CN107195385B - A kind of conductive carbon pastes, preparation method and application - Google Patents

A kind of conductive carbon pastes, preparation method and application Download PDF

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CN107195385B
CN107195385B CN201710343192.XA CN201710343192A CN107195385B CN 107195385 B CN107195385 B CN 107195385B CN 201710343192 A CN201710343192 A CN 201710343192A CN 107195385 B CN107195385 B CN 107195385B
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CN107195385A (en
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韩宏伟
江沛
李代宇
胡玥
荣耀光
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Huazhong University of Science and Technology
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    • H01—ELECTRIC ELEMENTS
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    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells

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Abstract

The invention discloses a kind of preparation methods of low-temperature conductive carbon slurry, including (1), and suitable carbon black and graphite are mixed ball milling, is uniformly mixed it；(2) appropriate solvent is added in uniformly mixed graphite and carbon black, ball milling makes solvent uniformly be wrapped in graphite and black carbon surface；(3) appropriate organic or inorganic binder and compound containing-COOH or-OH are added to the graphite and black carbon surface of uniformly package solvent, carbon pastes material can be obtained in ball milling.The method of the present invention can be prepared with high conductivity and flexible low temperature carbon pastes, and preparation process is simple and reliable by the technique of optimization.The present invention also provides the applications of the conductive carbon pastes being prepared using above-mentioned preparation method and above-mentioned conductive carbon pastes.

Description

A kind of conductive carbon pastes, preparation method and application
Technical field
The invention belongs to conductive carbon material technical field, more particularly, to a kind of conductive carbon pastes, preparation method and Using.
Background technique
Electrocondution slurry is to be uniformly distributed in the thick slurry formed in organic polymer binder with conductive material particle. With having in the fields such as solar battery, lithium ion battery, supercapacitor, energy catalysis to electrode for electrocondution slurry production Practical application.Electrocondution slurry is as a kind of intermediate products, through certain again after a period of time after silk-screen printing or thin film cladding At a temperature of completion of cure, finally obtain conductive film layer.Conductive carbon pastes are usually by conductive filler (such as metal powder, carbon materials Material, metal oxide etc.), a kind of composite material for constituting of binder, solvent and auxiliary agent.Film forming of the binder as electrocondution slurry Substance, while enhancing the caking property between particle to the mechanical strength and electric conductivity of enhanced film.Solvent makes conductive micro- Grain is evenly dispersed, forms the suspended substance or glue with suitable silk-screen printing or the coating of controllable viscosity and rheology bulk properties Body.Metal powder as conductive filler is usually bronze, silver powder or copper powder, although bronze and silver powder electric conductivity superior chemical Property is stablized, but its price is very expensive, its conductive performance of copper powder is excellent but it is easily oxidized；Metal as conductive filler Oxide, with high electric conductivity, but this metal oxide element with high electric conductivity is rare；Carbon material is either It all can be used as on electric conductivity, chemical stability and production cost and prepare electrocondution slurry.
Dye sensitization too can in the devices such as battery, perovskite solar battery etc. and supercapacitor to electrode often Using noble metals such as expensive platinum, gold as conductive material.If developing simple, high conductivity, hole with manufacture craft Rate is good, low energy consumption, the carbon pastes of good mechanical property can replace expensive metal electrode as electrode material completely.System at present Standby conductive carbon pastes more use graphite, carbon black, acetylene carbon black or nano-carbon material are as conductive filler, ethyl alcohol or pine tar Alcohol etc. is used as solvent, and organic polymer ethyl cellulose or acrylic resin, epoxy resin etc. are used as binder, then pass through ball Grinding process also has using stirring ultrasonic disperse technique, and then rotates and obtain carbon pastes.Electrode material applied to various fields In, it is typically passed through high temperature sintering (200 DEG C -600 DEG C) and obtains the good electrode of electric conductivity.
The carbon pastes made by the above method are on the one hand usually using a large amount of organic polymer as binder, not only So that cost of manufacture increases, simultaneously because it needs high temperature sintering carbonization to cause energy loss, remaining a large amount of holes after carbonization Also reduce the electric conductivity of carbon pastes；On the other hand it is by ball milling or ultrasonic disperse, and then rotates, and manufacture craft is very It is cumbersome.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of conductive carbon pastes, its preparation side Method and application, conductive carbon pastes preparation process is simple and reliable, and leads for a kind of low temperature good with high conductivity and mildness Thus electrical carbon slurry solves the technical problem that prior art conductive carbon pastes need high temperature sintering, preparation process cumbersome.
To achieve the above object, according to one aspect of the present invention, a kind of preparation method of conductive carbon pastes is provided, is wrapped Include following steps:
(1) carbon black and graphite are mixed according to mass ratio 10:0-0:10, ball milling obtains uniformly mixed carbon black and graphite Mixture；
(2) in the mixture for the carbon black and graphite for obtaining appropriate solvent addition step (1), ball milling obtains surface package There are the carbon black of the solvent and the mixture of graphite, the mixture and the solvent quality ratio of the carbon black and graphite are 1:1- 10；
(3) it is 10:1-1:10 with mass ratio by binder and compound containing-COOH, is added to what step (2) obtained Be coated in the carbon black of the solvent and the mixture of graphite, conductive carbon pastes can be obtained in ball milling, wherein binder and The gross mass and carbon black of compound containing-COOH and the total mass ratio of graphite are 10:1-1:10.
Preferably, step (2) solvent is terpinol.
Preferably, step (3) binder is titanate coupling agent or zirconic acid coupling agent.
Preferably, step (3) described binder is positive isopropyl titanate, tetrabutyl titanate, acetoacetate titanium compound, just One of butyl zirconates and triethanolamine polyalcohol zirconium composite are a variety of.
Preferably, step (3) binder is at least one of tetrabutyl titanate and tetraisopropyl titanate.
Preferably, step (3) is additionally added the compound containing-OH, and the compound containing-OH is preferably ethyl alcohol.
Preferably, step (3) compound containing-COOH is acetic acid.
Preferably, step (1) and step (2) Ball-milling Time are in 0.5-2 hours ranges.
Preferably, step (1) and step (2) described ball milling speed are within the scope of 100-200r/h.
Preferably, step (3) Ball-milling Time is 6-15 hours.
Preferably, step (3) described ball milling speed is within the scope of 100-400r/h.
Other side according to the invention provides a kind of conductive carbon pastes, according to preparation method described above It is prepared.
Other side according to the invention provides the application of conductive carbon pastes described in one kind, is applied to preparation and is situated between See solar battery.
Other side according to the invention provides a kind of mesoscopic solar cells, and back electrode layer is using described Conductive carbon pastes are made.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show Beneficial effect.
(1) its electric conductivity of conductive carbon pastes of the invention and flexibility reach excellent level, and optimal conductivity reaches 88 Ω μm, show broad application prospect.
(2) conductive carbon pastes of the invention are due to using organic or inorganic binder in the production process and containing carboxyl Or the compound of hydroxyl is as novel additive package, therefore the carbon pastes being prepared are being applied to preparation and are situated between see solar-electricity When the back electrode in pond, under 70 DEG C of low temperature sintering, while the conventional polymer it is not necessary that 400 DEG C of high temperature sintering are added is organic Binder, compared with traditional carbon pastes material, the present invention greatly reduces energy consumption.
(3) conductive carbon pastes manufacture craft of the present invention avoids the techniques such as complicated ultrasound, revolving, only with ball-milling technology, It is convenient and simple and fast.
Detailed description of the invention
Fig. 1 is the electric conductivity test chart for the carbon pastes material that embodiment 1 is prepared.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
A kind of preparation method of conductive carbon pastes provided by the invention comprising
(1) suitable carbon black and graphite are mixed into ball milling, is uniformly mixed it；
(2) appropriate solvent is added in uniformly mixed graphite and carbon black, ball milling makes solvent uniformly be wrapped in graphite and carbon Black surface；
(3) appropriate organic or inorganic binder and a small amount of compound containing-COOH are added to and uniformly wrap up solvent Carbon pastes material can be obtained in graphite and black carbon surface, ball milling.
Carbon black is nanometer carbon black, conductive carbon black or superconducting carbon black in step (1)；Graphite form is spherical or sheet, size It is 200nm-30 μm；Carbon black and the mass ratio of graphite mixing are 10:0-0:10, and the two can be selected only first, or being preferably 1:(2-10), further preferably 1:3.
The mixture of graphite and carbon black and solvent quality ratio are 1:(1-10 in step (2)), preferably 3:5, solvent is preferred For terpinol.
Step (3) the organic or inorganic binder is preferably at least one of tetrabutyl titanate, tetraisopropyl titanate. Step (3) the preferred acetic acid of compound for containing-COOH, the compound containing-OH is preferably ethyl alcohol；Organic or inorganic bonding The mass ratio of agent and the compound containing-COOH or-OH is 1:10-10:1, can preferably (2-10): 1, further preferably 8:1, gross mass and carbon black and graphite total mass ratio are 10:1-1:10, can be preferably 1:(4-8), further preferably 1: 3。
It can also (2) afterwards simultaneously the step of solvent is uniformly wrapped in graphite and black carbon surface between step (2) and step (3) Before carrying out step (3), add in right amount containing the compound of hydroxyl, such as ethyl alcohol；It is same to contain or directly in step (3) The compound of carboxyl adds compound in right amount containing hydroxyl together.
Step (1) is identical with Ball-milling Time in step (2), and the time can be in 0.5-2 hours ranges.In step (3) It is long that Ball-milling Time ratio states Ball-milling Time in step (1) and step (2), in preferably 6-15 hours range.Step (1) and step (2) ball milling speed is identical in, preferably within the scope of 100-200r/h.Ball milling speed and step (1) and step (2) in step (3) In ball milling it is same or higher, within the scope of preferably 100-400r/h.
The conductive carbon pastes that the present invention is prepared can be used for preparing the back electrode layer of mesoscopic solar cells.The present invention By adding novel additive package in carbon pastes preparation process, including organic or inorganic binder with contain-COOH or-OH Compound, under solvent such as terpinol existence condition, synergistic effect, the carbon pastes being prepared be low temperature carbon pastes, 70 It is DEG C i.e. sinterable to prepare carbon electrode, and it is not necessary that traditional high temperature, high polymer binder is added.Applicant of the present invention has found this hair Complexity occurs in low temperature for organic or inorganic binder, the compound containing-COOH or-OH and the solvent terpinol of bright middle addition Chemical reaction, for example FT-IR & FT-RAMAN spectra test result shows organic binder isopropyl titanate, acetic acid and pine tar Alcohol can generate when being blended containing organic group relevant to Ti-O-Ti, which plays the role of binder and plasticizer, So that improving the flexibility of carbon pastes, and can burn at 70 DEG C it is not necessary that high polymer binder is added when the carbon pastes are used for carbon electrode Knot completes, and greatly reduces energy consumption.
The following are embodiments:
Embodiment 1
(1) weigh carbon black: graphite quality ratio is 1:3, is transferred in ball mill, uses speed per hour for the ball mill ball of 200r/h 30min is ground, so that carbon black and graphite be made to be uniformly mixed, wherein graphite is the flake graphite of 15 micron grain sizes.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 3:5, is added in ball mill, connects With identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 8:1, and gross mass and carbon material mass ratio are 1:3, is added to In ball mill, then with identical speed per hour ball milling 10h, chemistry of the high speed conditions of sufficiently long time thus in carbon pastes is anti- Reaction environment should be provided, to be prepared for the carbon pastes.
Embodiment 2
(1) weigh carbon black: graphite quality ratio is 0:10, is transferred in ball mill, uses speed per hour for the ball mill of 200r/h Ball milling 30min, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 1:10, is added in ball mill, Then with identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 8:1, and gross mass and carbon material mass ratio are 1:3, is added to In ball mill, the ball milling 10h under the speed per hour of 400r/h, the high speed conditions of the sufficiently long time chemistry in carbon pastes thus Reaction provides reaction environment, to be prepared for the carbon pastes.
Embodiment 3
(1) weigh carbon black: graphite quality ratio is 10:0, is transferred in ball mill, uses speed per hour for the ball mill of 200r/h Ball milling 30min, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 10:1, is added in ball mill, Then with identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 8:1, and gross mass and carbon material mass ratio are 1:10, is added to In ball mill, then with identical speed per hour ball milling 10h, chemistry of the high speed conditions of sufficiently long time thus in carbon pastes is anti- Reaction environment should be provided, to be prepared for the carbon pastes.
Embodiment 4
(1) weigh carbon black: graphite quality ratio is 1:1, is transferred in ball mill, uses speed per hour for the ball mill ball of 200r/h 30min is ground, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 1:1, is added in ball mill, connects With identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.It is adjusted by controlling the quality of terpinol The viscosity of carbon pastes is saved, and then influences the thickness of film.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 10:1, and gross mass and carbon material mass ratio are 1:1, is added to In ball mill, then with identical speed per hour ball milling 10h, chemistry of the high speed conditions of sufficiently long time thus in carbon pastes is anti- Reaction environment should be provided, to be prepared for the carbon pastes.
Embodiment 5
(1) weigh conductive carbon black: graphite quality ratio is 1:5, is transferred in ball mill, uses speed per hour for the ball milling of 200r/h Machine ball milling 30min, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 1:5, is added in ball mill, connects With identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 1:10, and gross mass and carbon material mass ratio are 10:1, addition Into ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of the sufficiently long time chemistry in carbon pastes thus Reaction provides reaction environment, to be prepared for the carbon pastes.
Embodiment 6
(1) weigh carbon black: flake graphite mass ratio is 1:1, is transferred in ball mill, uses speed per hour for the ball milling of 200r/h Machine ball milling 30min, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 1:5, is added in ball mill, connects With identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) take tetraisopropyl titanate: acetic acid quality ratio is 5:1, and gross mass and carbon material mass ratio are 1:5, is added to In ball mill, then with identical speed per hour ball milling 10h, chemistry of the high speed conditions of sufficiently long time thus in carbon pastes is anti- Reaction environment should be provided to be prepared for the carbon pastes.
Embodiment 7
(1) weigh carbon black: graphite quality ratio is 1:1, is transferred in ball mill, uses speed per hour for the ball mill ball of 200r/h 30min is ground, so that carbon black and graphite be made to be uniformly mixed.
(2) weigh carbon material (gross mass of carbon black and graphite): terpinol mass ratio is 1:5, is added in ball mill, connects With identical speed per hour ball milling 1h, so that terpinol be made uniformly to be wrapped in carbon material surface.
(3) ethyl alcohol is added, the mixture quality ratio that wherein quality Yu step (2) of ethyl alcohol obtain is 1:10, so that carbon black More evenly with graphite mixing.
(4) take tetraisopropyl titanate: acetic acid quality ratio is 8:1, and gross mass and carbon material mass ratio are 1:3, is added to In ball mill, then with identical speed per hour ball milling 10h, chemistry of the high speed conditions of sufficiently long time thus in carbon pastes is anti- Reaction environment should be provided, and then carries out revolving to be prepared for the carbon pastes.
It should be noted that embodiment 1 is preferred embodiment, for the number of wherein design parameter in the various embodiments described above The selection of value range does not limit the present invention, and actually in the present invention, each design parameter can be selected according to the actual situation, Such as carbon black is preferably conductive carbon black, but may be nanometer carbon black, Super-conductive carbon etc.；Graphite is preferably flake graphite, but Or spherical graphite etc.；Carbon black and graphite quality may be 0:10-10:0 than being preferably 1:3；Carbon material (carbon black With the gross mass of graphite): terpinol mass ratio is also not necessarily limited to above-mentioned numerical value, and actually it can be 1:1-10；Step (1) and step Suddenly the Ball-milling Time in (2) is preferably identical, and the time can select in range at 0.5-2 hours, ball milling speed it is also preferred that identical, Such as within the scope of 100-200r/h；But the Ball-milling Time in the step of ball milling organic or inorganic binder is than step (1) and step Suddenly the Ball-milling Time in (2) is long, and in for example, 6-15 hours range, ball milling speed can be same or higher, for example, 100- Within the scope of 400r/h, such as 350r/h.
In addition, in the present invention, organic or inorganic binder be not limited to the above embodiments in it is several, preferably titanate esters are even Join agent, zirconic acid coupling agent, more preferably positive isopropyl titanate (tetra isopropyl titanate), positive butyl titanate (tetra n-butyl titanate), acetoacetate titanium compound (titanium ethyl acetoacetate ), complex normal-butyl zirconates (n-butyl zirconate), triethanolamine polyalcohol zirconium composite (zirconium Triethanolamine polyol complex) etc..
Organic or inorganic binder and compound containing-COOH or-OH are 10:1-1:10, gross mass with mass ratio It is 10:1-1:10 with carbon black and graphite total mass ratio.
Solvent in the present invention is not limited to terpinol, can be terpinol, n,N-Dimethylformamide, N, N- diformazan Yl acetamide, N, N- dimethylpropionamide, N, N- diethylformamide, N, N- diethyl acetamide, N, N- diethyl propionamide, Dimethyl sulfoxide, tetramethylene sulfoxide, pentamethylene sulfoxide, hexa-methylene sulfoxide, tetramethylene urea, N, N- dimethacrylate Urea, hexamethyl phosphoramide, N-Methyl pyrrolidone, N- ethyl pyrrolidone, methylene chloride, benzene,toluene,xylene, methane, second Alkane, propane, butane, pentane, hexane, octane, hexamethylene, cyclohexanone, toluene cyclohexanone, ether, acetone, butanone, acetic acid, acetic acid Acid anhydride, dioxane, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, pyridine, petroleum ether, n-butanol, isopropanol, nitrobenzene, Chlorobenzene, dichloro-benzenes, methylene chloride, ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl Positive acetone, isobutyl acetate, 2- nitropropane, n-butyl acetate, propylene glycol monomethyl ether, methyl isoamyl ketone, methyl amyl acetate, N-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethoxy ether, Cyclohexanone, glycol monobutyl ether, propylene glycol monopropyl ether, ethyl cellosolve acetate, isobutyrone, ethylene glycol third Ether, diacetone alcohol, butyl glycol ether, propandiol butyl ether, formic acid -2- ethylhexyl ester, butyl glycol ether acetic acid esters, dipropylene glycol first Ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, glycol hexyl ether, diethylene glycol second Ether acetic acid ester, butyl, the painting of ethylene glycol -2- ethyl hexyl ether, butyl acetic acid esters, the third two single phenyl ethers, first Base butanone, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, methanol, Ethyl alcohol, isopropanol, normal propyl alcohol, 2- butanol, isobutanol, methyl isobutyl carbinol, amylalcohol, cyclohexanol, naphtha, 100# solvent In oil, 150# solvent naphtha, 200# solvent naphtha, styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether and triethanolamine etc. It is any one or more.
Above-mentioned preparation method simple process, the conductive carbon pastes being prepared are a kind of low temperature, high conductivity, flexible Conductive material, Fig. 1 are that the flake graphite that partial size is 15 μm is the carbon pastes material resistance test chart that embodiment 1 is prepared, Resistivity can be down to 88 Ω μm.
This conductive carbon pastes can be sintered the back electrode as mesoporous solar battery, i.e., in the battery having had been filled with On, increase low temperature carbon pastes back electrode layer, the thickness of original high temperature back electrode can be greatly reduced, guarantees electron transfer layer and electricity The perovskite material filling of the sub- mesoporous inside in barrier layer is more, and charge transport properties are improved, so that cell photoelectric is imitated Rate greatly improves.
The carbon pastes that the present invention is prepared are applied to the back electrode of preparation mesoscopic solar cells, one embodiment In, low temperature back electrode porous membrane is directly printed on high temperature back electrode, < 100 DEG C sintering even thicker with a thickness of 10-20 μm The performance of perovskite light absorbent can not be destroyed, also can guarantee the high conductivity of back electrode.Back electrode porous membrane thickness It is reduced to nm or < 10 μm of rank by original 10 μm, guarantees that precursor solution more infiltrates between electron transfer layer or insulation Interlayer.
Prepared by the method a kind of carbon pastes with excellent properties such as low temperature, high conductivity, flexibilities, by it to original There is stable mesoporous solar battery to carry out structure and performance optimization, by solving the problems, such as that carbon is not high to electrode conductivuty, mentions Its high solar conversion efficiency.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of conductive carbon pastes, which comprises the steps of:
(1) carbon black and graphite are mixed according to mass ratio 10:0-0:10, ball milling obtains the mixed of uniformly mixed carbon black and graphite Close object；
(2) in the mixture for the carbon black and graphite for obtaining appropriate solvent addition step (1), ball milling obtains being coated with institute The carbon black of solvent and the mixture of graphite are stated, the mixture and the solvent quality ratio of the carbon black and graphite are 1:1-10；Institute Stating solvent is terpinol；
(3) it is 10:1-1:10 with mass ratio by binder and compound containing-COOH, is added to the surface that step (2) obtains Be enclosed in the carbon black of the solvent and the mixture of graphite, conductive carbon pastes can be obtained in ball milling, wherein binder and containing- The gross mass and carbon black of the compound of COOH and the total mass ratio of graphite are 10:1-1:10；The binder is titanate esters coupling Agent or zirconic acid coupling agent.
2. preparation method as described in claim 1, which is characterized in that step (3) described binder is positive isopropyl titanate, titanium One of sour N-butyl, acetoacetate titanium compound, normal-butyl zirconates and triethanolamine polyalcohol zirconium composite are a variety of.
3. preparation method as described in claim 1, which is characterized in that step (3) is additionally added the compound containing-OH.
4. preparation method as described in claim 1, which is characterized in that step (3) compound containing-COOH is vinegar Acid.
5. preparation method as described in claim 1, which is characterized in that step (1) and step (2) described Ball-milling Time are in 0.5- Within the scope of 2 hours, the ball milling speed is within the scope of 100-200r/h.
6. preparation method as described in claim 1, which is characterized in that step (3) Ball-milling Time is 6-15 hours, described Within the scope of ball milling speed 100-400r/h.
7. a kind of conductive carbon pastes, which is characterized in that it is prepared according to the preparation method as described in claim 1-6.
8. the application of conductive carbon pastes as claimed in claim 7, which is characterized in that be applied to preparation mesoscopic solar cells.
9. a kind of mesoscopic solar cells, which is characterized in that its back electrode layer uses conductive carbon pastes as claimed in claim 7 It is made.
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