CN1197929C - Producing carbon paper material functional adhesive using heavy petroleum component - Google Patents

Abstract

The present invention discloses a new technology using heavy petroleum components as functional adhesives of preparation of carbon paper materials, which relates to a preparation technology using heavy petroleum components as functional adhesives to prepare carbon paper materials, more specifically a new method using heavy petroleum components as functional adhesives to replace artificially synthesized macromolecule resin in the process of preparation of electrode diffusion layer carbon paper for proton exchange film fuel batteries. The method is characterized in that heavy petroleum components which are used as adhesives are cheap, the resources are rich, and the process of synthesizing macromolecule resin adhesives is omitted, so the production cost is reduced. The electrochemical performance of carbon paper which is produced by heavy petroleum components used as adhesives is good.

Description

Petroleum fraction is as the Producing carbon paper material functional adhesive of preparation carbon paper material

Refinery coke, petroleum pitch and slurry oil are that the high carbonaceous material of producing in the petroleum refining process is referred to as petroleum fraction.The present invention relates to petroleum fraction and prepare carbon paper material and technology of preparing thereof as Producing carbon paper material functional adhesive, in the used carbon paper materials process of preparation proton exchange membrane fuel cell electrode diffusion layer, replace the novel method of synthetic macromolecule resin specifically as Producing carbon paper material functional adhesive with petroleum fraction.

The electrode of Proton Exchange Membrane Fuel Cells generally is made up of diffusion layer and Catalytic Layer two portions, the goods that are used at present fuel battery diffusion layer both at home and abroad mainly are the carbon paper materials, and added additive such as tackiness agent and hole conditioning agent are closely related in the quality of carbon paper material electrochemical performance and the paper-making process.Common carbon paper material because carbon fiber matter is crisp, cuts off during making beating in copying the system process easily, and no self-bonding force between fiber, therefore needs adding tackiness agent and other fillers to make the carbon paper moulding.Used tackiness agent all was artificial synthetic high molecular resin binder in preparation carbon paper process in the past, and the high molecular resin binder synthesis technique of these synthetic is generally comparatively complicated, and production cost is higher; Particularly the high molecular resin binder of synthetic often adopts toxic substances such as formaldehyde, benzene to do raw material or thinner, very easily causes environmental pollution; Again because the carbon content rate of the macromolecule resin of synthetic is lower, the carbonizing degree of sample and degree of graphitization are also low under identical carbonization condition, so the electric conductivity of sample is also relatively low simultaneously.

The objective of the invention is to use the petroleum fraction of high carbon content rate to replace the macromolecule resin of the synthetic that in the past used as the used Producing carbon paper material functional adhesive of preparation proton exchange membrane fuel cell electrode diffusion layer carbon paper.It is advantageous that petroleum fraction is the byproduct of petrochemical complex, have aboundresources, low price, and carbon content rate height, the carbonizing degree of sample and degree of graphitization are also high under identical carbonization condition, so the electric conductivity of sample is also higher relatively.Therefore particularly petroleum fraction and gasoline, diesel oil etc. have good intermiscibility, available gasoline, diesel oil are made diluting solvent and avoided toxic substance such as use benzene, thereby have reduced in the use pollution to environment.In addition, petroleum fraction not only can be used as the shaping strength that tackiness agent improves carbon paper in preparation carbon paper process, but also can replace the hole conditioning agent of carbon powder material such as gac as carbon paper.Therefore be a kind of tackiness agent of multi-functional effect.

A kind of Producing carbon paper material functional adhesive that is used to prepare proton exchange membrane fuel cell electrode diffusion layer carbon paper provided by the invention, this function tamanori adopts petroleum fraction, and its adhesive consumption is 5-15% (wt).Wherein said oil heavy component comprises petroleum pitch and slurry oil.

The present invention provides a kind of simultaneously and has prepared the method for carbon paper material with petroleum fraction as tackiness agent, comprises the following steps: successively

A. carbon fiber or the carbon dust of selecting carried out activation treatment (activation treatment comprises once activation and re-activation);

B. prepare aqueous dispersant, make the carbon fiber after the activation in aqueous dispersant, disperse making beating then, make beating degree and be 15-30 ° carbon fiber slurries;

C. Mierocrystalline cellulose is disperseed making beating, make beating degree and be 15-30 ° cellulose pulp;

D. carbon fiber slurries, cellulose paper slurries and other auxiliary agents are mixed, add the petroleum fraction tackiness agent of 5-15% (wt), put into stirrer and mix stirring, can obtain the papermaking mixed slurry;

E. the wet papermaking technology is copied the paper moulding with the papermaking mixed slurry routinely;

F makes its typing with moulding sample oxidation pre-treatment, and carbonization then both can get the carbon paper of the present invention's preparation.

This advantage for preparing the method for fuel battery diffusion layer carbon paper is: as the low price of the petroleum fraction of tackiness agent, aboundresources has saved the process of synthetic macromolecule resin tackiness agent.The carbon paper chemical property of producing as tackiness agent with petroleum fraction is good.

The invention provides following example:

Embodiment 1

A. asphalt base carbon fiber is carried out one time activation treatment, activator is selected phosphoric acid.Activator level is 10% of a carbon fiber weight; Chemical activation atmosphere is nitrogen, and activation finishes with distilled water the activator eccysis.

B. the carbon fiber after will once activating is handled through re-activation again, selects iron trichloride to make catalyzer in the re-activation process, and atmosphere is steam atmosphere, and activation finishes and with distilled water catalyst wash removed.

C. the carbon fiber filament weak point is cut to the carbon fiber that length is 10mm;

D. the short carbon fiber of cutting is put into hollander and added dispersion agent and pull an oar.Dispersion agent is a polyoxyethylene.Wherein the dispersion agent add-on be paper heavy 0.5%;

E. wood pulp is carried out mechanical dispersion under suitable beating process condition, make beating degree and be 30 ° paper pulp;

F. at 100 ℃ carbon fiber dispersion liquid and slurries are mixed, add petroleum pitch (one of petroleum fraction) and mix stirring, both can obtain the papermaking mixed slurry;

G. the wet papermaking technology is made required carbon fibre composite paper with the papermaking mixed slurry routinely;

H. the carbon fiber paper that will manufacture paper with pulp out is prepared carbon paper 300 ℃ of oxidations through aftertreatment.

One of embodiment of the invention: in step f, after carbon fiber dispersion liquid and slurries mixing, the amount of the petroleum pitch of adding is 5% of a total amount, obtains the papermaking mixed slurry.

One of embodiment of the invention: in step f, after carbon fiber dispersion liquid and slurries mixing, the amount of the petroleum pitch of adding is 8% of a total amount, obtains the papermaking mixed slurry.

One of embodiment of the invention: in step f, after carbon fiber dispersion liquid and slurries mixing, the amount of the petroleum pitch of adding is 12% of a total amount, obtains the papermaking mixed slurry.

One of embodiment of the invention: in step f, after carbon fiber dispersion liquid and slurries mixing, the amount of the petroleum pitch of adding is 15% of a total amount, obtains the papermaking mixed slurry.

Character to sample of the present invention is tested, and the porosity and the volume resistivity data that obtain are listed in the table 1.

Table 1 carbon paper sample test result

Sample	Petroleum pitch consumption (%)	Carbon paper porosity (%)	Carbon paper volume specific resistance (Ω .cm)
				1#	5	80	0.09
2#	8	76	0.07
				3#	12	70	0.04
4#	15	68	0.02

The invention provides following embodiment 2

Replace petroleum pitch with the petroleum fraction refinery coke, copy paper, aftertreatment by above-mentioned steps, carbon paper character of the present invention is tested, the porosity and the volume resistivity data that obtain are listed in the table 2.

Table 2 carbon paper sample test result

Sample	Refinery coke consumption (%)	Carbon paper porosity (%)	Carbon paper volume specific resistance (Ω .cm)
				1#	5	82	0.08
2#	8	79	0.06
				3#	12	74	0.04
4#	15	70	0.01

The invention provides following embodiment 3

Replace petroleum pitch with the petroleum fraction slurry oil, copy paper, aftertreatment by above-mentioned steps, carbon paper character of the present invention is tested, porosity and volume resistivity data are listed in the table 3.

Table 3 carbon paper sample test result

Sample	Slurry oil consumption (%)	Carbon paper porosity (%)	Carbon paper volume specific resistance (Ω .cm)
				1#	5	81	0.10
2#	8	78	0.06
				3#	12	73	0.03
4#	15	70	0.01

Claims (3)

1. a Producing carbon paper material functional adhesive that is used to prepare proton exchange membrane fuel cell electrode diffusion layer carbon paper is characterized in that, is to adopt petroleum fraction as tackiness agent, and adhesive consumption is 5-15%.

2. Producing carbon paper material functional adhesive according to claim 1 is characterized in that used petroleum fraction comprises petroleum pitch and slurry oil.

3. method of using the described Producing carbon paper material functional adhesive of claim 1 to prepare proton exchange membrane fuel cell electrode diffusion layer carbon paper, its feature is comprising the following steps:

A. carbon fiber or the carbon dust of selecting carried out activation treatment;

B. prepare aqueous dispersant, make the carbon fiber after the activation in aqueous dispersant, disperse making beating then, make beating degree and be 15-30 ° carbon fiber slurries;

C. Mierocrystalline cellulose is disperseed making beating, make beating degree and be 15-30 ° cellulose pulp;

D. carbon fiber slurries, cellulose pulp and other auxiliary agent are mixed, add the petroleum fraction tackiness agent of 5-15%, put into stirrer and mix stirring, can obtain the papermaking mixed slurry;

E. the wet papermaking technology is copied the paper moulding with the papermaking mixed slurry routinely;

F. moulding sample oxidation pre-treatment is made its carbonization then of finalizing the design, can get the carbon paper of the present invention's preparation.