JPS6191005A - Metal sulfide - Google Patents

Abstract

PURPOSE:A metal sulfide solution in a dissolved state, providing a metal sulfide in a thin film state, useful as a catalyst, semiconductor, element for electricity generation, sensor, etc., obtained by reacting a metallic compound with a sulfur (compound) in a specific polar nonaqueous solvent. CONSTITUTION:A metallic compound (e.g., CdI2) consisting of a metallic element belonging to transition elements of a wide sense including silver and zinc groups is reacted with S or an S compound (e.g., H2S) in a polar nonaqueous solvent having a molecular formula shown by the formula I or II (R and R' are H or alkyl) optionally dissolving a high polymer compound (e.g., polyacrylonitrile) not to insolubilize a metal sulfide to be prepared. Consequently, a metal sulfide solution containing 0.4-3.1mol S based on 1mol metallic element, having >=an amount estimated from solubility in equilibrium, in a supersaturated state, in a metastable state or in a dissolved state of molecular aggregate with <=3X10<-6>cm particle diameter, is prepared.

Description

[Detailed Description of the Invention] Dissolution of a compound that was conventionally insoluble in a certain solvent into that solvent (hereinafter, the term "dissolution" includes dissolution in a supersaturated or metastable state and dissolution of a compound as a fine particle-like molecular group) ), the uses of that compound can be greatly expanded. The present invention is based on the discovery of a method for making metal sulfides exist in a dissolved state in a solvent that could not be dissolved by conventional methods, a solution obtained from the solution, metal sulfides recovered from the solution, and their It concerns usage, application, etc.

Metal sulfides have functions as semiconductors or catalysts,
It is used in various electric circuit elements, catalysts (see, for example, Kyoritsu Shuppan Co., Ltd., "Chemistry Dictionary", Vol. 9, p. 677). For example, CdS has photoconductivity (see the above-mentioned "Chemistry Encyclopedia").
(see Vol. 3, p. 585), it is also possible to produce solar cells made of copper sulfide and cadmium sulfide. In addition, some metal sulfides are used as conductors, phosphors, or positive electrode active materials for batteries such as lithium batteries (see each entry on metal sulfides in the aforementioned "Encyclopedia of Chemistry", for example, Vol. 9). Zinc sulfide on page 645). However, since a considerable number of metal sulfide compounds are poorly soluble, there are limitations to their use and application methods. For example, if a film is made from a composition consisting of a metal sulfide and a polymer compound, and the metal sulfide is uniformly dispersed in the film to obtain a film with various functions, it has not been possible to obtain a film with various functions due to the lack of an appropriate solvent. There were times when it was impossible. The present invention uses dimethyl sulfoxide, N,
When a solvent such as N-dimethylformamide is used, the metal sulfide produced by the reaction dissolves in the reaction solvent in an amount greater than the amount dissolved in the equilibrium state, and such a dissolved state can exist stably for a certain period of time. It is based on what was discovered. According to the present invention, a solution containing a dissolved metal sulfide, which was not known to dissolve in a non-aqueous solvent, can be obtained, and the use and application methods of metal sulfides are greatly expanded. A polar non-aqueous solvent having a functional group such as dimethyl sulfoxide or N,N-dimethylformamide attaches a ligand to the metal sulfide in the initial stage formed by a chemical reaction through a functional group or a bond, and semi-forms the metal sulfide. It is thought that it is dissolved in a stable state. Therefore, in these solvents, it is thought that the functional groups in the solvent molecules play a major role in dissolving metal sulfides, and when dissolving a polymer compound in a solvent in which metal sulfides are dissolved, It is desirable that the polymer compound has a functional group having similar properties.

Although aqueous solutions in which colloidal metal sulfides are dispersed in water have been known (refer to each item on metal sulfides in the above-mentioned "Encyclopedia of Chemistry"), the estimated value at equilibrium in a polar non-aqueous solvent is There is no known example of a solution containing dissolved metal sulfides in an amount greater than the above amount. In the solution obtained by the present invention, there are examples in which metal sulfides are dissolved in the solvent as fine particles, but in this case, the particle size of the fine particles is 3 × 10-6 (300
A = 0.03 μm) or less, and the surface energy cannot be ignored in metal sulfides with this particle size (Kagaku Special Edition No. 104, "Materials Technology in Advanced Fields" (1984))
(See pages 23 and 25) The presence of this surface energy is considered to be one of the reasons why the solution of the present invention can be obtained.

In addition, the production of fine particulate materials has recently become important (see the above-mentioned Kagaku Special Issue No. 104, page 23), and the present invention makes it possible to produce ultrafine particulate metal sulfides. Further, both the metal sulfide and the composition comprising the metal sulfide and the polymer compound obtained by the present invention generally have electrical conductivity, and the scope of claims 41 to 5 is as follows. It has the usage described in . Some of these uses have already been known for existing metal sulfides and are naturally foreseen for the metal sulfide of the present invention, but some of these uses are already known for the metal sulfide of the present invention. Alternatively, by using a composition, there is an advantage that the usage form can be changed, and the function and characteristics can be changed based on changes in the form such as fine particles.

Example 1. Cadmium iodide (CdI2) is dissolved in anhydrous N,N-dimethylformamide. When dry hydrogen sulfide gas (1.2 to 4 times the mole relative to CdI2) is introduced into this solution, the color of the solution, which was colorless before the reaction, changes from yellow to yellow-orange (the so-called cadmium yellow characteristic of CdS). color). The visible light absorption spectrum of this solution shows a shoulder absorption band at 450 nm, and the position of this absorption band has been reported for solid cadmium sulfide (J. Opt.
Soc. Am. , 46, 1013 (1956)). These facts suggest that cadmium sulfide was produced by the above reaction. However, the solution remained homogeneous even after the reaction, and almost no yellow precipitate, which is normally seen when cadmium sulfide is produced, was observed. Depending on the condition of the reaction, the reaction solution may become cloudy and a small amount of solid may be produced, but even in this case, the homogeneous solution obtained after removing the solid by filtration has the characteristic yellow color of cadmium sulfide. Approximately 20% as a liquid having a yellow-orange color
C. or lower, it exists as a stable and apparently homogeneous solution without precipitation for more than 10 hours. Furthermore, at a low temperature of about -20°C, it exists stably as an apparently uniform solution for more than two weeks. After preparing the solution, the solution was left at about -20°C overnight and then at about 0°C for about 2 hours. As a result of analyzing the solution using a light scattering method using an argon laser, it was found that about 4.5 x 10-
There were many fine particles with a particle size of 7 cm. When this solution was left under argon laser irradiation for about 7 hours, the particle size increased to about 7.times.10@-7 cm (70 A), but even in this state the solution appeared uniform. When this solution was allowed to stand for several more hours, it became cloudy and formation of solids was observed. In addition, an N,N-dimethylformamide solution similar to the above prepared by the reaction of CdI2 and H2S was prepared and immediately cooled to -15°C to -20°C, kept in this state for two weeks, and then heated with argon laser at around room temperature. As a result of analysis using a light scattering method using
There were many fine particles having the particle size of A). Also, if this solution is left for 22 hours, the particle size will be approximately 15 x 10-
Although the diameter increased to 7 cm (150 A), the solution appeared to be homogeneous even in this state. All of the above-mentioned fine particles are considered to be CdS.

In order to confirm the presence of CdS in these solutions, methyl alcohol, hexane, etc. were added to the solutions, and immediately yellow to yellow-orange precipitates were formed, and the solutions became almost colorless. This precipitate was collected by filtration, thoroughly washed, and then vacuum dried. Elemental analysis of this dried material (Cd is determined by ICP emission spectrometry after decomposing the sample with a mixture of sulfuric acid and nitric acid, S is SO produced by burning the sample with high frequency
2 by infrared analysis), it was found that this dried material was CdS (containing a trace amount of CdI2).

In addition, the powder X-ray diffraction diagram of the dried product is also the same as that of commercially available CdS powder
It matched with the line diffraction pattern (the diffraction lines were somewhat broad, suggesting that the CdS obtained in this example was amorphous to some extent). In addition, the amount of CdS recovered as a powdery precipitate is more than 60% of the amount calculated based on the reaction formula of CdI2+H2S→CdS+2HI, indicating that a considerable amount of CdS is dissolved in N,N-dimethylformamide. It was found that a solution was obtained. However, commercially available cadmium sulfide and cadmium sulfide once precipitated by the above procedure were not dissolved in N,N-dimethylformamide at all. This means that the CdS dissolved in the above N,N-dimethylformamide is dissolved in a metastable state, and once it becomes a more stable solid state, it is no longer N,N-dimethylformamide.
This shows that it has no equilibrium theory of solubility in N-dimethylformamide. The CdS recovered from the solution obtained in this example is considered to be a particulate substance. In this example, instead of H2S, (NH4)2S
A similar homogeneous solution of N,N-dimethylformamide in which CdS was dissolved could be obtained using the same method, and CdS was recovered from this solution in the same manner. A similar solution was obtained by reaction of CdI2 and Na2S. Furthermore, a cadmium compound such as CdCl2 can be used as a raw material instead of CdI2, and a similar solution containing dissolved CdS can be obtained by using dimethyl sulfoxide instead of N,N-dimethylformamide. . In addition, a thin film of CdS was obtained by spreading the solution obtained in this example on a glass plate and then evaporating the solvent using a vacuum device.

Example 2. Example 1. In place of the N,N-dimethylformamide used as a solvent in Example 1, the reaction was carried out using N,N-dimethylformamide in which polyacrylonitrile was dissolved. In the same manner as above, a yellow to yellow-orange solution containing CdS in a dissolved state was obtained. A composition consisting of CdS and polyacrylonitrile is prepared by taking a portion of this yellow or yellow-orange apparently uniform solution, spreading this solution on a glass plate, and removing N,N-dimethylformamide by evaporation under vacuum. I got it. This composition was found to be a semiconducting material in the form of a film and having an electrical conductivity of about 1.times.10@-7 Scm@-1. The electrical conductivity of this material increased significantly by applying pressure. It is thought that contact between particles was improved by pressurization.

Example 3. 3 mmol of CuI are dissolved in 30 ml of dimethyl sulfoxide and the gas is removed from the container containing this solution using a vacuum pump. Next, add about 110 ml to the container containing this solution.
Add cm3 (1 atm, room temperature) of dry H2S and stir. At this time, the solution, which was almost colorless before the reaction, turned dark yellowish brown. After the reaction was completed, the reaction solution was centrifuged, and a small amount of precipitate formed was removed by filtration using a thimble.

As a result of analyzing the apparently uniform solution thus obtained by a light scattering method using an argon laser, it was confirmed that this solution was a uniform solution. Approximately 15
When ml of acetone was added under N2 gas, a precipitate was formed that had a gray-black color characteristic of copper sulfide and was thought to be copper sulfide based on the reaction history. This black precipitate, once precipitated, was no longer soluble in dimethyl sulfoxide. Both commercially available black Cu2S and CuS were also insoluble in dimethyl sulfoxide.

Note that if the homogeneous solution obtained in this example is left at room temperature for a long time, a black precipitate will form, and the rate of precipitate formation is higher when the solution is placed in air than when it is placed under N2 gas. It was faster. It is thought that in addition to copper sulfide, some unreacted copper iodide is dissolved in the homogeneous solution obtained in this example, but the proportion of unreacted copper iodide can be increased by increasing the amount of H2S added to the reaction system. It is thought that this can be made so small that it can be ignored. The copper sulfide obtained in this example had electrical conductivity.

Example 4. Example 1. Polyacrylonitrile was dissolved in the N,N-dimethylformamide solution in which CdS was dissolved to obtain an apparently uniform solution. A portion of this solution was taken out and spread on a glass plate, and N,N-dimethylformamide was removed by evaporation under vacuum.
A composition consisting of S and polyacrylonitrile was obtained. This composition was found to be a semiconducting material in the form of a film and having an electrical conductivity of about 1.times.10@-7 Scm@-1. The electrical conductivity of this material increases with the application of pressure, indicating that this material can be used as a pressure-sensitive sensor. Further, a composition consisting of CdS and polyvinyl formal was obtained in the same manner as in this example except that polyvinyl formal was used instead of polyacrylonitrile. This composition was also a semiconducting material with an electrical conductivity of about 1.times.10@-7 S.cm@-1.

Example 5. Example 3. Take 5 ml of the homogeneous solution (prepared again) obtained in , and add 1 mL to this solution under nitrogen gas.
Add and dissolve 00 mg of polyacrylonitrile.

Even when polyacrylonitrile was added, no precipitate was formed. About 4.5 cm of the solution obtained in this way
After spreading the mixture uniformly on a 7 cm x 7 cm glass plate, the dimethyl sulfoxide was removed under vacuum to obtain a yellow to tan film, which was apparently transparent. The surface electrical conductivity of this film is the surface electrical conductivity of a known copper sulfide-treated polyacrylonitrile film (industrial product, number B22, film thickness 60 μm) obtained by treating the surface of a polyacrylonitrile film with a copper compound and a sulfur compound. It was almost the same. However, the electrical conductivity in the thickness direction of the film prepared in this example was 4 × 10-4 Scm-1 at room temperature, and the above-mentioned known industrial product copper sulfide-treated polyacrylonitrile film (No. B
22, film thickness 60 μm) at room temperature in the thickness direction of the film (4×10 −10 Scm −1 ). That is, the above-mentioned copper sulfide-treated polyacrylonitrile film (number B22 has a yellow to tan color almost the same as the film obtained in this example) is obtained by treating a polyacrylonitrile film, which normally has insulating properties, with a copper compound and a sulfur compound. Although it is known that this is due to the contamination of copper sulfide (for example, Polymon Prep
rints, Japan Vol. 31, No3, 1H1
1) In this known copper sulfide-treated polyacrylonitrile film, the conductive copper sulfide exists only in the surface layer of the film, and therefore, although the surface electrical conductivity of this film is high, the electrical conductivity in the thickness direction of the film is The results show that the conductivity is low. On the other hand, in the case of the film obtained in this example, it is thought that copper sulfide is uniformly dispersed throughout the film, and therefore, not only the surface electrical conductivity of the film but also the thickness direction of the film It also has high electrical conductivity and has practical advantages.

Example 6. Copper acetate (Cu(OCOCH3)2・H2O) 10mmo
1 is dissolved in 100 ml of dimethyl sulfoxide, and the gas in the container containing this solution is removed using a vacuum pump. A sufficient amount of dry H2S is then added to the vessel and the solution is stirred at room temperature. After the reaction was completed, a small amount of precipitate formed was removed by filtration under N2 gas to obtain a homogeneous solution. Even when this solution was stored at room temperature for a long time, the solution remained stable without precipitation (under N2 gas). On the other hand, when a large amount of acetone was added to a portion of this solution, a black or grayish black precipitate, characteristic of copper sulfide, was formed, and once formed, the precipitate was no longer soluble in dimethyl sulfoxide. . Based on the history of the reaction, this black or grayish black precipitate is thought to be copper sulfide, and in fact, the powder X-ray diffraction pattern of the material obtained by collecting and drying this precipitate is the powder X-ray diffraction pattern of CuS. matched. The solution obtained in this example had a black to dark green color. In addition, in this example, the acetic acid produced by the reaction was (Cu(OCOCH3)2+H2S→CuS+
2CH3COOH) is easily removed under vacuum. In this example, even when N,N-dimethylformamide was used in place of dimethyl sulfoxide, a solution thought to contain copper sulfide in a dissolved state was similarly obtained. In this case as well, the black or grayish black precipitate, which is thought to be copper sulfide, obtained by adding acetone to this solution was no longer soluble in N,N-dimethylformamide once it became a precipitate. The copper sulfide obtained in the example had electrical conductivity.

Example 7. A homogeneous solution was obtained by carrying out the H2S reaction with nickel acetate in dimethyl sulfoxide. When acetone was added to this solution, a black precipitate, believed to be nickel sulfide, was formed. A part of this black precipitate is soluble in dimethyl sulfoxide, but its solubility is low, and the solution obtained under the synthesis conditions clearly contains a large amount of the black compound, which is thought to be nickel sulfide, dissolved in a supersaturated or metastable state. I found out that there was. Commercially available nickel sulfide also dissolved in dimethyl sulfoxide, albeit in a very small amount. Also, ZnI2
A solution in which ZnS was similarly dissolved was obtained by the reaction of H2S and H2S. In addition, a composition consisting of ZnS and a polymer compound can be obtained by preparing a solution by dissolving a polymer compound such as polyacrylonitrile in this solution, separating a portion of this solution, and removing volatile components under vacuum. Ta. The reaction between ZnI2 and H2S was carried out in dimethyl sulfoxide.

Example 8. Example 2. and Example 5. (respectively, a film made of a composition made of cadmium sulfide and polyacrylonitrile, and a film made of a composition made of copper sulfide and polyacrylonitrile) and a similar film were coated on a transparent glass electrode plate (Matsuzaki Vacuum Co., Ltd.). (each formed on a separate transparent glass electrode plate). It was found that when the respective membrane surfaces were brought into contact and irradiated with light from the outside, an electromotive force was generated between the two membranes. Also, Example 5. Since the film obtained is electrically conductive, it is thought to function as a shielding material for electromagnetic waves.

Example 9. Example 6. Polyaclonitrile is dissolved in the dimethylsulfokimide solution in which copper sulfide is dissolved. At this time, copper sulfide did not precipitate. A portion of the solution thus obtained was spread on a glass plate and volatile components were removed under vacuum to obtain a composition containing copper sulfide and polyacrylonitrile. This composition is in the form of a film, and the electrical conductivity (value at room temperature) in the thickness direction of the film is determined when the weight ratio of copper sulfide to polyacrylonitrile in the composition is 0.
Approximately 10-11Sc at 25, 0.47, and 0.79, respectively.
m-1, 10-5 Scm-1, and 10-3 Scm-1, and the latter two samples showed semiconductivity.

Claims (1)

[Scope of Claims] (1) A solution obtained by reacting a metal compound and sulfur or a sulfur compound in a polar non-aqueous solvent to produce a metal sulfide, the solution containing the metal sulfide in a dissolved state. (
(including the dissolved state in a supersaturated state, the dissolved state in a metastable state, and the dissolved state as a molecular aggregate having a particle size of 3 x 10^-^6 (300 Å) or less of the metal sulfide) A solution characterized by: (2) As a polar non-aqueous solvent, either the molecular formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R and R' represent H or a substituent such as an alkyl group) Claim 1 obtained by using a compound represented by the following or by using a compound represented by any of the above molecular formulas as the main component of a polar nonaqueous solvent.
Solution as described in section. (3) The metal sulfide is dissolved in an amount exceeding the amount estimated from the solubility of the metal sulfide in the solution at equilibrium (dissolved state in a supersaturated state, dissolved state in a metastable state, and the dissolved state in which the metal sulfide 3 x 10^-^6cm (30
3. The solution according to claim 1 or 2, characterized in that the solution contains the compound in a dissolved state as a molecular aggregate having a particle size of 0 Å or less. (4) The metal sulfide is in a supersaturated state, metastable state, or 3 x 10^-^6cm (300 Å) of the metal sulfide.
The solution according to any one of claims 1 to 3, wherein the solution is dissolved in a dissolved state as a molecular aggregate having the following particle diameter. (5) The oxidation number of the metal element in the metal compound is +1 or +2
The solution according to any one of claims 1 to 4, which is obtained by using this metal compound in the reaction. (6) Any of claims 1 to 5 obtained by using this metal compound in a reaction when the metal element in the metal compound is a positive monovalent element or a positive divalent element. The solution described in. (7) Any of claims 1 to 6 obtained by using a metal compound in a reaction when the metal element of the metal compound belongs to a transition element in a broad sense including zinc group elements and copper group elements. Solution described in Crab. (8) The solution according to any one of claims 1 to 7, which is obtained by using a metal compound in a reaction when the metal element in the metal compound is a zinc group element. (9) The solution according to any one of claims 1 to 7, which is obtained by using a metal compound in a reaction when the metal element in the metal compound is a copper group element. (10) The solution according to any one of claims 1 to 7, which is obtained by using a metal compound in a reaction when the metal element in the metal compound is a Group VIII element. (11) The solution according to any one of claims 1 to 10, which is obtained using a compound containing a monovalent or divalent anion or an anionic ligand as the metal compound. (12) The solution according to any one of claims 1 to 11, which is obtained using a halogen compound or carboxylate of a metal element as the metal compound. (13) The solution according to any one of claims 1 to 12, which is obtained using a compound in which an organic group or an organic ligand is bonded to a metal element as the metal compound. (14) Claims 1 to 8 and 11 obtained by using a cadmium compound as a metal compound.
The solution according to any one of Items 1 to 13. (15) The solution according to any one of claims 1 to 8 and 11 to 13, which is obtained using a zinc compound as the metal compound. (16) Claims 1 to 7 and 9 and 1 obtained by using a copper compound as a metal compound.
The solution according to any one of Items 1 to 13. (17) The solution according to any one of claims 1 to 7, 10, and 11 to 13, which is obtained using a nickel compound as the metal compound. (18) When a sulfur compound is used in the reaction for obtaining a solution according to claims 1 to 17, it is understood that the sulfur compound can be obtained by using a sulfur compound soluble in the polar non-aqueous solvent as the sulfur compound. 18. A solution according to any one of claims 1 to 17. (19) When a sulfur compound is used in the reaction for obtaining the solution according to claims 1 to 17, the solution is obtained by using hydrogen sulfide as the sulfur compound. The solution according to any one of Items 1 to 17. (20) Claims 1 to 17 characterized in that the solution is obtained using a sulfur compound in the reaction for obtaining the solution described in Claims 1 to 17.
The solution described in any of the preceding paragraphs. (21) When a metal sulfide is produced by a reaction between a metal compound and sulfur or a sulfur compound, a compound derived from an element, group, or ligand bonded to a metal element in the metal compound before the reaction is produced. 21. A solution according to any one of claims 1 to 20 obtained when the compound has a volatility that can be removed using a vacuum device. (22) Claims 1 to 21, characterized in that the number of moles of sulfur per mole of metal element in the metal sulfide produced by the reaction is in the range of 0.4 to 3.1. A solution according to any of the above. (23) Claims 1 to 22 obtained by using a polar non-aqueous solvent in which a polymer compound is dissolved when obtaining any of the solutions described in claims 1 to 22. Solution according to any of paragraph 22. (24) A solution obtained by further dissolving a polymer compound in the solution according to any one of claims 1 to 23. (25) The solution according to claim 24, which is obtained using a polymer compound that does not insolubilize metal sulfides when the polymer compound is dissolved. (26) Claim 25 obtained by using a compound containing a nitrogen atom in the side chain or main chain as the polymer compound
or the solution according to any one of paragraphs 24 and 23. (27) The claim described in any one of claims 23 to 26 obtained using a polymer compound having a cyano group or a bonding unit represented by ▲a mathematical formula, a chemical formula, a table, etc. solution. (28) Claim 23 obtained by using a compound containing an oxygen atom in the side chain or main chain as the polymer compound
The solution according to any one of Items 1 to 25. (29) -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
The solution according to any one of claims 23 to 25 or claim 28, which is obtained using a polymer compound having a bonding unit represented by: (30) The solution according to any one of claims 23 to 25, which is obtained using a polymer compound containing sulfur in its side chain or main chain. (31) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Any of claims 23 to 25 or claim 30 obtained using a polymer compound having a bonding unit represented by ▼ solution. (32) The solution according to any one of claims 23 to 25, which is obtained using a halogen-containing polymer compound. (33) A metal sulfide recovered from the solution according to any one of claims 1 to 22. (34) A method for recovering metal sulfides by removing a solvent from a solution according to any one of claims 1 to 22. (36) The particle size of the recovered metal sulfide is 10^-^5
34. The metal sulfide according to claim 33, which is in the form of fine particles of 1000 Å or less. (37) A thin film-like metal sulfide obtained by developing the solution according to any one of claims 1 to 22 in a layered manner and removing the solvent. (38) A composition comprising a metal sulfide and a polymer compound recovered from the solution according to any one of claims 23 to 32. (39) The composition according to claim 38, wherein the metal sulfide is highly dispersed in the polymer compound. (40) A composition obtained by immersing a substance serving as a catalyst carrier in the solution according to any one of claims 1 to 32 to support metal sulfide on the carrier. (41) Claims 33 or 36 to 4
A method of using the metal sulfide or composition according to any one of items 0 to 0 as a hydrogenation catalyst. (42) Claims 33 or 36 to 4
A method of using the metal sulfide or composition according to any of items up to item 0 as a desulfurization catalyst. (43) Claims 33 or 36 to 3
A method of using the metal sulfide or composition according to any one of items 9 to 9 as a semiconductor. (44) Claims 33 or 36 to 3
A method of using the metal sulfide or composition according to any one of items 9 to 9 as a power generation element of a solar cell. (45) A method of using the metal sulfide or composition according to any one of claims 37 to 39 as an electromagnetic wave shielding material. (46) A method of using a kisaan metal sulfide or a composition as a political active material in a battery according to any one of claims 38 and 39. (48) The method of use according to claim 47, when the negative electrode active material of the battery is lithium. (49) Claims 33 or 36 to 3
A method of using the metal sulfide or composition according to any one of items 9 to 9 as an element of a photoconductive cell. (50) Claims 33 or 36 to 3
A method of using the metal sulfide or composition according to any of items 9 through 9 as a photosensitive substance. (51) Claims 33 or 36 to 3
A method of using the metal sulfide or composition according to any one of items 9 to 9 as a gas sensor for detecting gases.