1 equivalent hydrochloric acid that contains 2 weight % hydrogen peroxide, in addition, adopt with Embodiment C 1 identical operations and made gac.
Comparative example C1
As the acidic aqueous solution that will use, used the hydrochloric acid that does not contain hydrogen peroxide, in addition, adopt with Embodiment C 1 identical operations and made gac.
(evaluation)
After the gac 0.2g separately of the Embodiment C 1-C2, the comparative example C1 that obtain then decomposed with perchloric acid 20mL wet type with nitric acid 240mL, use inductively coupled plasma spectrometry analytical equipment (icp analysis device, IRIS AP, Japanese Thermo Electron corporate system) measured the remaining heavy metal content that comprises nickel, iron and zinc.Table 3 is expressed the result.
In addition, mediated and comprised Embodiment C 1-C2 and the 81 weight % of gac separately, conductive carbon black (hexin is black, Denki Kagaku Kogyo kabushiki) the 9 weight % of comparative example C1 and the mixture of tetrafluoroethylene (teflon (registered trademark) 6J, Mitsui-chemical company of Du Pont) 10 weight % that obtains.The kneaded material that obtains is configured as the sheet material of thickness 200 μ m by rolling system, use stamping-out device stamping-out to become the circle of diameter 11mm after, decompression has been made flaky polarizability electrode down 200 ℃ of dryings.
With the polarizability electrode that obtains in the glove box below the dew point-80 ℃ as shown in Figure 1 in Stainless Steel Case behind stacked in order collector component, polarizability electrode slice, polypropylene non-woven fabric, polarizability electrode slice, the collector component, make polarizability electrode dipping contain the polypropylene carbonate ester solution of 1 mole tetraethyl ammonium Tetrafluoroboric acid ester, the insulated enclosure pad of the polypropylene system of use, the loam cake and the filleting that cover Stainless Steel Case seal, and have made double-layer capacitor.
About the double-layer capacitor that obtains, use day to put motor system double-layer capacitor evaluating apparatus, at room temperature with average electrode surface area 4mA/cm
2Constant current charge then, reaches 1mA/cm with the constant voltage supplementary charging of 2.7V up to charging current till final voltage 2.7V
2, after supplementary charging finishes, with 2mA/cm
2Carry out constant current discharge, obtain the initial electrostatic capacity.After carrying out 50 these charge and discharge cycles, more at room temperature with average electrode surface area 4mA/cm
2Constant current charge then, reaches 1mA/cm with the constant voltage supplementary charging of 2.7V up to charging current till final voltage 2.7V
2, after supplementary charging finishes, the open placement after 50 hours, with 2mA/cm
2Carry out constant current discharge, obtain and place the back electrostatic capacity.Then, place the back electrostatic capacity, obtain self discharge conservation rate (%) thus divided by the initial electrostatic capacity of obtaining earlier.Table 3 is expressed the result who obtains.
Table 3
| Embodiment | Comparative example | ||
| C1 | C2 | C1 | |
| Ni content (ppm) | 8 | 6 | 22 |
| Fe content (ppm) | 0.3 | 0.2 | 0.6 |
| Zn content (ppm) | 0.1 | 0.3 | 0.8 |
| Heavy metal total content (ppm) | 10.3 | 8.6 | 23.6 |
| Initial electrostatic capacity (F/cc) | 33.2 | 33.7 | 32.6 |
| Place back electrostatic capacity (F/cc) | 32.3 | 32.4 | 22.3 |
| Self discharge conservation rate (%) | 97.2 | 96.1 | 68.4 |
Being known by table 3, is the double-layer capacitor that the gac of Embodiment C 1 below the 20ppm and Embodiment C 2 is made by the heavy metal total content, and the self discharge conservation rate demonstrates the value 90% or more, demonstrates the performance of excellence as double-layer capacitor.
On the other hand, by the double-layer capacitor that the heavy metal total content is made above the gac of the comparative example C1 of 20ppm, self discharge conservation rate less than 90% does not possess as the sufficient performance of double-layer capacitor.
Embodiment D1
Use has the spinning jet of the nozzle slit of 1000 diameter 0.2mm in the seam of wide 2mm, with the residue decomposition of thermal treatment oil and the optical anisotropy pitch melt jet spinning of 285 ℃ of Mettler softening temperatures that obtains, carry out not melt processed and carbonizing treatment, made mesophase asphalt carbon fiber (Petoka Materials system).
The mesophase asphalt carbon fiber that obtains is ground into 0.02mm, in the crushed material 100g that obtains, adds 95% potassium hydroxide 200g and mix, mixture is packed in the nickel system reaction tubes of 4 inches of diameters that nitrogen ingress pipe and waste pipe have been installed.This reaction tubes is placed in the Heat Emission Pipe in Cylindrical Furnace, and on one side with 100 milliliters (mL)/minute circulation nitrogen, one side is warmed up to 700 ℃ with 3.3 ℃/minute heat-up rate, keeps 1 hour in this temperature.Thereafter, the speed cool to room temperature with 5 ℃/minute obtains the activation treatment thing.
The activation treatment thing that obtains is filled in the pressure filter of diameter 3cm, uses 80 ℃ of 2 liters of ion exchanged waters (L), under the pressure of 0.2MPa, wash.Then, use 80 ℃ 1 equivalent hydrochloric acid 2L, under pressure 0.2MPa, wash.Re-use the 4L ion exchanged water, under 60 ℃ of temperature, pressure 0.2MPa, wash, obtain gac.With the gac that obtains 100 ℃ of heating 3 hours, then heating 8 hours under the pressure of 0.1MPa, drying under reduced pressure obtains the gac of drying regime thus.
Embodiment D2
Except replacement 1 equivalent hydrochloric acid in embodiment D1 uses 2 equivalent hydrochloric acid, made gac by other and embodiment D1 identical operations.
Embodiment D3
Except in embodiment D1, changing 80 ℃ of ion exchanged waters into 1L from 2L, made gac by other and embodiment D1 identical operations.
Except in embodiment D1, adopting down 80 ℃ 1 equivalent hydrochloric acid washs, made gac by other and embodiment D1 identical operations at 20 ℃.
Except replacement 1 equivalent hydrochloric acid in embodiment D1 uses 4 equivalent hydrochloric acid, made gac by other and embodiment D1 identical operations.
Except in embodiment D1, carrying out having made gac by other and embodiment D1 identical operations 80 ℃ the ion-exchange water washing under 20 ℃.
(evaluation)
After the gac 0.2g separately of the embodiment D1-D3, the Comparative Example D 1-D3 that obtain then decomposed with perchloric acid 20mL wet type with nitric acid 240mL, use inductively coupled plasma spectrometry analytical equipment (icp analysis device, IRIS AP, Japan Thermo Electron corporate system) measures the remaining heavy metal content that comprises nickel, also used atomic absorption spectrum analysing arrangement (polarisation Zeeman atom extinction photometer Z-5300, (strain) Hitachi system) to measure the remaining alkali metal content that comprises the potassium metal.Table 4 is expressed the result.
In addition, mediated the mixture of the 81 weight % of gac separately that comprise the embodiment D1-D3, the Comparative Example D 1-D3 that obtain, conductive carbon black (hexin is black, Denki Kagaku Kogyo kabushiki) 9 weight % and tetrafluoroethylene (teflon (registered trademark) 6J, Mitsui-chemical company of Du Pont) 10 weight %.The kneaded material that obtains is configured as the sheet material of thickness 200 μ m by rolling system, use stamping-out device stamping-out to become the circle of diameter 11mm after, decompression has been made flaky polarizability electrode down 200 ℃ of dryings.
With the polarizability electrode that obtains in the glove box below the dew point-80 ℃ as shown in Figure 1 in Stainless Steel Case behind stacked in order collector component, polarizability electrode slice, polypropylene non-woven fabric, polarizability electrode slice, the collector component, make polarizability electrode dipping contain the polypropylene carbonate ester solution of 1 mole tetraethyl ammonium Tetrafluoroboric acid ester, the insulated enclosure pad of the polypropylene system of use, the loam cake and the filleting that cover Stainless Steel Case seal, and have made double-layer capacitor.
About the double-layer capacitor that obtains, use day to put motor system double-layer capacitor evaluating apparatus, at room temperature with average electrode surface area 4mA/cm
2Constant current charge then, reaches 1mA/cm with the constant voltage supplementary charging of 2.7V up to charging current till final voltage 2.7V
2, after supplementary charging finishes, with 2mA/cm
2Carry out constant current discharge, obtain the initial electrostatic capacity.After carrying out 50 these charge and discharge cycles, more at room temperature with average electrode surface area 4mA/cm
2Constant current charge reaches 1mA/cm with the constant voltage supplementary charging of 2.7V up to charging current till final voltage 2.7V
2, after supplementary charging finishes, the open placement after 50 hours, with 2mA/cm
2Carry out constant current discharge, obtain the electrostatic capacity after the placement.Then, the electrostatic capacity after the placement is obtained self discharge conservation rate (%) thus divided by the initial electrostatic capacity of obtaining earlier.Table 4 is expressed the result who obtains.
Table 4
| Embodiment | Comparative example | |||||
| D1 | D2 | D3 | D1 | D2 | D3 | |
| Alkali metal content (ppm) | 83 | 92 | 182 | 183 | 124 | 273 |
| K content (ppm) | 82 | 91 | 181 | 183 | 123 | 272 |
| Heavy metal total content (ppm) | 14 | 13 | 13 | 21 | 22 | 18 |
| Ni content (ppm) | 7 | 4 | 11 | 18 | 21 | 12 |
| Fe content (ppm) | 6 | 7 | 1 | 1 | 0.5 | 4 |
| Cu content (ppm) | 0.1 | 0.1 | 0.1 | 0.2 | 0.1 | 0.2 |
| Zn content (ppm) | 0.1 | 0.1 | 0.1 | 0.15 | 0.08 | 0.25 |
| Ag content (ppm) | 0.05 | 0.02 | 0.06 | 0.09 | 0.02 | 0.07 |
| Initial electrostatic capacity (F/cc) | 33.2 | 33.7 | 33.4 | 32.8 | 34.2 | 33.1 |
| Place back electrostatic capacity (F/cc) | 32.1 | 32.7 | 31.8 | 22.5 | 19.6 | 26.8 |
| Self discharge conservation rate (%) | 96.6 | 97.0 | 95.3 | 68.5 | 57.3 | 81.2 |
Know by table 4, by the heavy metal total content is below the 20ppm and alkali metal content is the double-layer capacitor that the gac of the embodiment D1-D3 below the 200ppm is made, the self discharge conservation rate demonstrates the value more than 90%, demonstrates excellent performance as double-layer capacitor.
On the other hand, do not surpass 200ppm but heavy metal content surpasses the Comparative Example D 1-D2 of 20ppm and heavy metal content does not surpass 20ppm but alkali metal content surpasses the double-layer capacitor that the gac of the Comparative Example D 3 of 200ppm is made by alkali metal content, self discharge conservation rate less than 90% does not possess as the sufficient performance of double-layer capacitor.
Embodiment D4
To be filled into the activation treatment thing that embodiment D1 similarly obtains in the pressure filter of diameter 3cm,, under the pressure of 0.2MPa, wash with 2 liters of 80 ℃ of ion exchanged waters (L).Then, the Soda Ash Light 99.2min. 1L with 20 ℃ carbonate concentration 1 weight % washs under the pressure of 0.2MPa.Then, wash under the pressure of 0.2MPa with 80 ℃ 1 equivalent salt sour water 2L.Then, wash under the pressure of 0.2MPa with 30 ℃, 5% ammoniacal liquor 0.5L.At last, the ion exchanged water 3L washing with 60 ℃ obtains gac by drying.
Embodiment D5
To be filled into the activation treatment thing that embodiment D1 similarly obtains in the pressure filter of diameter 3cm, 2 liters (L) wash under the pressure of 0.2MPa with 80 ℃ of ion exchanged waters.Then, the Soda Ash Light 99.2min. 1L with 20 ℃ carbonate concentration 1 weight % washs under the pressure of 0.2MPa.Then, wash under the pressure of 0.2MPa with 80 ℃ 1 equivalent salt sour water 2L.Then, wash under the pressure of 0.2MPa with 30 ℃, 5% ammoniacal liquor 0.5L, and then under the pressure of 0.2MPa, wash with 80 ℃ 1 equivalent salt sour water 0.5L, last, wash with 60 ℃ ion exchanged water 3L, obtain gac by drying.
(evaluation)
After the gac 0.2g separately of the embodiment D4 that obtains and D5 then decomposed with perchloric acid 20mL wet type with nitric acid 240 milliliters (mL), use inductively coupled plasma spectrometry analytical equipment (icp analysis device, IRIS AP, Japan Thermo Electron corporate system) measures the remaining heavy metal content that comprises nickel, also used atomic absorption spectrum analysing arrangement (polarisation Zeeman atom extinction photometer Z-5300, (strain) Hitachi system) to measure the remaining alkali metal content that comprises the potassium metal.Table 5 is expressed the result.
In addition, use the embodiment D4 obtain and the gac separately of D5, similarly make double-layer capacitor, estimated initial electrostatic capacity (F/cc), electrostatic capacity (F/cc), self discharge conservation rate (%) after placing with embodiment D1.Table 5 is expressed the result who obtains.
In addition, be determined at the extraction carbon component of the gac that obtains among embodiment D4 and the D5 as shown below like that.Promptly possess stirrer, condenser, and thermometer and the glass there-necked flask of having put into the 1.5L of 700g toluene be placed in the gac 70g that embodiment D4 or D5 obtain, stirring makes it to disperse, 115 ℃ of reflux 1 hour, carried out the extraction of carbon component and handled.Behind the mixed solution cool to room temperature, the filtration treatment mixed solution heats the gac that filters out 3 hours at 100 ℃, then obtains the gac of drying regime by drying under reduced pressure (pressure 0.1MPa, heating 8 hours).By relatively extracting the gac weight before and after handling, obtain the extraction loss of weight.Table 5 is expressed the result who obtains.
Table 5
| Embodiment | ||
| D4 | D5 | |
| Alkali metal content (ppm) | 30 | 29 |
| K content (ppm) | 26 | 28 |
| Heavy metal total content (ppm) | 0.4 | 0.3 |
| Ni content (ppm) | 0.2 | 0.2 |
| Fe content (ppm) | Below the limit of detection | Below the limit of detection |
| Cu content (ppm) | Below the limit of detection | Below the limit of detection |
| Zn content (ppm) | Below the limit of detection | Below the limit of detection |
| Ag content (ppm) | Below the limit of detection | Below the limit of detection |
| Extract carbon component (wt%) | 0.09 | 0.08 |
| Initial electrostatic capacity (F/cc) | 34.1 | 34.3 |
| Place back electrostatic capacity (F/cc) | 33.6 | 34.1 |
| Self discharge conservation rate (%) | 98.5 | 99.7 |
When the washing sequence (hot water, hot hydrochloric acid and water) that replaces in embodiment D1-D3, carrying out, when washing by the order of " hot water, Soda Ash Light 99.2min., ammoniacal liquor, and hot water " (embodiment D4) or " hot water, Soda Ash Light 99.2min., ammoniacal liquor, hot hydrochloric acid and hot water " (embodiment D5), alkali metal component, the equal content of heavy metal composition reduce greatly, particularly can make the self discharge conservation rate approach 100%.
Industrial applicability
The 1st gac of the present invention, because alkali-metal total content is below the 100ppm, therefore when the starting material as electron device use, be difficult for taking place to separate out the branch crystallization phenomenon that causes, be difficult to cause faults such as short circuit, also demonstrate good self discharge conservation rate by alkali-metal reduction, and, when for example when water purification is made, using, can suppress basic metal stripping in water purification greatly, be suitable for the purposes of food and medicine manufacturing, water purification manufacturing, relevant electron device etc. as adsorption material.
In addition, the 2nd the present invention and the 3rd the present invention, because the total content of heavy metal is below the 20ppm, therefore when the starting material as electron device use, be difficult for taking place to separate out the branch crystallization phenomenon that causes by the reduction of heavy metal, be difficult to cause faults such as short circuit, also demonstrate good self discharge conservation rate.
Particularly in the 3rd gac of the present invention, also having alkali metal content is below the 200ppm, therefore, when the starting material as electron device use, be difficult for taking place to separate out the branch crystallization phenomenon that causes by the reduction of basic metal and heavy metal, therefore be difficult to cause faults such as short circuit, also demonstrate good self discharge conservation rate, be suitable as very much the starting material of electric, the electron device of double-layer capacitor etc.
Claims (4)
1. a gac is characterized in that, is activation treatment carbonaceous material and the gac that obtains, and the total content of heavy metal is below the 20ppm, and this heavy metal is at least a kind of metal that is selected from nickel, copper, zinc and iron, and wherein the content of iron is below the 0.3ppm.
2. gac according to claim 1, the content of nickel is below the 8ppm.
3. gac according to claim 1, the content of zinc is below the 1ppm.
4. gac according to claim 1, the content of copper is below the 1ppm.
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| CN101702379B (en) * | 2009-11-20 | 2012-09-05 | 青岛生物能源与过程研究所 | Method for preparing non-symmetrical electrochemical supercapacitor and electrode materials |
| US8198210B2 (en) * | 2010-05-27 | 2012-06-12 | Corning Incorporated | Halogenated activated carbon materials for high energy density ultracapacitors |
| US20150203356A1 (en) * | 2012-07-26 | 2015-07-23 | Kansai Coke And Chemicals Co., Ltd. | Activated carbon having high active surface area |
| CN104401988B (en) * | 2014-10-23 | 2016-07-13 | 山西新华化工有限责任公司 | The preparation method of low acid-soluble ash/acid-soluble ferrum ature of coal agglomerated activated carbon |
| WO2018140367A1 (en) * | 2017-01-27 | 2018-08-02 | Cabot Corporation | Supercapacitors containing carbon black particles cleaned with an acid |
| KR101948020B1 (en) * | 2017-08-14 | 2019-05-08 | 주식회사 티씨케이 | Method for manufacturing activated carbon for electrode material |
| CN110723733B (en) * | 2018-07-16 | 2021-11-02 | 深圳市环球绿地新材料有限公司 | Super-capacity carbon and preparation method and application thereof |
| CN115744895B (en) * | 2022-11-29 | 2024-07-05 | 广东凯金新能源科技股份有限公司 | Nitrogen-doped multi-carbon coated graphite composite material, composite material and secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6094338A (en) * | 1997-07-09 | 2000-07-25 | Mitsubishi Chemical Corporation | Electric double-layer capacitor |
| CN1334237A (en) * | 2000-07-25 | 2002-02-06 | 可乐丽股份有限公司 | Active carbon and its production method, polarizable electrode and double layer capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6094338A (en) * | 1997-07-09 | 2000-07-25 | Mitsubishi Chemical Corporation | Electric double-layer capacitor |
| CN1334237A (en) * | 2000-07-25 | 2002-02-06 | 可乐丽股份有限公司 | Active carbon and its production method, polarizable electrode and double layer capacitor |
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| Title |
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| JP平1-241811A 1989.09.26 |
| JP特开2002-43189A 2002.02.08 |
| JP特开2002-43190A 2002.02.08 |
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