CN107195385A - A kind of conductive carbon pastes, its preparation method and application - Google Patents

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

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Publication number
CN107195385A
CN107195385A CN201710343192.XA CN201710343192A CN107195385A CN 107195385 A CN107195385 A CN 107195385A CN 201710343192 A CN201710343192 A CN 201710343192A CN 107195385 A CN107195385 A CN 107195385A
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graphite
carbon
preparation
carbon black
ball milling
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CN107195385B (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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/02—Details
    • 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

Appropriate carbon black and graphite are mixed into ball milling the invention discloses a kind of preparation method of low-temperature conductive carbon slurry, including (1), it is well mixed；(2) appropriate solvent is added in well mixed graphite and carbon black, ball milling makes solvent uniformly be wrapped in graphite and black carbon surface；(3) compound by appropriate organic or inorganic binding agent and containing COOH or OH is added to the graphite and black carbon surface of uniform parcel solvent, ball milling, you can obtain carbon pastes material.The inventive method can be prepared with high conductivity and flexible low temperature carbon pastes by the technique of optimization, and preparation technology is simple and reliable.Present invention also offers the application of the conductive carbon pastes prepared using above-mentioned preparation method, and above-mentioned conductive carbon pastes.

Description

A kind of conductive carbon pastes, its preparation method and application
Technical field
The invention belongs to conductive carbon material technical field, more particularly, to a kind of conductive carbon pastes, its preparation method and Using.
Background technology
Electrocondution slurry is to be uniformly distributed in the thick slurry formed in organic polymer binding agent with conductive material particulate. Have in the fields such as solar cell, lithium ion battery, ultracapacitor, energy catalysis to electrode with what electrocondution slurry made Practical application.Electrocondution slurry is as a kind of intermediate products, through certain again after a while after silk-screen printing or thin film cladding At a temperature of completion of cure, finally give conductive film layer.Conductive carbon pastes are usually by conductive filler (such as metal dust, carbon materials Material, metal oxide etc.), a kind of composite for constituting of binding agent, solvent and auxiliary agent.Binding agent as electrocondution slurry film forming Material, while strengthening the caking property between particle so as to the mechanical strength and electric conductivity of enhanced film.Solvent causes conductive micro- Grain is dispersed, forms the suspended substance or glue of suitable silk-screen printing or coating with controllable viscosity and rheology bulk properties Body.It is typically bronze, silver powder or copper powder as the metal dust of conductive filler, although bronze and silver powder electric conductivity superior chemical Property is stable, but its price is very expensive, and its conductive performance of copper powder is excellent but it is easily oxidized；It is used as the metal of conductive filler Oxide, it has high electric conductivity, but this metal oxide element with high electric conductivity is rare；Carbon material is either All can be as preparing electrocondution slurry on electric conductivity, chemical stability and production cost.
Dye sensitization too can in the device such as battery, perovskite solar cell etc. and ultracapacitor to electrode often Conductive material is used as using noble metals such as expensive platinum, gold.If developed with manufacture craft is simple, high conductivity, hole Rate is good, energy consumption is low, good mechanical property carbon pastes can replace the metal electrode of costliness completely as electrode material.Make at present Standby conductive carbon pastes more use graphite, carbon black, acetylene carbon black or nano-carbon material are used as conductive filler, ethanol or pine tar Then alcohol etc. pass through ball as solvent, organic polymer ethyl cellulose or acrylic resin, epoxy resin etc. as binding agent Grinding process, also has using stirring ultrasonic disperse technique, and then revolving obtains 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.
On the one hand the carbon pastes made by the above method are used as binding agent usually using substantial amounts of organic polymer, not only So that cost of manufacture is raised, simultaneously because it needs high temperature sintering carbonization to cause a large amount of holes remained after energy loss, 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.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of conductive carbon pastes, its preparation side Method and application, conductive carbon pastes preparation technology are simple and reliable, and to be a kind of there is high conductivity and the good low temperature of mildness to lead Electrical carbon slurry, thus solving prior art conductive carbon pastes needs the cumbersome technical problem of high temperature sintering, preparation technology.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of preparation method of conductive carbon pastes, bag Include following steps：
(1) by carbon black and graphite according to mass ratio 10:0-0:10 mixing, ball milling obtains well mixed carbon black and graphite Mixture；
(2) in the carbon black and the mixture of graphite that obtain appropriate solvent addition step (1), ball milling obtains surface parcel There are the carbon black of the solvent and the mixture of graphite, the mixture of the carbon black and graphite is 1 with the solvent quality ratio:1- 10；
(3) compound by binding agent and containing-COOH is using mass ratio as 10:1-1:10, it is added to what step (2) was obtained In the mixture for being coated with the carbon black of the solvent and graphite, ball milling is that can obtain conductive carbon pastes, wherein binding agent and The total mass ratio of the gross mass of compound containing-COOH and carbon black and graphite is 10:1-1:10.
Preferably, step (2) described solvent is terpinol.
Preferably, step (3) described binding agent is titanate coupling agent or zirconic acid coupling agent.
Preferably, step (3) described binding agent is positive isopropyl titanate, tetrabutyl titanate, acetoacetate titanium compound, just One or more in butyl zirconates and triethanolamine polyalcohol zirconium composite.
Preferably, step (3) described binding agent 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 ethanol.
Preferably, step (3) compound containing-COOH is acetic acid.
Preferably, step (1) and step (2) described Ball-milling Time are in the range of 0.5-2 hours.
Preferably, step (1) and step (2) described ball milling speed are in the range of 100-200r/h.
Preferably, step (3) described Ball-milling Time is 6-15 hours.
Preferably, step (3) described ball milling speed is in the range of 100-400r/h.
According to another aspect of the present invention there is provided a kind of conductive carbon pastes, it is according to preparation method described above Prepare.
According to another aspect of the present invention there is provided a kind of application of described conductive carbon pastes, it is situated between applied to preparing See solar cell.
According to another aspect of the present invention there is provided a kind of mesoscopic solar cells, its dorsum electrode layer is using described Conductive carbon pastes are made.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show Beneficial effect.
(1) its electric conductivity of conductive carbon pastes and pliability of the invention reach excellent level, and optimal conductance reaches 88 Ω μm, show the prospect of being widely applied.
(2) conductive carbon pastes of the invention in manufacturing process due to employing organic or inorganic binding agent and containing carboxyl Or the compound of hydroxyl is as new additive package, therefore the carbon pastes prepared are seeing solar-electricity applied to preparation Jie During the back electrode in pond, it is under 70 DEG C of sintering of low temperature, while the conventional polymer that need not add 400 DEG C of sintering of high temperature is organic Binding agent, 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, Convenient and simple and fast.
Brief description of the drawings
Fig. 1 is the electric conductivity test chart for the carbon pastes material that embodiment 1 is prepared.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples 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 each embodiment of invention described below Not constituting conflict each other can just be mutually combined.
A kind of preparation method for conductive carbon pastes that the present invention is provided, it includes
(1) appropriate carbon black and graphite are mixed into ball milling, is well mixed it；
(2) appropriate solvent is added in well mixed graphite and carbon black, ball milling makes solvent uniformly be wrapped in graphite and carbon Black surface；
(3) appropriate organic or inorganic binding agent and a small amount of compound containing-COOH are added to uniform parcel solvent Graphite and black carbon surface, ball milling, you can obtain carbon pastes material.
Carbon black is nanometer carbon black, conductive carbon black or superconduction carbon black in step (1)；Graphite form is spherical or sheet, size For 200nm-30 μm；The mass ratio that carbon black and graphite are mixed is 10:0-0:10, the two only can be selected first, can also be preferably 1：(2-10), more preferably 1:3.
The mixture of graphite and carbon black and solvent quality ratio are 1 in step (2):(1-10), preferably 3:5, solvent is preferred For terpinol.
Step (3) the organic or inorganic binding agent 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 ethanol；Organic or inorganic is bonded The mass ratio of agent and the compound containing-COOH or-OH is 1:10-10:1, can be preferably (2-10):1, more preferably 8:1, its gross mass is 10 with carbon black and graphite total mass ratio:1-1:10, can be preferably 1:(4-8), more preferably 1: 3。
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 step (3) is carried out, the appropriate compound containing hydroxyl of addition, such as ethanol；Or directly in step (3), it is same to contain The compound of carboxyl adds the appropriate compound containing hydroxyl together.
Step (1) is identical with Ball-milling Time in step (2), and the time can be in the range of 0.5-2 hours.In step (3) It is long that Ball-milling Time ratio states Ball-milling Time in step (1) and step (2), in the range of preferably 6-15 hours.Step (1) and step (2) ball milling speed is identical in, preferably in the range of 100-200r/h.Ball milling speed and step (1) and step (2) in step (3) In ball milling it is same or higher, in the range of preferably 100-400r/h.
The conductive carbon pastes that the present invention is prepared can be used for the dorsum electrode layer for preparing mesoscopic solar cells.The present invention By adding new additive package, including organic or inorganic binder in carbon pastes preparation technology with containing-COOH or-OH Compound, under solvent such as terpinol existence condition, synergy, the carbon pastes prepared be low temperature carbon pastes, 70 It is DEG C i.e. sinterable to prepare carbon electrode, and traditional high temperature, high polymer binder need not be added.Applicant of the present invention has found this hair Complexity occurs in low temperature for organic or inorganic binding agent, the compound containing-COOH or-OH and the solvent terpinol of bright middle addition Chemical reaction, such as FT-IR ＆ FT-RAMAN spectra test result shows organic binder bond isopropyl titanate, acetic acid and pine tar Alcohol can be generated containing the organic group related to Ti-O-Ti when being blended, and the organic group plays a part of binding agent and plasticizer, So that the carbon pastes are used to that high polymer binder need not to be added during carbon electrode, improve the flexibility of carbon pastes, and can be in 70 DEG C of burnings Knot completes, and greatly reduces energy consumption.
It is embodiment below：
Embodiment 1
(1) carbon black is weighed：Graphite quality ratio is 1：3, it is transferred in ball mill, uses speed per hour for 200r/h ball mill ball 30min is ground, so that carbon black and graphite are well mixed, wherein graphite is the flake graphite of 15 micron grain sizes.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 3：5, added in ball mill, connect With identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 8:1, its gross mass is 1 with carbon material mass ratio:3, it is added to In ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are anti-for the chemistry in this carbon pastes Reaction environment should be provided, so as to be prepared for described carbon pastes.
Embodiment 2
(1) carbon black is weighed：Graphite quality ratio is 0：10, it is transferred in ball mill, uses speed per hour for 200r/h ball mill Ball milling 30min, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 1：10, added in ball mill, Then with identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 8:1, its gross mass is 1 with carbon material mass ratio:3, it is added to In ball mill, the ball milling 10h under 400r/h speed per hour, the high speed conditions of its sufficiently long time are the chemistry in this carbon pastes Reaction provides reaction environment, so as to be prepared for described carbon pastes.
Embodiment 3
(1) carbon black is weighed：Graphite quality ratio is 10：0, it is transferred in ball mill, uses speed per hour for 200r/h ball mill Ball milling 30min, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 10：1, added in ball mill, Then with identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 8:1, its gross mass is 1 with carbon material mass ratio:10, it is added to In ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are anti-for the chemistry in this carbon pastes Reaction environment should be provided, so as to be prepared for described carbon pastes.
Embodiment 4
(1) carbon black is weighed：Graphite quality ratio is 1：1, it is transferred in ball mill, uses speed per hour for 200r/h ball mill ball 30min is ground, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 1：1, added in ball mill, connect With identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.By controlling the quality of terpinol to adjust The viscosity of carbon pastes is saved, and then influences the thickness of film.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 10:1, its gross mass is 1 with carbon material mass ratio:1, it is added to In ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are anti-for the chemistry in this carbon pastes Reaction environment should be provided, so as to be prepared for described carbon pastes.
Embodiment 5
(1) conductive carbon black is weighed：Graphite quality ratio is 1：5, it is transferred in ball mill, uses speed per hour for 200r/h ball milling Machine ball milling 30min, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 1：5, added in ball mill, connect With identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 1:10, its gross mass is 10 with carbon material mass ratio:1, addition Into ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are the chemistry in this carbon pastes Reaction provides reaction environment, so as to be prepared for described carbon pastes.
Embodiment 6
(1) carbon black is weighed：Flake graphite mass ratio is 1：1, it is transferred in ball mill, uses speed per hour for 200r/h ball milling Machine ball milling 30min, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 1：5, added in ball mill, connect With identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) tetraisopropyl titanate is taken:Acetic acid quality ratio is 5:1, its gross mass is 1 with carbon material mass ratio:5, it is added to In ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are anti-for the chemistry in this carbon pastes Reaction environment should be provided to be prepared for described carbon pastes.
Embodiment 7
(1) carbon black is weighed：Graphite quality ratio is 1：1, it is transferred in ball mill, uses speed per hour for 200r/h ball mill ball 30min is ground, so that carbon black and graphite are well mixed.
(2) carbon material (gross mass of carbon black and graphite) is weighed:Terpinol mass ratio is 1：5, added in ball mill, connect With identical speed per hour ball milling 1h, so that terpinol is uniformly wrapped in carbon material surface.
(3) ethanol is added, the mixture quality ratio that wherein quality of ethanol is obtained with step (2) is 1:10 so that carbon black With graphite mixing evenly.
(4) tetraisopropyl titanate is taken:Acetic acid quality ratio is 8:1, its gross mass is 1 with carbon material mass ratio:3, it is added to In ball mill, then with identical speed per hour ball milling 10h, the high speed conditions of its sufficiently long time are anti-for the chemistry in this carbon pastes Reaction environment should be provided, and then carries out revolving to be prepared for described carbon pastes.
It should be noted that in the various embodiments described above, embodiment 1 is preferred embodiment, for the number of wherein design parameter The selection of value scope does not limit the present invention, and actually in the present invention, each design parameter can be selected according to actual conditions, Such as carbon black is preferably conductive carbon black, but it is also possible to be nanometer carbon black, Super-conductive carbon etc.；Graphite is preferably flake graphite, but Can also be spherical graphite etc.；Carbon black and graphite quality ratio preferably 1:3, but it is also possible to be 0:10-10:0；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 the range of 0.5-2 hours, ball milling speed it is also preferred that identical, Such as in the range of 100-200r/h；But the Ball-milling Time in the step of ball milling organic or inorganic binding agent is than step (1) and step Suddenly the Ball-milling Time in (2) is long, in the range of for example, 6-15 hours, and ball milling speed can be with same or higher, for example, 100- In the range of 400r/h, such as 350r/h.
In addition, in the present invention, organic or inorganic binding agent is not limited to several in above-described embodiment, and 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 binding agent and compound containing-COOH or-OH are using mass ratio as 10:1-1:10, its gross mass It is 10 with carbon black and graphite total mass ratio:1-1:10.
Solvent in the present invention is not limited to terpinol, and it can be terpinol, DMF, N, N- diformazans Yl acetamide, N, N- dimethylpropionamides, N, N- diethylformamides, N, N- diethyl acetamides, N, N- diethyl propionamides, Dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, pentamethylene sulfoxide, hexa-methylene sulfoxide, tetramethylene urea, N, N- dimethacrylates Urea, hexamethyl phosphoramide, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, dichloromethane, 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, dichloromethane, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl Positive acetone, isobutyl acetate, 2- nitropropanes, 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, DAA, butyl glycol ether, propandiol butyl ether, formic acid -2- ethylhexyl esters, butyl glycol ether acetic acid esters, DPG 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- ethyls 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, Ethanol, isopropanol, normal propyl alcohol, 2- butanol, isobutanol, methyl isobutyl carbinol, amylalcohol, cyclohexanol, naphtha, 100# solvents In oil, 150# solvent naphthas, 200# solvent naphthas, styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether and triethanolamine etc. It is any one or more.
Above-mentioned preparation method technique is simple, and the conductive carbon pastes prepared are a kind of low temperature, high conductivity, flexible Conductive material, Fig. 1 is that the flake graphite that particle diameter is 15 μm is the carbon pastes material resistance test chart that embodiment 1 is prepared, its Resistivity can as little as 88 Ω μm.
This conductive carbon pastes can sinter the back electrode as mesoporous solar cell, i.e., in the battery having had been filled with On, increase low temperature carbon pastes dorsum electrode layer, the thickness of original high temperature back electrode can be greatly reduced, it is ensured that 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 is greatly improved.
The carbon pastes that the present invention is prepared are applied to prepare the back electrode of mesoscopic solar cells, one embodiment In, low temperature back electrode porous membrane is directly printed on high temperature back electrode, and thickness is 10-20 μm even thicker,<100 DEG C of sintering The performance of perovskite light absorbent can not be destroyed, the high conductivity of back electrode is also can guarantee that.Back electrode porous membrane thickness Be reduced to by original 10 μm nm or<10 μm of ranks, it is ensured that precursor solution is more infiltrated between electron transfer layer or insulation Interlayer.
A kind of carbon pastes with excellent properties such as low temperature, high conductivity, flexibilities prepared using the present invention, by it to original There is stable mesoporous solar cell to carry out structure and performance optimization, by solving the problem of carbon is not high to electrode conductivuty, carry 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, it is not used to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include Within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of conductive carbon pastes, it is characterised in that comprise the following steps：
(1) by carbon black and graphite according to mass ratio 10:0-0:10 mixing, ball milling obtains the mixed of well mixed carbon black and graphite Compound；
(2) in the carbon black and the mixture of graphite that obtain 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 of the carbon black and graphite is 1 with the solvent quality ratio:1-10；
(3) compound by binding agent and containing-COOH is using mass ratio as 10:1-1:10, it is added to the surface that step (2) is obtained In the mixture for being enclosed with the carbon black of the solvent and graphite, ball milling is that can obtain conductive carbon pastes, wherein binding agent and containing- The total mass ratio of the gross mass of COOH compound and carbon black and graphite is 10:1-1:10.
2. preparation method as claimed in claim 1, it is characterised in that step (2) described solvent is terpinol.
3. preparation method as claimed in claim 1, it is characterised in that step (3) described binding agent be titanate coupling agent or Zirconic acid coupling agent, preferably positive isopropyl titanate, tetrabutyl titanate, acetoacetate titanium compound, normal-butyl zirconates and three second One or more in alcohol amine polyol zirconium composite.
4. preparation method as claimed in claim 1, it is characterised in that step (3) is additionally added the compound containing-OH, containing- OH compound is preferably ethanol.
5. preparation method as claimed in claim 1, it is characterised in that step (3) compound containing-COOH is vinegar Acid.
6. preparation method as claimed in claim 1, it is characterised in that step (1) and step (2) described Ball-milling Time are in 0.5- In the range of 2 hours, the ball milling speed is preferably in the range of 100-200r/h.
7. preparation method as claimed in claim 1, it is characterised in that step (3) described Ball-milling Time is 6-15 hours, described In the range of ball milling speed preferably 100-400r/h.
8. a kind of conductive carbon pastes, it is characterised in that it is prepared according to the preparation method as described in claim 1-7.
9. the application of conductive carbon pastes as claimed in claim 8, it is characterised in that applied to preparation mesoscopic solar cells.
10. a kind of mesoscopic solar cells, it is characterised in that its dorsum electrode layer uses conductive carbon paste as claimed in claim 8 Material is made.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113969068A (en) * 2020-07-24 2022-01-25 中国科学院宁波材料技术与工程研究所 Preparation method of carbon super-black light-absorbing coating
CN115000413A (en) * 2022-06-07 2022-09-02 南京工程学院 Heat-resistant carbon-coated aluminum foil for current collector of power battery and preparation method of heat-resistant carbon-coated aluminum foil
US12024636B2 (en) 2021-05-07 2024-07-02 Taiwan Textile Research Institute Conductive coating and manufacturing method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522213A (en) * 2011-12-03 2012-06-27 三峡大学 Preparation method for dye sensitization solar cell carbon counter electrodes
CN103021509A (en) * 2012-12-27 2013-04-03 中国科学院上海硅酸盐研究所 Carbon size for dye sensitization solar cell counter electrode
US20130266859A1 (en) * 2012-04-10 2013-10-10 Semiconductor Energy Laboratory Co., Ltd. Graphene oxide, positive electrode for nonaqueous secondary battery using graphene oxide, method of manufacturing positive electrode for nonaqueous secondary battery, nonaqueous secondary battery, and electronic device
CN104409134A (en) * 2014-11-14 2015-03-11 厦门惟华光能有限公司 Composite carbon electrode for solar cell and preparation method thereof
CN105633341A (en) * 2016-02-29 2016-06-01 北京鼎能开源电池科技股份有限公司 High-thermal-conductivity lithium ion battery positive plate and preparation method therefor
KR20160123191A (en) * 2015-04-15 2016-10-25 한국화학연구원 Cathode containing palladium/ceria nanoparticles for solid oxide electrolysis cell and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522213A (en) * 2011-12-03 2012-06-27 三峡大学 Preparation method for dye sensitization solar cell carbon counter electrodes
US20130266859A1 (en) * 2012-04-10 2013-10-10 Semiconductor Energy Laboratory Co., Ltd. Graphene oxide, positive electrode for nonaqueous secondary battery using graphene oxide, method of manufacturing positive electrode for nonaqueous secondary battery, nonaqueous secondary battery, and electronic device
CN103021509A (en) * 2012-12-27 2013-04-03 中国科学院上海硅酸盐研究所 Carbon size for dye sensitization solar cell counter electrode
CN104409134A (en) * 2014-11-14 2015-03-11 厦门惟华光能有限公司 Composite carbon electrode for solar cell and preparation method thereof
KR20160123191A (en) * 2015-04-15 2016-10-25 한국화학연구원 Cathode containing palladium/ceria nanoparticles for solid oxide electrolysis cell and preparation method thereof
CN105633341A (en) * 2016-02-29 2016-06-01 北京鼎能开源电池科技股份有限公司 High-thermal-conductivity lithium ion battery positive plate and preparation method therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113969068A (en) * 2020-07-24 2022-01-25 中国科学院宁波材料技术与工程研究所 Preparation method of carbon super-black light-absorbing coating
US12024636B2 (en) 2021-05-07 2024-07-02 Taiwan Textile Research Institute Conductive coating and manufacturing method thereof
CN115000413A (en) * 2022-06-07 2022-09-02 南京工程学院 Heat-resistant carbon-coated aluminum foil for current collector of power battery and preparation method of heat-resistant carbon-coated aluminum foil
CN115000413B (en) * 2022-06-07 2024-05-17 南京工程学院 Heat-resistant carbon-coated aluminum foil for power battery current collector and preparation method thereof

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