WO2011024687A1 - 非水電解液処理用ゼオライト及び非水電解液の処理方法 - Google Patents
非水電解液処理用ゼオライト及び非水電解液の処理方法 Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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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
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the 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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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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 novel non-aqueous electrolyte treatment zeolite and a non-aqueous electrolyte treatment method.
- non-aqueous electrolytes such as electrolytes for plating unstable metal ions, battery electrolytes such as lithium batteries, and capacitor electrolytes in aqueous solutions, remove impurities in the non-aqueous electrolyte. It is very important to remove. In these applications, the water content in the non-aqueous electrolyte must be 50 ppm or less. Therefore, when using it as a non-aqueous electrolyte, it is necessary to dehydrate these beforehand.
- Non-aqueous electrolyte dehydration methods that have been proposed so far include a method of preparing a non-aqueous electrolyte by drying both the non-aqueous solvent and the electrolyte, and then mixing the non-aqueous solvent and the electrolyte.
- Patent Document 1 A method of azeotropically dehydrating the product (Patent Document 1), a method of dehydrating a mixture of a non-aqueous solvent and an electrolyte (Patent Document 2), a method combining these (Patent Document 3), and the like Illustrated.
- these dehydration methods are roughly classified into two methods: 1) a method of dehydrating a non-aqueous electrolyte by distillation or drying, and 2) a method of dehydrating a non-aqueous electrolyte using zeolite. Is done.
- a non-aqueous solvent and an electrolyte are each dried and then mixed to prepare a non-aqueous electrolyte, or in a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent.
- azeotropic dehydration it is difficult to sufficiently remove moisture in the non-aqueous electrolyte. Therefore, in any of the methods, it is quite difficult to reduce the water content in the nonaqueous electrolytic solution to 50 ppm or less.
- Method 2 is a method of removing water in the non-aqueous electrolyte by the water adsorption ability of zeolite.
- zeolite since there are cations capable of ion exchange in zeolite, lithium ions in the non-aqueous electrolyte and cations in the zeolite cause an ion exchange reaction during the dehydration treatment. Therefore, in this method, moisture in the non-aqueous electrolyte is removed, but cations in the zeolite are eluted as impurities into the non-aqueous electrolyte and contaminate the non-aqueous electrolyte after moisture removal.
- Patent Document 3 As a method for dehydrating a non-aqueous electrolytic solution using zeolite, a method of suppressing an ion exchange reaction between a cation in zeolite and an ion in the electrolytic solution by not contacting the electrolytic solution with zeolite for a long time (Patent Document 3). ) Has been proposed. However, such a dehydration method has a complicated process. As described above, the dehydration ability in the nonaqueous electrolyte dehydration method using zeolite has been improved. However, the conventional method has problems such as sodium elution from zeolite or complicated process. It was. Therefore, until now, there has been no zeolite for non-aqueous electrolyte treatment that does not have sodium elution and enables dehydration of the non-aqueous electrolyte by a simple process.
- An object of the present invention relates to providing an industrially useful zeolite for treating non-aqueous electrolyte that can remove moisture without elution of sodium into the non-aqueous electrolyte.
- the present inventor has found that in the zeolite in which 97.5 mol% or more and 99.5 mol% or less of ion-exchangeable cations are ion-exchanged with lithium, lithium is contained in the zeolite. In spite of remaining ion-exchangeable cations, there is no elution of cations other than lithium, especially sodium, and no contamination in the non-aqueous electrolyte when dehydrating the non-aqueous electrolyte. The inventors have found that dehydration can be performed and have completed the present invention.
- the gist of the present invention resides in the following (1) to (7).
- a zeolite for non-aqueous electrolyte treatment wherein 97.5 mol% or more and 99.5 mol% or less of exchangeable cations are ion-exchanged with lithium.
- the zeolite for nonaqueous electrolyte treatment according to (1) above.
- the zeolite is at least one zeolite selected from the group consisting of A-type, chabasite, ferrierite, ZSM-5, and clinoptilolite. The zeolite for non-aqueous electrolyte treatment described in 1.
- a zeolite molded body for non-aqueous electrolyte treatment obtained by molding the zeolite for non-aqueous electrolyte treatment according to (1) above.
- the zeolite molded article for nonaqueous electrolyte treatment according to (4) above comprising 95% by weight or more of the zeolite for treating nonaqueous electrolyte.
- the nonaqueous electrolyte treatment zeolite described in (1) above, the nonaqueous electrolyte treatment zeolite molding described in (4) above, or both, and the nonaqueous electrolyte solution are brought into contact with each other.
- a method for producing a non-aqueous electrolyte is obtained.
- a lithium battery comprising the nonaqueous electrolyte treatment zeolite according to (1), the nonaqueous electrolyte treatment zeolite molding according to (4) or both, and a nonaqueous electrolyte.
- the zeolite for non-aqueous electrolyte treatment of the present invention and the molded product thereof cause a problem of elution of cations other than lithium such as sodium even though exchangeable cations in the zeolite are not completely ion-exchanged with lithium. Without dehydrating the non-aqueous electrolyte.
- the non-aqueous electrolyte treatment zeolite of the present invention 97.5 mol% or more and 99.5 mol% or less of exchangeable cations are ion-exchanged with lithium, preferably 98.0 mol% or more and 99.5 mol% or less are lithium. More preferably, 98.0 mol% or more and 99.0 mol% or less are ion exchanged with lithium.
- the ratio of lithium in exchangeable cations in zeolite is referred to as “lithium ion exchange rate”.
- the lithium ion exchange amount of the zeolite of the present invention is 99.5 mol% or less, preferably 99 0.0 mol% or less.
- the lithium ion exchange rate of the zeolite is 98.0 mol% or more and 99.0 mol% or less
- cation elution such as sodium from the zeolite does not occur, Not only can water in the non-aqueous electrolyte be removed, but a free acid can be removed at a high rate, which is preferable.
- the free acid is an acid such as hydrogen fluoride that is generated when the electrolyte in the nonaqueous electrolytic solution is decomposed.
- the kind (crystal type) of the zeolite for non-aqueous electrolyte treatment of the present invention is at least one zeolite selected from the group consisting of A type, chabazite, ferrierite, ZSM-5, and clinoptilolite. It is preferable that the zeolite is A-type zeolite.
- these zeolites are particularly suitable for zeolites for non-aqueous electrolyte treatment is not clear, but these zeolites have a pore size as small as about 6 mm or less, among which A-type zeolite has an 8-membered ring pore structure. The pore size is smaller than 4mm. Therefore, it is considered that the non-aqueous solvent of the non-aqueous electrolyte solution solvated with lithium ions hardly enters the zeolite pores, and therefore the non-aqueous solvent does not change chemically.
- the form of the zeolite for non-aqueous electrolyte treatment of the present invention can be any form such as a powder or a molded body, but is preferably a molded body that is easy to handle.
- zeolite is used as a molded body, it is preferable to perform molding by adding a binder.
- a binder As the binder used for molding, silica, alumina, clay and the like can be generally exemplified, and those having a low sodium content in the binder are preferable.
- binder for example, kaolin-based, bentonite-based, talc-based, virophilite-based, molysite-based, verculolite-based, montmorillonite-based, chlorite-based, and halloysite-based clays can be used.
- the amount of the binder added is not particularly limited, but it is preferable to add 10 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of powdered zeolite (hereinafter, zeolite powder). If the binder is less than 10 parts by weight with respect to 100 parts by weight of the zeolite powder, the zeolite molded body may collapse in use, and if it exceeds 50 parts by weight, the dehydration performance becomes insufficient.
- the binder in a molded object When using a binder and making a zeolite into a molded object, it is preferable to convert the binder in a molded object into a zeolite (binder-less) by alkali immersion. Thereby, the zeolite content ratio in the zeolite molded body can be increased, and ultimately all of the zeolite molded body can be made into zeolite.
- the zeolite content in the molded body is preferably 95% or more, and more preferably 100%. Due to the high zeolite content in the molded body, the dehydration efficiency of the non-aqueous electrolyte is increased.
- the shape of the molded body is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a trefoil shape, an elliptical shape, and a hollow shape.
- the size of the molded body is not particularly limited, and examples of the spherical or cylindrical diameter are about 0.3 mm to 5 mm.
- the method for producing a non-aqueous electrolyte treatment zeolite of the present invention is not particularly limited as long as the lithium ion exchange rate is in the range of 97.5 mol% or more and 99.5 mol% or less.
- lithium salt aqueous solution is passed over zeolite and ion exchanged with lithium. It is preferable to use a flow-type ion exchange method in which cations such as sodium are continuously discharged out of the system. Finally, in order to make the lithium ion exchange rate of the entire zeolite uniform, it is more preferable to circulate and use an aqueous lithium salt solution.
- the lithium salt used in the aqueous lithium salt solution is not particularly limited as long as it is water-soluble, and examples thereof include lithium nitrate, lithium sulfate, lithium carbonate, lithium hydroxide, and lithium chloride.
- the lithium concentration in the lithium salt aqueous solution is not particularly limited, but is preferably 1 mol% or more.
- the zeolite for non-aqueous electrolyte treatment of the present invention can be advanced by contacting with the non-aqueous electrolyte.
- a non-aqueous electrolyte dehydrated can be produced.
- the non-aqueous electrolyte from which the free acid has been sufficiently removed and sufficiently dehydrated can be produced by the zeolite for non-aqueous electrolyte treatment of the present invention.
- non-aqueous electrolyte that can be treated with the zeolite for treating non-aqueous electrolyte of the present invention is not particularly limited as long as it is a non-aqueous electrolyte.
- the non-aqueous electrolyte include at least one organic compound such as carbonates such as dimethyl carbonate and diethyl carbonate, sulfolanes such as sulfolane and dimethyl sulfoxide, lactones such as ⁇ -butyrolactone, and ethers such as dimethyl sulfoxide.
- Examples include a solvent in which at least one or more of lithium salts such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, and trifluoromethanesulfonic acid, and quaternary ammonium salts are dissolved.
- lithium salts such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, and trifluoromethanesulfonic acid, and quaternary ammonium salts are dissolved.
- the non-aqueous electrolyte is dehydrated using the non-aqueous electrolyte treatment zeolite of the present invention
- the method for dehydrating the zeolite is not particularly limited as long as it is a method and conditions for removing moisture from the zeolite.
- the dehydration treatment method of the non-aqueous electrolyte using the zeolite for non-aqueous electrolyte treatment of the present invention is not particularly limited as long as it is a method in which the non-aqueous electrolyte and the zeolite are in contact with each other.
- a method of circulating a nonaqueous electrolyte through a column packed with a nonaqueous electrolyte treatment zeolite or the like, or immersing the nonaqueous electrolyte treatment zeolite of the present invention in a prepared nonaqueous electrolyte and allowing to stand or stir A method etc. can be illustrated.
- the non-aqueous electrolyte dehydrated with the zeolite for non-aqueous electrolyte treatment of the present invention preferably has a sodium concentration of 50 ppm or less, and more preferably 40 ppm or less.
- the non-aqueous electrolyte treatment zeolite of the present invention may be added to the non-aqueous electrolyte solution in the lithium battery.
- the elution characteristics of sodium from zeolite were evaluated by immersing the zeolite in a high concentration lithium salt aqueous solution. That is, an accelerated test for elution of sodium from zeolite was performed by placing the zeolite in an environment in which lithium in the lithium salt aqueous solution easily exchanges ions with sodium in the zeolite. The maximum sodium elution concentration eluted in the non-aqueous electrolyte was estimated from the amount of sodium elution in such an environment.
- a 2 mol / L lithium chloride aqueous solution (prepared using a reagent manufactured by Kishida Chemical Co., Ltd., purity 99.0% or more) was used as the lithium salt aqueous solution.
- 10 g of the dehydrated zeolite molding was immersed in 100 g of the aqueous solution, and stirred at 30 ° C. and 180 rpm for 1 hour.
- the aqueous solution after stirring was filtered through a membrane filter to remove fine powder, and the sodium concentration in the aqueous solution after filtration was quantified by ICP measurement to measure the sodium elution concentration.
- the sodium concentration in the 2 mol / L lithium chloride aqueous solution before measuring the sodium elution concentration was 0.2 ppm.
- Example 1 To 100 parts by weight of sodium A-type zeolite, 25 parts by weight of kaolin clay, 4 parts by weight of CMC (carboxymethylcellulose) and water were mixed and kneaded to obtain a cylindrical molded body having a diameter of 1.5 mm ⁇ . After the molded body was dried, it was fired at 600 ° C. for 3 hours using a box furnace.
- the fired molded body was packed in a column, and a 6% aqueous sodium hydroxide solution was passed at 80 ° C. to convert the clay into A-type zeolite (binderless). 95% or more of the molded body after the binderless conversion was zeolite. Subsequently, the aqueous sodium hydroxide solution in the column was removed by washing with water, and then lithium ion exchange of the zeolite molding was performed. In lithium ion exchange, 15 times equivalent of 4 mol / L lithium chloride aqueous solution was circulated in one pass at 80 ° C. to contact the zeolite and lithium chloride aqueous solution, and finally the lithium chloride aqueous solution was circulated.
- the lithium ion exchange rate of the zeolite molding was homogenized.
- the molded zeolite after the lithium ion exchange was washed with water, dried at 70 ° C., and then calcined at 500 ° C. for 3 hours to dehydrate the zeolite.
- the obtained lithium ion exchange A-type zeolite molding had a lithium ion exchange rate of 99.0 mol%, and the remaining cation was sodium.
- the sodium concentration in the lithium salt aqueous solution after the treatment was 33 ppm.
- Example 2 The same treatment as in Example 1 was performed except that the amount of 4 mol / L lithium chloride aqueous solution passed was 25 times equivalent and the lithium ion exchange rate was 99.5 mol%.
- the sodium concentration in the aqueous lithium salt solution after the treatment was 18 ppm.
- Comparative Example 1 The same treatment as in Example 1 was performed except that the flow rate of the 4 mol / L lithium chloride aqueous solution was 10 times equivalent and the lithium ion exchange rate was 97.0 mol%.
- the sodium concentration in the aqueous lithium salt solution after the treatment was 103 ppm, which was significantly higher than the sodium concentration (0.2 ppm) in the aqueous lithium salt solution before the measurement of the sodium elution concentration.
- Comparative Example 2 LSX type zeolite containing sodium and potassium was used as the zeolite. Also, the binder-less process is carried out by using a mixed solution of 8% sodium hydroxide aqueous solution and 1% SiO 2 instead of 6% sodium hydroxide aqueous solution, and circulating this mixed solution through the zeolite at 90 ° C. The binder was converted to X-type zeolite. In the case of lithium ion exchange, the treatment was performed in the same manner as in Example 1 except that the flow rate of the lithium chloride aqueous solution was changed to 6 times equivalent.
- the obtained lithium-exchanged LSX type zeolite molding had a lithium ion exchange rate of 96.0 mol%, and the remaining cations were sodium and potassium.
- the sodium concentration in the lithium salt aqueous solution after the treatment was 130 ppm, and the sodium concentration (0. 2 ppm).
- the free acid concentration of the non-aqueous electrolyte was quantified by the titration method shown below. That is, 10 ml of the nonaqueous electrolyte solution after the dehydration treatment was weighed and precisely weighed, and then 100 ml of pure water cooled to about 0 ° C. was added to the nonaqueous electrolyte solution after the dehydration treatment to obtain a titration solution. The temperature of the titration solution was 0 to 5 ° C., and a 0.1 mol / L sodium hydroxide aqueous solution was added dropwise to determine the neutralization point. In addition, bromthymol blue powder was used as an indicator for indicating the neutralization point of titration.
- the neutralization point was defined as the point at which the titration solution to which the indicator was added changed from orange to bluish purple and the bluish purple persisted for 5 seconds. From the obtained neutralization point, the free acid concentration was determined as a hydrogen fluoride equivalent concentration based on the following formula.
- Free acid concentration (ppm) Amount of 0.1 mol / L sodium hydroxide aqueous solution required up to the neutralization point (ml) ⁇ hydrogen fluoride molecular weight ⁇ 100 / weight of non-aqueous electrolyte (g)
- the molecular weight of hydrogen fluoride was 20 g / mol.
- the non-aqueous electrolyte before dehydration had a water concentration of 124 ppm and a free acid concentration of 54 ppm, and sodium and potassium were not detected.
- Table 1 shows the measurement results of the nonaqueous electrolytic solution after the zeolite was immersed for 24 hours and dehydrated.
- the moisture removal rate and free acid removal rate in Table 1 indicate the ratios in which the moisture concentration and free acid concentration in the non-aqueous electrolyte after the dehydration treatment are changed from those before the dehydration treatment. Higher values indicate that moisture and free acid are removed. Therefore, the larger these values, the higher the dehydration characteristics and free acid removal characteristics of the zeolite for non-aqueous electrolyte of the present invention.
- Example 4 The same treatment as in Example 1 was conducted except that industrial lithium chloride (lithium purity 99.5 mol%) was used as the lithium chloride aqueous solution used for lithium ion exchange.
- the lithium ion exchange A-type zeolite obtained had a lithium ion exchange rate of 98 mol%, and the remaining cations were 1 mol% sodium and 1 mol% potassium.
- Example 5 The same procedure as in Example 1 was followed until the binder-less operation was performed, and lithium ion exchange was performed by bringing a 25-fold equivalent of 4 mol / L lithium chloride aqueous solution into contact with zeolite at 80 ° C.
- the zeolite molded body after the lithium ion exchange was washed with water, dried at 70 ° C., and calcined at 500 ° C. for 3 hours to perform dehydration treatment of the zeolite.
- the obtained lithium ion exchange A-type zeolite had a lithium ion exchange rate of 99.4 mol%, and the remaining cation was sodium.
- Example 3 Using this zeolite, the non-aqueous electrolyte was dehydrated under the same conditions as in Example 3. The results are shown in Table 1. There was no cation elution from the zeolite to the non-aqueous electrolyte, and water and free acid were removed from the non-aqueous electrolyte. Comparative Example 3 The same treatment as in Example 1 was performed except that a 6-fold equivalent of 4 mol / L lithium chloride aqueous solution was used for lithium ion exchange. The lithium ion exchange A-type zeolite obtained had a lithium ion exchange rate of 95 mol%, and the remaining cation was 5 mol% sodium.
- Example 4 The same test as in Example 3 was performed using this zeolite. The results are shown in Table 1. In the dehydration treatment of the non-aqueous electrolyte with the zeolite, water and free acid in the non-aqueous electrolyte were removed, but a large amount of sodium was eluted from the zeolite into the non-aqueous electrolyte. Comparative Example 4 Using the lithium ion exchange A-type zeolite (lithium ion exchange rate 97 mol%) obtained in the same manner as in Comparative Example 1, the non-aqueous electrolyte was dehydrated under the same conditions as in Example 3. The results are shown in Table 1.
- Comparative Example 5 Using the same lithium ion-exchanged LSX zeolite as in Comparative Example 2 (the lithium ion exchange rate was 96.0 mol%), the non-aqueous electrolyte was dehydrated under the same conditions as in Example 3. The results are shown in Table 1. The water removal ability of the zeolite of Comparative Example 5 was lower than that of the lithium ion exchange type A zeolite. Furthermore, elution of sodium and potassium from the zeolite to the non-aqueous electrolyte was observed. Moreover, the free acid concentration in the non-aqueous electrolyte increased due to contact with zeolite. It is presumed that LiPF 6 which is an electrolyte contained in the nonaqueous electrolytic solution was adsorbed on the zeolite and decomposed.
- the zeolite of the present invention can be used for dehydration of non-aqueous electrolytes, and in particular, can be used for dehydration of electrolytes used in lithium ion batteries, lithium ion capacitors and the like. Therefore, the industrial value of the present invention is remarkable.
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Abstract
Description
これまで提案されている非水電解液の脱水処理方法としては、非水溶媒と電解質をそれぞれ乾燥処理した後に両者を混合して非水電解液を調製する方法、非水溶媒と電解質とを混合したものを共沸脱水する方法(特許文献1)、非水溶媒と電解質とを混合したものをゼオライトで脱水処理する方法(特許文献2)、及びこれらを組み合わせた方法(特許文献3)などが例示されている。これらの脱水処理方法は技術的には、1)蒸留または乾燥によって非水電解液の脱水を行う方法、及び2)ゼオライトを使用して非水電解液の脱水を行う方法の2つに大別される。
このように、ゼオライトを用いた非水電解液の脱水方法における脱水能力の向上が図られてきたが、従来の方法ではゼオライトからのナトリウム溶出の問題、もしくは、プロセスの複雑化といった問題が生じていた。そのため、これまではナトリウム溶出がなく、かつ、簡便なプロセスにより非水電解液の脱水処理を可能にさせる非水電解液処理用ゼオライトはなかった。
(1)交換可能なカチオンの97.5mol%以上99.5mol%以下がリチウムでイオン交換されていることを特徴とする非水電解液処理用ゼオライト。
(2)好ましくは、交換可能なカチオンの98.0mol%以上99.0mol%以下がリチウムでイオン交換されていることを特徴とする上記(1)に記載の非水電解液処理用ゼオライト。
(3)好ましくは、ゼオライトが、A型、チャバサイト、フェリエライト、ZSM-5、及びクリノプチロライトから成る群から選ばれた少なくとも一種以上のゼオライトであることを特徴とする上記(1)に記載の非水電解液処理用ゼオライト。
(5)好ましくは、前記の非水電解液処理用ゼオライトを95重量%以上含んでなる上記(4)に記載の非水電解液処理用ゼオライト成型体。
(7)上記(1)に記載の非水電解液処理用ゼオライト、上記(4)に記載の非水電解液処理用ゼオライト成型体又はその両者と非水電解液を含んでなるリチウム電池。
なお、本発明においては、ゼオライト中の交換可能なカチオンの中でリチウムが占める割合を「リチウムイオン交換率」という。
リチウムイオン交換率が97.5mol%未満では、このようなゼオライトで非水電解液を処理した際に、ゼオライト中のリチウム以外の交換可能なカチオンの非水電解液中へ溶出が増大し、特にナトリウムの非水電解液中への溶出が急激に増大する。そのため、このようなゼオライトを使用して非水電解液の脱水処理を行った場合は、電池用の非水電解液として使用できないナトリウム濃度である、50ppmを超えるナトリウムがゼオライトから非水電解液へと溶出する。
ここで、遊離酸とは、非水電解液中の電解質が分解等することによって生成するフッ化水素等の酸のことである。
ゼオライトを成型体とする場合、バインダーを添加して成形を行うことが好ましい。
成形に使用するバインダーとしては、シリカ、アルミナ、及び粘土などが一般的に例示でき、バインダー中のナトリウム含有量が少ないものが好ましい。このようなバインダーとして、例えばカオリン系、ベントナイト系、タルク系、バイロフィライト系、モリサイト系、バーキュロライト系、モンモリロナイト系、クロライト系、及びハロイサイト系等の粘土が使用できる。
バインダーの一部又は全部をバインダーレス化した成型体では、成型体中のゼオライト含有率が95%以上であることが好ましく、100%であることがより好ましい。成型体中のゼオライト含有率が高いことにより、非水電解液の脱水効率が高くなる。
本発明の非水電解液処理用ゼオライトの製造方法は、リチウムイオン交換率が97.5mol%以上99.5mol%以下の範囲となるものであれば特に限定されるものではない。
リチウム塩水溶液中のリチウム濃度は特に限定はないが、1mol%以上であることが好ましい。
本発明の非水電解液処理用ゼオライト等は、リチウム電池内の非水電解液中に添加して用いてもよい。
(リチウムイオン交換率)
リチウムイオン交換後のゼオライトを溶解し、ICP測定によってゼオライト中のリチウム濃度、ナトリウム濃度及びカリウム濃度をそれぞれ定量した。定量したリチウム濃度、ナトリウム濃度及びカリウム濃度の合計をモル濃度で求め、当該濃度に対するリチウム濃度の割合をmol%で求めて、リチウムイオン交換率とした。
ゼオライトからのナトリウムの溶出特性は、ゼオライトを高濃度のリチウム塩水溶液中に浸漬することにより評価した。つまり、リチウム塩水溶液中のリチウムがゼオライト中のナトリウムとイオン交換し易い環境中にゼオライトを置くことにより、ゼオライトからのナトリウム溶出の加速的な試験を行った。この様な環境下におけるナトリウム溶出量により、非水電解液に溶出する最大ナトリウム溶出濃度を見積もった。
実施例1
ナトリウムA型ゼオライト100重量部にカオリン粘土25重量部、CMC(カルボキシメチルセルロース)4重量部と水を混合混練し、直径1.5mmφの円柱状の成型体とした。成型体は乾燥した後、箱形炉を使用して600℃で3時間焼成した。
引き続き、カラム内の水酸化ナトリウム水溶液を水洗して除去した後、ゼオライト成型体のリチウムイオン交換を行った。リチウムイオン交換は15倍当量の4mol/Lの塩化リチウム水溶液を80℃でワンパスで流通してゼオライトと塩化リチウム水溶液とを接触させた後、最終的に塩化リチウム水溶液を循環させた。これにより、ゼオライト成型体のリチウムイオン交換率を均質化した。リチウムイオン交換後のゼオライト成型体は水洗を行い、70℃で乾燥した後、500℃で3時間焼成してゼオライトの脱水処理を行った。
当該ゼオライト成型体を用いて、ナトリウム溶出濃度の測定を行った結果、処理後のリチウム塩水溶液中のナトリウム濃度は33ppmであった。
実施例2
4mol/Lの塩化リチウム水溶液の通液量を25倍当量にし、リチウムイオン交換率を99.5mol%とした以外は実施例1と同様の処理を行った。処理後のリチウム塩水溶液中のナトリウム濃度は18ppmであった。
4mol/Lの塩化リチウム水溶液の通液量を10倍当量にし、リチウムイオン交換率を97.0mol%とした以外は実施例1と同様の処理を行った。処理後のリチウム塩水溶液中のナトリウム濃度は103ppmであり、ナトリウム溶出濃度の測定前のリチウム塩水溶液中のナトリウム濃度(0.2ppm)と比べ大幅に増加した。
ゼオライトとしてナトリウム及びカリウムを含むLSX型ゼオライトを使用した。また、バインダーレス化を、6%の水酸化ナトリウム水溶液の代わりに8%の水酸化ナトリウム水溶液と1%のSiO2の混合溶液を使用して、この混合溶液をゼオライトに90℃で流通させてバインダーをX型ゼオライトへ転換した。リチウムイオン交換の際、塩化リチウム水溶液の通液量を6倍当量とした以外は実施例1と同様に処理した。
当該ゼオライト成型体を用いて、ナトリウム溶出濃度の測定を行った結果、処理後のリチウム塩水溶液中のナトリウム濃度は130ppmであり、ナトリウム溶出濃度の測定前のリチウム塩水溶液中のナトリウム濃度(0.2ppm)と比べ大幅に増加した。
(非水電解液を用いた水分除去、遊離酸除去及びカチオン溶出特性)
実施例3
実施例1で得られたリチウムイオン交換A型ゼオライト(リチウムイオン交換率99.0mol%)10gを、市販のリチウム電池用非水電解液(1mol/L-LiPF6 エチレンカーボネート:ジメチルカーボネート=1:2体積比率、キシダ化学製)100gに浸漬した。これを室温下で24時間静置して非水電解液を脱水処理し、処理後の非水電解液を回収した。得られた非水電解液は水分濃度をカールフィッシャー測定により定量し、カチオン濃度をICP測定により定量した。
なお、滴定の中和点を示すための指示薬として、ブロムチモールブルー粉末を使用した。中和点は、指示薬を添加した滴定用溶液が、橙色から青紫色に変り、青紫色が5秒間持続した点とした。求められた中和点より、以下の式に基づいて遊離酸濃度をフッ化水素換算濃度として求めた。
遊離酸濃度(ppm)=中和点までに要した0.1mol/Lの水酸化ナトリウム水溶液の滴下量(ml)×フッ化水素分子量×100/非水電解液の重量(g)
ここで、フッ化水素の分子量は20g/molとした。
ゼオライトを24時間浸漬して脱水処理した後の非水電解液の測定結果を表1に示す。なお、表1における水分除去率及び遊離酸除去率は、脱水処理後の非水電解液中の水分濃度及び遊離酸濃度が、脱水処理前のそれより変化した割合を示している。これらの値が大きいほど水分及び遊離酸が除去されていることを示す。そのため、これらの値が大きいほど本発明の非水電解液用ゼオライト等の脱水特性及び遊離酸除去特性が高いことを意味する。
実施例4
リチウムイオン交換に用いた塩化リチウム水溶液として工業用塩化リチウム(リチウム純度99.5mol%)を用いたこと以外は実施例1と同様に処理した。得られたリチウムイオン交換A型ゼオライトのリチウムイオン交換率は98mol%であり、残りのカチオンはナトリウム1mol%、カリウム1mol%であった。
実施例5
実施例1と同様にバインダーレス化まで行い、25倍当量の4mol/Lの塩化リチウム水溶液を80℃でゼオライトとを接触させてリチウムイオン交換を行った。リチウムイオン交換後のゼオライト成型体は水洗して、70℃で乾燥した後、500℃で3時間焼成してゼオライトの脱水処理を行った。得られたリチウムイオン交換A型ゼオライトのリチウムイオン交換率は99.4mol%であり、残りのカチオンはナトリウムであった。
比較例3
リチウムイオン交換に6倍当量の4mol/Lの塩化リチウム水溶液を使用したこと以外は、実施例1と同様の処理を行った。得られたリチウムイオン交換A型ゼオライトのリチウムイオン交換率は95mol%であり、残りのカチオンはナトリウム5mol%であった。
比較例4
比較例1と同様にして得たリチウムイオン交換A型ゼオライト(リチウムイオン交換率97mol%)を用いて、実施例3と同様な条件で非水電解液を脱水処理した。結果を表1に示す。当該ゼオライトによる非水電解液の脱水処理では、非水電解液中の水分および遊離酸は除去されるが、ゼオライトから非水電解液へのナトリウムの溶出が生じた。
比較例2と同じリチウムイオン交換LSXゼオライト(リチウムイオン交換率は96.0mol%)を用いて、実施例3と同様な条件で非水電解液を脱水処理した。結果を表1に示す。
比較例5のゼオライトの水分除去能力はリチウムイオン交換A型ゼオライトより低かった。更に、ゼオライトから非水電解液へのナトリウムとカリウムの溶出が認められた。また、非水電解液中の遊離酸濃度はゼオライトとの接触により増加した。非水電解液に含まれる電解質であるLiPF6がゼオライトに吸着して分解したと推定される。
Claims (7)
- 交換可能なカチオンの97.5mol%以上99.5mol%以下がリチウムでイオン交換されていることを特徴とする非水電解液処理用ゼオライト。
- 交換可能なカチオンの98.0mol%以上99.0mol%以下がリチウムでイオン交換されていることを特徴とする請求項1に記載の非水電解液処理用ゼオライト。
- ゼオライトが、A型、チャバサイト、フェリエライト、ZSM-5、及びクリノプチロライトから成る群から選ばれた少なくとも一種以上のゼオライトであることを特徴とする請求項1に記載の非水電解液処理用ゼオライト。
- 請求項1に記載の非水電解液処理用ゼオライトを成型してなる非水電解液処理用ゼオライト成型体。
- 前記非水電解液処理用ゼオライトを95重量%以上含んでなる請求項4に記載の非水電解液処理用ゼオライト成型体。
- 請求項1に記載の非水電解液処理用ゼオライト、請求項4に記載の非水電解液処理用ゼオライト成型体又はその両者と非水電解液を接触させることを特徴とする非水電解液の製造方法。
- 請求項1に記載の非水電解液処理用ゼオライト、請求項4に記載の非水電解液処理用ゼオライト成型体又はその両者と非水電解液を含んでなるリチウム電池。
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US10012438B2 (en) | 2015-07-31 | 2018-07-03 | Praxair Technology, Inc. | Method and apparatus for argon recovery in a cryogenic air separation unit integrated with a pressure swing adsorption system |
US10012437B2 (en) | 2015-07-31 | 2018-07-03 | Praxair Technology, Inc. | Method and apparatus for argon recovery in a cryogenic air separation unit integrated with a pressure swing adsorption system |
US10018413B2 (en) | 2015-07-31 | 2018-07-10 | Praxair Technology, Inc. | Method and apparatus for increasing argon recovery in a cryogenic air separation unit integrated with a pressure swing adsorption system |
US10024596B2 (en) | 2015-07-31 | 2018-07-17 | Praxair Technology, Inc. | Method and apparatus for argon recovery in a cryogenic air separation unit integrated with a pressure swing adsorption system |
US10066871B2 (en) | 2015-07-31 | 2018-09-04 | Praxair Technology, Inc. | Method and apparatus for argon rejection and recovery |
US10145609B2 (en) | 2015-07-31 | 2018-12-04 | Praxair Technology, Inc. | Method ad apparatus for argon recovery in a cryogenic air separation unit integrated with a pressure swing adsorption |
US11262125B2 (en) | 2018-01-02 | 2022-03-01 | Praxair Technology, Inc. | System and method for flexible recovery of argon from a cryogenic air separation unit |
Also Published As
Publication number | Publication date |
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KR101730674B1 (ko) | 2017-04-26 |
CN102481546A (zh) | 2012-05-30 |
KR20120044981A (ko) | 2012-05-08 |
US9084980B2 (en) | 2015-07-21 |
JP5699483B2 (ja) | 2015-04-08 |
JP2011071111A (ja) | 2011-04-07 |
US20120141868A1 (en) | 2012-06-07 |
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