CN117961080A - Flake silver powder and preparation method and application thereof - Google Patents
Flake silver powder and preparation method and application thereof Download PDFInfo
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- CN117961080A CN117961080A CN202211313470.4A CN202211313470A CN117961080A CN 117961080 A CN117961080 A CN 117961080A CN 202211313470 A CN202211313470 A CN 202211313470A CN 117961080 A CN117961080 A CN 117961080A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000001603 reducing effect Effects 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 10
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 112
- 238000001878 scanning electron micrograph Methods 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 238000006722 reduction reaction Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 239000002055 nanoplate Substances 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000220479 Acacia Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- LQCIDLXXSFUYSA-UHFFFAOYSA-N cerium(4+);tetranitrate Chemical compound [Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LQCIDLXXSFUYSA-UHFFFAOYSA-N 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011640 ferrous citrate Substances 0.000 description 1
- 235000019850 ferrous citrate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides flake silver powder, a preparation method and application thereof, wherein the method comprises the following steps: mixing the solution A and the solution B, and then reacting to prepare the flake silver powder; wherein the solution A comprises Ag +, silver nano-sheet seed crystal and ions with oxidation, the solution B comprises ions with reduction, and the ions with oxidation comprise at least one of Ce 4+ or Fe 3+. According to the preparation method of the flaky silver powder, a high-molecular dispersing agent or a high-molecular surfactant is not required to be added in the preparation process of the flaky silver powder, the flaky silver powder is prepared through a one-step reduction method, and under the combined action of the ions with the oxidation effect in the solution A and the silver nano-sheet seed crystal, the flakiness, the surface smoothness and the flatness of the prepared flaky silver powder are improved, and the conductivity of the prepared flaky silver powder is further improved.
Description
Technical Field
The invention belongs to the technical field of material manufacturing, and relates to flake silver powder, a preparation method and application thereof.
Background
With the rapid development of electronic products and photovoltaic industry, the research on low-temperature conductive silver paste becomes a current research hotspot. The most important component in the low-temperature conductive silver paste is silver powder, compared with point-point contact of non-flake silver powder, the flake silver powder has a unique two-dimensional structure and larger specific surface area, and a conductive network is formed by surface-to-surface and surface-to-line contact when the conductive silver paste is cured at low temperature, so that stronger conductive capability is obtained. At present, the synthesis method of micron-sized flake silver powder mainly comprises a chemical reduction-mechanical ball milling method and a chemical reduction method.
For example, CN104959625A discloses a method for preparing flake silver powder, which comprises the following steps: dissolving silver nitrate and a first surfactant in water to prepare a silver solution; dissolving ascorbic acid and a second surfactant in water to prepare a reducing solution; dissolving an alkaline regulator in water to prepare an alkaline aqueous solution; adding the silver solution and the alkaline aqueous solution into the reducing solution, and reacting to obtain silver powder; and placing the ball milling solvent, the third surfactant and the silver powder into a ball milling tank for ball milling to obtain the flake silver powder. For example, CN111872411a discloses a method for preparing nano silver powder, which comprises the following steps: dissolving a dispersing agent in water to prepare a dispersing agent solution, and adding a reducing agent to obtain a reducing solution; dissolving a silver source in water to obtain a silver source solution; dropwise adding a silver source solution into a reducing solution to obtain silver powder slurry; and centrifuging, washing and drying the silver powder slurry to obtain the nano silver powder, wherein the dispersing agent is preferably polyvinylpyrrolidone. For example, CN114367674a discloses a method for preparing silver powder, which mainly comprises the following steps: (1) Adding a dispersing agent into deionized water and silver nitrate, and stirring to a dissolved state to obtain a solution A; adding a dispersing agent into deionized water and a reducing agent, and stirring to a dissolved state to obtain a solution B; (2) Adding the solution B into the solution A, and obtaining a suspension C after the reaction is completed; (3) Adding alkali liquor into the suspension C, adjusting the pH to 9, adding a polyhydroxy polyamine chelating agent, continuously adding the alkali liquor, adjusting the pH to 14, heating, preserving heat and stirring, and collecting silver powder, wherein the dispersing agent is any one or more of gelatin, acacia and polyvinylpyrrolidone.
The process has the defects that the preparation process is complex, the flake silver powder with smooth and flat surface cannot be prepared, and the used organic dispersing agent is easy to adhere to the surface of the flake silver powder, so that the conductivity of the prepared flake silver powder is greatly reduced.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for producing plate-like silver powder, and use of the plate-like silver powder.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a method for preparing plate-like silver powder, comprising the steps of:
Mixing the solution A and the solution B, and then reacting to prepare the flake silver powder;
Wherein the solution A comprises Ag +, silver nano-sheet seed crystal and ions with oxidation, and the solution B comprises ions with reduction;
Wherein the ions with oxidation include at least one of Ce 4+ or Fe 3+.
According to the preparation method of the silver flake powder, a high-molecular dispersing agent or a high-molecular surfactant is not required to be added in the preparation process of the silver flake powder, the silver flake powder is prepared through a one-step reduction method, and under the combined action of ions with an oxidation effect in the solution A and silver nano-flake crystal seeds, the flakiness degree, the surface smoothness and the flatness of the prepared silver flake powder are improved, and the conductivity of the prepared silver flake powder is further improved.
In the invention, ag + in the solution A and ions with a reduction effect in the solution B are subjected to oxidation-reduction reaction, silver nano-sheet crystal seeds are taken as cores to prepare the sheet silver powder, the ions with an oxidation effect in the solution A can dissolve unstable non-sheet silver crystal nuclei in a reaction system, and defects can be generated on the surfaces of the silver nano-sheet crystal seeds due to the oxidation etching effect of the ions with the oxidation effect in the solution A, so that the growth of the sheet silver powder is promoted, and the finally prepared silver powder is of a relatively stable sheet structure.
In the invention, due to the existence of the silver nano-sheet seed crystal, when the solution A and the solution B are mixed, reduced Ag atoms are deposited on the silver nano-sheet seed crystal to continue growing, and the nucleation and growing processes are prevented from being carried out simultaneously, so that the function of regulating and controlling the size, the shape and the uniformity of silver powder is achieved.
The invention is not limited to the source of Ag +, and illustratively includes, but is not limited to, at least one of silver nitrate or silver sulfate.
Preferably, the concentration of Ag + in the A solution is 0.05-2mol/L, e.g., 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or 1mol/L.
In the invention, when the concentration of Ag + in the solution A is large, the proportion of the spherical silver powder in the prepared silver powder is increased; when the concentration of Ag + in the a solution is small, the production efficiency of the plate-like silver powder is low.
In the present invention, the types of silver nanoplate seeds include, but are not limited to, silver nanoplate colloids.
Preferably, the silver nanoplate seed has a mass of 0.001% -0.05% of the mass of Ag + in the a solution, for example 0.001%, 0.005%, 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, 0.045% or 0.05%.
In the invention, when the adding amount of the silver nano-sheet seed crystal is small, the flaky silver powder cannot be prepared, and when the adding amount of the silver nano-sheet seed crystal is large, the preparation cost of the flaky silver powder is increased.
Preferably, the concentration of the oxidizing ions is 0.015 to 1.0mol/L, for example 0.015mol/L、0.02mol/L、0.03mol/L、0.04mol/L、0.05mol/L、0.06mol/L、0.1mol/L、0.2mol/L、0.3mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L or 1.0mol/L, preferably 0.06 to 0.3mol/L.
In the present invention, since the concentration of Ag + in the a solution is higher than that of the oxidizing ions in the a solution, when the a solution and the B solution are mixed, the reducing ions in the B solution react preferentially with Ag + in the a solution.
Illustratively, the Ce 4+ is derived from a soluble cerium salt, and the invention is not limited to the type of soluble cerium salt, and illustratively includes, but is not limited to, at least one of ceric sulfate, ammonium ceric nitrate, or cerium (iv) nitrate.
In the present invention, the Fe 3+ is derived from a soluble iron salt, and the present invention does not limit the kind of the soluble iron salt, and illustratively includes, but is not limited to, at least one of ferric chloride, ferric nitrate, or ferric sulfate.
In the invention, when the concentration of the ions with the oxidation effect in the solution A is large, the silver nano-sheet seed crystal in the solution A is dissolved, the consumption of the reducing agent is increased, and when the concentration of the ions with the oxidation effect in the solution A is small, the effects of oxidizing etching and eliminating the non-sheet silver nano-sheet seed crystal cannot be achieved.
Preferably, the pH of the A solution is less than or equal to 1, for example 0.2, 0.4, 0.6, 0.8 or 1.
Preferably, the ions having a reducing effect include Fe 2+.
Illustratively, the Fe 2+ is derived from a soluble ferrous salt, and the present invention is not limited to the type of soluble ferrous salt, illustratively including but not limited to at least one of ferrous chloride, ferrous nitrate, or ferrous sulfate.
Preferably, the concentration of the ions having a reducing effect is 0.1 to 2mol/L, for example 0.1mol/L、0.2mol/L、0.3mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L or 2.0mol/L, preferably 1 to 2mol/L.
In the invention, when the concentration of the ions with the reduction effect in the solution B is higher, the reduction rate is higher, the synthesis of the flake silver powder is not easy, and when the concentration of the ions with the reduction effect in the solution B is lower, the yield of the flake silver powder is lower.
Preferably, the solution B also contains ions with shape guiding function.
Preferably, the ions with morphology-guiding effect comprise at least one of SO 4 2- or citrate.
In the present invention, the SO 4 2- is derived from sulfuric acid or soluble sulfate, and the present invention does not limit the type of the soluble sulfate, and illustratively includes but is not limited to at least one of FeSO 4、(NH4)2SO4、K2SO4 or Na 2SO4.
In the present invention, the citrate is derived from at least one of citric acid or soluble citrate, and the present invention does not limit the kinds of soluble citrate, and illustratively includes, but is not limited to, at least one of sodium citrate, ammonium citrate, potassium citrate, or ferrous citrate.
Preferably, the concentration of the ions having a morphology-directing effect in the B solution is 0.1-6mol/L, for example 0.1mol/L、0.3mol/L、0.5mol/L、0.7mol/L、0.9mol/L、1mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L、2.0mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L or 6.0mol/L, preferably 1-2mol/L.
In the invention, when the ion concentration with the shape guiding function in the solution B is higher, the Ag in the solution A can be adsorbed on the (111), (100) crystal faces and (110) crystal faces of the silver nano-sheet crystal seeds indiscriminately, so that silver crystal grains grow isotropically, and spherical silver powder is formed; when the concentration of the ions having the morphology-guiding effect in the B solution is low, the ions having the morphology-guiding effect are insufficient to cover the preferential adsorption crystal plane (111) in the silver nanoplate seed crystal, thereby also causing the formation of spherical silver powder.
Illustratively, the ions with morphology guiding effect and the ions with reducing effect in the B solution can be provided by one substance or two substances, for example, adding FeSO 4,FeSO4 to the solution provides both SO 4 2- with morphology guiding effect and Fe 2+ with reducing effect, simplifying the preparation steps.
Preferably, mixing the a solution and the B solution is performed as follows:
The solution A was added to the solution B with stirring.
In the present invention, the reason why the a solution is added to the B solution in a stirred state is to ensure that the prepared silver powder has better uniformity.
Preferably, the temperature of the reaction is 25-40 ℃, e.g. 25 ℃,30 ℃, 35 ℃ or 40 ℃.
Preferably, the reaction time is 0.5-2h, for example 0.5h, 1h, 1.5h or 2h.
Preferably, after the solution A and the solution B react, solid-liquid separation is carried out, and the separated solid is washed and dried to obtain the flake silver powder; the filtrate can be returned to be used for preparing the solution B after reduction treatment, so that the recycling is realized.
In the present invention, the solid-liquid separation method includes, but is not limited to, filtration or suction filtration.
The method of the reduction treatment is not limited in the present invention, and exemplary methods of the reduction treatment include, but are not limited to, an electro-reduction method or a chemical reduction method.
In one embodiment of the present invention, taking Fe 2+ as an example of the ion having a reducing effect in the B solution, the effect of Fe 2 + in the process of preparing the plate-like silver powder and the recovery method are described: in the preparation process of the flake silver powder, fe 2+ in the solution B is oxidized into Fe 3+ by Ag + and enters the filtrate, fe 3+ in the filtrate is converted into Fe 2+ by an electro-reduction method, so that the recycling is performed, and the electro-reduction method comprises the following steps:
The obtained filtrate is placed in a diaphragm electrolysis device, wherein an anode is an iron plate, a cathode is a stainless steel plate, a diaphragm is an anion exchange membrane, the electrolysis temperature is 50 ℃, the electrolysis time is 60min, the electrolysis current density is 250A/m 2, and the electricity consumption in the process is 1.5kWh/kg Fe.
During electrolysis, the cathode undergoes a reduction reaction: fe 3++e-→Fe2+, and the anode performs oxidation reaction: fe-2e -→Fe2+, thereby converting Fe 3+ in the filtrate into Fe 2+.
In still another embodiment of the present invention, taking Fe 2+ as an example of the ion having a reducing effect in the B solution, the effect of Fe 2+ in the preparation process of the plate-like silver powder and the recovery method are described: in the preparation process of the flake silver powder, fe 2+ in the solution B is oxidized into Fe 3+ by Ag + and enters the filtrate, fe 3+ in the filtrate is converted into Fe 2+ by a chemical reduction method, so that the cyclic utilization is realized, and the chemical reduction method comprises the following steps:
Mixing the obtained filtrate with a reducing agent, stirring to convert Fe 3+ in the filtrate into Fe 2+, and adding the filtrate after oxidation reduction into the solution B again.
In the above method, the kind of the reducing agent includes, but is not limited to, at least one of thiourea, elemental iron, elemental copper, elemental zinc, sulfide salt, sulfite, or ascorbic acid.
In the present invention, the detergents used for washing the separated solids include, but are not limited to, at least one of water or ethanol.
In a second aspect, there is provided a silver powder prepared by the method according to the first aspect of the present invention, wherein the mass percentage of the plate-like silver powder in the silver powder is greater than 95%.
The silver powder has higher flaking degree, smoother and smoother surface, and is beneficial to improving the conductivity of the silver powder.
Preferably, the silver powder has a D50 of 2-3 μm, for example 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm or 3 μm.
Preferably, the silver powder has a D90 of 5-6 μm, for example 5.1 μm, 5.2 μm, 5.3 μm, 5.4 μm, 5.5 μm, 5.6 μm, 5.7 μm, 5.8 μm, 5.9 μm or 6 μm.
The third method provides an application of the silver powder in the second aspect of the invention in preparing conductive silver paste.
The silver powder has better conductivity, and can greatly improve the conductivity of the conductive silver paste, especially the conductivity of the low-temperature conductive silver paste when being used for preparing the conductive silver paste.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the silver flake powder, a high-molecular dispersing agent or a high-molecular surfactant is not required to be added in the preparation process of the silver flake powder, the silver flake powder is prepared through a one-step reduction method, and under the combined action of ions with an oxidation effect in the solution A and silver nano-flake crystal seeds, the flakiness degree, the surface smoothness and the flatness of the prepared silver flake powder are improved, and the conductivity of the prepared silver flake powder is further improved. In addition, the invention can realize the recycling of the B solution by a simple electro-reduction method or a chemical reduction method, and has the advantages of green, high efficiency and low cost.
(2) The silver powder provided by the invention has higher flaking degree and better conductivity, and when the silver powder is used for filling conductive silver paste, the conductivity of the conductive silver paste is obviously improved, and particularly the conductivity of the low-temperature conductive silver paste is improved.
Drawings
FIG. 1 is a flowchart of preparing a plate-like silver powder according to an embodiment of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the silver powder of example 1;
FIG. 3 is a graph showing the particle size distribution of the silver powder in example 1;
FIG. 4 is an SEM image of the silver powder of example 2 and a commercial plate-like silver powder produced by a ball-milling method;
FIG. 5 is an X-ray diffraction (XRD) pattern of the silver powder of example 2;
FIG. 6 is an SEM image of silver powder of example 3;
FIG. 7 is an SEM image of silver powder of examples 4-7;
FIG. 8 is an SEM image of silver powder of examples 8-11;
FIG. 9 is an SEM image of silver powder of examples 12-14;
FIG. 10 is an SEM image of silver powder of example 15;
FIG. 11 is an SEM image of silver powder of comparative examples 1-5;
FIG. 12 is an SEM image of silver powder of comparative example 6;
Fig. 13 shows the results of the bulk resistivity test of commercial plate-like silver powder-filled conductive silver paste prepared in example 2 and ball milling.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The "room temperature" in the examples of the present invention is defined as 25 ℃.
An embodiment of the present invention provides a method for preparing plate-like silver powder, as shown in fig. 1, fig. 1 is a flowchart of preparing plate-like silver powder according to an embodiment of the present invention, and specifically includes the following steps: and adding the solution A into the solution B for reduction reaction, filtering after the reaction to obtain micron-sheet silver powder, and re-entering the filtrate obtained by filtering into the solution B through an electro-reduction method or a chemical reduction method to realize the recycling of the filtrate.
Example 1
The embodiment provides a preparation method of flake silver powder, which comprises the following steps:
(1) Preparation of solution A: weighing silver nitrate and ceric ammonium nitrate, dissolving in deionized water, adding 100mL of silver nano-flake colloid with the concentration of 10mg/L, and adding water to dilute to 1L, wherein the concentration of Ag + in the solution A is 0.3mol/L, the concentration of Ce 4+ is 0.06mol/L, the mass of the silver nano-flake colloid is 0.003% of the mass of Ag +, and the pH value of the solution A is 0.5;
(2) Preparation of solution B: weighing ferrous sulfate, dissolving in deionized water, and diluting to 900mL, wherein the concentration of Fe 2+ is 1mol/L, and the concentration of SO 4 2- is 1mol/L;
(3) And (3) rapidly pouring the solution A into the solution B at the temperature of 30 ℃ under the stirring state, reacting for 30min, filtering, washing the obtained solid with water and ethanol, and drying at the temperature of 60 ℃ to obtain the flake silver powder.
Example 2
The embodiment provides a preparation method of flake silver powder, which comprises the following steps:
(1) Preparation of solution A: weighing silver nitrate and ceric ammonium nitrate, dissolving in deionized water, adding 300mL of silver nano-sheet colloid with the concentration of 40mg/L, and adding water to dilute to 1L, wherein the concentration of Ag + in the solution A is 1mol/L, the concentration of Ce 4+ is 0.13mol/L, the mass of the silver nano-sheet colloid is 0.01% of the mass of Ag +, and the pH value of the solution A is 0.6;
(2) Preparation of solution B: weighing ferrous sulfate and sodium sulfate, dissolving in deionized water, and diluting to 2L, wherein the concentration of Fe 2+ is 1.2mol/L, and the concentration of SO 4 2- is 2mol/L;
(3) And (3) rapidly pouring the solution A into the solution B at the temperature of 30 ℃ under the stirring state, reacting for 40min, filtering, washing the obtained solid with water and ethanol, and drying at 50 ℃ to obtain the flake silver powder.
Example 3
The embodiment provides a preparation method of flake silver powder, which comprises the following steps:
(1) Preparation of solution A: weighing silver nitrate and ferric nitrate, dissolving in deionized water, adding 500mL of silver nano-sheet colloid with the concentration of 40mg/L, and adding water to dilute to 1L, wherein the concentration of Ag + in the solution A is 1.5mol/L, the concentration of Fe 3+ is 0.3mol/L, the mass of nano-silver seed crystal is 0.012% of the mass of Ag +, and the pH value of the solution A is 0.4;
(2) Preparation of solution B: weighing ferrous chloride and citric acid, dissolving in deionized water, and diluting to 1.5L, wherein the concentration of Fe 2+ is 1.5mol/L, and the concentration of citrate is 2.0mol/L;
(3) And (3) rapidly pouring the solution A into the solution B at the temperature of 30 ℃ under the stirring state, reacting for 30min, filtering, washing the obtained solid with water and ethanol, and drying at the temperature of 60 ℃ to obtain the flake silver powder.
Example 4
The difference from example 2 was only that the concentration of Fe 2+ in the B solution was 0.5mol/L and that of SO 4 2- was 0.5mol/L.
Example 5
The difference from example 2 was only that the concentration of Fe 2+ in the B solution was 1mol/L and that of SO 4 2- was 1mol/L.
Example 6
The difference from example 2 was only that the concentration of Fe 2+ in the B solution was 1.5mol/L and that of SO 4 2- was 1.5mol/L.
Example 7
The difference from example 2 was only that the concentration of Fe 2+ in the B solution was 2mol/L and that of SO 4 2- was 2mol/L.
Example 8
The only difference from example 1 is that 50mL of 20mg/L silver nanoplate colloid was added to the A solution.
Example 9
The only difference from example 1 is that 100mL of 20mg/L silver nanoplate colloid was added to the A solution.
Example 10
The only difference from example 1 is that 150mL of silver nanoplate colloid with a concentration of 20mg/L was added to the A solution.
Example 11
The only difference from example 1 is that 200mL of silver nanoplate colloid with a concentration of 20mg/L was added to the A solution.
Example 12
The only difference from example 2 is that the Ce 4+ concentration in the A solution was 0.01mol/L.
Example 13
The only difference from example 2 is that the Ce 4+ concentration in the A solution was 0.03mol/L.
Example 14
The only difference from example 2 is that the Ce 4+ concentration in the A solution was 0.05mol/L.
Example 15
The only difference from example 2 is that the concentration of SO 4 2- in the B solution is 0.5mol/L.
Comparative example 1
The only difference from example 2 is that no silver nanoplate seed crystal was added to the solution a and no ceric ammonium nitrate was added to the solution B.
Comparative example 2
The difference from example 2 is only that no silver nanoplate seed crystal was added to the solution a and equimolar Ce 3+ was added to the solution B.
Comparative example 3
The only difference from example 2 is that no silver nanoplate seed was added to the a solution.
Comparative example 4
The only difference from example 2 is that no ceric ammonium nitrate was added to the B solution.
Comparative example 5
The only difference from example 2 is that Ce 3+ was added in equimolar amounts to the B solution.
Comparative example 6
The only difference from example 2 is that the ions having an oxidizing effect in the solution A are hypochlorite in equimolar numbers.
Fig. 2 is an SEM image of the silver powder in example 1, wherein b in fig. 2 is a partial enlarged view of a in fig. 2, and it can be seen from fig. 2 that the silver powder prepared in example 1 is a plate-like silver powder, the average particle diameter of the plate-like silver powder is 3.0 μm, the average thickness is 0.2 μm, and the particle size of the plate-like silver powder is relatively uniform.
Fig. 3 shows the particle size distribution of the silver powder of example 1. As can be seen from fig. 3, the silver powder of example 1 has a narrower particle size distribution, indicating that the silver powder of example 1 has a more uniform particle size distribution, and as can be seen from fig. 3, the silver powder of example 1 has a D50 (particle cumulative distribution of 50% of the particle size, also known as average particle size or median diameter) of 2.83 μm.
Fig. 4 is an SEM image of the silver powder of example 2 and the commercial plate-shaped silver powder prepared by the ball milling method (GY-1, new material limited in hua-nan state), wherein a of fig. 4 is an SEM image of the silver powder of example 2, and b of fig. 4 is an SEM image of the commercial plate-shaped silver powder prepared by the ball milling method, and it can be seen from a of fig. 4 that the silver powder of example 2 has a plate-shaped structure and has a hexagonal shape, the average particle diameter of the silver powder is 5.4 μm, the average thickness of the silver powder is 0.4 μm, the dispersibility and uniformity of the silver powder of example 2 are superior to those of the commercial plate-shaped silver powder prepared by the ball milling method, and the surface of the silver powder of example 2 is smoother and flatter, which is advantageous to increase the contact area between the plate-shaped silver powders, thereby improving the conductivity of the plate-shaped silver powder.
Fig. 5 is an XRD pattern of the silver powder in example 2, and it can be seen from fig. 5 that the silver powder prepared in example 2 has a sharp peak and a narrow half-width of the XRD peak, indicating that the silver powder prepared in example 2 is an elemental silver with good crystallinity.
Fig. 6 is an SEM image of the silver powder in example 3, and it can be seen from fig. 6 that the silver powder in example 3 is also a silver powder with a higher degree of flaking, and the surface of the silver powder is smoother and smoother.
Fig. 7 is an SEM image of the silver powder in examples 4 to 7, wherein a in fig. 7 is an SEM image of the silver powder in example 4, B in fig. 7 is an SEM image of the silver powder in example 5, d in fig. 7 is an SEM image of the silver powder in example 6, and e in fig. 7 is an SEM image of the silver powder in example 7, and it can be seen from fig. 7 that when the concentrations of Fe 2+ and SO 4 2- in the B solution are low, a silver powder with a higher degree of flaking and smoother surface cannot be obtained.
Fig. 8 is an SEM image of the silver powder in examples 8 to 11, wherein a in fig. 8 is an SEM image of the silver powder in example 8, b in fig. 8 is an SEM image of the silver powder in example 9, d in fig. 8 is an SEM image of the silver powder in example 10, and e in fig. 8 is an SEM image of the silver powder in example 11, and it can be seen from fig. 8 that the silver powder prepared is a plate-like silver powder when the addition amount of the silver nano-plate seed crystal in the solution a reaches a certain ratio.
Fig. 9 is an SEM image of the silver powder in examples 12 to 14, wherein a in fig. 9 is an SEM image of the silver powder in example 12, b in fig. 9 is an SEM image of the silver powder in example 13, c in fig. 9 is an SEM image of the silver powder in example 14, and as can be seen from fig. 9, the silver powder prepared in example 12 is spherical, the silver powder prepared in example 13 is a mixture of spherical and plate, the silver powder prepared in example 14 is a mixture of spherical and plate, and the proportion of plate-like silver powder in the silver powder in example 14 is greater than that in example 13.
Fig. 10 is an SEM image of the silver powder of example 15, from which it can be seen that when the concentration of SO 4 2- having the morphology-guiding effect in the B solution is reduced, the plate-like silver powder content in the prepared silver powder is correspondingly reduced.
Fig. 11 is an SEM image of the silver powder of comparative examples 1 to 5, in which a of fig. 11 is an SEM image of the silver powder of comparative example 1, b of fig. 11 is an SEM image of the silver powder of comparative example 2, c of fig. 11 is an SEM image of the silver powder of comparative example 3, d of fig. 11 is an SEM image of the silver powder of comparative example 4, e of fig. 11 is an SEM image of the silver powder of comparative example 5, and it can be seen from fig. 11 that the silver powder prepared in comparative examples 1 and 2 is spherical, i.e., if the silver nano-sheet seed crystal and Ce 4+ are not added in the reaction system, the silver powder prepared in comparative example 3 is a mixture of the silver flake powder and the spherical silver powder, indicating that the addition of Ce 4+ is somewhat advantageous for the preparation of the silver flake powder, but if not acting together with the silver nano-sheet seed crystal, the silver powder prepared in comparative examples 4 and 5 is in a small particle size, indicating that the silver nano-sheet seed crystal is simply added or the silver nano-sheet seed crystal is not used in combination with 3+, and the silver flake powder cannot be prepared.
Fig. 12 is an SEM image of the silver powder of comparative example 6, from which it can be seen that when Ce 4+ is substituted with hypochlorite which also has an oxidizing effect, the silver powder produced is spheroidal, indicating that not all ions having an oxidizing effect can be used for the production of the plate-like silver powder of the present application.
And (3) performance detection:
the conductive properties of the commercial flake silver powder filled conductive silver pastes prepared in example 2 and ball milling were tested. Preparing conductive silver paste:
Mixing silver powder and a catalyst carrier according to the proportion of 80:20 to obtain conductive silver paste, wherein the composition and the mass ratio of the catalyst carrier are as follows: divalent esters (dibasic acid esters): saturated resin (polyethylene): polyamide wax = 77:2:1.
Conductive performance test of conductive silver paste:
The prepared conductive silver paste was screen-printed on a polyethylene terephthalate (PET) film to form a thin film circuit (10 mm×100 mm), and then placed in an oven to be solidified for 30min at 160 ℃ and then subjected to a bulk resistivity test after being cooled to room temperature, the test results are shown in fig. 13, wherein the inset in fig. 13 is a physical diagram of the thin film circuit, the "self-made plate-like silver powder" in fig. 13 represents the silver powder-filled conductive silver paste prepared in example 2, and the "commercial plate-like silver powder" in fig. 13 represents the commercial plate-like silver powder-filled conductive silver paste prepared by the ball milling method. As can be seen from fig. 13, the volume resistivity of the silver powder-filled conductive silver paste prepared in example 2 of the present invention was 1.2x -5 Ω·cm, which is far lower than that of the commercial flake silver powder-filled conductive silver paste prepared by the ball milling method (8x -5 Ω·cm), on the premise of the same silver powder content, and the above results indicate that the silver powder-filled conductive silver paste prepared in the present invention has more excellent conductive properties.
Analysis:
As can be seen from the data in examples 1-3, the preparation method in the examples of the invention can prepare the micron-sized flake silver powder, and the surface of the prepared flake silver powder is smoother and smoother, and the dispersibility and uniformity are better.
As can be seen from the data of examples 2 and 4 to 7, when the concentration of the ions having the morphology guiding effect and the ions having the reducing effect in the solution B is low, silver powder having a smooth and flat surface cannot be prepared, and the degree of flaking of the prepared silver powder is low.
As can be seen from the data of examples 1 and 8-11, the silver nano-plate colloid concentration in the solution A can be used for preparing silver powder with higher flaking degree within a certain range.
As can be seen from the data of examples 2 and examples 12 to 14, the concentration of Ce 4+ in the a solution has a great influence on the silver powder prepared, and when the concentration of Ce 4+ in the a solution is small, the silver powder with smooth and flat surface cannot be prepared, and the degree of flaking of the prepared silver powder is low.
As can be seen from the data of example 2 and example 15, the concentration of the ions having the morphology-guiding effect in the B solution has a significant effect on the preparation of the silver powder, and when the concentration of the ions having the morphology-guiding effect is low, the silver powder having a high degree of flaking cannot be prepared.
As can be seen from the data of example 2 and comparative examples 1 to 5, silver powder having a high degree of flaking could be produced only by the mutual cooperation of the silver nanoplate seed crystal and the ions having an oxidizing effect, and silver powder having a high degree of flaking could not be produced either by the mere addition of the silver nanoplate seed crystal or by the mere addition of the ions having an oxidizing effect.
As can be seen from the data of example 2 and comparative example 6, not all the ions having the oxidation function can produce silver powder having a smooth and flat surface and a high degree of flaking.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for producing a plate-like silver powder, comprising the steps of:
Mixing the solution A and the solution B, and then reacting to prepare the flake silver powder;
Wherein the solution A comprises Ag +, silver nano-sheet seed crystal and ions with oxidation, and the solution B comprises ions with reduction;
Wherein the ions with oxidation include at least one of Ce 4+ or Fe 3+.
2. The method according to claim 1, wherein the concentration of Ag + in the a solution is 0.05-2mol/L;
preferably, the mass of the silver nano-sheet seed crystal is 0.001% -0.05% of the mass of Ag + in the solution A;
preferably, the concentration of the ions having an oxidizing effect is 0.015 to 1.0mol/L, preferably 0.06 to 0.3mol/L.
3. The method according to claim 1 or 2, wherein the pH of the a solution is less than or equal to 1.
4. A method according to any one of claims 1 to 3, wherein the ions having a reducing effect comprise Fe 2 +;
Preferably, the concentration of the ions having a reducing effect is 0.1 to 2mol/L, preferably 1 to 2mol/L.
5. The method of any one of claims 1-4, wherein the solution B further comprises ions having a morphology-directing effect;
Preferably, the ions with morphology guidance comprise at least one of SO 4 2- or citrate;
Preferably, the concentration of the ions with morphology-guiding effect in the solution B is 0.1-6mol/L, preferably 1-2mol/L.
6. The method according to any one of claims 1 to 5, wherein mixing the a solution and the B solution is performed in the following manner:
adding the solution A into the solution B under stirring;
Preferably, the temperature of the reaction is 25-40 ℃;
preferably, the reaction time is 0.5-2h.
7. The method according to any one of claims 1 to 6, wherein the solution a and the solution B are subjected to solid-liquid separation after being reacted, and the separated solid is washed and dried to obtain the flake silver powder; the filtrate can be returned to be used for preparing the solution B after reduction treatment, so that the recycling is realized.
8. Silver powder prepared by the method according to any one of claims 1 to 7, wherein the mass percentage of plate-like silver powder in the silver powder is more than 95%.
9. The silver powder of claim 8, wherein the D50 of the silver powder is 2-3 μm;
Preferably, the silver powder has a D90 of 5-6 μm.
10. Use of the silver powder according to claim 8 or 9 for the preparation of conductive silver paste.
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