Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G19/00—Compounds of tin
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/90—Other crystal-structural characteristics not specified above
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area

Definitions

• the present invention relates to an SnS dispersion and a method for producing the same, and more specifically to an SnS dispersion and SnS particles that have good dispersibility and do not precipitate during storage, as well as a method for producing SnS particles and a method for producing an SnS dispersion.
• Patent Document 1 proposes a method for producing a tin sulfide film with crystals oriented in a specific direction by a vacuum plating method.
• the method for producing a tin sulfide film is characterized in that the substrate temperature is controlled to a range of 120 to 400° C. and the film formation rate is controlled to a range of 0.05 to 0.5 ⁇ m/min, and the tin sulfide film crystals are oriented in a specific direction.
• Patent Document 2 proposes a method for producing tin sulfide that is industrially simple and safe, and can prevent contamination of the reaction system by unreacted sulfur without using special equipment such as high-pressure equipment or harmful substances such as mercury. Specifically, the method proposes a method for producing tin sulfide, which is characterized by mechanochemically treating a workpiece containing metallic tin and sulfur, in which the content of sulfur relative to the content of metallic tin is 1 to 4 in terms of molar ratio (S/Sn) of atomic conversion, to react the metallic tin with the sulfur to obtain tin sulfide.
• S/Sn molar ratio
• Patent Document 3 proposes a method for producing a powder containing stannous sulfide, which has good energy efficiency and production efficiency and can be produced continuously.
• the proposed method includes a step of introducing tin powder and sulfur powder or lumps into a mill, the ratio of the number of sulfur atoms to the number of tin atoms (S/Sn) being 0.95 or more and 1.50 or less, and a step of operating the mill to mechanically activate the tin and sulfur, and carrying out a chain synthesis reaction by the heat of the synthesis reaction of the tin and sulfur, the step being carried out at a temperature inside the mill lower than the melting point of sulfur.
• Patent Document 4 proposes a method for obtaining a high purity chalcogenide compound of about 1:1 between Group 14 and Group 16 elements of the periodic table, which was previously difficult, and specifically, the proposed method includes a method of obtaining a high purity chalcogenide compound of about 1:1 between Group 14 and Group 16 elements of the periodic table, which has the general formula: M 1 M 2 x [wherein M 1 represents an element of Group 14 of the periodic table, M 2 represents an element of Group 16 of the periodic table, and x represents 0.9 to 1.1. and a method for producing the same, in which the chalcogenide compound is present in an amount of 90 mol % or more as determined by X-ray diffraction measurement.
• the tin sulfide proposed above and the tin sulfide obtained by the manufacturing method have not yet been able to achieve the required performance.
• the inventors have thoroughly investigated the reasons why previously proposed tin sulfides are unable to achieve the desired performance, and have discovered that one of the causes is poor dispersibility in the dispersion liquid, which is the state before the tin sulfide is used.
• obtaining tin sulfide with good dispersibility is important in achieving the desired performance, and a tin sulfide dispersion liquid that has good dispersibility and does not precipitate during storage is required.
• the object of the present invention is to provide a dispersion of SnS particles that has good dispersibility and does not precipitate during storage, a method for producing SnS particles and SnS dispersion, and a method for producing SnS particles.
• the present inventors discovered that the above object could be achieved by dispersing SnS particles produced by carrying out a vapor deposition process under specific temperature conditions in a dispersion of SnS particles, and thus completed the present invention. That is, the present invention provides the following inventions. 1. A SnS dispersion in which SnS particles are dispersed in an aqueous or alcoholic dispersion, the dispersed SnS particles having an average major axis of 100 to 2000 nm, an average minor axis of 50 to 1000 nm, and an average aspect ratio (major axis/minor axis) of 1.2 to 1.6. 2.
• a method for producing SnS particles comprising a vapor deposition step of heating a SnS raw material contained in an evaporation source container to capture SnS in a capture container, and an isolation step of separating the resulting vapor from the capture container to obtain SnS particles, wherein the evaporation source container is heated to a temperature of 700 to 900° C. in the vapor deposition step, and the maximum capture container temperature of the capture container is 80 to 130° C. 13.
• a method for producing an SnS dispersion according to 1, comprising a deposition step of heating the SnS raw material contained in an evaporation source container to capture SnS in a capture container, an isolation step of separating the resulting deposition from the capture container to obtain SnS particles, and a dispersion step of dispersing the deposition obtained in the isolation step in an aqueous or alcoholic dispersion, wherein the deposition step has a heating temperature of the evaporation source container of 700 to 900° C. and the maximum capture container temperature of the capture container is 80 to 130° C. 15.
• the SnS dispersion of the present invention has good dispersibility and does not precipitate during storage.
• the SnS particles of the present invention constitute the above-mentioned SnS dispersion of the present invention, and can exhibit excellent properties. Furthermore, according to the manufacturing method of the SnS dispersion of the present invention, it is possible to manufacture a dispersion of SnS particles that has good dispersibility and does not precipitate during storage. According to the manufacturing method of the SnS particles of the present invention, it is possible to obtain SnS particles that constitute the above-mentioned SnS dispersion that can exhibit excellent properties.
• the SnS particles obtained from the SnS dispersion of the present invention can exhibit excellent properties, and are therefore useful as a raw material in the energy-related field, lubricant field, etc.
• FIG. 1 is a schematic diagram showing a deposition apparatus for carrying out a deposition step in the method for producing a SnS dispersion liquid of the present invention.
• FIG. 2 is an SEM photograph (a photograph substituting a drawing) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in Example 1.
• FIG. 3 is an SEM photograph (a drawing substitute photograph) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in Example 2.
• FIG. 4 is an SEM photograph (a drawing substitute photograph) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in Example 3.
• FIG. 2 is an SEM photograph (a photograph substituting a drawing) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in Example 1.
• FIG. 3 is an SEM photograph (a drawing substitute photograph) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in Example 2.
• FIG. 5 is a drawing substitute photograph showing the dispersion state of the SnS dispersion, in which (a) shows the initial state of the SnS dispersion obtained in Example 1, (b) shows the state of the SnS dispersion obtained in Example 1 after 17 hours, (c) shows the initial state of the SnS dispersion obtained in Example 2, (d) shows the state of the SnS dispersion obtained in Example 2 after 17 hours, (e) shows the initial state of the SnS dispersion obtained in Example 3, (f) shows the state of the SnS dispersion obtained in Example 3 after 17 hours, (g) shows the initial state of the SnS dispersion obtained in the comparative example, and (h) shows the state of the SnS dispersion obtained in the comparative example after 17 hours.
• FIG. 6 is an SEM photograph (a drawing substitute photograph) showing the particle state of SnS particles dispersed in the SnS dispersion liquid obtained in the comparative example.
• FIG. 7 is a chart showing the results of XRD measurement of the SnS particles obtained in the examples and comparative examples.
• FIG. 8 is a drawing substitute photograph showing the dispersion state of the SnS dispersion, in which (a) shows the initial state of the SnS dispersion obtained in Example 4, (b) shows the initial state of the SnS dispersion obtained in Example 5, (c) shows the initial state of the SnS dispersion obtained in Example 6, (d) shows the initial state of the SnS/acetylene black dispersion obtained in Example 7, (e) shows the tin sulfide/acetylene black mixed particles obtained in Example 7, (f) shows the initial state of the dispersion obtained by redispersing the particles obtained in Example 7 in water, (g) shows the initial state of the SnS/acetylene black dispersion obtained in Example 8, (h) shows the tin sulfide/acetylene black mixed particles obtained in Example 9, and (i) shows the initial state of the dispersion obtained by redispersing the particles obtained in Example 8 in water.
• FIG. 9 is a chart showing the particle size distribution of the SnS particles or SnS ⁇ acetylene black particles obtained in Examples 4 to 8.
• 10(a) to (d) are SEM photographs (drawing substitute photographs) showing the particle state of SnS.acetylene black particles dispersed in the SnS dispersions obtained in Examples 7 and 8, respectively.
• the SnS dispersion of the present invention is a SnS dispersion in which SnS particles are dispersed in a water or alcohol-based dispersion, and the average particle diameter (average of major axes) and average aspect ratio (major axis/minor axis) of the dispersed SnS particles are within a specific range.
• the SnS particles of the present invention are obtained from the SnS dispersion of the present invention, and have an average particle diameter (average of major axes) and average aspect ratio (major axis/minor axis) within a specific range.
• the SnS particles of the present invention are extracted (taken out) from the SnS particles that constitute the above-mentioned SnS dispersion and dried,
• the SnS particles (SnS particles of the present invention) dispersed in the SnS dispersion have an average major axis of 100 to 2000 nm, preferably 100 to 500 nm, and most preferably 100 to 200 nm.
• the average minor axis of the particles is 50 to 1000 nm, preferably 50 to 200 nm, and most preferably 50 to 150 nm.
• the average aspect ratio (major axis/minor axis) is 1.2 to 1.6. The measurement method for these will be described in detail in the Examples, but all of them can be measured using the SnS dispersion.
• the SnS particles of the present invention are particles whose average major axis, average minor axis, and average aspect ratio measured in the SnS dispersion are within the above ranges. It is believed that the average major axis, the average minor axis, and the average aspect ratio within the above ranges improve the dispersibility in the dispersion liquid, and thus improve various performances of the SnS particles themselves to the required level.
• the average major axis is the average value of the diameter of the longest part of the particle, and the average minor axis is the average value of the diameter of the shortest part of the particle.
• the average thickness of the SnS particles is preferably 100 to 1000 nm, more preferably 100 to 300 nm.
• the particle size distribution (scattering intensity basis, D10) of the SnS particles is preferably in the range of 100 to 200 nm.
• the particle size distribution (scattering intensity basis, D50) of the SnS particles is preferably in the range of 100 to 700 nm, more preferably 200 to 500 nm.
• the particle size distribution (scattering intensity basis, D90) of the SnS particles is preferably in the range of 500 to 1500 nm.
• the average thickness and the particle size distribution (particularly D50) within the above ranges further improve the dispersibility, and thus improve the required performance.
• the specific surface area of the SnS particles is preferably 5 m 2 /g or more in terms of improving dispersibility, more preferably 5 to 20 m 2 /g, and most preferably 8 to 15 m 2 /g, as measured by BET.
• the SnS particles of the present invention are obtained by drying SnS particles dispersed in a SnS dispersion.
• the SnS particles obtained by drying the SnS particles may vary depending on the purity of the raw materials used, but the SnS purity measured by XRD is preferably 90% by mass or more, and more preferably 95 to 100% by mass. This purity can be achieved by the manufacturing method described later, and thus a dispersion having particles with better dispersibility and exhibiting the desired characteristics can be obtained.
• dried means a state in which the moisture of the SnS particles taken out of the dispersion liquid has been removed, and usually means a state in which the moisture content is 0.1 mass% or less.
• the moisture content can be measured using a conventional method without particular restrictions.
• the drying method can be performed using a conventional method without particular restrictions, but it can be dried by drying at 50 to 100 ° C. for 1 to 10 hours under reduced pressure using a vacuum dryer.
• SnS particles having an average major axis of preferably 100 to 500 nm, more preferably 100 to 200 nm, an average minor axis of preferably 50 to 200 nm, most preferably 50 to 150 nm, and an average aspect ratio (major axis/minor axis) of 1.2 to 1.6 are considered to be excellent in dispersibility and useful as materials in various fields.
• the average thickness is 100 to 300 nm and the particle size distribution (scattering intensity standard, D50) is 200 to 500 nm.
• Such SnS particles can be obtained by extracting SnS particles from a SnS dispersion liquid obtained through an ultrasonic dispersion process in the manufacturing method described below, and drying the SnS particles in the same manner as the drying method described above.
• the manufacturing method for the SnS dispersion liquid corresponds to a manufacturing method for SnS particles.
• the SnS particles in the present invention may contain other particles. Examples of the other particles include acetylene black, carbon nanotubes, graphene, graphene oxide, graphite, silicon, silicon oxide, silicon carbide, and the like.
• the form of "containing” includes a state in which the SnS particles and other particles are simply dispersed and mixed, as well as a state in which each of the particles is aggregated and each of the aggregates is further aggregated, and a state in which each of the particles is aggregated.
• the blending ratio of the other particles is preferably SnS 99 to 70: other particles 1 to 30 (weight ratio, total amount 100).
• the water-based dispersion used in the SnS dispersion of the present invention can be water or a mixture of water and a water-soluble organic solvent.
• organic solvent alcohols such as ethanol, isopropanol (IPA), methanol, etc. can be used, and the mixing ratio is not particularly limited.
• Alcohol-based dispersion As the alcohol-based dispersion used in the SnS dispersion of the present invention, ethanol, isopropanol (IPA), methanol, etc. can be used.
• the concentration of the SnS particles (including the case where other particles are included) in the aqueous dispersion is preferably 0.0001 to 50% by mass, more preferably 0.0001 to 25% by mass, even more preferably 0.001 to 20% by mass, and most preferably 0.01 to 10% by mass. If it is less than this range, it may be difficult to obtain the characteristics of the SnS particles, and if it exceeds this range, the dispersibility may decrease, resulting in particle aggregation and a decrease in particle performance, which is not preferable.
• the absorbance of the dispersion is preferably 0.15 or more at a wavelength of 600 nm, and preferably 0.1 or more at a wavelength of 1250 nm.
• the transmittance is preferably 70% or less at a wavelength of 600 nm.
• the mass absorption coefficient of the dispersion (0.001% by mass) is preferably 15000 cm -1 or more, more preferably 50000 to 80000 cm -1 , at a wavelength of 600 nm.
• the absorbance, transmittance, and mass absorption coefficient are all at a SnS particle concentration of 0.001% by mass, and are preferably within the above ranges from the viewpoint of improving dispersibility.
• the measurement method is as described in the examples.
• the absorbance is preferably 1 or more at a wavelength of 600 nm, and preferably 0.8 or more at a wavelength of 1250 nm.
• the transmittance is preferably 5 or less at a wavelength of 600 nm.
• the mass absorption coefficient is preferably 25 cm -1 or more, more preferably 50 to 80 cm -1 .
• the production method of SnS particles of the present invention can be carried out by carrying out a deposition process in which the SnS raw material contained in an evaporation source container is heated to capture SnS in a capture container, and an isolation process in which the resulting deposition product is separated from the capture container to obtain SnS particles.
• the SnS particles that constitute the above-mentioned SnS dispersion liquid of the present invention can be obtained, but particularly preferred SnS particles among the above-mentioned SnS particles of the present invention can be obtained by carrying out the production method of the SnS dispersion liquid described below, drying the obtained SnS dispersion liquid, and extracting (taking out) the SnS particles from the SnS dispersion liquid.
• the method for producing the SnS dispersion of the present invention is a method for producing the SnS dispersion of the present invention described above, and can be carried out by carrying out a deposition process in which the SnS raw material contained in an evaporation source container is heated to capture SnS in a capture container, an isolation process in which the resulting deposition product is separated from the capture container to obtain SnS particles, and a dispersion process in which the deposition product obtained in the isolation process is dispersed in an aqueous dispersion.
• the deposition process and the isolation process are common to the method for producing SnS particles and the method for producing SnS dispersion.
• the method for producing SnS dispersion can be carried out by further carrying out the dispersion process in addition to the method for producing SnS particles. Therefore, the following explanation of the method for producing SnS particles also applies to the method for producing SnS dispersion.
• the SnS raw material used in the present invention is not particularly limited in terms of its purity as long as it is a bulk SnS raw material, but it is preferable to use one with a purity of 90% or more.
• the deposition process is a process of heating the SnS raw material contained in the evaporation source container to capture SnS in a capture container, and can be performed using a deposition apparatus shown in FIG. 1.
• the deposition apparatus 1 shown in FIG. 1 includes a chamber 10 that can be sealed and evacuated, a heater 20 installed in the chamber 10, an evaporation source container 30, and a capture container 40.
• the evaporation source container 30 is configured to accommodate an evaporation source therein, and a thermometer (not shown) is installed in the evaporation source container 30 so that the temperature can be measured.
• the evaporation source container 30 can be heated by the heater 20.
• the capture container 40 is installed at a predetermined distance from the evaporation source container 30, and a thermometer (not shown) is installed so that the temperature can be measured.
• a thermometer (not shown) is installed so that the temperature can be measured.
• the heater, the evaporation source container, and the capture container those usually used in this type of deposition apparatus can be used without any particular limitation.
• the capture vessel may be made of glass such as borosilicate glass, or metal such as alumina, as long as it is heat-resistant and does not denature the SnS particles to be deposited.
• the chamber 10 is connected to a vacuum pump to reduce pressure and to a vacuum state, and is also equipped with a valve to return from the reduced pressure state to a normal pressure state.
• thermometer not shown in the figure, a normal thermocouple or the like can be used.
• the temperature measurement point it is preferable to measure the temperature near the side of the evaporation source vessel because the influence of the heater is reduced, and it is preferable to measure the temperature on the back side of the captured surface of the capture vessel for the same reason.
• the heating temperature of the evaporation source vessel 30 (the temperature measured by the thermometer) is 700 to 900°C
• the maximum capture vessel temperature of the capture vessel 40 is 80 to 130°C. If these are outside this range, the SnS dispersion of the present invention described above cannot be prepared.
• the capture vessel 40 is installed at a predetermined distance from the evaporation source vessel 30. This distance is important in adjusting the maximum capture vessel temperature of the capture vessel 40 and needs to be changed depending on the size of the chamber 10 and the amount of SnS raw material, but the maximum capture vessel temperature can be adjusted by adjusting this distance. In order to obtain a better quality dispersion, it is preferable that the average capture rate in the deposition process is 20 mg/min or more.
• the deposition process ends when the SnS raw material, which is the evaporation source, in the evaporation source vessel 30 runs out. It is preferable to maintain the pressure during the process at 5 Pa to 1 ⁇ 10 ⁇ 5 Pa.
• the isolation process is a process in which the obtained deposition product is separated from the capture container to obtain SnS particles. Specifically, it can be performed by mechanically peeling off and collecting the SnS particles in the capture container 40. This peeling and collection can be performed using any conventional method that can be used to produce particles by deposition and then isolate and collect them, without any particular restrictions. This process can also be used to isolate and collect the SnS particles attached to the capture container by repairing them in a volatile solvent such as ethanol. By obtaining an ethanol dispersion in this way, it is possible to reduce the loss of SnS particles due to scattering during collection.
• the obtained SnS particles can be used as is, and in the case of repairing them using a volatile solvent, the volatile solvent can be removed and the SnS particles can be dried to obtain SnS particles.
• an SnS dispersion can be obtained by carrying out the dispersion process described below.
• the dispersion step is a step necessary for carrying out the method for producing the SnS dispersion of the present invention, and is a step in which the SnS particles obtained as a deposition product in the isolation step are put into the aqueous or alcoholic dispersion and the SnS particles are dispersed by a conventional method to obtain the SnS dispersion of the present invention.
• the dispersion step may further include an ultrasonic dispersion step in which ultrasonic dispersion is performed preferably at an amplitude of 50 to 150 ⁇ m, more preferably 100 to 130 ⁇ m.
• the ultrasonic dispersion step may be performed using an ultrasonic device used for normal dispersion, such as an ultrasonic homogenizer, and the frequency may be any, but may be 20 Hz to 60 Hz.
• an ultrasonic device used for normal dispersion such as an ultrasonic homogenizer
• the frequency may be any, but may be 20 Hz to 60 Hz.
• a drying step must be performed to dry the SnS dispersion liquid to obtain SnS particles.
• This drying step can be performed, for example, by drying at 50 to 100°C under reduced pressure for 1 to 10 hours using a vacuum dryer, although the temperature and time may vary depending on the amount of SnS particles to be dried.
• Example 1 The above-mentioned deposition process was carried out using the deposition apparatus shown in FIG. 1. 13 g of bulk tin sulfide (with a purity of about 98%) was placed in the deposition source container 30 as a raw material. The distance between the deposition source container 30 and the capture container 40 was set to 12.3 cm. Next, the pressure in the chamber was evacuated to the 5 ⁇ 10 ⁇ 4 Pa range using a vacuum pump, and the deposition source container was heated to 900° C. by a heater and heated at 900° C. for 4 hours. The maximum temperature of the capture container 40 was 101° C.
• the pressure during the process was 5 ⁇ 10 ⁇ 3 Pa to 1 ⁇ 10 ⁇ 4 Pa.
• the average capture rate measured by the above-mentioned measurement method was 46.7 mg/min.
• the isolation process and the dispersion process were carried out. First, the capture container 40 in the vacuum chamber 1 was removed, ethanol was poured into the capture container 40, and SnS (hereinafter also referred to as "tin sulfide”) was peeled off from the glass container to obtain a tin sulfide ethanol solution. Ethanol was removed from the obtained tin sulfide ethanol solution.
• the removal was performed by drying the tin sulfide ethanol solution under reduced pressure in a vacuum dryer (drying temperature 70°C, 4 hours) to perform an isolation process. Pure water was added to 0.4 g of dried tin sulfide, and stirring was performed by a normal stirring method (stirring with a stirrer), to obtain 8 g of a 5 mass% tin sulfide aqueous solution (SnS dispersion of the present invention). The SnS particles in the obtained dispersion were dried to obtain SnS particles, and the following tests were performed using the obtained tin sulfide. A particle shape photograph is shown in FIG. 2, the XRD results are shown in FIG. 7, and other results are shown in Table 1.
• a precipitation test was performed using the obtained SnS dispersion.
• the storage container was thoroughly stirred by hand before the precipitation test was started.
• the precipitation test was performed by checking the precipitation state at the start and the precipitation state after 17 hours.
• the results are shown in Figures 3(a) and (b).
• the following measurements were also performed using the obtained SnS dispersion.
• the results are shown in Table 1.
• the obtained SnS dispersion (concentration 5 mass%) was used as it was for measurement.
• the particle size distribution measurement was performed using an Anton Paar particle size distribution measurement device "Litesizer (registered trademark) 500".
• the measurement method used a dynamic light scattering method to measure the particle size distribution based on the scattering intensity, and D10, D50, and D90 were calculated.
• the zeta potential measurement was also performed using the same device.
• the pH at the time of measurement was 7.
• Absorbance and transmittance The obtained SnS dispersion (5% by mass) and the diluted solution obtained by diluting this dispersion (5% by mass) with pure water to 0.001% by mass were used to perform measurements using an ultraviolet-visible near-infrared spectrophotometer (product name "V770”) manufactured by JASCO Corporation.
• Table 1 shows the major axis A and minor axis B dimensions of the tin sulfide particles obtained from the image.
• the thickness L dimension was measured using a laser microscope (manufactured by Keyence Corporation, product name "KEYENCE VK-9700”). A and B were obtained by visually detecting about 50 particles from the image, and the average was taken.
• the SnS dispersion was dried under reduced pressure in a vacuum dryer. The drying temperature was set to 70°C, and the drying time was about 4 hours.
• the tin sulfide (SnS) powder of the present invention was obtained.
• the obtained tin sulfide powder was used to identify the tin sulfide powder using an X-ray diffraction device "XRD" (manufactured by Malvern Panalytical, product name “Empyrean”).
• XRD X-ray diffraction device
• the measurement results are shown in FIG. 7. As a result, no peaks other than those of tin sulfide were detected, and the purity of tin sulfide was determined to be 99% by mass or more.
• the specific surface area was measured by the BET measurement method (specific surface area/pore distribution measuring device, trade name "BELSORP-max” manufactured by Microtrack BEL Co., Ltd.). The results are shown in Table 1.
• Example 2 A SnS dispersion was prepared in the same manner as in Example 1, except that in the dispersion process, in addition to normal stirring, the following ultrasonic dispersion process was performed, and various tests and measurements were carried out.
• Ultrasonic dispersion process Using an ultrasonic homogenizer (QSONICA ultrasonic homogenizer, product name "Q125"), the obtained 5 mass% SnS dispersion was dispersed for 50 minutes at a frequency of 20 kHz and an amplitude of 60 ⁇ m. The results are shown in Figures 3, 5, and 7, and in Table 1.
• Example 3 A SnS dispersion was obtained in the same manner as in Example 2, except that the frequency was 20 kHz and the amplitude was 120 ⁇ m.
• Various tests and measurements were carried out on the obtained SnS dispersion in the same manner as in Example 1. The results are shown in Figures 4, 5, and 7, and in Table 1.
• the SnS dispersion of the present invention shows no precipitation even after 17 hours, demonstrating excellent dispersibility.
• the dispersion of the comparative example shows precipitation over time, showing poor dispersibility. Therefore, the SnS particles of the present invention have such excellent dispersibility that they are believed to be able to exhibit excellent properties in a variety of applications.
• Example 4 Pure water was added to 0.8 g of dried tin sulfide obtained in the same manner as in Example 1, and the mixture was stirred by a normal stirring method (stirring with a stirrer) to prepare 8 g of a 10 mass % aqueous tin sulfide solution (SnS dispersion).
• the obtained SnS dispersion was dispersed for 90 minutes using an ultrasonic homogenizer (QSONICA ultrasonic homogenizer, product name "Q125”) at a frequency of 20 kHz and an amplitude of 120 ⁇ m to obtain a SnS dispersion of the present invention (the obtained dispersion is shown in FIG. 8(a)).
• the obtained SnS dispersion was used to measure particle size distribution.
• the solvent used was pure water, which is the same solvent as the SnS dispersion, and the SnS dispersion was diluted to 0.001 mass% and measured.
• the particle size distribution was measured using an Anton Paar particle size distribution measuring device "Litesizer (registered trademark) 500".
• the measurement method used a dynamic light scattering method to measure the particle size distribution based on the scattering intensity, and D10, D50, and D90 were calculated. The obtained results are shown in Table 2 and FIG. 9.
• Example 5 Pure water was added to 1.6 g of dried tin sulfide obtained in the same manner as in Example 1, and the mixture was stirred by a normal stirring method (stirring with a stirrer) to prepare 8 g of a 20 mass % aqueous tin sulfide solution (SnS dispersion).
• the obtained SnS dispersion was dispersed for 90 minutes using an ultrasonic homogenizer (QSONICA ultrasonic homogenizer, product name "Q125”) at a frequency of 20 kHz and an amplitude of 120 ⁇ m to obtain a SnS dispersion of the present invention (the obtained dispersion is shown in FIG. 8(b)).
• the obtained SnS dispersion was used to measure particle size distribution.
• the solvent used was pure water, which is the same solvent as the SnS dispersion, and the SnS dispersion was diluted to 0.001 mass% and measured.
• the particle size distribution was measured using an Anton Paar particle size distribution measuring device "Litesizer (registered trademark) 500".
• the measurement method used a dynamic light scattering method to measure the particle size distribution based on the scattering intensity, and D10, D50, and D90 were calculated. The obtained results are shown in Table 2 and FIG. 9.
• Example 6 Isopropyl alcohol (special grade 2-propanol, manufactured by Kanto Chemical Co., Ltd.) was added to 1.6 g of dried tin sulfide obtained in the same manner as in Example 1, and the mixture was stirred by a normal stirring method (stirring with a stirrer) to prepare 8 g of a 20 mass% tin sulfide isopropyl alcohol solution (SnS.IPA dispersion obtained by dispersing SnS in IPA).
• SnS.IPA 20 mass% tin sulfide isopropyl alcohol solution
• the SnS-IPA dispersion was dispersed for 90 minutes at a frequency of 20 kHz and an amplitude of 120 ⁇ m using an ultrasonic homogenizer (QSONICA ultrasonic homogenizer, product name "Q125”) to obtain a SnS dispersion of the present invention.
• the resulting dispersion is shown in FIG. 8(c).
• the obtained SnS-IPA dispersion was used to measure particle size distribution.
• the solvent used was isopropyl alcohol, which is the same solvent as the SnS-IPA dispersion, and the SnS-IPA dispersion was diluted to 0.001 mass% and measured.
• the particle size distribution was measured using an Anton Paar particle size distribution measuring device "Litesizer (registered trademark) 500".
• the measurement method used a dynamic light scattering method to measure the particle size distribution based on the scattering intensity, and D10, D50, and D90 were calculated.
• Example 7 The same procedure as in Example 6 was carried out to obtain a 20 mass % SnS/IPA dispersion. Separately, acetylene black (DENKA BLACK Li Li-100 powdered product manufactured by Denka Co., Ltd., average particle size: 35 nm, specific surface area: 68 m 2 /g, bulk density: 0.04 g/ml) was prepared.
• acetylene black DENKA BLACK Li Li-100 powdered product manufactured by Denka Co., Ltd., average particle size: 35 nm, specific surface area: 68 m 2 /g, bulk density: 0.04 g/ml
• This acetylene black was added to a 20% by mass SnS/IPA dispersion so that the ratio of tin sulfide to acetylene black was 95:5, and dispersion and mixing were performed for 1 hour using ultrasonic waves (AS ONE ultrasonic cleaner ASU-2, oscillation circuit: separate excitation type, high frequency output: 40 W, oscillation frequency: 42 kHz), to prepare a tin sulfide/acetylene black mixed dispersion (SnS dispersion of the present invention, SnS and acetylene black concentration: 20.8% by mass). The obtained results are shown in FIG. 8(d). The obtained tin sulfide/acetylene black mixed dispersion liquid was heated at 70° C.
• FIG. 8( e ) An image of tin sulfide particles taken with a field emission scanning electron microscope/transmission electron microscope "FE-SEM" (JSM-6500F manufactured by JEOL, hereinafter referred to as SEM) is shown in Fig. 10(a).
• FE-SEM field emission scanning electron microscope/transmission electron microscope
• a tin sulfide/acetylene black mixed dispersion was diluted to 0.01% by mass, dried in the same manner, and photographed with an SEM to confirm the dispersion state of acetylene. The result is shown in Fig. 10(b).
• the particle size distribution was measured using the obtained tin sulfide/acetylene mixed particles. 0.1 g of tin sulfide/acetylene black mixed particles was used, and pure water was added thereto to prepare a 0.01% by mass aqueous dispersion, which was then measured. The particle size distribution was measured using an Anton Paar particle size distribution measuring device "Litesizer (registered trademark) 500". The measurement method used was dynamic light scattering, and the particle size distribution was measured based on the scattering intensity, and D10, D50, and D90 were calculated. The results are shown in Table 2 and FIG. 9.
• Example 8 The same procedure as in Example 6 was carried out to obtain a 20 mass % SnS/IPA dispersion. Acetylene black was added to the 20% by mass SnS/IPA dispersion so that the mass ratio of tin sulfide to acetylene black was 90:10, and ultrasonic dispersion and mixing was carried out for 1 hour to prepare a tin sulfide/acetylene black mixed dispersion (SnS dispersion of the present invention, SnS and acetylene black concentration: 21.7% by mass). The obtained dispersion is shown in FIG. 8(g). Thereafter, tin sulfide/acetylene black mixed particles were obtained in the same manner as in Example 7.
• FIG. 8(h) An image of the tin sulfide/acetylene black mixed particles taken by FE-SEM is shown in FIG. 10(c).
• the tin sulfide/acetylene black mixed dispersion was also diluted to 0.01% by mass, dried in the same manner, and photographed using an SEM to confirm the dispersion state of acetylene.
• the result is shown in FIG. 10(d).
• the particle size distribution was measured in the same manner as in Example 7. The results are shown in Table 2 and FIG.

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