WO2008069207A1 - リチウム塩およびその製造方法 - Google Patents
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- WO2008069207A1 WO2008069207A1 PCT/JP2007/073405 JP2007073405W WO2008069207A1 WO 2008069207 A1 WO2008069207 A1 WO 2008069207A1 JP 2007073405 W JP2007073405 W JP 2007073405W WO 2008069207 A1 WO2008069207 A1 WO 2008069207A1
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- Prior art keywords
- lithium salt
- general formula
- alkyl group
- raw material
- formula
- Prior art date
Links
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 155
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 153
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000000126 substance Substances 0.000 claims abstract description 67
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 85
- 238000003786 synthesis reaction Methods 0.000 claims description 85
- 239000002994 raw material Substances 0.000 claims description 54
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 238000007086 side reaction Methods 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 29
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 230000037427 ion transport Effects 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000007784 solid electrolyte Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101100520660 Drosophila melanogaster Poc1 gene Proteins 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 101100520662 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PBA1 gene Proteins 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 imide lithium salt Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/26—Amides of acids of phosphorus containing P-halide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
-
- 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
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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 lithium salt that can be used, for example, as a supporting salt for an electrolytic solution, and a method for producing the same.
- Lithium salts generally include LiPF and LiBF.
- Non-aqueous solvent for imide lithium salt represented by
- Patent Document 2 Li N (C F SO) (C F SO) (where m and n are independent of each other; integers of! To 4) m 2m + l 2 n 2n + l 2
- a lithium secondary battery in which an imide lithium salt represented by the formula (1) is dissolved in a non-aqueous solvent is disclosed.
- these lithium salts contain only one Li cation in the molecular structure, the Li ion transport number is low! / And! /.
- Patent Document 3 one or both of LiPF and LiBF is used as an electrolyte.
- lithium phosphate salts having a plurality of Li in the molecular structure generally have a problem of low solubility in solvents, and it is difficult to sufficiently improve the Li ion transport number. It was.
- Patent Document 1 Japanese Patent Laid-Open No. 7-85888
- Patent Document 2 Japanese Patent Laid-Open No. 2001-68154
- Patent Document 3 Japanese Patent Laid-Open No. 10-189043
- the present invention has been made in view of the above circumstances, and for example, when used as a supporting salt for an electrolytic solution,
- the lithium salt characterized by having the chemical structure represented by these is provided.
- an electrolyte solution having a high Li ion transport number can be obtained by using, for example, as a supporting salt for the electrolyte solution.
- X represents a halogen atom.
- a lithium salt characterized by having a chemical structure represented by:
- a method for producing a lithium salt comprising a synthesis step of synthesizing a lithium salt having a chemical structure represented by the formula:
- a lithium salt capable of obtaining an electrolytic solution or a solid electrolyte membrane having a high Li ion transport number can be obtained by performing the above synthesis step.
- R and R may be the same or different from each other
- a lithium salt capable of obtaining an electrolytic solution or a solid electrolyte membrane having a high Li ion transport number can be obtained by performing the above synthesis step.
- Fig. 1 is a 19 F-NMR chart of a trisubstituted lithium salt obtained by a synthesis example.
- FIG. 4 is a 31 P-NMR chart of a disubstituted lithium salt obtained by a synthesis example.
- FIG. 5 is a graph showing the results of impedance measurement of an electrolyte containing a trisubstituted lithium salt
- the lithium salt of the present invention has a chemical structure represented by the general formula (1) (first embodiment) and has a chemical structure represented by the general formula (2) (second embodiment). It can be roughly divided into S.
- the lithium salt of the present invention will be described for each embodiment.
- the lithium salt of this embodiment is characterized by having the chemical structure represented by the general formula (1) described above. According to this embodiment, the lithium salt has three Li in the molecular structure. Therefore, for example, by using it as a supporting salt of the electrolytic solution, an electrolytic solution having a high Li ion transport number can be obtained.
- Li P Li P
- lithium phosphates with multiple Li in the molecular structure are generally
- the lithium salt of this embodiment which has the problem of low solubility in the liquid, can be dissolved in a predetermined solvent described later, and can be used as a supporting salt for the electrolytic solution. Further, the lithium salt of this embodiment can be used as a solid electrolyte without being dissolved in a solvent.
- R to R may be the same as or different from each other.
- R to R are a fluoroalkyl group, an alkyl group, or phenyl.
- At least one of R to R is fluoro.
- R to R are fluoroalkyl groups. More preferable.
- the fluoroalkyl group is one in which all hydrogens of the alkyl group are substituted with fluorine.
- the carbon number o0 and the number of elements of the fluoroalkyl group are not particularly limited, but among them, it is preferably in the range of! In particular, in this embodiment, the fluoroalkyl group is preferably CF.
- the alkyl group may be a linear alkyl group or a branched alkyl group. Further, the number of carbon atoms of the alkyl group is not particularly limited, but it is preferably within the range of 1-4. Examples of the alkyl group include CH.
- the phenyl group usually has a hydrogen bonded to a benzene ring.
- the hydrogen group may be a fluorine-substituted phenyl group in which the hydrogen is substituted with fluorine.
- R may be a fluorine-substituted phenyl group.
- the fluorine-substituted phenyl group for example, C F can be mentioned.
- the lithium salt has a chemical structure represented by the formula (1-1).
- the lithium salt of this embodiment can be made to have a solvent S such as propylene carbonate. Therefore, it is useful as a supporting salt for the electrolytic solution.
- This electrolytic solution can be used for general electrochemical devices such as a primary battery, a secondary battery, an electrolytic capacitor, and an electric double layer capacitor. Further, the lithium salt of this embodiment can also be used as a solid electrolyte of the above electrochemical device.
- the lithium salt of this embodiment is 19 FN It can be identified by MR, 31 P-NMR and plasma emission analysis (ICP).
- the lithium salt of this embodiment is characterized by having the chemical structure represented by the general formula (2) described above.
- an electrolyte solution having a high Li ion transport number can be obtained by using, for example, as a supporting salt of the electrolyte solution.
- lithium phosphates with multiple Li in the molecular structure are generally
- the lithium salt of this embodiment which has the problem of low solubility in the liquid, can be dissolved in a predetermined solvent described later, and can be used as a supporting salt for the electrolytic solution. Further, the lithium salt of this embodiment can be used as a solid electrolyte without being dissolved in a solvent.
- R and R may be the same or different from each other.
- the R and R forces are more preferably the same functional group.
- R and R are a fluoroalkyl group, an alkyl group or a phenyl group.
- the fluoroalkyl group, the alkyl group, and the phenyl group are the same as those described in “1. First embodiment”, and thus the description thereof is omitted here.
- the fluoroalkyl group is preferably CF.
- X represents a halogen atom.
- the halogen atom include a fluorine atom (F), a chlorine atom (C1), a bromine atom (Br), iodine (I) and the like.
- X is preferably a halogen atom heavier than a chlorine atom (C1). S is preferable, and X is more preferably a chlorine atom (C1)! /.
- the lithium salt has a chemical structure represented by the formula (2-1). It has been confirmed that this lithium salt has higher solubility in organic solvents than the lithium salt represented by the above formula (11). [0050] [Chemical 10]
- the lithium salt of this embodiment may be a solvent such as propylene carbonate. Therefore, it is useful as a supporting salt for the electrolytic solution.
- This electrolytic solution can be used for general electrochemical devices such as a primary battery, a secondary battery, an electrolytic capacitor, and an electric double layer capacitor. Further, the lithium salt of this embodiment can also be used as a solid electrolyte of the above electrochemical device.
- the lithium salt of this embodiment can be identified by 19 FN MR, 31 P-NMR, plasma emission analysis (ICP) and the like.
- R represents a fluoroalkyl group, an alkyl group, or a phenyl group.
- X represents a halogen atom.
- the lithium salt characterized by having the chemical structure represented by these can be provided.
- the fluoroalkyl group, the arnolequinol group, the phenyl group, and the halogen atom are the same as those described in "2. Second embodiment", and thus the description thereof is omitted here.
- R is preferably -CF
- X is a salt.
- the method for producing a lithium salt of the present invention comprises an embodiment for producing a lithium salt having a chemical structure represented by the general formula (1) (third embodiment) and a chemical structure represented by the general formula (2). It is possible to divide it roughly into the embodiment (fourth embodiment) for producing the lithium salt. Hereinafter, the method for producing a lithium salt of the present invention will be described for each embodiment.
- the method for producing a lithium salt according to this embodiment includes the following general formula (3-1) to general formula (3-3)
- a lithium salt capable of obtaining an electrolytic solution or a solid electrolyte membrane having a high Li ion transport number can be obtained.
- Lithium salt synthase A Raw material for lithium synthesis B
- Reaction 1 includes trifluoromethanesulfonic acid amide (CF) under an inert gas atmosphere such as Ar.
- LiC H n-butyllithium
- a raw material A for lithium salt synthesis As will be described later, in this embodiment, a single lithium salt synthesis raw material A may be used to synthesize lithium salts, and a plurality of lithium salt synthesis raw materials A may be used. You can synthesize! /.
- Reaction 2 is carried out under an inert gas atmosphere such as Ar, with phosphoric acid trichloride (POC1, lithium salt).
- inert gas atmosphere such as Ar
- POC1 phosphoric acid trichloride
- reaction 2 is POC1
- the synthesis step in this embodiment includes a raw material A for synthesizing a lithium salt having a chemical structure represented by the general formula (31) to the general formula (3-3) described above, and the general formula (4) described above.
- a raw material A for synthesizing a lithium salt having a chemical structure represented by the general formula (31) to the general formula (3-3) described above and the general formula (4) described above.
- the lithium salt synthesis raw material B having the chemical structure represented by reacting the lithium salt synthesis raw material A with the lithium salt synthesis raw material B the above-mentioned general formula (1)
- This is a step of synthesizing a lithium salt having the chemical structure represented.
- the lithium salt synthesis raw material A used in the present embodiment has a chemical structure represented by the general formula (3-1) to the general formula (3-3) described above.
- R to R in the general formula (3 1) to the general formula (3-3) are described in the above “ ⁇ ⁇ lithium salt 1. first embodiment”.
- R to R are the same functional group, that is, the general formula (3— ;!) to
- the lithium salt synthesis raw material B used in this embodiment has a chemical structure represented by the general formula (4).
- X in the general formula (4) is the same as X in the general formula (2) described in the above-mentioned “A. Lithium salt 2. Second embodiment”, and the description thereof is omitted here.
- X is preferably a chlorine atom (C1).
- the solvent used in the reaction is not particularly limited as long as it can dissolve the lithium salt synthesis raw materials A and B. Specific examples include jetyl etherol, tetrahydrofuran (THF ), Mentioning ethanol, methanol, etc.
- the reaction temperature of the lithium salt synthesis raw materials A and B is not particularly limited. 1S For example, it is preferably in the range of 10 ° C to 5 ° C. In particular, in this embodiment, when the lithium salt synthesis raw materials A and B are reacted, it is preferably reacted in an ice bath.
- the amount of the lithium salt synthesis raw materials A and B used is not particularly limited as long as the lithium salt represented by the general formula (1) can be obtained.
- the use amount of the lithium salt synthesis raw material B is 1, it is preferable to use the lithium salt synthesis raw material A within a range of 3 to 15 and even within a range of 5 to 9 on a molar basis.
- the lithium salt synthesis raw material A it is preferable to add 5 equivalents or more of the lithium salt synthesis raw material A to the lithium salt synthesis raw material B.
- the lithium salt synthesis raw material A is less than 3 equivalents, the NH of the phosphoramide is acidified, so it is estimated that TfNH and phosphorus amide are generated by the H—Li exchange.
- a method for removing the side reaction product for example, a method using a difference in solubility can be cited.
- the solvent used in the method using the difference in solubility include Examples include tilether, alcohols, acetone, acetic acid, hexane, cyclohexane, pentane, water, black mouth form, benzene, ethyl acetate, methyl propionate, black mouth form, pyridine, and dimethylformamide.
- the solubility test using these solvents is appropriately performed, the most suitable solvent for separating the main reaction product and the side reaction product is selected, and the lithium salt is purified. It is preferable.
- a mixture of lithium salts containing 2-substituents but hardly containing one-substituents may be obtained.
- the tri-substituted product has low solubility in jetyl ether, and the di-substituted product has high solubility in jetyl ether. Therefore, suspension washing with a lithium salt mixture using jet ether is performed. 3)
- the substitution product can be left in the filtrate, the 2 substitution product can be transferred to the filtrate, and both can be separated.
- the method for producing the lithium salt according to this embodiment includes the following general formulas (3-1) and (3-2).
- R and R may be the same or different from each other.
- a lithium salt capable of obtaining an electrolytic solution or a solid electrolyte membrane having a high Li ion transport number can be obtained.
- the synthesis step in the present embodiment is represented by the lithium salt synthesis raw material A having the chemical structure represented by the general formula (3-1) and the general formula (3-2) described above and the general formula (4) described above.
- the lithium salt synthesis raw material B having the chemical structure is reacted with the lithium salt synthesis raw material A and the lithium salt synthesis raw material B, and is expressed by the above-described general formula (2). This is a step of synthesizing a lithium salt having a chemical structure.
- R and R are preferably fluoroalkyl groups.
- X is a chlorine atom
- the lithium salt synthesis raw material A is in a range of 2 to 10 on a molar basis, Among these, it is preferable to use within the range of 4-9.
- the purification process in this embodiment will be described.
- the specific purification method and the like are the same as the contents described in the above “1. Third embodiment”, and thus the description thereof is omitted here.
- a method for producing a lithium salt can be provided.
- the present invention is not limited to the above embodiment.
- the above embodiment is merely an example, and has any configuration that is substantially the same as the technical idea described in the claims of the present invention and that exhibits the same operational effects. Are also included in the technical scope of the present invention.
- Lithium salts were synthesized according to Reaction 1 and Reaction 2 described above.
- a solution was obtained by dissolving in ethyl ether solution. Next, n-butyllithium / hexane (1.59M, 8.45 ml, manufactured by Aldrich) was slowly added while stirring the solution in an ice bath. Thereafter, the temperature of the solution was raised to room temperature to obtain a raw material A-containing solution for synthesizing lithium salt.
- a solution was obtained by mixing with the ether solution. Next, while the solution was stirred in an ice bath, the lithium salt synthesis raw material A-containing solution was slowly added dropwise.
- FIG. 1 and FIG. 2 show the results of 19 F-NMR and 31 P-NMR of the compound (11), which is a 3-substituted product, respectively.
- the results of 19 F-NMR and 31 P NMR of compound ( 21 ), which is a disubstituted product, are shown in FIGS. 3 and 4, respectively.
- the trisubstituted lithium salt (compound (1 1)) obtained in the synthesis example was added at concentrations of 0.5M and 1.0M.
- the conductivity of the electrolytic solution was measured in the same manner as in Example 1 except that the obtained electrolytic solution was used. The results are shown in Table 1.
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US12/447,961 US8026394B2 (en) | 2006-12-05 | 2007-12-04 | Lithium salt and method for producing thereof |
KR1020097009294A KR101062097B1 (ko) | 2006-12-05 | 2007-12-04 | 리튬염 및 그의 제조 방법 |
CN2007800431551A CN101541817B (zh) | 2006-12-05 | 2007-12-04 | 锂盐及其制造方法 |
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JP2006-328457 | 2006-12-05 | ||
JP2006328457A JP4665894B2 (ja) | 2006-12-05 | 2006-12-05 | リチウム塩およびその製造方法 |
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WO2008069207A1 true WO2008069207A1 (ja) | 2008-06-12 |
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Family Applications (1)
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PCT/JP2007/073405 WO2008069207A1 (ja) | 2006-12-05 | 2007-12-04 | リチウム塩およびその製造方法 |
Country Status (5)
Country | Link |
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US (1) | US8026394B2 (ja) |
JP (1) | JP4665894B2 (ja) |
KR (1) | KR101062097B1 (ja) |
CN (1) | CN101541817B (ja) |
WO (1) | WO2008069207A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016088766A1 (ja) * | 2014-12-01 | 2016-06-09 | セントラル硝子株式会社 | 2価のアニオンを有するイミド酸化合物及びその製造方法 |
JP2016105370A (ja) * | 2014-12-01 | 2016-06-09 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
JP2016117636A (ja) * | 2014-12-01 | 2016-06-30 | セントラル硝子株式会社 | 2価のアニオンを有するイミド酸化合物及びその製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016006381A1 (ja) * | 2014-07-09 | 2016-01-14 | 日本電気株式会社 | 非水電解液及びリチウムイオン二次電池 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
PL3796450T3 (pl) * | 2019-09-18 | 2024-05-13 | Samsung Sdi Co., Ltd. | Dodatek, elektrolit do akumulatora litowego i akumulator litowy go zawierający |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008001672A (ja) * | 2006-06-26 | 2008-01-10 | Toyota Motor Corp | リチウム塩およびその製造方法 |
Family Cites Families (3)
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JP3311104B2 (ja) | 1993-09-17 | 2002-08-05 | 株式会社東芝 | リチウム二次電池 |
JPH10189043A (ja) | 1996-12-26 | 1998-07-21 | Hitachi Ltd | リチウム2次電池 |
JP4020571B2 (ja) | 1999-06-25 | 2007-12-12 | 三洋電機株式会社 | リチウム二次電池 |
-
2006
- 2006-12-05 JP JP2006328457A patent/JP4665894B2/ja active Active
-
2007
- 2007-12-04 US US12/447,961 patent/US8026394B2/en active Active
- 2007-12-04 WO PCT/JP2007/073405 patent/WO2008069207A1/ja active Application Filing
- 2007-12-04 CN CN2007800431551A patent/CN101541817B/zh not_active Expired - Fee Related
- 2007-12-04 KR KR1020097009294A patent/KR101062097B1/ko active IP Right Grant
Patent Citations (1)
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---|---|---|---|---|
JP2008001672A (ja) * | 2006-06-26 | 2008-01-10 | Toyota Motor Corp | リチウム塩およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
XU K. ET AL.: "A new protonation chemistry of phosphazenes and the formation of bis(sulfonyl)imides", INORGANIC CHEMISTRY COMMUNICATIONS, vol. 2, no. 6, 1999, pages 261 - 264, XP002723370, DOI: doi:10.1016/S1387-7003(99)00060-X * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016088766A1 (ja) * | 2014-12-01 | 2016-06-09 | セントラル硝子株式会社 | 2価のアニオンを有するイミド酸化合物及びその製造方法 |
JP2016105370A (ja) * | 2014-12-01 | 2016-06-09 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
JP2016117636A (ja) * | 2014-12-01 | 2016-06-30 | セントラル硝子株式会社 | 2価のアニオンを有するイミド酸化合物及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20090085615A (ko) | 2009-08-07 |
KR101062097B1 (ko) | 2011-09-02 |
JP2008137979A (ja) | 2008-06-19 |
CN101541817A (zh) | 2009-09-23 |
JP4665894B2 (ja) | 2011-04-06 |
CN101541817B (zh) | 2012-02-15 |
US8026394B2 (en) | 2011-09-27 |
US20100036160A1 (en) | 2010-02-11 |
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