CN117600482A - Preparation method of flake silver powder with high tap density - Google Patents
Preparation method of flake silver powder with high tap density Download PDFInfo
- Publication number
- CN117600482A CN117600482A CN202410093440.XA CN202410093440A CN117600482A CN 117600482 A CN117600482 A CN 117600482A CN 202410093440 A CN202410093440 A CN 202410093440A CN 117600482 A CN117600482 A CN 117600482A
- Authority
- CN
- China
- Prior art keywords
- silver powder
- tap density
- solution
- high tap
- spherical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 70
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 55
- 239000002270 dispersing agent Substances 0.000 claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 48
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 27
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 27
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 27
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims abstract description 27
- 235000010378 sodium ascorbate Nutrition 0.000 claims abstract description 26
- 229960005055 sodium ascorbate Drugs 0.000 claims abstract description 26
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 238000007493 shaping process Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 10
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 5
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 241000978776 Senegalia senegal Species 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229930016911 cinnamic acid Natural products 0.000 claims description 4
- 235000013985 cinnamic acid Nutrition 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000002003 electrode paste Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000004576 sand Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a preparation method of flake silver powder with high tap density, and relates to the technical field of metal powder preparation. The preparation method comprises the steps of preparing a silver nitrate solution, a reducing agent solution and a dispersing agent solution, wherein the reducing agent solution contains ascorbic acid and sodium ascorbate; then adding a silver nitrate solution and the dispersing agent solution into the reducing agent solution, and fully reacting to obtain spherical cluster silver powder; shaping the spherical cluster silver powder to obtain spherical silver powder; adding spherical silver powder into ethanol, adding a grinding aid, fully and uniformly mixing, performing sanding treatment, and separating, washing and drying to obtain the high tap density flake silver powder. Through the mode, the invention can prepare the flake silver powder with controllable size and high tap density by a simple process and with less dispersant consumption. The electrode paste of the solar cell is prepared based on the flake silver powder, so that the photoelectric conversion efficiency of the solar cell is improved.
Description
Technical Field
The invention relates to the technical field of metal powder preparation, in particular to a preparation method of high tap density flake silver powder.
Background
The conductive silver paste is a main material in the solar photovoltaic cell and mainly comprises conductive silver powder, organic resin and an organic solvent, wherein the conductive silver powder mainly comprises spherical silver powder and flake silver powder. The photoelectric conversion efficiency of the solar cell is closely related to the compactness of the grid line thick film, and the silver powder with high tap density is favorable for forming a denser grid line thick film, so that the photoelectric conversion efficiency of the solar photovoltaic cell is improved. Therefore, the high tap density of the silver powder plays a vital role in improving the photoelectric conversion efficiency of the solar photovoltaic cell.
At present, the silver powder with high tap density is mainly spherical silver powder, and the tap density can reach 6g/cm 3 The tap density of the flake silver powder is almost 4.5g/cm 3 The following is given. For example, the patent publication No. CN105345012A provides a method for preparing a high-conductivity plate-like silver powder and application thereof. The patent uses high-purity spherical or spheroidal silver powder as a main material, and adds graphite powder, a ball milling auxiliary agent and a ball milling solvent for ball milling for a certain time to obtain flake silver powder. However, the tap density of the flake silver powder prepared by the method is not high, and is only 3.4-4.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And the ball milling time of the mode is as long as 10-20 hours, which is unfavorable for continuous production.
In view of this, there is still a need for a method for preparing a high tap density silver flake having a high tap density, which can satisfy the actual production needs, to solve the above-mentioned problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the preparation method of the flake silver powder with high tap density, which can simply, conveniently and efficiently prepare the flake silver powder with controllable size and high tap density, so that the solar cell prepared based on the flake silver powder has higher photoelectric conversion efficiency.
In order to achieve the above object, the present invention provides a method for preparing high tap density flake silver powder, comprising the steps of:
s1, respectively preparing a silver nitrate solution, a reducing agent solution and a dispersing agent solution; the reducing agent solution contains ascorbic acid and sodium ascorbate;
s2, adding the silver nitrate solution and the dispersing agent solution into the reducing agent solution, and fully stirring to obtain a reaction solution;
s3, settling the reaction liquid, removing supernatant, and washing, filtering and drying the settled silver powder to obtain spherical cluster silver powder;
s4, shaping the spherical cluster silver powder to obtain spherical silver powder;
s5, adding the spherical silver powder into ethanol to obtain a mixed solution; adding grinding aid into the mixed solution, and performing sanding treatment after fully and uniformly mixing; and separating, washing and drying the silver powder after sanding treatment to obtain the high tap density flake silver powder.
As a further improvement of the invention, in the step S1, the mass ratio of the ascorbic acid to the sodium ascorbate in the reducing agent solution is 1:1-2; the ratio of the mass of silver nitrate in the silver nitrate solution to the total mass of ascorbic acid and sodium ascorbate in the reducing agent solution is 1:0.6-1.0.
As a further improvement of the invention, in the step S1, the ratio of the mass of the dispersing agent in the dispersing agent solution to the mass of the silver nitrate in the silver nitrate solution is 0.02-0.15:1.
As a further improvement of the present invention, the dispersing agent is gum arabic or polyvinylpyrrolidone.
As a further improvement of the invention, in the step S1, the concentration of the silver nitrate solution is 500-1500 g/L.
As a further improvement of the invention, in the step S2, the silver nitrate solution and the dispersing agent solution are simultaneously added into the reducing agent solution, the stirring speed is 200-300 r/min, and the stirring time is 15-25 min.
As a further improvement of the invention, in the step S4, the shaping treatment is carried out for 10-15 min, and the particle size of the spherical silver powder is 3-6 mu m.
As a further improvement of the invention, in the step S5, the spherical silver powder accounts for 20-30wt% of the total mass of the mixed solution formed by mixing the ethanol and the spherical silver powder.
As a further improvement of the invention, in the step S5, the sanding treatment is carried out for 10-30 min, the particle size of the high tap density flake silver powder is 4-15 mu m, and the thickness is 0.5-1.2 mu m.
As a further improvement of the invention, in the step S5, the grinding aid is one or more of oleic acid, tween 80, stearic acid, octylamine, hexadecylamine, 12-hydroxystearic acid and cinnamic acid; the mass ratio of the grinding aid to the spherical silver powder is 0.001-0.01:1.
The beneficial effects of the invention are as follows:
1. according to the preparation method of the high tap density flake silver powder, provided by the invention, the two reducing agents of the ascorbic acid and the sodium ascorbate are compounded according to a specific proportion, and the compounded reducing agent is used for reducing the silver nitrate, so that on one hand, the particle size of the silver powder can be effectively controlled, and the tap density of the flake silver powder finally prepared is improved; on the other hand, compared with a single reducing agent, the compound reducing agent can effectively reduce the consumption of the dispersing agent, and the reduction of the consumption of the dispersing agent can not only save the cost of raw materials, but also avoid the problems of incomplete washing of the dispersing agent, high difficulty in treatment of the dispersing agent washing liquid and the like caused by excessive consumption of the dispersing agent.
2. According to the preparation method of the high tap density flake silver powder, provided by the invention, on the basis of adopting the ascorbic acid and sodium ascorbate to compound the reducing agent, the consumption of the reducing agent and the dispersing agent and related parameters are further regulated and controlled, the spherical cluster silver powder can be prepared, the cluster on the surface of the spherical cluster silver powder is modified through shaping treatment, the spherical silver powder with controllable size can be obtained, and the flake silver powder with high tap density can be obtained after sanding treatment. In the sanding treatment process, the added grinding aid can also play a role in surface coating, so that the prepared silver powder and the organic resin are better compatible, and the preparation of silver paste is facilitated. The solar cell front electrode silver paste prepared based on the high tap density flake silver powder has the characteristics of paste rolling, roll non-sticking, easy off-screen printing, extremely small shrinkage and compact sintering film, and the prepared solar cell has higher photoelectric conversion efficiency.
Drawings
Fig. 1 is an SEM image of the spherical silver powder prepared in example 1.
Fig. 2 is an SEM image of the plate-like silver powder prepared in example 1.
Fig. 3 is an SEM image of the plate-like silver powder prepared in comparative example 3.
Fig. 4 is an SEM image of the plate-like silver powder prepared in comparative example 4.
Fig. 5 is an SEM image of the plate-like silver powder prepared in comparative example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of flake silver powder with high tap density, which comprises the following steps:
s1, respectively preparing a silver nitrate solution, a reducing agent solution and a dispersing agent solution;
s2, adding the silver nitrate solution and the dispersing agent solution into the reducing agent solution, and fully stirring to obtain a reaction solution;
s3, settling the reaction liquid, removing supernatant, and washing, filtering and drying the settled silver powder to obtain spherical cluster silver powder;
s4, shaping the spherical cluster silver powder to obtain spherical silver powder;
s5, adding the spherical silver powder into ethanol to obtain a mixed solution; adding grinding aid into the mixed solution, and performing sanding treatment after fully and uniformly mixing; and separating, washing and drying the silver powder after sanding treatment to obtain the high tap density flake silver powder.
Wherein the reducing agent solution contains ascorbic acid and sodium ascorbate. According to the invention, the reducing agent is formed by compounding the ascorbic acid and the sodium ascorbate, so that on one hand, the particle size of the silver powder can be effectively controlled, and the tap density of the finally prepared flaky silver powder can be improved; on the other hand, compared with a single reducing agent, the compound reducing agent can effectively reduce the dosage of the dispersing agent. The dispersing agent used for preparing the silver powder is generally an organic matter with large molecular weight, if the dispersing agent is used too much, the cost of raw materials can be increased, the problems of too high COD in the washing liquid and high degradation treatment difficulty can be caused in the subsequent washing process, and pollution is easy to cause. And in addition, excessive dispersing agents are difficult to wash thoroughly in the washing process, and are easy to wrap the inside and the surface of the silver powder, so that the conductivity of the silver powder is influenced.
Specifically, in the step S1, the mass ratio of the ascorbic acid to the sodium ascorbate in the reducing agent solution is preferably 1:1-2; the ratio of the mass of silver nitrate in the silver nitrate solution to the total mass of ascorbic acid and sodium ascorbate in the reducing agent solution is preferably 1:0.6-1.0; the ratio of the mass of the dispersant in the dispersant solution to the mass of the silver nitrate in the silver nitrate solution is preferably 0.02 to 0.15:1.
Through the mode, the particle size of the silver powder can be effectively regulated and controlled, and the spherical cluster silver powder with the particle size range of 4-7 mu m can be prepared only by a small amount of dispersing agent.
More preferably, in the step S1, the concentration of the silver nitrate solution is preferably 500-1500 g/L; the reducing agent solution is formed by mixing an ascorbic acid solution and a sodium ascorbate solution, and the concentrations of the ascorbic acid solution and the sodium ascorbate solution are preferably 150-200 g/L; the concentration of the dispersing agent solution is preferably 40-60 g/L, and the dispersing agent is preferably gum arabic or polyvinylpyrrolidone.
In the step S2, the silver nitrate solution and the dispersant solution are preferably added into the reducer solution at the same time, the stirring speed is preferably 200-300 r/min, and the stirring time is preferably 15-25 min.
In step S3, the precipitated silver powder is preferably washed with water and ethanol.
In step S4, the shaping process is performed in a shaper. The rotating speed of the bed knife in the shaping machine is preferably 4000-5000 r/min, the rotating speed of the side knife is preferably 3000-4000 r/min, and the shaping treatment time is preferably 10-15 min. Through the shaping treatment, the surface cluster structure of the spherical cluster silver powder obtained in the step S3 can be trimmed, and the spherical silver powder with a smooth and complete surface can be obtained. The particle diameter of the spherical silver powder is preferably 3-6 μm.
In step S5, the spherical silver powder preferably accounts for 20-30wt% of the total mass of the mixed solution formed by mixing ethanol and the spherical silver powder, the mass ratio of the grinding aid to the spherical silver powder is preferably 0.001-0.01:1, and the grinding aid is preferably one or more of oleic acid, tween 80, stearic acid, octylamine, hexadecylamine, 12-hydroxystearic acid and cinnamic acid. The addition of the grinding aid can play a role in coating the surface of the silver powder, is favorable for better compatibility of the prepared silver powder and the organic resin, and is convenient for preparing silver paste.
The sanding treatment process is carried out in a sand mill, zirconia balls are filled in the sand mill, the mass of the zirconia balls is preferably 1.5-8 times that of spherical silver powder, and the diameter of the zirconia balls is preferably 0.4-1.0 mm. When the sand grinding treatment is carried out, the rotating speed of the sand grinding machine is preferably 800-2000 r/min, and the sand grinding treatment time is preferably 10-30 min.
By the method, the particle size of the prepared high tap density flake silver powder is 4-15 mu m, the thickness is 0.5-1.2 mu m, and the tap density is 5-6 g/cm 3 。
Based on the characteristics of high tap density, good conductivity, easy compatibility with organic resin and the like of the flake silver powder, the flake silver powder is prepared into silver paste which is applied to a front electrode of a solar cell, and the flake silver powder has the characteristics of paste rolling, roll sticking prevention, easy net falling during printing, extremely small shrinkage and compact sintered film, so that the prepared solar cell has higher photoelectric conversion efficiency, and the photoelectric conversion efficiency can reach 19% -20%.
The method for preparing the high tap density plate-like silver powder provided by the invention is described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of high tap density flake silver powder, which comprises the following steps:
s1, dissolving silver nitrate in water to prepare 100mL of silver nitrate solution with mass concentration of 1500g/L; respectively preparing 300mL of ascorbic acid solution with the mass concentration of 167g/L and 400mL of sodium ascorbate solution with the mass concentration of 200g/L, and then mixing the ascorbic acid solution and the sodium ascorbate solution to obtain a reducer solution; the dispersant polyvinylpyrrolidone was dissolved in water to prepare 100mL of a dispersant solution having a mass concentration of 50 g/L.
S2, simultaneously pouring the silver nitrate solution and the dispersing agent solution prepared in the step S1 into the reducing agent solution, and stirring for 20min at a rotating speed of 260r/min to obtain a reaction solution.
S3, settling the reaction liquid obtained in the step S2, and removing the supernatant to obtain settled silver powder; washing the obtained settled silver powder with water and ethanol in sequence, and then filtering and drying the settled silver powder in sequence to obtain the spherical cluster silver powder with the particle size range of about 4-7 mu m.
And S4, placing the spherical cluster silver powder obtained in the step S3 into a shaping machine for shaping, setting the rotating speed of a bottom cutter of the shaping machine to 4500r/min, the rotating speed of a side cutter to 3500r/min, and shaping for 15min to obtain spherical silver powder with the particle size range of about 3-6 mu m, wherein an SEM (scanning electron microscope) diagram is shown in figure 1.
S5, taking 80g of the spherical silver powder obtained in the step S4, and adding the spherical silver powder into 250mL of ethanol to obtain a mixed solution; adding 0.4g of grinding aid into the mixed solution, wherein the grinding aid is prepared by mixing 0.1g of hexadecylamine and 0.3g of 12-hydroxystearic acid; after fully and evenly mixing, the mixture is guided into a sand mill for sand milling treatment. Wherein the diameter of the zirconia balls in the sand mill is 0.4mm, the mass of the zirconia balls is 8 times of the mass of the spherical silver powder, the rotating speed of the sand mill is 1500r/min, and the sand milling time is 20min. Finally, separating, washing and drying the silver powder after sanding treatment to obtain the flake silver powder with high tap density, wherein an SEM (scanning electron microscope) diagram is shown in figure 2.
Through detection, the particle size range of the high tap density flake silver powder prepared by the embodiment is about 4-15 mu m, the thickness range is about 0.5-1.2 mu m, and the tap density is 5.53g/cm 3 。
The high tap density flake silver powder prepared in the embodiment is mixed with spherical submicron silver powder and resin to prepare conductive silver paste; and printing the silver paste to obtain the solar cell. Through detection, the photoelectric conversion efficiency of the solar cell prepared based on the flake silver powder is 19.98%.
Comparative examples 1 to 2
Comparative examples 1 to 2 respectively provide a method for preparing silver powder, which is mainly different from example 1 in that the composition of the reducing agent is changed. Comparative examples 1 to 2 the reducing agent prepared by compounding ascorbic acid and sodium ascorbate in example 1 was replaced with 700mL of ascorbic acid solution having a mass concentration of 173g/L, so that the molar mass of the reducing agent was substantially the same as that in example 1. Among them, in comparative example 1, in order to ensure uniform dispersion of silver powder, the amount of the dispersant solution was increased from 100mL to 600mL, and in comparative example 2, only 100mL of the dispersant solution was added as in example 1. The remaining steps and parameters in comparative examples 1 to 2 are the same as those in example 1, and are not described here again.
Wherein, the silver powder is seriously agglomerated due to the too small amount of the dispersant in comparative example 2, and the particle size range of the silver powder obtained in step S3 is about 8 to 13 μm, and the large-sized spherical particles cannot be all ground into flakes according to the method of steps S4 to S5 in example 1 due to the too large particles, so that the flake silver powder cannot be obtained. Comparative example 1 the above problems in comparative example 2 were ameliorated by increasing the amount of the dispersant to six times that in example 1, and the silver powder was subjected to the subsequent treatments according to steps S4 to S5 to obtain plate-like silver powder.
The tap density of the flake silver powder prepared in comparative example 1 was examined to be 4.73g/cm 3 . The plate-like silver powder prepared in comparative example 1 was further applied to the preparation of a solar cell in the same manner as in example 1, and the solar cell using the plate-like silver powder in comparative example 1The photoelectric conversion efficiency of (2) was 18.56%.
As can be seen from the above results compared with example 1, when only a single ascorbic acid solution was used as the reducing agent, a large amount of dispersing agent was required to avoid the aggregation of silver powder, and when the amount of dispersing agent was increased to 6 times that of example 1, although the problem of aggregation of silver powder could be improved, too much dispersing agent also caused the problem of incomplete cleaning of dispersing agent, and the residual dispersing agent was wrapped inside and on the surface of silver powder, affecting the conductivity of silver powder, and further affecting the photoelectric conversion efficiency of the solar cell, resulting in lower tap density of the produced plate-like silver powder and lower photoelectric conversion efficiency of the solar cell. In example 1, two reducing agents, namely ascorbic acid and sodium ascorbate, are compounded according to a specific proportion, so that the dosage of the dispersing agent can be greatly reduced, and the tap density of the flake silver powder can be improved.
Comparative example 3
This comparative example provides a method for producing plate-like silver powder, differing from example 1 only in that the composition of the reducing agent is changed. In this comparative example, the reducing agent was 700mL of sodium ascorbate solution having a mass concentration of 194.8g/L, so that the molar mass of the reducing agent was substantially the same as in example 1, and the remaining steps were the same as in example 1, and will not be described again.
Tap density of the flake silver powder prepared in this comparative example was 3.87g/cm 3 The SEM image is shown in fig. 3. The plate-like silver powder was applied to the preparation of solar cell paste in the manner of example 1, and the photoelectric conversion efficiency of the obtained solar cell sheet was 16.24%.
As can be seen from fig. 3, the silver powder has a smaller particle diameter, most of the silver powder still exists as spherical particles below 1 μm after sanding, and the sanding process easily enables the small-size flake silver powder to be connected into the large-size flake silver powder, so that the tap density of the finally obtained silver powder is lower, and further the photoelectric conversion efficiency of the solar cell is affected.
Comparative example 4
This comparative example provides a method for producing plate-like silver powder, which differs from example 1 only in that the mass ratio of ascorbic acid to sodium ascorbate in the reducing agent is changed. In this comparative example, the reducing agent was formed by mixing 400mL of an ascorbic acid solution having a mass concentration of 167g/L and 300mL of a sodium ascorbate solution having a mass concentration of 200g/L, and the remaining steps were the same as in example 1, and will not be described again.
Experimental process shows that compared with the embodiment 1, the morphology of the silver powder particles prepared in the steps S1-S3 is changed, wherein the size range of large-particle silver powder is about 6-8 mu m, but a plurality of small particles exist in the silver powder, and the particle size of the silver powder particles is uneven. The tap density of the flake silver powder prepared in this comparative example was detected to be 4.82g/cm 3 The SEM image is shown in fig. 4. The plate-like silver powder was applied to the preparation of solar cell paste in the manner of example 1, and the photoelectric conversion efficiency of the obtained solar cell sheet was 17.38%.
Comparative example 5
The comparative example provides a method for preparing flake silver powder, which is different from example 1 only in that the ascorbic acid in example 1 is replaced with an equivalent amount of isoascorbic acid, and simultaneously sodium ascorbate is replaced with an equivalent amount of sodium isoascorbate, and the rest of the steps are identical to example 1, and are not repeated here.
The experimental process shows that compared with the embodiment 1, the morphology of the silver powder particles prepared by the steps S1-S3 is changed, and the particle size range is about 0.8-1.3 mu m. The tap density of the flake silver powder prepared in this comparative example was 3.28g/cm 3 An SEM image thereof is shown in fig. 5. The plate-like silver powder was applied to the preparation of solar cell paste in the manner of example 1, and the photoelectric conversion efficiency of the obtained solar cell sheet was 15.06%.
As can be seen from fig. 5, the silver powder has a smaller particle size, and the silver flakes after sanding have a smaller size, and the silver flakes are very thin, resulting in a lower tap density of the finally obtained silver powder, thereby affecting the photoelectric conversion efficiency of the solar cell.
In other embodiments of the present invention, the present invention may be appropriately modified based on embodiment 1. The method comprises the following steps: in the step S1, the mass ratio of the ascorbic acid to the sodium ascorbate in the reducing agent solution can be 1:1-2The ratio of the mass of silver nitrate to the total mass of ascorbic acid and sodium ascorbate in the reducing agent solution can be adjusted within the range of 1:0.6-1.0, the ratio of the mass of the dispersing agent to the mass of silver nitrate can be adjusted within the range of 0.02-0.15:1, gum arabic can also be used as the dispersing agent, and the concentration of the silver nitrate solution can be adjusted within the range of 500-1500 g/L. In the step S2, the stirring speed can be adjusted within the range of 200-300 r/min, and the stirring time can be adjusted within the range of 15-25 min. In the step S4, the shaping time can be adjusted within 10-15 min. In the step S5, the mass fraction of the spherical silver powder in the mixed solution can be adjusted within the range of 20-30wt%; the sanding time can be adjusted within the range of 10-30 min; the mass ratio of the grinding aid to the spherical silver powder can be adjusted within the range of 0.001-0.01:1, and the used grinding aid can be one or more of oleic acid, tween 80, stearic acid, octylamine, hexadecylamine, 12-hydroxystearic acid and cinnamic acid. The tap density of the flake silver powder prepared based on the method can reach 5-6 g/cm 3 All belong to the protection scope of the invention.
In summary, the invention provides a preparation method of high tap density flake silver powder, and relates to the technical field of metal powder preparation. The preparation method comprises the steps of preparing a silver nitrate solution, a reducing agent solution and a dispersing agent solution, wherein the reducing agent solution contains ascorbic acid and sodium ascorbate; then adding a silver nitrate solution and the dispersing agent solution into the reducing agent solution, and fully reacting to obtain spherical cluster silver powder; shaping the spherical cluster silver powder to obtain spherical silver powder; adding spherical silver powder into ethanol, adding a grinding aid, fully and uniformly mixing, performing sanding treatment, and separating, washing and drying to obtain the high tap density flake silver powder. Through the mode, the invention can prepare the flake silver powder with controllable size and high tap density by a simple process and with less dispersant consumption. The electrode paste of the solar cell is prepared based on the flake silver powder, so that the photoelectric conversion efficiency of the solar cell is improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the flake silver powder with high tap density is characterized by comprising the following steps of:
s1, respectively preparing a silver nitrate solution, a reducing agent solution and a dispersing agent solution; the reducing agent solution contains ascorbic acid and sodium ascorbate;
s2, adding the silver nitrate solution and the dispersing agent solution into the reducing agent solution, and fully stirring to obtain a reaction solution;
s3, settling the reaction liquid, removing supernatant, and washing, filtering and drying the settled silver powder to obtain spherical cluster silver powder;
s4, shaping the spherical cluster silver powder to obtain spherical silver powder;
s5, adding the spherical silver powder into ethanol to obtain a mixed solution; adding grinding aid into the mixed solution, and performing sanding treatment after fully and uniformly mixing; and separating, washing and drying the silver powder after sanding treatment to obtain the high tap density flake silver powder.
2. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S1, the mass ratio of the ascorbic acid to the sodium ascorbate in the reducing agent solution is 1:1-2; the ratio of the mass of silver nitrate in the silver nitrate solution to the total mass of ascorbic acid and sodium ascorbate in the reducing agent solution is 1:0.6-1.0.
3. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S1, the ratio of the mass of the dispersing agent in the dispersing agent solution to the mass of the silver nitrate in the silver nitrate solution is 0.02-0.15:1.
4. The method for preparing high tap density plate-like silver powder according to claim 3, wherein: the dispersing agent is gum arabic or polyvinylpyrrolidone.
5. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S1, the concentration of the silver nitrate solution is 500-1500 g/L.
6. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S2, the silver nitrate solution and the dispersing agent solution are simultaneously added into the reducing agent solution, the stirring speed is 200-300 r/min, and the stirring time is 15-25 min.
7. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S4, the shaping treatment is performed for 10-15 min, and the particle size of the spherical silver powder is 3-6 mu m.
8. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S5, the spherical silver powder accounts for 20-30wt% of the total mass of the mixed solution formed by mixing ethanol and the spherical silver powder.
9. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S5, the sanding treatment is performed for 10-30 min, the particle size of the high tap density flake silver powder is 4-15 mu m, and the thickness of the high tap density flake silver powder is 0.5-1.2 mu m.
10. The method for preparing the high tap density plate-like silver powder according to claim 1, wherein: in the step S5, the grinding aid is one or more of oleic acid, tween 80, stearic acid, octylamine, hexadecylamine, 12-hydroxystearic acid and cinnamic acid; the mass ratio of the grinding aid to the spherical silver powder is 0.001-0.01:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410093440.XA CN117600482A (en) | 2024-01-23 | 2024-01-23 | Preparation method of flake silver powder with high tap density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410093440.XA CN117600482A (en) | 2024-01-23 | 2024-01-23 | Preparation method of flake silver powder with high tap density |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117600482A true CN117600482A (en) | 2024-02-27 |
Family
ID=89956566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410093440.XA Pending CN117600482A (en) | 2024-01-23 | 2024-01-23 | Preparation method of flake silver powder with high tap density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117600482A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005146387A (en) * | 2003-11-18 | 2005-06-09 | Mitsui Mining & Smelting Co Ltd | Dendrite-shaped fine silver powder, and its production method |
| KR20130142852A (en) * | 2012-06-20 | 2013-12-30 | (주)이건이엔씨 | Method for preparing silver cluster of micro-size consisting of agglomerate nano-silver particle |
| CN103506630A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院理化技术研究所 | Method for preparing flaky silver powder with ultralow apparent density |
| CN104400000A (en) * | 2014-11-07 | 2015-03-11 | 中国船舶重工集团公司第七一二研究所 | Method for preparing spherical silver powder |
| CN105345012A (en) * | 2015-07-20 | 2016-02-24 | 昆明贵金属研究所 | Preparation method and application for high-conductivity flake-shaped silver powder |
| CN105458286A (en) * | 2015-11-30 | 2016-04-06 | 成都市天甫金属粉体有限责任公司 | Production method of mono-dispersed silver powder |
| JP2018104724A (en) * | 2016-12-22 | 2018-07-05 | 住友金属鉱山株式会社 | Production method of silver-coated copper powder |
| CN112296351A (en) * | 2020-09-29 | 2021-02-02 | 湖南诺尔得材料科技有限公司 | Preparation method of high-tap-density ultrafine silver powder |
| CN114101699A (en) * | 2021-11-26 | 2022-03-01 | 昆明银科电子材料股份有限公司 | Method for preparing high-crystallization silver powder for heat-conducting adhesive through rapid reduction |
| CN116713477A (en) * | 2023-06-09 | 2023-09-08 | 桂林电子科技大学 | Preparation method and application method of nano silver powder |
-
2024
- 2024-01-23 CN CN202410093440.XA patent/CN117600482A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005146387A (en) * | 2003-11-18 | 2005-06-09 | Mitsui Mining & Smelting Co Ltd | Dendrite-shaped fine silver powder, and its production method |
| KR20130142852A (en) * | 2012-06-20 | 2013-12-30 | (주)이건이엔씨 | Method for preparing silver cluster of micro-size consisting of agglomerate nano-silver particle |
| CN103506630A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院理化技术研究所 | Method for preparing flaky silver powder with ultralow apparent density |
| CN104400000A (en) * | 2014-11-07 | 2015-03-11 | 中国船舶重工集团公司第七一二研究所 | Method for preparing spherical silver powder |
| CN105345012A (en) * | 2015-07-20 | 2016-02-24 | 昆明贵金属研究所 | Preparation method and application for high-conductivity flake-shaped silver powder |
| CN105458286A (en) * | 2015-11-30 | 2016-04-06 | 成都市天甫金属粉体有限责任公司 | Production method of mono-dispersed silver powder |
| JP2018104724A (en) * | 2016-12-22 | 2018-07-05 | 住友金属鉱山株式会社 | Production method of silver-coated copper powder |
| CN112296351A (en) * | 2020-09-29 | 2021-02-02 | 湖南诺尔得材料科技有限公司 | Preparation method of high-tap-density ultrafine silver powder |
| CN114101699A (en) * | 2021-11-26 | 2022-03-01 | 昆明银科电子材料股份有限公司 | Method for preparing high-crystallization silver powder for heat-conducting adhesive through rapid reduction |
| CN116713477A (en) * | 2023-06-09 | 2023-09-08 | 桂林电子科技大学 | Preparation method and application method of nano silver powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111922356B (en) | Microcrystalline silver powder with nano-silver surface structure and preparation method thereof | |
| CN108134090A (en) | A kind of nanometer of bismuth/carbon composite and preparation method thereof | |
| DE112006000205B4 (en) | Photocatalytic processes for the preparation of electrocatalyst materials | |
| CN108336345A (en) | A kind of preparation method of nano-micro structure silicium cathode material | |
| WO2016095559A1 (en) | Method for dispersing composite conductive agent in electrode slurry of lithium ion capacitor | |
| CN109830685A (en) | A kind of composite conducting slurry, preparation method and the usage | |
| CN109732102B (en) | Monodisperse conductive silver powder suitable for high-temperature and low-temperature silver pastes and preparation method thereof | |
| CN109411713A (en) | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery | |
| CN111180741A (en) | Carbon-coated current collector coated with three-dimensional graphene powder and preparation method thereof | |
| CN111785944B (en) | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste | |
| CN113399679A (en) | Preparation method of high-tap aging-resistant superfine silver powder for electronic paste | |
| CN114420372B (en) | Preparation method of nano silver powder for preparing silver electrode on back of solar cell | |
| CN107732195A (en) | A kind of graphite modified method and graphite/silicon composite | |
| CN117600482A (en) | Preparation method of flake silver powder with high tap density | |
| CN115642236B (en) | Silicon-based anode material, preparation method and application thereof | |
| Ren et al. | Carbon/binder free 3D Si@ Cu2O anode for high performance lithium ion battery | |
| CN1505593A (en) | Methods of making a niobium metal oxide | |
| CN114749654A (en) | Blocky superfine silver powder and preparation method and application thereof | |
| CN114464799A (en) | Iron oxide nanoparticle/flake iron hydroxide/multilayer graphene composite material and preparation method thereof | |
| CN113399670A (en) | Double-element equivalent transformation high-entropy alloy powder and preparation method thereof | |
| CN108039476B (en) | Nano indium oxide/carbon composite material and preparation method thereof | |
| CN105251996A (en) | Core-shell structure copper-coated iron nanometer composite powder and preparation method and application thereof | |
| TWI379908B (en) | Method for continuously fabricating silver nanowire | |
| Li et al. | Novel Fe-doped BiOI nanosheets attaching surface Fe (III) clusters: Additional superoxide radical and enhanced charge separation efficiency for remarkable tetracycline decomposition | |
| CN114933324B (en) | Ce (cerium) 2 O 2 S@C core-shell nanostructure composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |