CN113618075A - Preparation method of filling high-purity nano material of ultralow-resistivity conductive paste - Google Patents
Preparation method of filling high-purity nano material of ultralow-resistivity conductive paste Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000011049 filling Methods 0.000 title claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010949 copper Substances 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 42
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- 238000004880 explosion Methods 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 229910052786 argon Inorganic materials 0.000 claims description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- HDCUKDHYRMGLRT-UHFFFAOYSA-L [Ag+2].[O-]C(=O)C([O-])=O Chemical group [Ag+2].[O-]C(=O)C([O-])=O HDCUKDHYRMGLRT-UHFFFAOYSA-L 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a method for preparing a high-purity nano material filled with conductive paste with ultralow resistivity, which is characterized in that a chemical method is utilized to prepare a nano material mainly comprising nano copper, silver nitrate is added in the preparation process, silver oxalate generated by the silver nitrate is reduced into simple substance Ag under a high-temperature state, the simple substance Ag has good conductivity as same as the nano copper on one hand, and the simple substance Ag has very strong oxidability as an oxidant on the other hand, and can be obviously increased in a roasting furnaceStrong CO, CO2The gas explosion effect of the method can cut the simple substance copper generated along with the simple substance Ag into the nano copper with finer and more uniform particles, thereby effectively avoiding the generation of oxides, improving the purity of the nano material and reducing the resistivity. The resistivity of the nano material prepared by the invention is reduced to 26.9 mu omega cm from 12.6 mu omega cm of the existing common material, and is close to the theoretical resistivity of copper of 1.75 mu omega cm, and the effect is obvious.
Description
Technical Field
The invention relates to a preparation method of a high-purity nano material filled with ultralow-resistivity conductive paste.
Background
A large amount of nano silver powder and nano copper powder with low resistivity are required for printing conductive coatings, conductive ink and conductive silk-screen printing in the electronic industry, wherein the nano silver powder is precious metal and is expensive, so that the application range and upgrading of electronic materials are severely limited; the nanometer copper powder is base metal and has good conductivity, but the nanometer copper powder is easy to oxidize, and the resistivity of the copper after oxidation can be increased by ten thousand times, so that the conductivity of the copper is influenced.
The nanometer material (10-100nm) has the characteristics of small size, large specific surface area, quantum size effect, macroscopic quantum tunneling effect and the like, and is different from the conventional material. The property of the copper powder is closely related to the granularity of the copper powder, the property of the copper powder is changed along with the reduction of the granularity, and particularly, the optical, electrical, magnetic, mechanical and chemical properties of the nano copper powder with the granularity distributed between 1 and 100nm are obviously changed. Based on these outstanding properties, the copper nanoparticles have been widely used in the fields of high-energy catalysts, lubricant additives, conductive materials, toughening materials, etc.
The main methods for preparing the nano-copper in the global market so far are a gas phase method, a liquid phase method, a mechanical method, an electric arc method and a chemical method. Wherein:
gas phase method: difficulty in controlling copper oxidation;
liquid phase method: in the process of drying the water, the copper and the oxygen in the water are easy to oxidize;
a mechanical grinding method: high grinding cost, low efficiency, expensive equipment and large potential safety hazard (grinding generates heat, spontaneous combustion and explosion);
an arc method: under high temperature conditions, it is difficult to control the oxidation of copper.
As can be seen, the nano copper powder is easy to be oxidized in the production process, and is the biggest problem in the preparation of the nano copper powder at present. The electrical resistivity of the oxidized copper is greatly increased, so that the electrical conductivity of the oxidized copper is seriously influenced, and the preparation cost and the sale price of the existing nano copper powder are high, so that the industrial production and application are difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a filling high-purity nano material of ultralow-resistivity conductive paste, which can effectively avoid oxide generation, improve the purity of the nano material and reduce the resistivity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a filling high-purity nano material of ultralow-resistivity conductive paste comprises the following steps:
(1) adding oxalic acid into a mixed aqueous solution of copper nitrate and silver nitrate to react, and filtering after the reaction is finished to obtain a mixture crystal of copper oxalate and silver oxalate;
(2) filling the mixture crystal of the copper oxalate and the silver oxalate obtained in the step (1) into a roasting furnace, firstly introducing argon to exhaust air in the roasting furnace, then introducing mixed gas of the argon and carbon monoxide, keeping the atmosphere of the argon and the carbon monoxide, heating the roasting furnace, and reacting at the temperature of 250-400 ℃;
the reaction process is as follows:
A、CuC2O4·2H2O＝CuO+CO↑+CO2↑+2H2O↑；Ag2C2O4·2H2O＝Ag2O+CO↑+CO2↑+2H2O↑；
B、2CuC2O4+2H2O＝Cu2O+2CO↑+2CO2↑+2H2O↑；
C、CuO+2CO+1/2O2＝Cu+2CO2↑；
D、Cu2O+CO＝2Cu+CO2↑；Ag2O+CO＝2Ag+CO2↑；
the above reaction is a chain reaction, and the CO generated in step A, B is immediately reacted with CuO and Cu2O、Ag2Reducing the copper into a simple substance of copper and a simple substance of silver by O reaction, and simultaneously generating CO2Completing the reaction of step C, D; in the process, CO and CO generated by the reaction2Forming gas explosion, and cutting the copper simple substance and the silver simple substance into nano powder; in the simple substance generation of nano silverAt the moment of formation, the gas explosion effect is enhanced, so that the copper simple substance is cut into nano powder with smaller granularity;
o in step C2Trace oxygen from impure argon;
(3) stopping heating after the reaction in the step (2) is finished, continuously introducing mixed gas of argon and carbon monoxide until the furnace temperature is reduced to below 40 ℃, and stopping introducing the argon and the carbon monoxide; taking out the obtained nano copper powder, putting the nano copper powder into an ethanol solution with the oxalic acid content of 1%, uniformly dispersing the nano copper powder by ultrasonic oscillation, standing the nano copper powder at normal temperature and filtering the nano copper powder; and drying the obtained solid nano copper powder in a vacuum constant temperature box at 60 ℃, naturally cooling the constant temperature box to below 40 ℃, taking out the nano copper powder, and carrying out vacuum sealing, packaging and storing.
Preferably, in the step (1), the weight of the added silver nitrate is 0.001% -2% of the total weight of the copper nitrate and the silver nitrate, and more preferably 0.01% -0.1%. Silver nitrate is added in the reaction process, mainly for enhancing the gas explosion effect, so that the particle size of the obtained product is smaller and more uniform; silver nitrate forms silver oxalate after passing through the step (1), the silver oxalate forms simple substance nano Ag in the step (2), the simple substance Ag has good conductivity as the nano copper on one hand, and the simple substance Ag has very strong oxidability on the other hand, and can be used as an oxidant to obviously enhance CO and CO in a roasting furnace2The gas explosion effect of (2); and because the cost of the silver nitrate is higher, the addition amount of the silver nitrate is reduced as much as possible on the basis of meeting the requirement of enhancing the gas explosion effect, so that the cost is reduced.
In the invention, in the step (1), ammonia water is used for adjusting the pH value of the reaction liquid to be kept between 1.16 and 4.16 all the time in the reaction process, and after the reaction is finished, the reaction liquid is filtered. The pH value is adjusted to be 1.16-4.16, so that the sizes of crystal particles of copper oxalate and silver oxalate can be increased, the crystal particles are in a convenient filtering state of mixed crystals of the copper oxalate and the silver oxalate and water, the vacuum pump negative pressure separation is favorably adopted, and the industrial production is facilitated.
Preferably, in the step (2), argon gas is introduced to achieve the reduction of CuO with a trace amount of oxygen contained in the argon gas, wherein the purity of the argon gas is 99.6% to 99.9%.
Preferably, in the step (2), 90-99.9% of argon and 0.1-10% of carbon monoxide are introduced according to volume content. The carbon monoxide is introduced to facilitate the copper oxide and the silver oxide to be completely reduced into simple substance copper and simple substance silver.
The nano-material prepared by the invention can be well applied to electronic conductive materials such as conductive ink slurry, conductive paint and conductive coating, and because the requirements on the particle size and the purity of the nano-copper in the fields are very high, the nano-copper powder can partially replace noble metal silver after the oxidizability of the nano-copper is solved and the purity of the nano-copper is improved, so that the cost is reduced.
Compared with the prior art, the invention has the advantages that: the invention utilizes a chemical method to prepare nano material mainly comprising nano copper, silver nitrate is added in the preparation process, silver oxalate generated by the silver nitrate is reduced into simple substance Ag under a high temperature state, the simple substance Ag has good conductivity as the nano copper on one hand, and the simple substance Ag has very strong oxidability on the other hand, and can be used as an oxidant to obviously enhance CO and CO in a roasting furnace2The gas explosion effect of the method can cut the simple substance copper generated along with the simple substance Ag into the nano copper with finer and more uniform particles, improve the purity and the particle fineness of the nano material and reduce the resistivity.
Drawings
FIG. 1 is an SEM image of a product at 20nm in an example of the present invention;
FIG. 2 is a SEM image of a product at 50nm in an example of the present invention;
FIG. 3 is an SEM image of a product of 100nm in an example of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example (b):
the preparation method of the filling high-purity nano material of the ultralow-resistivity conductive paste comprises the following steps:
(1) preparing a mixed aqueous solution containing 10% of copper nitrate and 0.001% of silver nitrate (the mixed aqueous solution contains 10g of copper nitrate, 1mg of silver nitrate and 89.999g of water), starting stirring, adding oxalic acid powder while stirring, detecting the change of the pH value, adding 1% ammonia water when the pH value is lower than 1.16 to adjust the pH value to be within the range of 1.16-4.16, stopping adding when the cumulative addition amount of the oxalic acid powder is 4.9g, continuing stirring, reacting for 40 minutes, and filtering to obtain a crystal mixture of copper oxalate and silver oxalate, wherein the size of the copper oxalate and silver oxalate crystals is about 1 mm;
(2) filling the crystal mixture of the copper oxalate and the silver oxalate obtained in the step (1) into a roasting furnace, firstly introducing 99.9% of argon to exhaust air in the roasting furnace, and then introducing 99.9% of mixed gas of the argon and carbon monoxide, wherein the volume content of the argon is 99% and the volume content of the carbon monoxide is 1%; keeping the atmosphere of introducing argon and carbon monoxide, heating the roasting furnace, and reacting at 400 ℃;
the reaction process is as follows:
A、CuC2O4·2H2O＝CuO+CO↑+CO2↑+2H2O↑；Ag2C2O4·2H2O＝Ag2O+CO↑+CO2
↑+2H2O↑；
B、2CuC2O4+2H2O＝Cu2O+2CO↑+2CO2↑+2H2O↑；
C、CuO+2CO+1/2O2＝Cu+2CO2↑；
D、Cu2O+CO＝2Cu+CO2↑；Ag2O+CO＝2Ag+CO2↑；
the above reaction is a chain reaction, and the CO generated in step A, B is immediately reacted with CuO and Cu2O, Ag2O, and generates CO2Completing the reaction of step C, D; in the process, CO and CO generated by the reaction2Forming gas explosion, and cutting the copper simple substance and the silver simple substance into nano powder; at the moment of generating the nano silver simple substance, the gas explosion effect is enhanced, so that the copper simple substance is cut into nano powder with smaller granularity;
o in step C2Trace oxygen from impure argon;
(3) after the reaction in the step (2) is carried out for 30min, stopping heating, continuously introducing mixed gas of argon and carbon monoxide until the furnace temperature is reduced to below 40 ℃, and stopping introducing the argon and the carbon monoxide; taking out the obtained nano copper powder, putting the nano copper powder into an ethanol solution with the volume content of 1% oxalic acid, oscillating and dispersing the nano copper powder uniformly by ultrasonic waves, standing the nano copper powder at normal temperature and filtering the nano copper powder; drying the obtained solid nano copper powder in a vacuum constant temperature box at 60 ℃, naturally cooling the constant temperature box to below 40 ℃, taking out the nano copper powder, and carrying out vacuum sealing, packaging and storing;
as shown in FIGS. 1, 2 and 3, the particle size of the obtained nano material is mainly 2-100 nm, and the particles are uniformly dispersed.
The resistivity of the nano material prepared by the embodiment is reduced to 26.9 mu omega cm from 12.6m omega cm of the existing common material, the theoretical resistivity of the nano material is close to 1.75 mu omega cm of copper, and the conductive effect is remarkably improved.
Comparative example 1:
the preparation method of the filling high-purity nano material of the conductive paste with ultralow resistivity comprises the following steps:
(1) preparing an aqueous solution with 10% of copper nitrate content (the aqueous solution contains 10g of copper nitrate and 90g of water), starting stirring, adding oxalic acid powder while stirring, detecting the change of pH value, adding 1% ammonia water when the pH value is lower than 1.16 to adjust the pH value to be within the range of 1.16-4.16, stopping adding when the cumulative adding amount of the oxalic acid powder is 4.9g, continuously stirring, reacting for 40 minutes, and filtering to obtain a crystal mixture of copper oxalate and silver oxalate, wherein the size of the copper oxalate and silver oxalate crystals is about 1 mm;
(2) filling the crystals of the copper oxalate obtained in the step (1) into a roasting furnace, firstly introducing 99.9% of argon to exhaust air in the roasting furnace, and then introducing 99.9% of mixed gas of the argon and carbon monoxide, wherein the volume content of the argon is 99% and the volume content of the carbon monoxide is 1%; keeping the atmosphere of introducing argon and carbon monoxide, heating the roasting furnace, and reacting at 400 ℃;
the reaction process is as follows:
A、CuC2O4·2H2O＝CuO+CO↑+CO2↑+2H2O↑；
B、2CuC2O4+2H2O＝Cu2O+2CO↑+2CO2↑+2H2O↑；
C、CuO+2CO+1/2O2＝Cu+2CO2↑；
D、Cu2O+CO＝2Cu+CO2↑；
the above reaction is a chain reaction, and the CO generated in step A, B is immediately reacted with CuO and Cu2The O reaction reduces the copper into a simple substance of copper and generates CO2Completing the reaction of step C, D; in the process, CO and CO generated by the reaction2Cutting the copper simple substance;
o in step C2Trace oxygen from impure argon;
(3) after the reaction in the step (2) is carried out for 30min, stopping heating, continuously introducing mixed gas of argon and carbon monoxide until the furnace temperature is reduced to below 40 ℃, and stopping introducing the argon and the carbon monoxide; taking out the obtained powder product, putting the powder product into an ethanol solution with the volume content of 1% oxalic acid, ultrasonically oscillating and uniformly dispersing, standing at normal temperature and filtering; and drying the obtained solid copper powder in a vacuum constant temperature box at 60 ℃, naturally cooling the constant temperature box to below 40 ℃, taking out the copper powder, and carrying out vacuum sealing, packaging and storing.
According to the detection, although partial nanometer copper powder is generated in the comparative example, the CO and the CO are generated in the reaction process2The cutting force of the copper simple substance is weak, so that part of copper powder still exists in larger particles and cannot completely reach the nanometer level.
Comparative example 2:
the preparation method of the filling high-purity nano material of the conductive paste with ultralow resistivity comprises the following steps:
(1) preparing an aqueous solution with 10% of copper nitrate content (the aqueous solution contains 10g of copper nitrate and 90g of water), starting stirring, adding oxalic acid powder while stirring, detecting the change of pH value, adding 1% ammonia water when the pH value is lower than 1.16 to adjust the pH value to be within the range of 1.16-4.16, stopping adding when the cumulative adding amount of the oxalic acid powder is 4.9g, continuously stirring, reacting for 40 minutes, and filtering to obtain a crystal mixture of copper oxalate and silver oxalate, wherein the size of the copper oxalate and silver oxalate crystals is about 1 mm;
(2) filling the crystals of the copper oxalate obtained in the step (1) into a roasting furnace, firstly introducing 99.9% of argon to exhaust air in the roasting furnace, and then introducing 99.9% of argon; heating the roasting furnace in the atmosphere of introducing argon, and reacting at 400 ℃;
the reaction process is as follows:
A、CuC2O4·2H2O＝CuO+CO↑+CO2↑+2H2O↑；
B、2CuC2O4+2H2O＝Cu2O+2CO↑+2CO2↑+2H2O↑；
C、CuO+2CO+1/2O2＝Cu+2CO2↑；
D、Cu2O+CO＝2Cu+CO2↑；
the above reaction is a chain reaction, and the CO generated in step A, B is immediately reacted with CuO and Cu2The O reaction reduces the copper into a simple substance of copper and generates CO2Completing the reaction of step C, D; in the process, CO and CO generated by the reaction2Cutting the copper simple substance;
o in step C2Trace oxygen from impure argon;
(3) after the reaction in the step (2) is carried out for 30min, stopping heating, continuing introducing argon until the furnace temperature is reduced to below 40 ℃, and stopping introducing argon; taking out the obtained powder product, putting the powder product into an ethanol solution with the volume content of 1% oxalic acid, ultrasonically oscillating and uniformly dispersing, standing at normal temperature and filtering; and drying the obtained solid copper powder in a vacuum constant temperature box at 60 ℃, naturally cooling the constant temperature box to below 40 ℃, taking out the copper powder, and carrying out vacuum sealing, packaging and storing.
According to the detection, although partial nanometer copper powder is generated in the comparative example, the CO and the CO are generated in the reaction process2The cutting force for the copper simple substance is weaker, so that part of copper powder still exists in larger particles and cannot completely reach the nano level, and the particle size of the nano level particles is larger than that of the comparative example 1, which shows that carbon monoxide is introduced while argon is introduced, so that the cutting strength for the copper simple substance in the reaction process is favorably enhanced.
Claims (5)
1. A preparation method of a filling high-purity nano material of ultralow-resistivity conductive paste is characterized by comprising the following steps:
(1) adding oxalic acid into a mixed aqueous solution of copper nitrate and silver nitrate to react, and filtering after the reaction is finished to obtain a mixture of copper oxalate and silver oxalate;
(2) loading the mixture of the copper oxalate and the silver oxalate obtained in the step (1) into a roasting furnace, firstly introducing argon to exhaust air in the roasting furnace, then introducing mixed gas of the argon and carbon monoxide, keeping the atmosphere of the argon and the carbon monoxide, heating the roasting furnace, and reacting at the temperature of 250-400 ℃;
the reaction process is as follows:
A、CuC2O4·2H2O＝CuO+CO↑+CO2↑+2H2O↑；Ag2C2O4·2H2O＝Ag2O+CO↑+CO2↑+2H2O↑；
B、2CuC2O4+2H2O＝Cu2O+2CO↑+2CO2↑+2H2O↑；
C、CuO+2CO+1/2O2＝Cu+2CO2↑；
D、Cu2O+CO＝2Cu+CO2↑；Ag2O+CO＝2Ag+CO2↑；
the above reaction is a chain reaction, and the CO generated in step A, B is immediately reacted with CuO and Cu2O、Ag2Reducing the copper into a simple substance of copper and a simple substance of silver by O reaction, and simultaneously generating CO2Completing the reaction of step C, D; in the process, CO and CO generated by the reaction2Forming gas explosion, and cutting the copper simple substance and the silver simple substance into nano powder; at the moment of generating the simple substance of silver, the gas explosion effect is enhanced, so that the simple substance of copper is cut into nanometer powder with smaller granularity;
o in step C2Trace oxygen from impure argon;
(3) stopping heating after the reaction in the step (2) is finished, continuously introducing mixed gas of argon and carbon monoxide until the furnace temperature is reduced to below 40 ℃, and stopping introducing the argon and the carbon monoxide; taking out the obtained nano copper powder, putting the nano copper powder into an ethanol solution with the volume content of 1% oxalic acid, oscillating and dispersing the nano copper powder uniformly by ultrasonic waves, standing the nano copper powder at normal temperature and filtering the nano copper powder; and drying the obtained solid nano copper powder in a vacuum constant temperature box at 60 ℃, naturally cooling the constant temperature box to below 40 ℃, taking out the nano copper powder, and carrying out vacuum sealing, packaging and storing.
2. The method for preparing filled high-purity nano-materials of the ultralow-resistivity conductive paste according to claim 1, wherein the filling step comprises the following steps: in the step (1), the weight of the added silver nitrate is 0.001-2% of the total weight of the copper nitrate and the silver nitrate.
3. The method for preparing filled high-purity nano-materials of the ultralow-resistivity conductive paste according to claim 1, wherein the filling step comprises the following steps: in the step (1), after the reaction is finished, firstly, ammonia water is used for adjusting the pH value of the reaction liquid to 1.16-4.16, and then, filtering is carried out.
4. The method for preparing filled high-purity nano-materials of the ultralow-resistivity conductive paste according to claim 1, wherein the filling step comprises the following steps: in the step (2), the purity of the introduced argon is 99.6-99.9%.
5. The method for preparing filled high-purity nano-materials of the ultralow-resistivity conductive paste according to claim 1, wherein the filling step comprises the following steps: in the step (2), 90-99.9% of argon and 0.1-10% of carbon monoxide are introduced according to the volume content.
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