CN111995964B - Composite nano conductive filler and preparation and application thereof - Google Patents
Composite nano conductive filler and preparation and application thereof Download PDFInfo
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- CN111995964B CN111995964B CN202010919507.2A CN202010919507A CN111995964B CN 111995964 B CN111995964 B CN 111995964B CN 202010919507 A CN202010919507 A CN 202010919507A CN 111995964 B CN111995964 B CN 111995964B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of conductive materials, and particularly discloses a novel composite nano conductive filler as well as preparation and application thereof. The composite nano conductive filler is a nano silver composite material formed by nano silver particles and porous graphite carbon and has a porous foam-like structure; the conductive filler is prepared by sequentially and physically grinding and mixing glucose, silver oxide powder and a nitrogen source and then calcining the mixture in a high-temperature molten state. The nano-silver composite material prepared by the invention has good dispersibility, high stability and excellent conductivity, can replace the conventional conductive filler silver powder, and can be prepared into conductive silver colloid together with specific resin, curing agent, auxiliary agent and the like according to a proportion, so that the electron moving rate in the conductive silver colloid can be effectively improved, the resistivity is reduced, and the conductive effect of the conductive silver colloid is further improved. The invention provides a novel conductive material with excellent performance for the fields of transfer welding of sensors, electronic devices, circuit boards and the like.
Description
Technical Field
The invention relates to the technical field of conductive materials, in particular to a composite nano conductive filler and preparation and application thereof.
Background
As a substitute for conventional tin-lead solder, conductive silver paste is widely used in the electronics industry, such as IC packaging, LED packaging, and MEMS sensor packaging. The conductive silver adhesive has the advantages that: (1) the welding wire is green and environment-friendly, does not contain substances harmful to human bodies and the environment such as lead and the like, is simple in use process, does not need pre-cleaning and post-welding cleaning, and does not have secondary pollution; (2) the process conditions are mild, the soldering temperature of the tin-lead soldering paste is not higher than 200 ℃, and the curing of the conductive silver paste can be completed only by 80-180 ℃. For heat-sensitive devices, the conductive silver paste can minimize thermal stress and damage; (3) the line resolution is high, compared with the line resolution between 381 mu m to 635 mu m of tin-lead soldering paste, the line resolution of the conductive silver paste below 100 mu m is more suitable for fine pitch manufacturing, and can meet the trend of miniaturization, integration and functionalization of modern electronic devices. (4) The operation process is simple, the steps of pre-baking, reflow soldering and the like in the tin-lead soldering paste process are not needed, the process is simple and convenient, the production cost of enterprises is greatly reduced, and the product competitiveness is improved.
The conductive silver adhesive is mainly formed by mixing base resin, a curing agent, a conductive filler and the like, belongs to an electronic adhesive which can generate certain electric conduction, heat conduction and mechanical properties after thermosetting or photocuring, and combines conductive particles together through the bonding action of the base resin to form a conductive path so as to realize the conductive connection of a bonded material. The conductive silver adhesive has simple process and easy operation, can improve the production efficiency and avoid the environmental pollution caused by heavy metal lead in tin-lead solder.
However, the existing conductive silver adhesive generally has the defects of higher volume resistivity, lower heat conductivity coefficient, poorer heat resistance and the like. The existing conductive silver adhesive is mainly used for improving the conductivity, the tension, the bonding property and the like by changing the product ingredients and the preparation method thereof, such as the preparation and the modification of conductive fillers.
Aiming at the current problems of the conductive silver adhesive, the invention provides a nano composite material for the conductive silver adhesive and a preparation method thereof, which can further improve the comprehensive conductivity and stability of the conductive silver adhesive on the basis of the prior art.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a composite nano conductive filler, and a preparation and an application thereof, for solving the problems of poor conductivity and stability of conductive silver colloid in the prior art.
To achieve the above and other related objects, a first aspect of the present invention provides a composite nano conductive filler, which is a nano silver composite material formed by nano silver particles and porous graphitic carbon, and has a porous foam-like structure.
Further, the nano silver particles are formed by reducing silver oxide powder by a nitrogen source at high temperature, and the porous graphite carbon is formed by calcining and carbonizing glucose at high temperature under the protection of inert gas.
Furthermore, the composite nano conductive filler is prepared by sequentially and physically grinding and mixing glucose, silver oxide powder and a nitrogen source and then calcining the mixture in a high-temperature molten state.
Further, the preparation method of the silver oxide powder comprises the following steps: and (3) dropwise adding a sodium carbonate solution into a silver nitrate solution under a stirring state to generate a silver carbonate precipitate, filtering, collecting and cleaning the precipitate, and finally drying to obtain silver oxide powder.
Optionally, the molar ratio of the silver nitrate solution to the sodium carbonate solution is 0.8-1:1, preferably 1: 1. The addition of excessive sodium carbonate can make silver precipitate out completely in the form of silver carbonate, which is unstable and can be decomposed to produce silver oxide by heating.
Alternatively, an aqueous inorganic filter membrane is used in the filtration to collect the silver oxide precipitate.
Further, the calcining temperature of the glucose calcined and carbonized under the environment of high temperature and inert gas protection to form the porous graphite carbon is 700 ℃ or above. The electric conductivity of the graphite carbon is superior to that of disordered carbon, and the calcining temperature is selected to be 700 ℃ or above, so that the graphite carbon can be formed under the protection of inert gas.
Further, the nitrogen source is inorganic ammonium salt or organic amine.
Optionally, the inorganic ammonium salt is selected from at least one of ammonium carbonate and ammonium sulfate, and the organic amine is selected from at least one of urea and thiourea.
Furthermore, the nano silver particles are spherical, and the particle size is 400-600 nm.
The second aspect of the invention provides a preparation method of a composite nano conductive filler, which comprises the following steps:
(1) mixing and grinding glucose and silver oxide powder in an agate mortar by taking the glucose, the silver oxide powder and a nitrogen source, and then adding the nitrogen source for secondary mixing and grinding;
(2) transferring the ground mixture into a quartz crucible, placing the quartz crucible into a high-temperature furnace, and heating and calcining the quartz crucible in the inert gas protection atmosphere;
(3) and taking the quartz crucible out of the high-temperature furnace, cooling to room temperature, taking out the materials in the quartz crucible, and grinding and sieving to obtain the composite nano conductive filler.
Further, in the step (1), the molar ratio of the glucose to the silver oxide powder to the nitrogen source is 5 to (0.1-3) to 2.
Further, in the step (1), the nitrogen source is inorganic ammonium salt or organic amine. Different types of nitrogen sources are selected to obtain composite nano conductive materials with different properties.
Further, the inorganic ammonium salt is selected from at least one of ammonium carbonate and ammonium sulfate, and the organic amine is selected from at least one of urea and thiourea.
Further, in the step (2), the milled mixture is heated to 700 ℃ or more in a high-temperature furnace and calcined.
Further, in the step (2), the calcination time of the milled mixture in the high temperature furnace is 1 to 2 hours.
Further, in the step (3), the size of the mesh used for sieving is 50 × 50 μm.
In a third aspect, the present invention provides the use of the composite nano conductive filler according to the first aspect or the composite nano conductive filler prepared by the preparation method according to the second aspect in the preparation of conductive silver paste.
In a fourth aspect, the invention provides a conductive silver adhesive, which comprises the composite nano conductive filler according to the first aspect or the composite nano conductive filler prepared by the preparation method according to the second aspect.
As mentioned above, the composite nano conductive filler, the preparation and the application thereof have the following beneficial effects:
(1) in the invention, under a high-temperature environment, inorganic ammonium salt or organic amine is decomposed to form active nitrogen free radicals or overflows in the form of ammonia gas, and the reductive active nitrogen free radicals fully reduce and grind silver oxide in the mixture at different positions of pores to generate nano silver particles; meanwhile, partial decomposition gas overflows, and air holes are formed in the graphite carbon matrix formed by high-temperature carbonization of glucose to provide a supporting framework for the nano-silver particles, so that the agglomeration of the nano-silver particles is avoided, and the stability of the nano-silver composite material is improved. In the composite nano conductive filler prepared by the invention, glucose is used as a graphite carbon source to provide a nano silver particle dispersion matrix, a porous support framework and an electron transfer channel, and the nano silver particles are dispersed in the graphite carbon matrix with a porous structure formed by carbonizing glucose, so that the nano silver particles can be effectively prevented from agglomerating, and the dispersion performance of the nano silver particles is improved.
(2) In the invention, the nano-silver composite materials with different nano-silver particle doping amounts can be prepared by adjusting the doping amount of the silver oxide powder in the raw materials; by adjusting the source of the reduced nitrogen, the nano-silver composite material with different particle size distribution can be prepared.
(3) The nano-silver composite material prepared by the invention has good dispersibility, high stability and excellent conductivity, can replace the conventional conductive filler silver powder, and can be prepared into conductive silver colloid together with specific resin, curing agent, auxiliary agent and the like according to a proportion, so that the electron moving rate in the conductive silver colloid can be effectively improved, the resistivity is reduced, and the conductive effect of the conductive silver colloid is further improved. The invention provides a novel conductive material with excellent performance for the fields of transfer welding of sensors, electronic devices, circuit boards and the like.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a composite nano conductive filler, which is a nano silver composite material formed by nano silver particles and porous graphite carbon and has a porous foam-like structure; the nano silver particles are spherical and have the particle size of 400-600 nm.
Specifically, the nano silver particles are formed by reducing silver oxide powder by a nitrogen source at high temperature. The nitrogen source is inorganic ammonium salt or organic amine, the inorganic ammonium salt is selected from at least one of ammonium carbonate and ammonium sulfate, and the organic amine is selected from at least one of urea and thiourea. Different types of nitrogen sources are selected to obtain the composite nano conductive filler with different properties.
The preparation method of the silver oxide powder comprises the following steps: and (3) dropwise adding a sodium carbonate solution into a silver nitrate solution under a stirring state to generate a silver carbonate precipitate, filtering, collecting and cleaning the precipitate, and finally drying to obtain silver oxide powder.
Specifically, the molar ratio of the silver nitrate solution to the sodium carbonate solution is 0.8-1:1, and the silver oxide powder in the following examples is obtained by reacting the silver nitrate solution and the sodium carbonate solution in the molar ratio of 1: 1. The addition of excessive sodium carbonate can make silver precipitate out completely in the form of silver carbonate, which is unstable and can be decomposed to produce silver oxide by heating.
Specifically, an aqueous inorganic filter membrane is used for filtering and collecting the silver oxide precipitate.
Specifically, the porous graphite carbon is formed by calcining and carbonizing glucose at high temperature under the protection of inert gas. The calcining temperature of the glucose calcined and carbonized under the environment of high temperature and inert gas protection to form the porous graphite carbon is 700 ℃ or above. The electric conductivity of the graphite carbon is superior to that of disordered carbon, and the calcining temperature is selected to be 700 ℃ or above, so that the graphite carbon can be formed under the protection of inert gas.
The preparation method of the composite nano conductive filler comprises the following steps:
(1) weighing glucose, silver oxide powder and a nitrogen source according to the molar concentration ratio of 5 to (0.1-3) to 2;
(2) firstly, mixing and grinding glucose and silver oxide powder in an agate mortar, and then adding a nitrogen source for secondary mixing and grinding;
(3) transferring the ground mixture into a quartz crucible, and placing the quartz crucible in a high-temperature furnace;
(4) adjusting temperature rising and heat preservation procedures, heating to 700 ℃ or above under the protection of inert gas, and calcining for 1-2 hours;
(5) and taking the quartz crucible out of the high-temperature furnace, cooling to room temperature, taking out the materials in the quartz crucible, grinding, and sieving by a 50 x 50 mu m sieve to obtain the composite nano conductive filler.
In the preparation method of the composite nano conductive filler, under a high-temperature environment, inorganic ammonium salt or organic amine is decomposed to form active nitrogen free radicals or overflows in the form of ammonia gas, and the reductive active nitrogen free radicals fully reduce and grind silver oxide in a mixture at different positions of pores to generate nano silver particles; meanwhile, partial decomposition gas overflows, and air holes are formed in the graphite carbon matrix formed by high-temperature carbonization of glucose to provide a supporting framework for the nano-silver particles, so that the agglomeration of the nano-silver particles is avoided, and the stability of the nano-silver composite material is improved. The glucose is used as a graphite carbon source, a dispersion matrix, a porous support framework and an electron transfer channel are provided for the nano-silver particles, and the nano-silver particles are dispersed in the graphite carbon matrix with the porous structure formed by carbonizing glucose, so that the nano-silver particles are effectively prevented from being agglomerated.
The nano-silver composite material prepared by the invention has good dispersibility, high stability and excellent conductivity, can replace the conventional conductive filler silver powder, and can be prepared into conductive silver colloid together with specific resin, curing agent, auxiliary agent and the like according to a proportion, so that the electron moving rate in the conductive silver colloid can be effectively improved, the resistivity is reduced, and the conductive effect of the conductive silver colloid is further improved. The invention provides a novel conductive material with excellent performance for the fields of transfer welding of sensors, electronic devices, circuit boards and the like.
By adjusting the amount of silver oxide powder incorporated in the raw materials, nano-silver composites having different amounts of nano-silver particle incorporation can be prepared according to the above-described preparation methods, and with the information of the following examples and comparative examples.
Example 1
1.8g of glucose, 0.0462g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 0.1: 2, mixed and ground, and then calcined for 1h at 700 ℃ in a high-temperature furnace.
Example 2
1.8g of glucose, 0.462g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 1: 2, mixed and ground, and then calcined for 1h at 700 ℃ in a high-temperature furnace.
Example 3
1.8g of glucose, 0.852g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 2 and the molar ratio of 5: 2, mixed and ground, and then calcined for 1h at 700 ℃ in a high-temperature furnace.
Example 4
1.8g of glucose, 1.278g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 3: 2, mixed and ground, and then calcined in a high-temperature furnace at 700 ℃ for 1 h.
Example 5
1.8g of glucose, 0.852g of silver oxide powder and 0.24g of urea are weighed according to the molar ratio of 5: 2, mixed and ground, and then calcined for 1h at 700 ℃ in a high-temperature furnace.
Example 6
1.8g of glucose, 0.852g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 2, mixed and ground, and then calcined for 1h at 900 ℃ in a high-temperature furnace.
Example 7
1.8g of glucose, 0.852g of silver oxide powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 2, mixed and ground, and then calcined for 2 hours at 700 ℃ in a high-temperature furnace.
Comparative example 1
1.8g of glucose, 0.852g of commercial silver powder and 0.36g of ammonium carbonate are weighed according to the molar ratio of 5: 2, mixed and ground, and then calcined for 1h at 700 ℃ in a high-temperature furnace.
Comparative example 2
According to the molar ratio of 5: 2, 1.8g of glucose, 0.852g of commercial nano copper powder and 0.36g of ammonium carbonate are weighed, mixed, ground and calcined for 1 hour at 700 ℃ in a high-temperature furnace.
In order to better show the superiority of the nano-silver composite material of the present invention, the materials obtained in examples 1 to 7 and comparative examples 1 to 2 were compared and examined in terms of conductivity, stability and nanoparticle dispersibility:
each 30 heavy samples such as the nano-silver composite materials prepared in examples 1 to 7 and comparative examples 1 to 2 were selected, and then divided into 3 groups of 10 parallel samples for comparative testing and data analysis.
(1) Test samples conductivity:
10 samples of the nano silver composite materials of examples 1 to 7 and comparative examples 1 to 2 were selected and divided into 7 groups, and the resistivity of each test sample of each group was measured by a resistance measuring instrument, and the average value of the resistance of each group sample was calculated, and the results are shown in table 1.
TABLE 1 results of resistance test on samples of examples 1 to 7 and comparative examples 1 to 2
As can be seen from table 1, the nano silver composites in examples 1 to 7 have lower electrical resistance than the nano silver composites in comparative examples 1 to 2. According to the ohm's law equation: as can be seen from I ═ U/R, the smaller the resistance value, the larger the current. This shows that the nano silver composite material of the present invention has better conductivity, wherein the nano silver composite materials prepared in examples 4 and 5 have better conductivity.
(2) Testing the stability of the sample:
10 samples of examples 1 to 7 and comparative examples 1 to 2 were selected, divided into 7 groups, and the test samples were immersed in an absolute ethanol solution, stored in a sealed state for one month (30 days), and then taken out, prepared, and the dispersion of nanoparticles was observed by a scanning electron microscope to determine the stability of the material, with the results shown in table 2.
TABLE 2 results of stability test of samples of examples 1 to 7 and comparative examples 1 to 2
As can be seen from table 2, the dispersion properties of the nano silver composites of examples 1 to 7 are superior to those of comparative examples 1 to 2, wherein, as can be seen from examples 1 to 4, increasing the doping amount of silver oxide can increase the dispersion properties of the nano silver composites, but too much doping amount of silver oxide can decrease the dispersibility of the obtained nano silver composites; as can be seen from the comparison of examples 3 and 5, compared with the case where inorganic ammonium salt (ammonium carbonate) is used as a nitrogen source and organic amine (urea) is used as a nitrogen source, the nano silver composite material prepared by the method has better dispersibility and more excellent stability; as can be seen from comparison of example 3 with examples 5 and 6, the dispersion property of the nano-silver composite material can be improved by increasing the calcination temperature and time.
(3) Test sample particle size distribution:
10 samples of examples 1 to 7 and comparative examples 1 to 2 were selected, divided into 7 groups, and each test sample was ultrasonically dispersed and tested for particle size distribution using a hydrated particle size tester:
TABLE 3 results of particle size test of samples of examples 1 to 7 and comparative examples 1 to 2
As can be seen from Table 3, the average particle size of the nano-silver composite particles in examples 1 to 4 gradually increased with the increase of the molar amount of doped silver, which indicates that the nano-silver composite material having a smaller particle size can be obtained by decreasing the doping amount of the silver oxide powder; as can be seen from comparative examples 3 and 5, compared with the case where inorganic ammonium salt (ammonium carbonate) is used as a nitrogen source and organic amine (urea) is used as a nitrogen source, a nano silver composite material with a smaller particle size can be prepared; as can be seen from comparison of examples 3, 6 and 7, the nano-silver composite material having a smaller particle size can be obtained by increasing the calcination temperature and time;
the foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. The composite nano conductive filler is characterized in that the composite nano conductive filler is a nano silver composite material formed by nano silver particles and porous graphite carbon and has a porous foam-like structure; the nano silver particles are formed by reducing silver oxide powder by a nitrogen source at high temperature, and the nitrogen source is inorganic ammonium salt or organic amine; the porous graphite carbon is formed by calcining and carbonizing glucose at high temperature under the protection of inert gas; the composite nano conductive filler is prepared by sequentially and physically grinding and mixing glucose, silver oxide powder and a nitrogen source and then calcining the mixture in a high-temperature molten state.
2. The composite nano-conductive filler according to claim 1, characterized in that: the preparation method of the silver oxide powder comprises the following steps: and (3) dropwise adding a sodium carbonate solution into a silver nitrate solution under a stirring state to generate a silver carbonate precipitate, filtering, collecting and cleaning the precipitate, and finally drying to obtain silver oxide powder.
3. The composite nano-conductive filler according to claim 2, characterized in that: the dosage ratio of the silver nitrate solution to the sodium carbonate solution is 0.8-1: 1;
and/or, an aqueous inorganic filter membrane is used when the silver oxide precipitate is filtered and collected;
and/or the calcining temperature of the glucose calcined and carbonized under the high-temperature and inert gas protection environment to form the porous graphite carbon is 700 ℃ or above.
4. The composite nano-conductive filler according to claim 1, characterized in that: the nano silver particles are spherical and have the particle size of 400-600 nm.
5. The preparation method of the composite nano conductive filler is characterized by comprising the following steps of:
(1) mixing and grinding glucose and silver oxide powder in an agate mortar by taking the glucose, the silver oxide powder and a nitrogen source, and then adding the nitrogen source for secondary mixing and grinding; the nitrogen source is inorganic ammonium salt or organic amine;
(2) transferring the ground mixture into a quartz crucible, placing the quartz crucible into a high-temperature furnace, and heating and calcining the quartz crucible in the inert gas protection atmosphere;
(3) and taking the quartz crucible out of the high-temperature furnace, cooling to room temperature, taking out the materials in the quartz crucible, and grinding and sieving to obtain the composite nano conductive filler.
6. The method of claim 5, wherein: in the step (1), the molar concentration ratio of the glucose, the silver oxide powder and the nitrogen source is 5 (0.1-3) to 2;
and/or, in the step (2), the grinding mixture is heated to 700 ℃ or above in a high-temperature furnace for calcination;
and/or, in the step (2), the calcination time of the grinding mixture in a high-temperature furnace is 1-2 hours;
and/or, in the step (3), the size of the screen used for sieving is 50 x 50 μm.
7. The method of claim 6, wherein: the inorganic ammonium salt is selected from at least one of ammonium carbonate and ammonium sulfate, and the organic amine is selected from at least one of urea and thiourea.
8. Use of the composite nano conductive filler according to any one of claims 1 to 4 or the composite nano conductive filler prepared by the preparation method according to any one of claims 5 to 7 for preparing conductive silver paste.
9. An electrically conductive silver paste comprising the composite nano-conductive filler according to any one of claims 1 to 4 or the composite nano-conductive filler prepared by the preparation method according to any one of claims 5 to 7.
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