CN116283622A - Nickel metal powder and method for producing nickel metal powder - Google Patents
Nickel metal powder and method for producing nickel metal powder Download PDFInfo
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- CN116283622A CN116283622A CN202310050228.0A CN202310050228A CN116283622A CN 116283622 A CN116283622 A CN 116283622A CN 202310050228 A CN202310050228 A CN 202310050228A CN 116283622 A CN116283622 A CN 116283622A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 title description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 47
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 47
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 41
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229920002521 macromolecule Polymers 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011858 nanopowder Substances 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 239000003985 ceramic capacitor Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- CKIIJIDEWWXQEA-UHFFFAOYSA-N 2-(bromomethyl)-1,3-dioxolane Chemical compound BrCC1OCCO1 CKIIJIDEWWXQEA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KTOIESNTVCLSFG-UHFFFAOYSA-N 1-chloropropan-2-ol;sodium Chemical compound [Na].CC(O)CCl KTOIESNTVCLSFG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying 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
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- B22F1/05—Metallic powder characterised by the size or surface area of the 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
- C07C217/40—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the same carbon atom of the carbon skeleton, e.g. amino-ketals, ortho esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses metal nickel powder and a manufacturing method of the metal nickel powder, and relates to the technical field of powder material preparation. The method for producing the metallic nickel powder comprises the following steps: taking a surfactant-macromolecule system as a soft template, and preparing metal nickel powder by adopting a liquid-phase chemical reduction method; the surfactant includes anionic surfactants; the anionic surfactant is obtained by modifying a chemical structure shown in a formula I through sulfonation reaction by 3-chlorine-2-hydroxy propane sodium sulfonate:
i, a step of I; the macromolecules include hydroxyethyl cellulose. The metal nickel powder provided by the invention has lower average particle size, improved high-temperature sintering performance, better dispersion stability and obviously improved product quality.
Description
Technical Field
The invention belongs to the technical field of powder material preparation, and particularly relates to metal nickel powder and a manufacturing method of the metal nickel powder.
Background
Metallic nickel is far more stable to air and humidity than iron, and is excellent in corrosion resistance, heat resistance and wear resistance, and therefore, can be used as stainless steel for kitchens, tableware and the like. Further, the material is excellent in heat radiation characteristics and electric characteristics, and therefore, the material can be used as a material for nickel-metal hydride batteries and lithium ion batteries, and in addition to these, the material can be used as an electrode Material for Laminated Ceramic Capacitors (MLCCs) which are indispensable as components for mobile phones and personal computers.
With the miniaturization and the increase of capacity of ceramic capacitors, the internal electrodes of the conventional laminated ceramic capacitors are also thinned and low in resistance, and in general, peeling between an electrode layer and a dielectric layer or cracking of the electrode layer is likely to occur during manufacturing and firing of the laminated capacitors, and if coarse particles exist in nickel powder, the surface of the electrode layer is increased in roughness, so that the phenomenon of short circuit or voltage drop between electrode layers is caused, which causes potential safety hazards to high-reliability automotive rule-level MLCCs, and new technical requirements for nickel powder large particles, particle size distribution and sintering performance are required to be raised for the problems.
Disclosure of Invention
The invention aims to provide a metal nickel powder and a manufacturing method thereof, wherein the metal nickel powder has lower average particle diameter, improved high-temperature sintering performance, better dispersion stability and obviously improved product quality.
The technical scheme adopted by the invention for achieving the purpose is as follows:
an anionic surfactant is obtained by modifying a chemical structure shown in a formula I through sulfonation reaction by 3-chlorine-2-hydroxy propane sodium sulfonate:
the invention firstly adopts bromoacetaldehyde dimethyl acetal and tri (2-amino ethyl) amine to prepare an intermediate through chemical bonding, and then adopts 3-chloro-2-hydroxy propane sodium sulfonate to carry out sulfonation treatment to obtain an anionic surfactant with a novel structure, and the anionic surfactant has good surface activity; the particle size structure of the metal nickel powder can be effectively improved by applying the particle size distribution agent to the preparation process of the metal nickel powder, the particle size distribution is narrower, and the average particle size is reduced; meanwhile, the high-temperature sintering performance of the metal nickel powder is obviously improved, and the initial oxidation temperature is increased; the dispersion performance of the metal nickel powder is obviously improved, and the quality of the prepared metal powder product is higher. The reason for this may be that the anionic surfactant with a novel structure is prepared, has more active groups, better interacts with macromolecules, is connected in series by macromolecular chains, and may form a network-like ordered self-assembly body, so that metal ions can be attached on the micelle interface, a space network structure forms a three-dimensional barrier, and the possible steric hindrance or electrostatic effect can improve the stability of metal nanoparticles and place agglomeration; and the transition growth of particles can be prevented, the average particle size of metal nano particles is effectively reduced, and the particle size distribution is improved.
Preferably, the surface tension of the anionic surfactant is 20-30 mN/m.
The invention also discloses a preparation method of the anionic surfactant, which comprises the following steps:
step one: mixing bromoacetaldehyde dimethyl acetal and tri (2-aminoethyl) amine, adding absolute ethyl alcohol for dissolution, carrying out reflux reaction for 8-12 h, filtering, washing with 0.8-1.2M sodium hydroxide solution and deionized water for 2-3 times in sequence, recrystallizing, filtering and drying to obtain an intermediate A;
step two: and mixing the intermediate A and 3-chloro-2-hydroxy sodium propane sulfonate, adding absolute ethyl alcohol for dissolution, then adding triethylamine, reacting for 2-4 hours at 75-85 ℃, washing the reaction product with acetone for 2-4 times, and evaporating to constant weight at room temperature to obtain the anionic surfactant.
Preferably, in the first step, the molar ratio of bromoacetaldehyde dimethyl acetal to tri (2-aminoethyl) amine is 3.1-3.4: 1, a step of; the solid-to-liquid ratio of bromoacetaldehyde dimethyl acetal to absolute ethyl alcohol is 0.1-0.2 g:1mL.
Preferably, in the second step, the molar ratio of the intermediate A to the sodium 3-chloro-2-hydroxy propane sulfonate is 1: 3-4; the solid-liquid ratio of the intermediate A to the absolute ethyl alcohol is 0.5-0.8 g:1mL; the mol ratio of triethylamine to the intermediate A is 3-3.3: 1.
a method of manufacturing metallic nickel powder, comprising: taking a surfactant-macromolecule system as a soft template, and preparing metal nickel powder by adopting a liquid-phase chemical reduction method;
the above surfactant comprises the anionic surfactant of claim 1; the macromolecules include hydroxyethyl cellulose.
Preferably, in the method for producing metallic nickel powder, nickel ions are derived from NiCl 2 。
More specifically, the method for producing the metallic nickel powder comprises:
preparation of NiCl 2 -surfactant-macromolecule water solution, keeping the temperature in a water bath at 40-45 ℃ for 1-3 hours; and (3) regulating the pH value of the system to 10.5-11.5 by using a sodium carbonate solution with the concentration of 2-3M, adding excessive hydrazine hydrate, uniformly mixing, reacting at 65-75 ℃ until the color of the solution turns black, cooling rapidly until no bubble is generated, centrifuging to obtain a precipitate, washing 2-4 times by using ultrapure water and absolute ethyl alcohol in sequence, and drying to obtain the metal nickel powder.
Preferably, the molar ratio of hydrazine hydrate to nickel ions is 20-30: 1.
preferably, the surfactant may also be SDS.
Note that NiCl 2 In surfactant-macromolecule aqueous solution, niCl 2 The concentration is 30-40 mM; the concentration of the surfactant is 6-30 mM; the concentration of macromolecules is 2-20 g/L.
Further, niCl 2 In surfactant-macromolecule aqueous solution, the concentration of surfactant and macromolecule needs to be optimized and adjusted according to the change of the species.
Note that NiCl 2 -the surfactant-macromolecule aqueous solution system comprises:
（1）NiCl 2 （30~40mM）-SDS（10-12 mM) -hydroxyethylcellulose (2-6 g/L) aqueous solution;
（2）NiCl 2 (30-40 mM) -anionic surfactant (6-8 mM) -hydroxyethylcellulose (8-10 g/L) in water.
More preferably, modified hydroxyethylcellulose is used instead of hydroxyethylcellulose.
The modified hydroxyethyl cellulose is obtained by chemically modifying hydroxyethyl cellulose with 2-bromomethyl-1, 3-dioxolane. The invention adopts 2-bromomethyl-1, 3-dioxolane to chemically modify hydroxyethyl cellulose to obtain modified hydroxyethyl cellulose, and the modified hydroxyethyl cellulose is compounded with a surfactant for use, and is applied to the preparation process of metal nickel powder, so that the average particle size of metal nano powder is further reduced, the high-temperature sintering performance is enhanced, and better dispersion stability is shown. The reason for this may be that the modification of hydroxyethyl cellulose with 2-bromomethyl-1, 3-dioxolane introduces oxygen-containing groups, and the network structure formed with the surfactant is optimized, thereby having a beneficial effect on the particle size structure and performance of the metallic nickel powder.
Specifically, the preparation method of the modified hydroxyethyl cellulose comprises the following steps:
adding isopropanol into hydroxyethyl cellulose, and stirring for 20-30 min to obtain a solution with the concentration of 7-9wt%; slowly dropwise adding a sodium hydroxide solution with the concentration of 2-4wt% under the condition of stirring, introducing nitrogen for 20-30 min after the dropwise adding, and swelling and activating for 24-30 h under the sealed condition; then placing the mixture in a water bath condition at 75-85 ℃, slowly dropwise adding an isopropanol solution of 2-bromomethyl-1, 3-dioxolane with the concentration of 0.5-0.8 g/mL, and introducing nitrogen again for 10-15 min after the dropwise adding is finished, and reacting for 3-5 h under a closed condition; and then cooling rapidly with cold water, washing with n-hexane for 2-4 times, washing with 80% acetone for 2-4 times, soaking with 80% acetone for 4-6 hours, neutralizing the pH to 7-8 with glacial acetic acid, filtering, washing with acetone for 3-5 times, soaking for 4-6 hours, filtering again, and vacuum drying at 40-45 ℃ for 4-6 hours to obtain the modified hydroxyethyl cellulose.
Preferably, the addition amount of the 2-bromomethyl-1, 3-dioxolane is 23-27 wt% of the hydroxyethyl cellulose.
Preferably, the solid content of the modified hydroxyethyl cellulose is 85-90%.
Further, niCl 2 -surfactant-macromolecule aqueous solution system concentration is: niCl 2 (30-40 mM) -anionic surfactant (8-10 mM) -modified hydroxyethylcellulose (5-8 g/L) in water.
The invention also discloses the metal nickel powder obtained by the manufacturing method, and the average particle size of the metal nickel powder is 100-400 nm.
Preferably, the initial oxidation temperature of the metallic nickel powder is > 420 ℃; more preferably, the initial oxidation temperature of the metallic nickel powder is > 440 ℃.
It is a further object of the present invention to provide the use of the above anionic surfactant for the preparation of metal nanopowders.
Preferably, the metal nano-powder comprises a metal nickel powder or a metal gold powder.
The invention also aims to disclose the application of the metal nickel powder in preparing the electrode material of the chip type multilayer ceramic capacitor.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly adopts bromoacetaldehyde dimethyl acetal and tri (2-amino ethyl) amine to prepare an intermediate through chemical bonding, and then carries out sulfonation treatment to obtain an anionic surfactant with a novel structure, which is applied to the preparation process of metal nickel powder, can effectively improve the particle size structure of the metal nickel powder, obviously reduces the average particle size and obtains an ultrafine metal powder product; meanwhile, the high-temperature sintering performance of the metal nickel powder is obviously improved, and the dispersion performance of the metal nickel powder is improved. Meanwhile, the modified hydroxyethyl cellulose is obtained by adopting 2-bromomethyl-1, 3-dioxolane to chemically modify the hydroxyethyl cellulose, and the modified hydroxyethyl cellulose is compounded with a surfactant for use, is applied to the preparation process of metal nickel powder, and is used for further reducing the average particle size of metal nano powder, enhancing the high-temperature sintering performance and showing better dispersion stability.
Therefore, the invention provides the metal nickel powder and the manufacturing method thereof, the metal nickel powder has lower average particle diameter, improved high-temperature sintering performance, better dispersion stability and obviously improved product quality.
Drawings
FIG. 1 is an infrared spectrum of an anionic surfactant of the present invention;
FIG. 2 is an infrared spectrum of modified hydroxyethylcellulose in the present invention;
fig. 3 is an SEM image of metallic nickel powder in the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following describes in detail various embodiments of the present invention with reference to the embodiments. However, those of ordinary skill in the art will understand that in various embodiments of the present invention, numerous technical details have been set forth in order to provide a better understanding of the present application. However, the technical solutions claimed in the present application can be implemented without these technical details and with various changes and modifications based on the following embodiments.
Example 1:
preparation of anionic surfactant:
step one: mixing bromoacetaldehyde dimethyl acetal and tris (2-aminoethyl) amine (the molar ratio is 3.3:1), adding absolute ethyl alcohol (the solid-to-liquid ratio of bromoacetaldehyde dimethyl acetal to absolute ethyl alcohol is 0.15g:1 mL), dissolving, carrying out reflux reaction for 12h, filtering, washing with 1M concentration sodium hydroxide solution and deionized water for 3 times in sequence, recrystallizing, filtering and drying to obtain an intermediate A; 1 H NMR（400 MHz，CDCl 3 ）：δ：5.09（t，3H，-CH），3.43（s，18H，-CH 3 ），2.81（d，6H，-CH 2 ），2.30~2.50（m，12H，-C 2 H）；
step two: mixing the intermediate A and 3-chlorine-2-hydroxy sodium propane sulfonate (molar ratio of 1:3.4), adding absolute ethyl alcohol (solid-to-liquid ratio of the intermediate A to the absolute ethyl alcohol is 0.6g:1 mL) for dissolution, then adding triethylamine (molar ratio of the intermediate A to the intermediate A is 3.2:1), reacting for 3 hours at 80 ℃, washing the reaction product with acetone for 3 times, and evaporating to constant weight at room temperature to obtain the anionic surfactant (surface tension is 26.8mN/m, and is measured by adopting a full-automatic surface tension meter).
Manufacturing metallic nickel powder:
preparation of NiCl 2 (34 mM) -anionic surfactant (7 mM) -hydroxyethylcellulose (9 g/L) in water bath at 42℃for 2h; and regulating the pH value of the system to 11.0 by using a sodium carbonate solution with the concentration of 2.5M, adding excessive hydrazine hydrate (the molar ratio of the hydrazine hydrate to nickel ions is 26:1), uniformly mixing, reacting at 70 ℃ until the color of the solution becomes black, cooling rapidly until no bubbles are generated, centrifuging to obtain a precipitate, washing with ultrapure water and absolute ethyl alcohol for 4 times in sequence, and drying to obtain the metal nickel powder.
Example 2:
the metallic nickel powder was produced in a manner different from that of example 1 in that: preparation of NiCl 2 (32 mM) -anionic surfactant (6 mM) -hydroxyethylcellulose (8 g/L) in water; the molar ratio of hydrazine hydrate to nickel ions is 21:1.
the preparation of the anionic surfactant was the same as in example 1.
Example 3:
the metallic nickel powder was produced in a manner different from that of example 1 in that: preparation of NiCl 2 (37 mM) -anionic surfactant (8 mM) -hydroxyethylcellulose (10 g/L) in water; the molar ratio of hydrazine hydrate to nickel ions is 28:1.
the preparation of the anionic surfactant was the same as in example 1.
Example 4:
the metallic nickel powder was produced in a manner different from that of example 1 in that: preparation of NiCl 2 (34 mM) -SDS (11 mM) -hydroxyethylcellulose (5 g/L).
Example 5:
the metallic nickel powder was produced in a manner different from that of example 1 in that: preparation of NiCl 2 (34 mM) -anionic surfactant (9 mM) -modified hydroxyethylcellulose (6 g/L) in water.
Preparation of the modified hydroxyethyl cellulose:
adding isopropanol into hydroxyethyl cellulose, and stirring for 25min to obtain a solution with the concentration of 8 wt%; slowly dropwise adding a sodium hydroxide solution with the concentration of 3.2wt% under the condition of stirring, introducing nitrogen for 25min after the dropwise adding, and swelling and activating for 24h under the airtight condition; then placing the mixture in a water bath at 80 ℃, slowly dripping an isopropanol solution of 2-bromomethyl-1, 3-dioxolane with the concentration of 0.6g/mL (the added amount is 25.4wt% of hydroxyethyl cellulose), introducing nitrogen again for 13min after the dripping is finished, and reacting for 4h under a closed condition; then cooling with cold water rapidly, washing with n-hexane for 4 times, washing with 80% acetone for 4 times, soaking with 80% acetone for 5 hours, neutralizing pH to 7.6 with glacial acetic acid, filtering, washing with acetone for 5 times, soaking for 5 hours, filtering again, and vacuum drying at 45deg.C for 5 hours to obtain modified hydroxyethyl cellulose (solid content of 88.2%).
Example 6:
the metallic nickel powder was produced in a manner different from that of example 5 in that: preparation of NiCl 2 (34 mM) -SDS (10 mM) -modified hydroxyethylcellulose (7 g/L) solution.
The modified hydroxyethyl cellulose was prepared as in example 5.
Test example 1:
infrared sign
The testing is carried out by adopting a Fourier infrared spectrometer, and the testing wavelength is 4000-500 cm -1 。
The above test was performed on the anionic surfactant prepared in example 1, and the results are shown in fig. 1. From the analysis of the figure, 3395cm -1 Characteristic absorption peak of-OH appears nearby, 3000-2800 cm -1 Characteristic absorption peak of methyl and methylene appears in the range of 1435cm -1 Characteristic absorption peak of C-N bond appears nearby, 1355cm -1 、1062cm -1 The characteristic absorption peak of the sulfonic acid group appears nearby, and the above result indicates that the anionic surfactant in example 1 was successfully produced.
The modified hydroxyethyl cellulose prepared in example 5 and hydroxyethyl cellulose were subjected to the above test, and the results are shown in fig. 2. From the analysis in the figure, it can be seen that the modified hydroxyethylcellulose prepared in example 5 was infrared compared to the infrared test results of hydroxyethylcellulose1456cm of spectrum -1 、1400cm -1 The asymmetric and symmetric bending vibration absorption peaks of the nearby methyl groups, methylene groups varied to varying degrees, indicating successful preparation of the modified hydroxyethylcellulose in example 5.
SEM characterization
The test was performed using a scanning electron microscope. And (3) dispersing and dripping the powder sample to be tested after washing by absolute ethyl alcohol on a copper sample table, volatilizing and drying at room temperature, performing surface metal spraying treatment, and then placing the powder sample into an instrument for testing. The operating voltage was 20kV.
The above test was performed on the metallic nickel powder prepared in example 1, and the results are shown in fig. 3. From the analysis of the figure, the metal nickel powder prepared in the example 1 is basically spherical, and the surface of the metal nickel powder presents a special shape of needle superposition and is uniformly distributed. The particle size distribution of the particles was narrower in the SEM image of the product prepared in example 1 than the test results of the metallic nickel powder prepared in example 4.
Test example 2:
particle size measurement
The above test was performed on the metallic nickel powders prepared in examples 1 to 6, and the results are shown in table 1:
table 1 average particle diameter test results
From the data analysis in table 1, the average particle size of the metal nickel powder prepared in example 1 is obviously lower than that of example 4, which shows that the metal nickel powder prepared by the method of the invention is prepared by compounding the anionic surfactant prepared by the method of the invention with hydroxyethyl cellulose, and the average particle size of the metal powder can be effectively reduced, so that a finer nickel powder product can be obtained. Example 5 has better effect than example 1, and example 6 has better effect than example 4, which shows that after 2-bromomethyl-1, 3-dioxolane is adopted to modify hydroxyethyl cellulose, the hydroxyethyl cellulose is compounded with a surfactant to prepare metal nickel powder, so that the particle size of the nickel powder can be further reduced, and the particle size distribution of the nickel powder can be improved.
Test example 3:
sintering temperature measurement
The oxidation temperature is tested by TG 209 F1 of German resistant company, the initial oxidation temperature is characterized by the sintering temperature, and if the initial oxidation temperature is high, the sintering temperature of the product is high.
Determination of dispersibility
The passing rate of the sieve can reflect the dispersibility of the product, and the better the dispersibility is, the higher the passing rate of the nickel powder on the sieve is. And (5) sieving the prepared metal nickel powder with a 100-mesh sieve, and calculating the sieving passing rate.
The above test was performed on the metallic nickel powders prepared in examples 1 to 6, and the results are shown in table 2:
TABLE 2 sintering Performance level Dispersion Property test results
From the data analysis in table 2, the initial oxidation temperature of the metal nickel powder prepared in example 1 is significantly higher than that of example 4, which indicates that the prepared metal nickel powder has better stability when the anionic surfactant prepared by the invention is compounded with hydroxyethyl cellulose, and the initial oxidation temperature is improved, and the high-temperature sintering performance is improved. The effect of example 5 is obviously better than that of example 1, and the effect of example 6 is better than that of example 4, which shows that after the hydroxyethyl cellulose is modified by 2-bromomethyl-1, 3-dioxolane, the metallic nickel powder is prepared by compounding the modified hydroxyethyl cellulose with a surfactant, so that the high-temperature sintering capacity of the nickel powder can be further improved. Meanwhile, the sieving passing rate of the metal nickel powder prepared in the embodiment 1 is obviously higher than that of the embodiment 4, which shows that the prepared metal nickel powder has better dispersibility when the anionic surfactant prepared by the invention is compounded with hydroxyethyl cellulose. The effect of example 5 is obviously better than that of example 1, and the effect of example 6 is better than that of example 4, which shows that after the hydroxyethyl cellulose is modified by 2-bromomethyl-1, 3-dioxolane, the metallic nickel powder is prepared by compounding the modified hydroxyethyl cellulose with a surfactant, so that the dispersibility of the nickel powder can be further improved, the occurrence of product agglomeration phenomenon is reduced, and the product quality is improved.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. An anionic surfactant is obtained by modifying a chemical structure shown in a formula I through sulfonation reaction by 3-chlorine-2-hydroxy propane sodium sulfonate:
2. the anionic surfactant according to claim 1, characterized in that: the surface tension of the anionic surfactant is 20-30 mN/m.
3. A method of manufacturing metallic nickel powder, comprising: taking a surfactant-macromolecule system as a soft template, and preparing metal nickel powder by adopting a liquid-phase chemical reduction method;
the surfactant comprises the anionic surfactant of claim 1; the macromolecule includes hydroxyethyl cellulose.
4. A method of producing metallic nickel powder according to claim 3, wherein: in the method for producing metallic nickel powder, nickel ions are derived from NiCl 2 。
5. The metallic nickel powder obtained by the production process according to claim 3, wherein the average particle diameter is 100 to 400nm.
6. The metallic nickel powder according to claim 5, wherein: the initial oxidation temperature of the metallic nickel powder is more than 420 ℃.
7. Use of an anionic surfactant according to claim 1 for the preparation of metal nanopowders.
8. The use according to claim 7, characterized in that: the metal nano-powder comprises metal nickel powder or metal gold powder.
9. The use of the metal nickel powder according to claim 5 for preparing a chip-type multi-layer ceramic capacitor electrode material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6447571B1 (en) * | 1998-07-15 | 2002-09-10 | Toho Titanium Co., Ltd. | Metal powder |
| KR20050118837A (en) * | 2004-06-15 | 2005-12-20 | 주식회사 엘지생활건강 | Mixed surfactant system |
| CN113579247A (en) * | 2021-08-17 | 2021-11-02 | 化学与精细化工广东省实验室潮州分中心 | Preparation method of nano nickel powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6447571B1 (en) * | 1998-07-15 | 2002-09-10 | Toho Titanium Co., Ltd. | Metal powder |
| KR20050118837A (en) * | 2004-06-15 | 2005-12-20 | 주식회사 엘지생활건강 | Mixed surfactant system |
| CN113579247A (en) * | 2021-08-17 | 2021-11-02 | 化学与精细化工广东省实验室潮州分中心 | Preparation method of nano nickel powder |
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