WO2006101141A1 - 溶融塩組成物及びその利用 - Google Patents
溶融塩組成物及びその利用 Download PDFInfo
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- WO2006101141A1 WO2006101141A1 PCT/JP2006/305736 JP2006305736W WO2006101141A1 WO 2006101141 A1 WO2006101141 A1 WO 2006101141A1 JP 2006305736 W JP2006305736 W JP 2006305736W WO 2006101141 A1 WO2006101141 A1 WO 2006101141A1
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- molten salt
- natfsi
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/70—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using melts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a molten salt composition and use thereof, and in particular, a molten salt composition containing two or more MTFSIs having an alkali metal M as a cation and imido-one (TFSI) as a lion, and It is about its use.
- a molten salt composition containing two or more MTFSIs having an alkali metal M as a cation and imido-one (TFSI) as a lion, and It is about its use.
- Molten salt is a salt in a molten state, and slag force melted at high temperature is known to have a wide and temperature range up to room temperature molten salt (also called ionic liquid etc.) that becomes liquid at room temperature. Speak.
- room temperature molten salt also called ionic liquid etc.
- molten salts can give different functionality depending on the combination of force thiones and key-ons, a wide variety of salts have been developed for various applications.
- bistrifluoromethylsulfamideamione (commonly known as imidoone, TFSI _ , N (SO CF)) is known as a key ion that gives a salt having a relatively low melting point.
- the O group is very negative electrically and the charge on the nitrogen atom in the TFSI
- EMImTFSI 1-ethyl-3-methylimidazolium trifluoromethylsulfamide
- Non-patent document 1 detailed studies of these salts as molten salts have never been made
- LiTFSI has been widely studied for its application as an electrolyte supporting salt for lithium ion secondary batteries.
- the properties of LiTFSI alone as a molten salt have not been studied.
- NaTFSI and KTFSI have been studied for polymer composites, but very few have been reported (see Non-Patent Documents 2 and 3).
- CsTFSI there are no reports of related research or physical properties other than the crystal structure described above. There is no report about RbTFSI.
- the salt MTFSI whose cation is an alkali metal, is considered to be applied to batteries and the like, and is a very promising material.
- Detailed examination has not been made, and its application is limited as it is.
- it is indispensable to lower the melting point of the electrolyte and expand the operating temperature range. No such attempt has been reported!
- the present invention has been made in view of the above-mentioned problems, and its purpose is to reduce the melting point of the electrolyte or to deposit a specific metal, ceramic or the like with respect to MTFSI. It is an object to provide a technique that can be eluted and that enables a wide range of applications regarding electrolytes and the use thereof.
- M Li, Na, K, Rb, Cs
- the binary system states of NaTFSI-LiTFSI, NaT FSI-KTFSI, NaTFSI-CsTFSI, LiTFSI-KTFSI were examined in detail, focusing on NaTFSI.
- the eutectic temperature power in each eutectic composition of the system has found a new fact that it is significantly lower than the melting point of the single salt, and has completed the present invention.
- the present invention has been completed based on powerful new findings and includes the following inventions.
- a substance represented by the following chemical formula (1) A molten salt composition containing two or more kinds of molten salts MTFSI having TFSI as anion and alkali metal M as a cation.
- the above molten salt MTFSI is LiTFSI, NaTFSI, KTFSI, RbTFSI, and CsTFSI.
- the molten salt composition according to 1) which is selected from the group consisting of
- the above molten salt composition is a binary composition in which two types of molten salt MTFSI are mixed, LiTFSI-NaTFSI mixed system, LiTFSI-KTFSI mixed system, LiTFSI-CsTFSI mixed system, NaTFSI- KTFSI mixed system, NaTFSI—CsTFSI mixed system, or KTFSI—CsTF
- a charging method including a step of charging using the battery according to any one of 5) to 7) above
- An electrodeposition method including a step of depositing a metal or ceramic using the electrolytic solution described in 4) above.
- a film forming method comprising:
- the eutectic temperature is remarkably reduced as compared with the melting point of a single salt containing only one MTFSI.
- the usable temperature range can be expanded by setting the composition and ratio. Therefore, by using the molten salt composition according to the present invention, the melting point of the electrolyte can be lowered, and there are advantages in terms of energy efficiency and safety.
- the operating temperature range can be expanded, there is an advantage that the selectivity of the material is improved when applied to a battery.
- FIG. 1 is a diagram schematically showing the configuration of an experimental apparatus used in an example of the present invention.
- FIG. 2 is a diagram showing a synthetic procedure of a molten salt performed in an example of the present invention.
- FIG. 3 is a diagram showing an electrochemical measurement apparatus used in an example of the present invention.
- FIG. 4 is a view showing a TG curve of LiTFSI in an example of the present invention.
- FIG. 5 is a diagram showing a TG curve of NaTFSI in an example of the present invention.
- FIG. 6 is a diagram showing a TG curve of KTFSI in an example of the present invention.
- FIG. 7 is a diagram showing a CsTFSI TG curve in an example of the present invention.
- FIG. 8 is a diagram showing a LiTFSI DSC curve in an example of the present invention.
- FIG. 9 is a diagram showing a DSC curve of NaTFSI in an example of the present invention.
- FIG. 10 is a diagram showing a KTFSI DSC curve in an example of the present invention.
- FIG. 11 is a diagram showing a DSC curve of CsTFSI in an example of the present invention.
- FIG. 12 (a) is a diagram showing the results of cyclic voltammetry of LiTFSI in the example of the present invention, and is a diagram showing the results when Ni is used as an electrode.
- FIG. 12 (b) is a diagram showing the results of cyclic voltammetry of LiTFSI in the examples of the present invention, and is a diagram showing the results when glassy carbon is used as an electrode.
- FIG. 13 (a) is a diagram showing the results of cyclic voltammetry of NaTFSI in an example of the present invention, and is a diagram showing results when Ni is used as an electrode.
- FIG. 13 (b) is a diagram showing the results of cyclic voltammetry of NaTFSI in the example of the present invention, and is a diagram showing the results when glassy carbon is used as an electrode.
- FIG. 14 (a) is a view showing the results of cyclic voltammetry of KTFSI in the example of the present invention, and showing the results when Ni is used as an electrode.
- FIG. 14 (b) is a diagram showing the results of cyclic voltammetry of KTFSI in the example of the present invention, and is a diagram showing the results when glassy carbon is used as an electrode.
- FIG. 15 (a) is a diagram showing the results of cyclic voltammetry of CsTFSI in the example of the present invention, and shows the results when Ni is used as an electrode.
- FIG. 15 (b) shows the results of cyclic voltammetry of CsTFSI in the example of the present invention. It is a figure which shows the result at the time of using glassy carbon as an electrode.
- FIG. 17 is a diagram showing a binary phase diagram created by plotting each endothermic peak of a LiTFSI-NaTFSI mixed salt in an example of the present invention.
- FIG. 19 is a diagram showing a binary phase diagram created by plotting each endothermic peak of a KTFSI-NaTFSI mixed salt in an example of the present invention.
- FIG. 21 is a diagram showing a binary phase diagram created by plotting each endothermic peak of a NaTFSI-CsTFSI mixed salt in an example of the present invention.
- FIG. 23 is a diagram showing a binary system phase diagram created by plotting each endothermic peak of a LiTFSI-KTFSI mixed salt in an example of the present invention.
- FIG. 25 is a diagram showing a binary phase diagram created by plotting each endothermic peak of a LiTFSI-CsTFSI mixed salt in an example of the present invention.
- FIG. 27 is a diagram showing a binary phase diagram created by plotting each endothermic peak of a KTFSI-CsTFSI mixed salt in an example of the present invention.
- FIG. 28 is a graph showing the thermal decomposition temperature of each single salt used in the examples of the present invention.
- FIG. 29 is a diagram showing the melting point of each single salt used in the examples of the present invention.
- FIG. 30 is a diagram showing a eutectic composition and a eutectic temperature of each mixed salt in an example of the present invention.
- the present invention is a mixture having a melting point lower than that of a single salt by mixing two or more kinds of alkali metal imide salts (MTFSI). It was obtained based on the research results of the present inventors that a salt composition can be obtained. Therefore, the molten salt composition is first described and then its use is described.
- MTFSI alkali metal imide salts
- Imido refers to an amide having an imino group, and it is strictly inappropriate to call a TFSI ion without an imino group as an imide. Therefore, it will be used as a common name in this specification.
- the molten salt composition according to the present invention may be a molten salt composition containing two or more types of molten salt MTFSI having the substance TFSI represented by the chemical formula (1) as a cation and an alkali metal M as a cation.
- TFSI substance represented by the chemical formula (1)
- an alkali metal M as a cation.
- the molten salt composition according to the present invention has a characteristic that the melting point (eutectic temperature) is remarkably reduced as compared with the melting point of the single salt due to the constitution having two or more types of MTFSI.
- the electrochemical characteristics and melting temperature can be changed by adjusting the composition and ratio of the molten salt to be mixed. For this reason, there is an advantage that the degree of freedom in selection of the operating temperature and materials in a wide range of applications to batteries and the like is improved.
- the alkali metal M examples include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Therefore, the molten salt MTFSI is preferably selected from the group consisting of LiTFSI, NaTFSI, KTFSI, RbTFSI, and CsTFSI.
- a composition containing two kinds of molten salts selected from the group consisting of LiTFSI, NaTFSI, KTFSI, RbTFSI, and CsTFSI a so-called binary composition is preferred.
- binary composition examples include the LiTFSI-NaTFSI system, LiTFSI-KTFSI system, LiTFSI-CsTFSI system, NaTFSI-KTFSI system, NaTFSI-CsTFSI system, or KTFSI-CsTFSI system.
- LiTFSI-KTFSI system and LiTFSI-CsTFSI system which are applicable to lithium batteries
- NaTFSI-KTFSI mixed system and NaTFSI-CsTFSI mixed system can deposit metallic sodium.
- electrolytes for lithium batteries, sodium-sulfur batteries, and zebra batteries the range of applications is further expanded and the development of technology is expected if these metals have the property of being easily deposited.
- the molten salt composition is preferably configured so that two or more of the mixed molten salts are in the vicinity of a composition (eutectic composition) exhibiting a eutectic.
- a composition eutectic composition
- the LiTFSI ratio in the Li TFSI-NaTFSI system is preferably 0.1 to 0.6.
- the ratio of LiTFSI is preferably 0.2 to 0.8.
- the composition with X 0.43, which is the composition with the lowest eutectic temperature (eutectic composition)
- the ratio of NaTFSI is preferably 0.05-0.6.
- the composition having the lowest eutectic temperature (eutectic composition) X 0.
- a composition of 33 is preferred.
- the NaTFSI ratio is preferably 0.03 to 0.6.
- X is the composition with the lowest eutectic temperature (eutectic composition).
- the eutectic temperature is changed by changing the composition and ratio of the molten salt.
- the optimum temperature range can be set according to the purpose of use, and there is also an advantage that the range of application is widened.
- the molten salt composition according to the present invention has a wide range from a low temperature range, which cannot be used with conventional single salt molten salts, to a medium to high temperature range that can be used with conventional single salts. Can be used in a range.
- the molten salt composition according to the present invention can be used, for example, at 110 ° C to 470 ° C.
- molten salt used in the present invention a conventionally known molten salt MTFSI having an alkali metal M as a cation and TFSI as a key can be suitably used.
- the manufacturing method can utilize a conventionally well-known method,
- the concrete means etc. are not specifically limited. For example, the method shown in the Example mentioned later can be used.
- the molten salt composition according to the present invention has a specific effect when the melting temperature (eutectic temperature) is lowered. For this reason, it is excellent in safety, corrosion prevention, and energy cost. That is, if the melting temperature is lowered and the molten salt can be used at a low temperature, the use of energy for heating can be reduced. In addition, molten salts generally tend to corrode materials such as metals, and their properties increase in reaction rate with increasing temperature. As a result. Therefore, if molten salt can be used at a low temperature, the progress of corrosion can be expected to decrease. If it can be used at low temperatures, the possibility of accidents such as spilling of high-temperature objects due to rupture of equipment materials due to material corrosion will be reduced.
- the melting temperature eutectic temperature
- the molten salt composition according to the present invention has the advantage that the eutectic temperature is lowered while the decomposition temperature does not change from that in the case of a single salt, so that the temperature range between the melting point and the decomposition temperature is widened and the operability is improved. There is.
- the molten salt composition according to the present invention has various advantages over the conventional molten salt and electrolyte, and can be said to be particularly advantageous in the following points. That is, for example, an ionic liquid or a molten salt that can be applied to an electrolytic solution for a lithium battery, electrodeposition of a base metal at a low temperature, or the like must have a low melting point and a lower reduction potential.
- an ionic liquid or a molten salt that can be applied to an electrolytic solution for a lithium battery, electrodeposition of a base metal at a low temperature, or the like must have a low melting point and a lower reduction potential.
- conventional electrolytes in which electrolytes are dissolved in organic solvents and ionic liquids of imide salts with organic cations as counterions are used in organic solvents or at higher potentials before these metals are reduced and precipitated. The organic cation may be decomposed.
- the alkali metal imide salt is used as a molten salt that does not dissolve in an organic solvent, and by mixing a plurality of types of molten salts, the temperature is lower than that in the case of a single salt.
- molten salt As an electrolyte, it is possible to cause electrochemical reactions that are difficult in an aqueous solution system, and a wide variety of research and development has been conducted for various applications. For example, some molten salts have various melting points. Salts having a melting point in the middle temperature range are advantageous for applications as electrolytes in electrochemical devices operating at medium to high temperatures.
- the molten salt composition according to the present invention has a melting temperature in the medium temperature to high temperature range, and thus can be used particularly in the medium temperature to high temperature range. Therefore, for example, in the above temperature range, an electrolytic solution or an electrode containing the molten salt composition described in the above ⁇ 1> column. It can be used as a solution.
- the melting point composition (eutectic temperature) of the molten salt composition according to the present invention is lower than that of a single salt, safety, width of material selection, energy Very good in terms of cost. For this reason, such advantages can also be used in the use of a molten salt compound.
- the use of the electrolytic solution or the electrolyte is not particularly limited, and can be used for a wide variety of products using the electrolyte known in the present application. For example, it can be used as an electrolyte for batteries.
- molten salt composition according to the present invention as an electrolytic solution or an electrolyte
- a solvent it is intended to use a molten salt obtained by melting the salt itself as an electrolyte or electrolyte.
- Such use is very preferable because it is not necessary to use a solvent. This is because the volatile and flammable electrolyte solution due to the presence of the solvent does not cause problems such as ignition and explosion due to the reaction with the alkali metal.
- the molten salt composition according to the present invention is ( 0 No organic solvent, GO itself melts at a relatively low temperature, (m) Alkali metal imide salt and its eutectic salt as low temperature molten salt, (iv) Melting temperature of these salts Strength It has excellent characteristics in that it is stable even at high temperatures, and (V) it can precipitate alkali metal in molten salt.
- sodium-sulfur batteries for example, sodium-sulfur batteries, zebra batteries, lithium secondary batteries (stationary type, high output, for load leveling) that operate at lower temperatures, etc. It can be used as an electrolyte for a wide variety of batteries.
- the advantage as a large-sized battery using an alkali metal imide salt is great. For example, it can be used for charging surplus power at night in a power facility or the like. It can also be used for lithium secondary batteries for electric vehicles and hybrid vehicles.
- a large Li-ion battery is configured using the molten salt composition according to the present invention, it is preferably used in a temperature range in which generation of dendrites is suppressed. Specifically, 150 ° C ⁇ 20 It is preferable to use at a temperature of about o ° c.
- the conventional single salt molten salt has been unable to be used sufficiently in this temperature range, but the molten salt composition according to the present invention can be used in such a temperature range.
- the present invention also includes a charging method using a battery using the molten salt composition.
- the specific method of the charging method is not particularly limited, and any other known processes, conditions, equipment used, etc. may be used as long as the above battery is used. According to this charging method, it can charge efficiently.
- the fact that the molten salt composition according to the present invention can be used as an electrolyte is clear from the fact that the molten salt composition has good electrical conductivity.
- the molten salt composition according to the present invention can be used as an electrolyte for electrodeposition under conditions where an aqueous solution cannot be used and a high-temperature molten salt cannot be used in the LIGA process. Can be used.
- the molten salt composition of the present invention When the molten salt composition of the present invention is used as an electrolyte for a battery, when one alkali metal functions as a battery, the other alkali metal exhibits a solvent function. . That is, in the molten salt composition of the present invention, at least two kinds of alkali metal salts are mixed, and therefore, when the electrolysis is applied with voltage, the alkali metal that is easily reduced to the negative electrode is precipitated first. come. Therefore, when used as an electrolyte for a battery, the negative electrode of the battery becomes an alkali metal electrode that is more likely to be reduced in this way.
- the molten salt composition according to the present invention when the molten salt composition according to the present invention was electrochemically measured, it was confirmed that the alkali metal constituting each single salt showed a property of being reduced and precipitated. That is, an electrochemically base metal such as an alkali metal can be deposited. For this reason, by utilizing this characteristic, the molten salt composition according to the present invention can be used as, for example, a plating solution in which a target metal having a lower reducibility than an alkali metal is dissolved as a metal salt. Examples of such target metals include alkaline earth metals, rare earth metals, Group 5 and Group 6 refractory metals, and the like.
- the molten salt composition according to the present invention has been confirmed by cyclic voltammetry that the force sword limit is precipitation of an alkali metal or an alloy thereof. . Because of this, the reductive decomposition of TFSI, which is a key, does not occur, It can be said that the metal and the various metals described above can be deposited.
- the electrolytic solution containing the molten salt composition according to the present invention can be used in an electrodeposition method, a film formation method (Metch), a surface treatment method, and the like.
- the electrodeposition method according to the present invention is not particularly limited as long as the electrolytic solution containing the molten salt composition is used, and other steps, conditions, and specific configurations of equipment used are particularly limited. is not.
- any method can be used as long as the method includes an electrodeposition step in which the molten salt composition is used as an electrolyte, and electrolysis is performed to deposit the metal or ceramics.
- this electrodeposition method it can be suitably used for electroplating.
- the method for forming a film according to the present invention is not particularly limited with respect to the specific configuration of other steps, conditions, equipment used, etc., as long as the electrolytic solution containing the molten salt composition is used. Is not something
- This film forming method is a method including a wet process in which the above molten salt composition is used as an electrolyte, and this is electrolyzed to deposit a metal or ceramic, and the surface is covered with the metal or ceramic. That is.
- a method including at least the electrodeposition method and a step of covering the surface of the substance with a metal or ceramics deposited by the electrodeposition method can be given.
- the present film forming method the surface of the substance can be uniformly coated, and a surface-finished product can be obtained.
- the surface treatment method according to the present invention is not particularly limited with respect to the specific configuration of other steps, conditions, equipment used, etc., as long as the electrolytic solution containing the molten salt composition is used. Is not something Any method may be used as long as the so-called molten salt composition is used as an electrolyte and the surface of the substance is treated. Examples of such surface treatments include surface treatments such as oxide coating, nitride coating, carbide coating, and silicide coating. For this reason, according to this surface treatment method, the effect of imparting functions such as high hardness, wear resistance, and corrosion resistance to the surface can be obtained.
- the present invention is not limited, and a material that is a target of a film forming method or a surface treatment method using a conventionally known electrolytic solution / electrolyte can be suitably implemented.
- a material that is a target of a film forming method or a surface treatment method using a conventionally known electrolytic solution / electrolyte can be suitably implemented.
- metal or composite A metal film or a ceramic film can be formed on the surface of gold, ceramics or plastic, or the surface of a metal or alloy can be treated.
- it can be used for surface finishing operations such as jewelry and home appliances.
- Fig. 1 shows the corrosion resistance reaction line used in the experiment.
- the main body consists of a SUS316 stainless steel pipe (outer diameter lZ2inch) with excellent corrosion resistance, which is connected to the SUS316 stainless steel vacuum valve (Whitey) using a joint and Kel-F tip using a swage lock. .
- a pipe with an outer diameter of lZ4 inch was used for the connection part of the reaction tube.
- An oil rotary vacuum pump is connected to this reaction line.
- a glass cold trap is installed just before the pump, and this is cooled with liquid nitrogen, so that water and corrosive gases are contained in the pump. Prevented entering. Corrosive gases such as fluorine and fluoride gas can be removed through a chemical trap using soda lime as roughing. When passing through this chemical trap, the pressure loss is large and the degree of vacuum does not increase. Therefore, the NORB can directly exhaust the gas without passing through the chemical trap.
- the maximum vacuum of this line is about 10 _2 Torr order.
- MTFSI was synthesized according to the following reaction formula.
- thermogravimetric analysis was performed.
- Thermogravimetric analysis was performed using a differential thermal / thermogravimetric simultaneous measurement apparatus (Shimadzu Corporation, DTG-60 / 60H). The aluminum cell used was washed with ethanol and distilled water before measurement and dried sufficiently, and then a sample was put in and measured. The scanning speed was lOKmin- 1 . The measurement was performed in a nitrogen gas atmosphere. Since LiTFSI has deliquescence, the temperature was first measured up to 573K to remove moisture. For NaTFSI, KTFSI, and CsTFSI, Yanagi-j was determined as it was.
- Differential scanning calorimetry was performed using a differential scanning calorimeter (Shimadzu Corporation, DSC60). SE The aluminum was made of aluminum. A sample was put in a cell in a glove box under an argon atmosphere, and the cell was sealed using a sealer and crimper (Shimadzu Corporation, SSC-30), and used for measurement. The scanning speed was lOKmin- 1 . The measurement was performed in a nitrogen gas atmosphere. Differential scanning calorimetry of mixed salts of NaTFSI and other salts was performed by changing the molar fraction X of NaTFSI from 0.05 to 0.95 every 0.05. Once heated to 533K, the room
- Electrochemical measurement was performed using an electrochemical measuring device HZ-3000 (Hokuto Denko). Cyclic voltammetry was performed using a glass cell. Nickel wire and glassy carbon rod were used for the working electrode, glassy carbon rod for the counter electrode, and silver wire as the pseudo reference electrode for the reference electrode.
- Figure 3 shows a schematic diagram of the measuring device. The measurement was performed in a glove box under an argon atmosphere with a heater maintained at a bath temperature about 30K higher than the melting point of the salt.
- Figures 4 to 7 show the TG curves for each single salt MTFSI.
- the pyrolysis temperature was determined by taking the contact point between the baseline and the TG curve after weight loss.
- Figure 22 shows the thermal decomposition temperature of each single salt. It was found that the thermal decomposition temperature tends to increase as the size of the cation increases. This is consistent with the general thermal stability of ionic crystals in which large cations stabilize large ions.
- Figures 8 to 11 show DSC curves of each single salt MTFSI.
- the melting point was determined by taking the intersection of the baseline extension and the endothermic peak tangent on the DSC curve.
- Figure 23 shows the melting point of each single salt. Unlike the trend of pyrolysis temperature, it was found that the melting point of the single salt was higher in the case of NaTFSI.
- a small endothermic peak was confirmed around 373K. This is a force that is considered to correspond to the evaporation of a very small amount of water that could not be removed by vacuum drying. I can say that. Power that may be considered to correspond to a phase transition I know that! / ⁇ ⁇ .
- TFSI ion is very strong and has resistance to reduction! It is difficult to think of it as a reduction of TFSI.
- Impurities may include HTFS I, which is a raw material of salt, alkali metal carbonate, or strong water that is generated during synthesis and cannot be removed by vacuum drying.
- HTFS I is a raw material of salt, alkali metal carbonate, or strong water that is generated during synthesis and cannot be removed by vacuum drying.
- the pH of the aqueous salt solution was neutral, it is unlikely that HTFSI and carbonate were mixed.
- CsTFSI the endothermic peak corresponding to the evaporation of water in the DSC curve was strong.
- This endothermic peak originates from LiTFSI and is considered to correspond to the phase transition of the mixed salt and so on.
- FIG. 1 Shown in A binary system phase diagram created by plotting these endothermic peaks is shown in FIG.
- An endothermic peak was observed around 463 K across the composition range, which was wider on the NaTFSI side than the eutectic composition. This endothermic peak gradually decreases as X increases.
- the degree was found to be about 383K. In this system, an endothermic peak was observed near 413K on the side where NaTFSI was higher than the eutectic composition, but it gradually decreased as X increased.
- the endothermic peak near K disappears as X increases, and instead the endothermic peak near 403K.
- the melting point of the eutectic composition was very close to that of the latter salt, taking a value and not much lowering.
- Shown in Figure 23 shows a binary phase diagram created by plotting these endothermic peaks.
- An endothermic peak was observed at around 500K across the composition range, which was wider on the LiTFSI side than the eutectic composition.
- FIG. 1 Shown in A binary system phase diagram created by plotting these endothermic peaks is shown in FIG.
- LiTFSI Shown in Figure 27 shows a binary phase diagram created by plotting these endothermic peaks.
- the eutectic temperature was hardly lowered. For this reason, no eutectic composition is shown.
- the eutectic point is not shown, for example, it is lower than KTFSI single salt at 50%, and it becomes an electrolyte that moves K + ions at a temperature, so that it can be used as a molten salt composition according to the present invention. Let me add that just in case.
- FIG. 28 shows the thermal decomposition temperature of each single salt
- FIG. 29 shows the melting point of each single salt
- FIG. 30 shows the eutectic composition and eutectic temperature of each mixed salt. From these results, it can be seen that the eutectic temperature of the binary molten salt composition obtained by mixing two types of molten salts used in this Example is significantly lower than that of a single salt.
- the molten salt composition according to the present invention can lower the melting point as compared with the case of a single salt.
- the usable temperature range can be expanded by setting the composition and ratio of the molten salt. For this reason, by using the molten salt composition according to the present invention, the melting point of the electrolyte can be lowered, which is advantageous in terms of energy efficiency and safety.
- the operating temperature range can be expanded, there are also advantages such as improved material selectivity when applied to batteries. Therefore, it can be used in a wide range of industries such as plating, semiconductor, and battery industries.
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Abstract
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Claims
Priority Applications (3)
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EP06729703A EP1862452A1 (en) | 2005-03-23 | 2006-03-22 | Molten salt composition and use thereof |
US11/886,781 US8257868B2 (en) | 2005-03-23 | 2006-03-22 | Molten salt composition and use thereof |
JP2007509311A JPWO2006101141A1 (ja) | 2005-03-23 | 2006-03-22 | 溶融塩組成物及びその利用 |
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US (1) | US8257868B2 (ja) |
EP (1) | EP1862452A1 (ja) |
JP (1) | JPWO2006101141A1 (ja) |
KR (1) | KR20070114323A (ja) |
WO (1) | WO2006101141A1 (ja) |
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US9391341B2 (en) | 2011-06-29 | 2016-07-12 | Sumitomo Electric Industries, Ltd. | Manufacturing method for molten salt battery and molten salt battery |
JP2013084548A (ja) * | 2011-09-30 | 2013-05-09 | National Institute Of Advanced Industrial & Technology | リチウム二次電池 |
JP2019096541A (ja) * | 2017-11-27 | 2019-06-20 | トヨタ自動車株式会社 | 全固体電池 |
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US20090212743A1 (en) | 2009-08-27 |
US8257868B2 (en) | 2012-09-04 |
EP1862452A1 (en) | 2007-12-05 |
JPWO2006101141A1 (ja) | 2008-09-04 |
KR20070114323A (ko) | 2007-11-30 |
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