CN111492529B - Preparation method of composite conductive slurry - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003381 stabilizer Substances 0.000 claims abstract description 39
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 38
- 239000011858 nanopowder Substances 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 238000000227 grinding Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000011324 bead Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- -1 argon ion Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/10—Energy storage using batteries
Abstract
A preparation method of composite conductive slurry; uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1-2mm, closing the opening of the grinding device, grinding for 3-4 hours, adding a stabilizer, and continuously grinding for 2-3 hours to obtain nano powder a; adding zinc oxide and a stabilizing agent into a ball milling tank, and carrying out ball milling for 8-12 hours at the speed of 100-300 r/min to obtain nano powder b; uniformly mixing the nano powder a and the nano powder b, and reacting to obtain composite powder; and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 0.5-1 hour to obtain the composite conductive slurry. The prepared composite conductive slurry has high conductivity and stability, is not easy to agglomerate, and has simple process, low cost and convenient industrial production.
Description
Technical Field
The invention belongs to the field of electrode materials, and particularly relates to a preparation method of composite conductive slurry.
Background
Since the first report that the composite metal oxide can be used as a negative electrode material of a secondary lithium battery in the Science journal of the Fuji film company in 1997, the conductive paste has wide application in a plurality of fields such as displays, electric appliance housings, gas sensors, solar photoelectric conversion and the like in the IT field. The conductive phase of the electronic paste is mainly noble metal powder such as platinum, palladium, gold, silver and the like, and the price of the silver is relatively low, so that the commercialization degree of the silver paste is highest. In recent years, the price of silver is higher and higher, the production cost of the silver paste is increased, and the silver paste has the problem of silver ion migration.
Porous silicon (porous Si) is a novel one-dimensional nano photonic crystal material, has a quantum sponge-shaped microstructure with nano silicon atom clusters as a framework, and can be formed by electrochemical anodic corrosion or chemical corrosion of monocrystalline silicon. As early as 1956, uhlri, bell laboratories, usa, first discovered and reported that a porous silicon film could be formed by electrochemical etching. Uhlir found that when the anodic current density was low, electrochemical etching of single crystal silicon in a concentrated hydrofluoric acid electrolyte yielded a thin film with a porous structure different from that of the brightly polished surface, i.e., porous silicon. In 1958, d.turner studied the mechanism of anodic oxidation film formation and discussed the etching conditions and related properties of porous silicon films in detail. In the electrochemical anodization process, there are two cases, when the current density is greater than a certain critical point (the critical point is related to the type, resistivity, concentration and composition of the etching solution and other factors of the silicon wafer), an electrochemical polishing phenomenon occurs, and the porous silicon film is peeled off from the silicon substrate. When the current density is lower than this critical point, a porous silicon thin film having silicon pillars on the order of countless nanometers is formed. In 1990, Canham, a british scientist, irradiated a porous silicon surface with ultraviolet light and an argon ion laser at room temperature, found that it had a strong visible Photoluminescence (PL). The size of silicon in the nano-porous silicon is smaller than the Bohr radius of excitons, and the nano-porous silicon has obvious quantum confinement effect, so that the band width is increased due to the splitting of the energy band, and the band gap energy is a function of the size of a silicon column. However, since porous silicon is an indirect bandgap semiconductor, the emission spectrum is wide, the wavelength range is from the ultraviolet region to the near infrared region, and the quantum efficiency of photoluminescence is between 1% and 10%. The peak position and intensity of porous silicon photoluminescence is related to porosity. Porosity is the percentage of the pore volume in a porous silicon layer relative to the total volume of the silicon layer being etched. The ability to photoluminescence is strong when the porosity is greater than 80%. However, the porous layer with large porosity has fast luminescence decay and is not stable enough. The electronic band gap structure, electron-phonon coupling, and the like can be deduced through the study of photoluminescence spectra. Porous silicon also has good reflective properties, with a reflectance spectrum of up to 99% over a range of wavelengths. The porous silicon has good electroluminescent property, can generate electrons and holes under the excitation of light or electricity, and carriers can emit light in a composite mode, move directionally under the action of an electric field, generate electric signals and store energy. The characteristics of porous silicon in the aspects of optics and electricity create a new path for the integration and development of all-silicon-based photoelectron, and rapidly arouse the hot trend of research on porous silicon at home and abroad. However, porous silicon is not as conductive as metal ions and has a problem of dispersibility.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the composite conductive paste, and the composite conductive paste prepared by the invention has high conductivity and stability, is not easy to agglomerate, has simple process and low cost, and is convenient for industrial production.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1-2mm, closing the opening of the grinding device, grinding for 3-4 hours, adding a stabilizer, and continuing to grind for 2-3 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizing agent into a ball milling tank, and carrying out ball milling for 8-12 hours at the speed of 100-300 r/min to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 800 ℃ and 1400 ℃ at the heating rate of 6-9 ℃/min, preserving the heat for 2-3 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 0.5-1 hour to obtain the composite conductive slurry.
Preferably, the weight ratio of the porous silicon to the carbon source in the step (1) is 1-5: 1.
preferably, the stabilizer in the step (1) is an organic tin stabilizer or an organic antimony stabilizer.
Preferably, the preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (3) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 10-11 hours, the reaction temperature is 120-135 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
Preferably, the inert gas in step (3) is helium, neon or argon.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, raw material porous silicon and a carbon source react at high temperature to form a part of silicon bond-carbon bond to form silicon-carbon-oxygen polymer, a part of porous silicon undergoes redox reaction to generate silicon dioxide, and most of porous silicon reacts with the carbon source to generate a plurality of compounds with in-situ carbon coating on the surface, so that the conductivity is increased.
2. By adding the organic tin stabilizer or the organic antimony stabilizer during grinding, the slurry can be more stable, and tin and antimony are metal ions and also have a conductive effect.
3. The composite conductive slurry prepared by the invention has high conductivity and stability, is not easy to agglomerate, has simple process and low cost, and is convenient for industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The specific techniques or conditions are not indicated in the examples, and the techniques or conditions described in the literature in the art are performed in accordance with the instructions. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1mm, closing the opening of the grinding device, grinding for 3 hours, adding a stabilizer, and continuing to grind for 2 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizer into a ball milling tank, and carrying out ball milling for 8 hours at 100 revolutions per minute to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 800 ℃ at the heating rate of 6 ℃/min, preserving the heat for 2 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 0.5 hour to obtain the composite conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 1: 1.
the stabilizer in the step (1) is an organic tin stabilizer.
The preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (2) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 10 hours, the reaction temperature is 120 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
And (4) helium is used as the inert gas in the step (3).
Example 2
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 2mm, closing the opening of the grinding device, grinding for 4 hours, adding a stabilizer, and continuing to grind for 3 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizer into a ball milling tank, and carrying out ball milling at 300 revolutions per minute for 12 hours to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 1400 ℃ at the heating rate of 9 ℃/minute, preserving the heat for 3 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain the composite conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 5: 1.
the stabilizer in the step (1) is an organic tin stabilizer.
The preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3Obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 11 hours, the reaction temperature is 135 ℃,and (3) obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
And (4) the inert gas in the step (3) is neon.
Example 3
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1mm, closing the opening of the grinding device, grinding for 3.5 hours, adding a stabilizer, and continuing to grind for 2.5 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizer into a ball milling tank, and carrying out ball milling for 10 hours at 200 revolutions per minute to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 1000 ℃ at the heating rate of 8 ℃/min, preserving the heat for 2.5 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain the composite conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 3: 1.
the stabilizer in the step (1) is an organic tin stabilizer or an organic antimony stabilizer.
The preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (2) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 10.5 hours, the reaction temperature is 130 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
Preferably, the inert gas in the step (3) is argon.
Comparative example 1
The procedure is as in example 1, except that no stabilizer is added in step (1).
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 2mm, closing the opening of the grinding device, and grinding for 7 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizer into a ball milling tank, and carrying out ball milling at 300 revolutions per minute for 12 hours to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 1400 ℃ at the heating rate of 9 ℃/minute, preserving the heat for 3 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain the composite conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 5: 1.
the stabilizer in the step (1) is an organic tin stabilizer.
The preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (2) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 11 hours, the reaction temperature is 135 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
And (4) the inert gas in the step (3) is neon.
Comparative example 2
The procedure is as in example 2, except that no nanopowder b is added.
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 2mm, closing the opening of the grinding device, grinding for 4 hours, adding a stabilizer, and continuing to grind for 3 hours to obtain nano powder a;
(2) placing the nano powder a in a tubular furnace with inert gas backflow, heating to 1400 ℃ at the heating rate of 9 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with the furnace; and uniformly mixing the nano powder a, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain the conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 5: 1.
the stabilizer in the step (1) is an organic tin stabilizer.
And (3) the inert gas in the step (2) is neon.
Comparative example 3
The procedure is the same as in example 3 except for the step (3).
A preparation method of composite conductive paste comprises the following steps:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1mm, closing the opening of the grinding device, grinding for 3.5 hours, adding a stabilizer, and continuing to grind for 2.5 hours to obtain nano powder a;
(2) adding zinc oxide and a stabilizer into a ball milling tank, and carrying out ball milling for 10 hours at 200 revolutions per minute to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, and heating for reaction at 1000 ℃ for 2.5 hours to obtain composite powder;
(4) and uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain the composite conductive slurry.
The weight ratio of the porous silicon to the carbon source in the step (1) is 3: 1.
the stabilizer in the step (1) is an organic tin stabilizer or an organic antimony stabilizer.
The preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (2) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 10.5 hours, the reaction temperature is 130 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
The composite conductive pastes prepared in examples 1 to 3 and comparative examples 1 to 3 were allowed to stand for 3 days, observed and subjected to a performance test, and the results are shown in table 1:
TABLE 1
| The existence of agglomeration phenomenon is observed by naked eyes | Fineness (nm) | Fluidity (2.5rpm/10.0rpm) | |
| Example 1 | Is free of | 8 | 1.7 |
| Example 2 | Is free of | 10 | 1.9 |
| Example 3 | Is free of | 9 | 1.9 |
| Comparative example 1 | Light and slight | 17 | 1.2 |
| Comparative example 2 | Light and slight | 17 | 1.2 |
| Comparative example 3 | Light and slight | 15 | 1.3 |
The composite conductive slurry obtained in the examples 1-3 and the comparative examples 1-3 is coated on two sides of a conventional aluminum foil of a 16u lithium battery by using a spraying technology, the coating thickness of a single-sided coating is 1u-1.5u, the thickness of a double-sided coating is 2u-3u by drying measurement, and performance tests are carried out, wherein the obtained results are shown in table 2:
TABLE 2
As can be seen in tables 1 and 2: the composite conductive slurry prepared by the preparation method has excellent performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (3)
1. The preparation method of the composite conductive paste is characterized by comprising the following steps of:
(1) uniformly mixing porous silicon, a carbon source and carbonate, putting the mixture into a grinding device, adding glass beads with the diameter of 1-2mm, closing the opening of the grinding device, carrying out grinding treatment for 3-4 hours, adding a stabilizer, and continuing the grinding treatment for 2-3 hours to obtain nano powder a, wherein the stabilizer is an organic tin stabilizer or an organic antimony stabilizer;
(2) adding zinc oxide and a stabilizing agent into a ball milling tank, and carrying out ball milling for 8-12 hours at the speed of 100-300 r/min to obtain nano powder b;
(3) uniformly mixing the nano powder a and the nano powder b, placing the mixture in a tubular furnace with inert gas backflow, heating the mixture to 800 ℃ and 1400 ℃ at the heating rate of 6-9 ℃/min, preserving the heat for 2-3 hours, and cooling the mixture to room temperature along with the furnace to obtain composite powder;
(4) uniformly mixing the composite powder, the adhesive and deionized water to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution for 0.5-1 hour to obtain composite conductive slurry;
wherein the preparation method of the zinc oxide in the step (2) comprises the following steps: slowly dripping NaOH ethanol solution with the concentration of 0.01mol/L into ZnNO with the concentration of 0.01mol/L3And (3) obtaining a mixed solution in ethanol, placing the mixed solution in a reaction kettle for reaction, wherein the reaction time is 10-11 hours, the reaction temperature is 120-135 ℃, obtaining a reaction product after the reaction, and washing and drying the reaction product to obtain the zinc oxide.
2. The method for preparing composite conductive paste according to claim 1, wherein the weight ratio of the porous silicon to the carbon source in the step (1) is 1-5: 1.
3. the method for preparing composite conductive paste according to claim 1, wherein the inert gas in the step (3) is helium, neon or argon.
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| PCT/CN2017/113289 WO2019104460A1 (en) | 2017-11-28 | 2017-11-28 | Method for preparing composite conductive paste |
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| CN102005303A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN104157840A (en) * | 2014-08-15 | 2014-11-19 | 南京师范大学 | Preparation method of graphene coated silica nanotube composite negative electrode material for lithium ion battery |
| CN104617272A (en) * | 2015-02-03 | 2015-05-13 | 东莞市迈科科技有限公司 | Method for preparing porous silicon-carbon composite material |
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| US9005816B2 (en) * | 2013-03-06 | 2015-04-14 | Uchicago Argonne, Llc | Coating of porous carbon for use in lithium air batteries |
| CN104817272B (en) * | 2015-03-31 | 2017-06-06 | 济南大学 | The adsorbent of metal ion is adsorbed with as the application of colouring agent, gained colouring agent and its preparation and application |
| CN106099113B (en) * | 2016-06-30 | 2019-07-02 | 中南大学 | A kind of core-shell structure Si-C composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005303A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN104157840A (en) * | 2014-08-15 | 2014-11-19 | 南京师范大学 | Preparation method of graphene coated silica nanotube composite negative electrode material for lithium ion battery |
| CN104617272A (en) * | 2015-02-03 | 2015-05-13 | 东莞市迈科科技有限公司 | Method for preparing porous silicon-carbon composite material |
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