CN114350208B - Preparation method of additive-free metal sulfide ink-jet printing ink - Google Patents
Preparation method of additive-free metal sulfide ink-jet printing ink Download PDFInfo
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- CN114350208B CN114350208B CN202210070130.7A CN202210070130A CN114350208B CN 114350208 B CN114350208 B CN 114350208B CN 202210070130 A CN202210070130 A CN 202210070130A CN 114350208 B CN114350208 B CN 114350208B
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Abstract
The invention provides a preparation method of additive-free nickel sulfide, cobalt sulfide and zinc sulfide ink for ink-jet printing. And obtaining the metal sulfide nano-particles by controlling various parameters in a one-step solvothermal method and a cooling process. The metal sulfide ink with ultrahigh dispersion stability is prepared by uniform dispersion according to a proper proportion, and a microelectronic device prepared by the metal sulfide ink has excellent performance in the field of energy storage or photocatalysis; the viscosity of the ink is 1-5 cP, and the surface tension is 20-70 mN/m. The preparation method avoids the conventional technologies of mechanical grinding, additive-assisted dispersion and the like in the traditional ink-jet printing ink, and fundamentally solves the problems of poor stability, easy blockage of a nozzle and the like of the metal sulfide ink-jet printing ink.
Description
Technical Field
The invention relates to a preparation method of ink-jet printing ink, in particular to a preparation method of multi-sulfide additive-free ink.
Background
The ink-jet printing technology is a precise fluid micro-distribution technology with high process repeatability, and is also called a micro-nano deposition system; in the working process, because no heating and shearing stress is generated, the solvent characteristics such as molecular activity can not be changed, so that the system can be applied to the fields of photoelectric devices, organic electronics, multiple construction of materials and the like to a certain extent. The metal sulfide is rich in content and low in price, and the electronegativity of sulfur ions is lower than that of oxygen ions, so that the microstructure of the generated metal sulfide is more stable than that of corresponding metal oxides, and the metal sulfide is more favorable for electron transmission. In addition, the electrochemical activity of the metal sulfide is higher than that of the oxide, and the nickel sulfide, the cobalt sulfide and the zinc sulfide have extremely high performance in the fields of energy storage and photocatalysis, and are considered to be microelectronic materials with great development prospects.
At present, the problems of the metal sulfide ink-jet printing ink are that:
problem 1: the nano particles are easy to aggregate and precipitate, the printing stability of equipment is influenced, and the quality guarantee period is short. The existing sulfide preparation method is to dissolve metal salt and sulfur source in water or organic solvent or mixed solution of water and organic matter, then to heat or calcine the reaction kettle to a set temperature and keep the temperature for a period of time to obtain the target product. The larger functional material is crushed into small particles under the action of mechanical force and dispersed in a system, and due to the factors of high surface energy, particle quantum tunnel effect, unbalanced van der waals force and the like, the risk of blocking a spray head due to sedimentation caused by aggregation of large particles exists, the printing stability is poor, the performance is deteriorated, and the quality guarantee period is short.
Problem 2: additives such as surfactants have a negative effect on the material properties. In order to reduce the surface energy of the metal sulfide, a large amount of surfactant is often added into the existing metal sulfide ink; the adsorption of the nano particles on the surface of the nano particles produces the reinforced three-dimensional protection effect and inhibits the coagulation phenomenon of nano materials. Due to poor conductivity and steric hindrance effect of the surfactant, the conductivity, electrochemical activity and ion diffusion accessibility of the microelectronic device are reduced, and the performance of the microelectronic device is negatively affected.
Therefore, improving the existing ink preparation process to overcome the above two difficulties of mutual toggle has become the key to the migration and wide application of current ink-jet printing technology to the functional material field. In addition, the preparation of nanoparticles with appropriate size overcomes the obstacles of high surface energy, quantum tunneling of particles, unbalanced van der waals force and the like, and the realization of dynamic balance between the surface force of functional materials and the acting force between polar molecules of solvents is a major challenge faced by researchers at present.
Disclosure of Invention
In view of the above-mentioned problems, it is an effective solution to prepare a metal sulfide which can be stably dispersed in a suitable dispersant without using an additive such as a surfactant. The invention realizes the dynamic balance of the intermolecular force between the nanometer functional material and the dispersant by utilizing the template to inhibit the agglomeration phenomenon generated in the crystallization process and regulating the nucleation and the nuclear growth rate of the functional material, and prepares the metal sulfide ink with ultrahigh dispersion stability on the premise of ensuring the performance of the functional material.
A method of making an additive-free metal sulfide ink-jet printing ink, the method comprising the steps of:
step 1: dispersing 0.4-0.6 g of metal salt A and 0.2-0.3 g of thioacetamide in 25mL of reaction solvent B, stirring for 1-6 hours, dispersing 1-2g of template polyvinylpyrrolidone in 25mL of deionized water, stirring for 1-6 hours, mixing, and stirring for 6-24 hours to form a raw material liquid C.
Step 2: transferring the raw material liquid C obtained in the step 1 into a polytetrafluoroethylene inner container to carry out solvothermal reaction, wherein the reaction temperature is set to be 120-180 ℃; after the solvent is heated for 12 to 24h, cooling the reaction kettle by water cooling, wherein the water temperature is 5 to 15 ℃, and the water flow rate is controlled to be 1 to 3L min -1 (ii) a A colloid E containing metal sulfide D particles having a particle diameter of 10 to 100nm is formed.
And step 3: adding 100-150mL of acetone into the metal sulfide colloid E generated in the step 2 to precipitate a metal sulfide D, centrifuging and washing for 5-10 times to remove template polyvinylpyrrolidone and other impurities, and drying in vacuum to obtain pure metal sulfide particles D; weighing 50-100mg of metal sulfide particles D and 10-20mL of a dispersing agent F, fully mixing, and carrying out ultrasonic treatment for 15-60 minutes under an ice bath condition, wherein the power is set to be 500W; filtering the mixture through a 0.22 mu m needle filter to obtain the ink containing the metal sulfide D.
Step 1, the metal salt A comprises nickel chloride or cobalt acetate or zinc acetate;
step 1, the mass ratio of the metal salt A, the sulfur source and the template is (2);
the reaction solvent B in the step 1 comprises ethylene glycol and water or ethanol and water;
step 2, the metal sulfide D comprises cobalt sulfide or nickel sulfide or zinc sulfide;
and 3, the dispersing agent F comprises ethanol or N, N-dimethylformamide or N-methylpyrrolidone or ethanol and isopropanol or ethanol and water and isopropanol.
Description of the technology
1. In the step 1, metal ions and a sulfur source are fully and uniformly dispersed in the template through magnetic stirring, so that metal sulfides are orderly crystallized, aggregation in the crystallization process is avoided, and particles which are not beneficial to ink stability and have different sizes are formed.
2. In the step 2, the high-pressure reaction kettle is a closed system and is placed in an oven to carry out the solvothermal reaction, and the pressure is changed along with the reaction temperature. According to the relationship curve of crystal nucleation and growth, in order to achieve the supercooling degree suitable for nucleation and inhibiting crystal nucleus growth, the solvent heating temperature is set to be 160-180 ℃.
3. In the step 2, the reaction kettle is cooled by water cooling, the water temperature is 5 to 15 ℃, and the water flow rate is controlled to be 1 to 3L min -1 . The reaction system has proper supercooling degree and supersaturation degree due to proper temperature difference, so that the purposes of promoting nucleation rate and inhibiting crystal nucleus growth in the crystallization process are achieved, and the small-size metal sulfide nanospheres with proper sizes are finally formed.
4. The small-size nanospheres of the metal sulfide generated by the solvothermal method have higher specific surface area, and can be mutually infiltrated and diffused with the dispersing agent under the high-temperature and high-pressure environment, so that the dispersing agent can be successfully coated on the surface of the nanoparticles. The dispersant can form a layer of solvated molecular film on the surfaces of the particles to hinder the mutual contact between the particles, increase the distance between the particles, avoid the formation of bridging hydroxyl and real chemical bonds, play a certain role in steric hindrance, form steric resistance potential energy, enlarge the potential barrier between the particles and balance the surface acting force of the metal sulfide nano particles; thereby effectively preventing it from agglomerating and stably dispersing it in a suitable dispersant.
5. And (3) ultrasonic treatment under an ice bath condition is carried out, so that the phenomenon that excessive heat energy and mechanical energy are converted into kinetic energy of the nano particles is prevented, the probability of mutual collision of the nano particles is increased, and further agglomeration is caused.
6. In the step 3, the filtering operation is carried out by adopting a nylon needle type filter with the aperture of 0.22 mu m, so that the uniformity of the functional material is ensured, and the ink quality is further improved.
7. In the step 1, cobalt sulfide is used for replacing polyvinylpyrrolidone as a template, and zinc acetate is used as a metal salt to prepare the cobalt sulfide/zinc sulfide core-shell structure nano material ink-jet printing ink by repeating the steps.
Advantageous effects
1. The metal sulfide nanospheres which can stably exist in the dispersing agent are generated by a solvothermal method, and can stably exist under a relative centrifugal force of 6800 g without mechanical grinding and dispersing, so that the problem of poor stability of easy sedimentation of ink is fundamentally eliminated; has an ultra-long shelf life at normal temperature and pressure.
2. After ink-jet printing, the dispersant completely evaporates and the deposited material has only one component of metal sulfide, ensuring its conductivity, electrochemical activity and accessibility for ionic diffusion, and verified by ac impedance testing. Meanwhile, the unique micro-nano deposition effect of the equipment enables the active sites of the metal sulfide to have higher utilization rate and more excellent performance under unit volume.
Drawings
And the first figure is an XRD (X-ray diffraction) diagram of the cobalt sulfide and cobalt sulfide/zinc sulfide core-shell structure nanoparticles.
And the second diagram is an XRD diagram of the zinc sulfide nanoparticles.
And the third diagram is an XRD diagram of the nickel sulfide nano particles.
Figure four is a TEM image of a. Cobalt sulfide b. Zinc sulfide c. Cobalt sulfide/zinc sulfide d. Nickel sulfide.
Figure five is a, cobalt sulfide b, zinc sulfide c, cobalt sulfide/zinc sulfide nickel sulfide ink jet printing of drop-dropped optical images.
Figure six is an optical image of nickel sulfide ink.
Figure seven is a comparison of the ac impedance test for the nickel sulfide ink without and with additives.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
A method of making an additive-free metal sulfide ink-jet printing ink, the method comprising the steps of:
step 1: dispersing 0.4-0.6 g of metal salt A and 0.2-0.3 g of thioacetamide in 25mL of reaction solvent B, stirring for 1-6 hours, dispersing 1-2g of template polyvinylpyrrolidone in 25mL of deionized water, stirring for 1-6 hours, mixing, and stirring for 6-24 hours to form a raw material liquid C;
and 2, step: transferring the raw material liquid C obtained in the step 1 into a polytetrafluoroethylene inner container for solvothermal reaction, wherein the reaction temperature is set to be 120-180 ℃; after the solvent is heated for 12 to 24h, cooling the reaction kettle by water cooling, wherein the water temperature is 5 to 15 ℃, and the water flow rate is controlled to be 1 to 3L min -1 (ii) a Generating a colloid E containing metal sulfide D particles with the particle size of 10 to 100nm;
and step 3: adding 100 to 150mL of acetone into the metal sulfide colloid E generated in the step 2 to precipitate a metal sulfide D, centrifuging and washing for 5 to 10 times to remove template polyvinylpyrrolidone and other impurities, and drying in vacuum to obtain pure metal sulfide particles D; weighing 50-100mg of metal sulfide particles D and 10-20mL of a dispersing agent F, fully mixing, and carrying out ultrasonic treatment for 15-60 minutes under an ice bath condition, wherein the power is set to be 500W; filtering the mixture by a 0.22 mu m needle filter to obtain the ink containing the metal sulfide D;
the metal salt A in the step 1 is cobalt acetate or zinc acetate or nickel chloride;
step 1, the mass ratio of the metal salt A to the sulfur source to the template is 2;
the reaction solvent B in the step 1 is ethylene glycol and water or ethanol and water;
step 2, the metal sulfide D is cobalt sulfide or nickel sulfide or zinc sulfide;
and 3, the dispersing agent F in the step 3 is ethanol or N, N-dimethylformamide or N-methylpyrrolidone or ethanol and isopropanol or ethanol and water and isopropanol.
Example 2
A method of making an additive-free metal sulfide ink jet printing ink as in example 1, which is substantially the same as example 1 except that: the metal salt A in the step 1 is cobalt acetate, the generated metal sulfide is cobalt sulfide, and the temperature in the step 2 is set to be 120-160 ℃.
Example 3
A method of making an additive-free metal sulfide ink jet printing ink as in example 1, which is substantially the same as example 1 except that: the metal salt A in the step 1 is zinc acetate, the generated metal sulfide is zinc sulfide, and the temperature is set to be 120-140 ℃.
Technical description and technical effects: optimizing the preparation method of the zinc sulfide nano-particles.
Example 4
A method of making an additive-free metal sulfide ink jet printing ink as in example 1, which is substantially the same as example 1 except that: the metal salt A in the step 1 is nickel chloride, and the generated metal sulfide is nickel sulfide.
Example 5
A method of making an additive-free nickel sulfide ink-jet printing ink as in example 4, which is substantially the same as example 4 except that: the reaction temperature described in step 2 was set to 180 ℃.
Technical description and technical effects: the upper limit of the supercooling degree and the supersaturation degree is improved, so that the size of the nano particles has a higher controllable range.
Example 6
A method of making an additive-free nickel sulfide ink-jet printing ink as in example 5, which is substantially the same as example 5 except that: the reaction time described in step 2 was set to 18 hours.
Technical description and technical effects: the crystallinity of the nickel sulfide nano particles is improved.
Example 7
A process for preparing an additive-free nickel sulfide ink-jet printing ink as set forth in example 6, which is substantially the same as example 6 except that: 0.4g of nickel chloride, 0.2g of thioacetamide and 1g of polyvinylpyrrolidone in the step 1.
Technical description and technical effects: prevents the agglomeration caused by the over-high precipitation speed of crystal grains due to the reduction of solubility under the state of high temperature and high pressure.
Example 8
A method of making an additive-free metal sulfide ink jet printing ink as in example 7, which is substantially the same as example 7 except that: the water cooling parameter in the step 2 is that the water temperature is 5 ℃, and the flow rate is set to be 2L min -1 。
Technical description and technical effects: further increasing the supercooling degree and the supersaturation degree and further reducing the size of the sulfide nano particles.
Example 9
A method of making an additive-free nickel sulfide ink jet printing ink as in example 8, which is substantially the same as example 8 except that: the stirring time of the raw material liquid in the step 1 is 24 hours; the dispersing agent is prepared by selecting 18mL of ethanol and 2mL of isopropanol and carrying out ultrasonic treatment for 60 minutes.
Technical description and technical effects: the steric hindrance effect of the template is fully exerted, the agglomeration phenomenon of crystal grains in the crystallization process is inhibited, and the uniform and stable additive-free ink is prepared.
Claims (8)
1. A method of making an additive-free metal sulfide ink-jet printing ink, the method comprising the steps of:
step 1: dispersing 0.4-0.6 g of metal salt A and 0.2-0.3 g of thioacetamide in 25mL of reaction solvent B, stirring for 1-6 h, dispersing 1-2g of template polyvinylpyrrolidone in 25mL of deionized water, stirring for 1-6 h, mixing, and stirring for 6-24h to form a raw material solution C;
step 2: will be described in step 1Transferring the raw material liquid C into a polytetrafluoroethylene inner container to carry out solvothermal reaction, wherein the reaction temperature is set to be 120-180 ℃; after the mixture is heated by a solvent for 12 to 24h, cooling the reaction kettle by water cooling, wherein the water temperature is 5 to 15 ℃, and the water flow rate is controlled to be 1 to 3L min -1 (ii) a Generating a colloid E containing metal sulfide D particles with the particle size of 10 to 100nm;
and 3, step 3: adding 100-150mL of acetone into the metal sulfide colloid E generated in the step 2 to precipitate a metal sulfide D, centrifuging and washing for 5-10 times to remove template polyvinylpyrrolidone and other impurities, and drying in vacuum to obtain pure metal sulfide particles D; weighing 50-100mg of metal sulfide particles D and 10-20mL of a dispersing agent F, fully mixing, and carrying out ultrasonic treatment for 15-60 min under an ice bath condition, wherein the power is set to be 500W; filtering the ink by a 0.22-micron needle head filter to obtain the D ink containing the metal sulfide;
step 1, the metal salt A is cobalt acetate or nickel chloride;
step 1, the mass ratio of the metal salt A to thioacetamide to polyvinylpyrrolidone is 2;
the reaction solvent B in the step 1 is ethylene glycol and water or ethanol and water;
step 2, the metal sulfide D is cobalt sulfide or nickel sulfide or zinc sulfide;
and 3, the dispersing agent F in the step 3 is ethanol or N, N-dimethylformamide or N-methylpyrrolidone or ethanol and isopropanol or ethanol and water and isopropanol.
2. A method of preparing an additive-free ink-jet printing ink comprising a metal sulfide as claimed in claim 1, wherein: the metal salt A in the step 1 is cobalt acetate, the generated metal sulfide D is cobalt sulfide, and the temperature in the step 2 is set to be 120-160 ℃.
3. The method of claim 1 for preparing an additive-free ink-jet ink of metal sulfide, wherein the method comprises: the metal salt A in the step 1 is nickel chloride, and the generated metal sulfide D is nickel sulfide.
4. A method of preparing an additive-free metal sulfide ink jet printing ink as claimed in claim 3, wherein: the reaction temperature described in step 2 was set to 180 ℃.
5. The method of claim 4, wherein the ink-jet ink comprises: the reaction time described in step 2 was set to 18h.
6. The method of claim 5 for preparing an additive-free ink-jet printing ink of a metal sulfide, wherein: 0.4g of nickel chloride, 0.2g of thioacetamide and 1g of polyvinylpyrrolidone in the step 1.
7. The method of claim 6, wherein the ink-jet ink comprises: the water cooling parameter in the step 2 is that the water temperature is 5 ℃, and the flow rate is set to be 2L min -1 。
8. The method of claim 7, wherein the ink-jet ink comprises: the stirring time of the raw material liquid in the step 1 is 24 hours; the dispersing agent is selected from 18mL of ethanol and 2mL of isopropanol, and ultrasonic treatment is carried out for 60min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515255A (en) * | 2012-01-09 | 2012-06-27 | 西南大学 | Method for preparing zinc sulfide nanospheres |
| CN103221471A (en) * | 2010-11-22 | 2013-07-24 | E.I.内穆尔杜邦公司 | Semiconductor inks, films, coated substrates and methods of preparation |
| CN113173605A (en) * | 2021-04-27 | 2021-07-27 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103221471A (en) * | 2010-11-22 | 2013-07-24 | E.I.内穆尔杜邦公司 | Semiconductor inks, films, coated substrates and methods of preparation |
| CN102515255A (en) * | 2012-01-09 | 2012-06-27 | 西南大学 | Method for preparing zinc sulfide nanospheres |
| CN113173605A (en) * | 2021-04-27 | 2021-07-27 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
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