WO2010122867A1 - 電気化学ディバイス用電解質、これを用いる電解液および非水電解液電池 - Google Patents
電気化学ディバイス用電解質、これを用いる電解液および非水電解液電池 Download PDFInfo
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- WO2010122867A1 WO2010122867A1 PCT/JP2010/054912 JP2010054912W WO2010122867A1 WO 2010122867 A1 WO2010122867 A1 WO 2010122867A1 JP 2010054912 W JP2010054912 W JP 2010054912W WO 2010122867 A1 WO2010122867 A1 WO 2010122867A1
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- electrolyte
- battery
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- aqueous
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- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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 an electrolyte used for an electrochemical device such as a lithium battery, a lithium ion battery, and an electric double layer capacitor, an electrolyte for a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery using the electrolyte.
- an electrochromic display in which a color change is caused by an electrochemical reaction can be given.
- electrochemical devices are generally composed of a pair of electrodes and an ionic conductor filling them.
- a solution in which a salt (AB) composed of a cation (A + ) and an anion (B ⁇ ) called an electrolyte is dissolved in a solvent, a polymer, or a mixture thereof is used.
- AB salt
- B ⁇ anion
- this electrolyte is dissolved, it dissociates into a cation and an anion, and conducts ions.
- this electrolyte is dissolved in a sufficient amount in a solvent or a polymer.
- a solvent other than water is often used as a solvent, and there are currently only a few types of electrolytes having sufficient solubility in such organic solvents and polymers.
- LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 and LiCF 3 SO 3 are the only electrolytes for lithium ion batteries.
- the cation portion is often determined by the device, such as the lithium ion of a lithium battery, but the anion portion can be used if the condition that the solubility is high is satisfied.
- Non-Patent Document 1 lithium bis (biphenyldiolato) borate has been proposed as a novel electrolyte (Patent Document 1), but the problem is that the solubility in nonaqueous organic solvents and the oxidation resistance in the battery are insufficient. It has become. Also, a novel electrolyte in which electron-withdrawing Cl is bonded as a substituent on a lithium bis (salicylate) borate and its ligand has been proposed (Non-Patent Document 1). Has insufficient ionic conductivity and oxidation resistance, and Cl-substituted derivatives have improved ionic conductivity and oxidation resistance, but have a problem of extremely low solubility instead.
- non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed.
- a non-aqueous electrolyte or a non-aqueous electrolyte quasi-solidified with a gelling agent is used as an ionic conductor.
- the structure is as follows.
- a solvent one or several kinds of mixed solvents selected from aprotic ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and the like are used, and lithium is used as a solute.
- Salts that is, LiPF 6 , LiBF 4 , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, etc. are used.
- Non-aqueous electrolyte-related technology is no exception, and it has been proposed to suppress degradation due to decomposition of the electrolyte on the surface of an active positive electrode or negative electrode with various additives.
- it has been proposed to suppress deterioration and improve battery characteristics by adding vinylene carbonate to an electrolytic solution (Patent Document 2), and adding cyclohexylbenzene and tetrahydronaphthalene (Patent Document 3).
- Patent Document 2 vinylene carbonate
- Patent Document 3 cyclohexylbenzene and tetrahydronaphthalene
- the present inventors have found an electrolyte having a novel chemical structural feature, and have found an electrolyte for a non-aqueous electrolyte battery and a non-aqueous electrolyte battery that are excellent using the electrolyte.
- the present invention has been reached.
- the present invention is an electrolyte for an electrochemical device having a chemical structural formula represented by the general formula (1).
- M is a group 13 or group 15 element in the periodic table
- a + is an alkali metal ion or onium ion
- m is 1 to 4 when M is group 13, and 1 to 6 when group 15 is group 15.
- N is 0-3 when M is group 13, 0-5 when group 15 is selected
- R is halogen, C1-C10 halogenated alkyl, C6-C20 aryl, or C6-C20 halogen Aryl, or in these structures, in place of hydrogen, halogen, chain or cyclic alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, sulfonyl group, amino group, cyano group, carbonyl group
- An acyl group, an amide group, a hydroxyl group, or a structure in which nitrogen, sulfur, or oxygen is introduced in place of carbon may be used, and n Rs are independent of each other and may be of the same type. But to represent good that each is intended to provide
- M is either B or P
- a + is any one cation selected from the group consisting of Li ion, Na ion, K ion, or quaternary alkyl ammonium ion
- R I is an electrolyte for an electrochemical device characterized by being a functional group of fluorine, phenyl group, or pentafluorophenyl group
- the anion moiety of the general formula (1) is [BF 3 (PO 2 F 2 ) ] - , [BF 2 (PO 2 F 2 ) 2 ] - , [BF (PO 2 F 2 ) 3] -, [B ( PO 2 F 2) 4] -, [PF 5 (PO 2 F 2)] -, [PF 4 (PO 2 F 2) 2] -, [PF 3 (PO 2 F 2 ) 3] -, [PF 2 (PO 2 F 2) 4] -, [PF (PO 2 F 2) 5] -, [P (PO 2 F 2) 6] -, [B (C 6 H
- the electrolyte for electrochemical devices is contained in a non-aqueous organic solvent, or the electrolyte for electrochemical devices is contained as an additive in an electrolyte for a non-aqueous battery comprising a non-aqueous organic solvent and a solute.
- the present invention provides an electrolyte for a nonaqueous electrolyte battery.
- the non-aqueous organic solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, or ethyl methyl carbonate, or the addition concentration of the electrolyte for an electrochemical device is relative to the electrolyte for a non-aqueous electrolyte battery. 0.01 to 10.0% by mass, or the solute is LiPF 6 , LiBF 4 , (CF 3 SO 2 ) 2 NLi, or (C 2 F 5 SO 2 ) 2 NLi.
- the present invention provides an electrolyte for a nonaqueous electrolyte battery.
- the electrolyte solution includes the electrolyte solution for a non-aqueous electrolyte battery.
- a non-aqueous electrolyte battery characterized by the above is provided.
- a novel electrolyte corresponding to an electrochemical device can be provided.
- the chemical structural formula of LiB (C 6 H 5 ) 3 (PO 2 F 2 ) is
- lithium ions are listed as A + , but as cations other than lithium ions, for example, sodium ions, potassium ions, cesium ions, silver ions, copper ions, tetrabutylammonium ions, tetraethylammonium ions, tetramethylammonium ions Triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, hydrogen ion, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion, and the like are also used.
- lithium ions, sodium ions, potassium ions, and quaternary alkyl ammonium ions are preferable.
- the electrolyte for electrochemical devices of the present invention has an ionic metal complex structure, and M at the center thereof is selected from Group 13 or Group 15 elements of the Periodic Table.
- M at the center thereof is selected from Group 13 or Group 15 elements of the Periodic Table.
- any of Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf, or Sb, and B or P is preferable.
- various elements can be used as the central M, Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As , Sc, Hf, or Sb is relatively easy to synthesize.
- B or P in addition to the ease of synthesis, it has excellent properties in all aspects such as low toxicity, stability, and cost.
- ligand portion that is a feature of the electrolyte for an electrochemical device (ionic metal complex) of the present invention.
- the organic or inorganic part bonded to M is referred to as a ligand.
- R in the general formula (1) is selected from halogen, C1 to C10 halogenated alkyl, C6 to C20 aryl, C6 to C20 aryl halide, or in place of hydrogen in these structures , Halogen, chain or cyclic alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, sulfonyl group, amino group, cyano group, carbonyl group, acyl group, amide group, hydroxyl group, or instead of carbon , Nitrogen, sulfur, or oxygen introduced structures. Further, the n Rs are independent of each other and may be different types or the same.
- the halogen used in R is particularly preferably fluorine, and the ion conductivity is very high due to the improvement in dissociation of the electrolyte due to its strong electron-withdrawing property and the improvement in mobility due to the reduction in size. Become.
- PO 2 F 2 described in the general formula (1) as another type of ligand is an electron-withdrawing ligand that exhibits the greatest feature of the present invention.
- this ligand is relatively compact, its electron-withdrawing property is enhanced by the effect of fluorine and oxygen bonded to phosphorus, and the movement due to the improvement in the degree of dissociation of the electrolyte and the reduction in size due to the effect.
- the degree of ionic conductivity increases.
- the withstand voltage is high, and the life of the battery using this electrolyte is extended.
- m and n related to the number of ligands described so far are determined by the type of M at the center, and m is 1 to 4 when M is a group 13, In the case of Group 15, 1 to 6 and n is preferably M, 0 to 3 in the case of Group 13, and 0 to 5 in the case of Group 15.
- the method for synthesizing the electrolyte for an electrochemical device of the present invention is not particularly limited.
- LiBF 3 (PO 2 F 2 )
- LiPO 2 equimolar with BF 3 in a non-aqueous solvent It can be synthesized by a method of reacting F 2 or a method of removing LiF by reacting LiBF 4 with an equimolar amount of LiPO 2 F 2 .
- LiBF 2 (PO 2 F 2 ) 2 a method of reacting BF 3 with 2 moles of LiPO 2 F 2 in a non-aqueous solvent, or reacting LiBF 4 with 2 moles of LiPO 2 F 2 to produce LiF Can be synthesized by a method of removing
- LiPF 5 (PO 2 F 2 ) it can be synthesized by a method in which PF 5 and equimolar LiPO 2 F 2 are reacted in a non-aqueous solvent.
- an electrochemical device When an electrochemical device is constituted using the electrolyte for an electrochemical device of the present invention, its basic constituent elements include an ion conductor, a negative electrode, a positive electrode, a current collector, a separator, a container, and the like.
- the ionic conductor a mixture of an electrolyte and a non-aqueous solvent or polymer is used. If a non-aqueous solvent is used, this ionic conductor is generally called a non-aqueous electrolyte, and if a polymer is used, it becomes a polymer solid electrolyte.
- the polymer solid electrolyte includes those containing a non-aqueous solvent as a plasticizer.
- non-aqueous electrolyte battery An electrochemical device using a non-aqueous solvent in the ionic conductor and a negative electrode material capable of occluding and releasing lithium in the negative electrode is called a non-aqueous electrolyte battery.
- the non-aqueous solvent is not particularly limited as long as it is an aprotic solvent capable of dissolving the electrolyte for an electrochemical device of the present invention.
- an aprotic solvent capable of dissolving the electrolyte for an electrochemical device of the present invention.
- carbonates, esters, ethers, lactones, nitriles, Amides, sulfones and the like can be used.
- Examples include propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl acetate, methyl propionate, dimethoxyethane, diethyl ether, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, Examples include dioxane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, ⁇ -butyrolactone, ⁇ -valerolactone, and the like. Moreover, an ionic liquid etc. can also be mentioned.
- propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate are particularly preferable from the viewpoint of electrochemical stability against oxidation and reduction and chemical stability related to reaction with heat and solute.
- the polymer mixed with the electrolyte is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound.
- examples thereof include polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like.
- a plasticizer is added to these polymers, the above-mentioned aprotic non-aqueous solvent can be used.
- the concentration of the electrolyte for electrochemical devices of the present invention in these ionic conductors is not particularly limited, but the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L.
- the upper limit is 2.5 mol / L or less, preferably 2.0 mol / L or less, and more preferably 1.5 mol / L or less.
- concentration is less than 0.5 mol / L, the ionic conductivity is decreased, thereby reducing the cycle characteristics and output characteristics of the nonaqueous electrolyte battery. If the viscosity increases, the ionic conduction may be lowered, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery may be degraded.
- the type of solute of the electrolyte for the non-aqueous electrolyte battery is not particularly limited, and any lithium salt should be used. Can do.
- An electrolyte lithium salt is mentioned.
- One kind of these solutes may be used alone, or two or more kinds of solutes may be mixed and used in any combination and ratio according to the application.
- LiPF 6 , LiBF 4 , (CF 3 SO 2 ) 2 NLi, and (C 2 F 5 SO 2 ) 2 NLi are preferable in view of the energy density, output characteristics, life, etc. of the battery.
- the concentration of these solutes is not particularly limited, but the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L or more, and the upper limit is 2.5 mol / L. / L or less, preferably 2.0 mol / L or less, more preferably 1.5 mol / L or less.
- concentration is less than 0.5 mol / L, the ionic conductivity is decreased, thereby reducing the cycle characteristics and output characteristics of the nonaqueous electrolyte battery.
- the concentration exceeds 2.5 mol / L the electrolyte solution for the nonaqueous electrolyte battery is reduced. If the viscosity increases, the ionic conduction may be lowered, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery may be degraded.
- the addition concentration is 0.01% by mass or more, preferably 0.03% by mass with respect to the electrolyte for a non-aqueous electrolyte battery. More preferably, it is 0.05% by mass or more, and is 10.0% by mass or less, preferably 5.0% by mass or less, and more preferably 2.0% by mass or less.
- the effects of improving the durability such as cycle characteristics and high temperature storage stability of the nonaqueous electrolyte battery and suppressing the increase in internal resistance are not sufficiently obtained, while 10.0% by mass.
- an additive generally used in the electrolyte for a non-aqueous electrolyte battery of the present invention may be added at an arbitrary ratio.
- Specific examples include cyclohexylbenzene, biphenyl, t-butylbenzene, vinylene carbonate, vinyl ethylene carbonate, difluoroanisole, fluoroethylene carbonate, propane sultone, dimethyl vinylene carbonate, etc., overcharge prevention effect, negative electrode film formation effect, positive electrode protection Examples thereof include compounds having an effect.
- non-aqueous electrolyte battery electrolyte in a quasi-solid state with a gelling agent or a crosslinked polymer as used in a non-aqueous electrolyte battery called a lithium polymer battery.
- the lithium metal which can occlude / release lithium the alloy and intermetallic compound of lithium and another metal, various carbon materials, artificial graphite, natural graphite, metal oxide, metal nitride , Activated carbon, conductive polymer and the like are used.
- the positive electrode material is not particularly limited.
- lithium-containing transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , and lithium-containing transition metals A composite oxide in which a plurality of transition metals such as Co, Mn, Ni, etc.
- transition metal in the lithium-containing transition metal composite oxide is replaced with a metal other than the transition metal, olivine and LiFePO4, LiCoPO 4, phosphoric acid compound of a transition metal such as LiMnPO4 called, oxides such as TiO 2, V 2 O 5, MoO 3, TiS 2, sulfides such as FeS, or polyacetylene, polyparaphenylene, polyaniline, and polypyrrole Conductive polymers such as activated carbon, polymers that generate radicals, carbon materials, etc. Is used.
- the positive electrode or negative electrode material is added with acetylene black, ketjen black, carbon fiber, or graphite as a conductive material, and polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin as a binder, and further molded into a sheet shape.
- An electrode sheet can be used.
- a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber or the like is used as the separator for preventing contact between the positive electrode and the negative electrode.
- An electrochemical device having a coin shape, cylindrical shape, square shape, aluminum laminate sheet shape or the like is assembled from each of the above elements.
- An electrolyte solution with a concentration of 1.0 mol / L was prepared using LiBF 3 (PO 2 F 2 ) obtained in Example 1 as an electrolyte.
- a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material, and a battery charge / discharge test was actually performed.
- the test cell was produced as follows.
- a charge / discharge test was performed at an environmental temperature of 25 ° C. using the cell produced by the above method. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated.
- the initial discharge capacity was 350 mAh / g based on the mass of the negative electrode.
- the discharge capacity retention rate after 500 cycles expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity, was 86%.
- An electrolyte solution having a concentration of 1.0 mol / L was prepared using LiBF 2 (PO 2 F 2 ) 2 as an electrolyte.
- Example 2 Using this electrolytic solution, a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material in the same manner as in Example 2, and a battery charge / discharge test was actually performed.
- a charge / discharge test was conducted at an environmental temperature of 25 ° C. using the produced cell. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated.
- the initial discharge capacity was 362 mAh / g based on the mass of the negative electrode.
- the discharge capacity maintenance factor after 500 cycles represented by the percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity was 88%.
- An electrolyte solution having a concentration of 1.0 mol / L was prepared using LiPF 5 (PO 2 F 2 ) as an electrolyte.
- Example 2 Using this electrolytic solution, a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material in the same manner as in Example 2, and a battery charge / discharge test was actually performed.
- a charge / discharge test was conducted at an environmental temperature of 25 ° C. using the produced cell. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated.
- the initial discharge capacity was 361 mAh / g based on the mass of the negative electrode.
- LiPF 6 is 1.2 mol / L as a solute in a mixed solvent of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 2, and 3.0% by mass of LiBF 3 (PO 2 F 2 ) as a compound of the general formula (1).
- the electrolyte solution for nonaqueous electrolyte batteries was prepared so that it might become.
- a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material, and a battery charge / discharge test was actually performed.
- the test cell was produced as follows.
- a charge / discharge test was conducted at an ambient temperature of 60 ° C. using the cell produced by the above method. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated. Then, the degree of deterioration of the cell was evaluated by the discharge capacity retention rate after 500 cycles and the cell resistance value at room temperature after 500 cycles. The capacity retention rate is expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 91%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is 7 ⁇ .
- a charge / discharge test was performed in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiBF (PO 2 F 2 ) 3 and the addition concentration was 0.01% by mass.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 73%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 12 ⁇ .
- a charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiPF 5 (PO 2 F 2 ) and its addition concentration was 10.0% by mass.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 94%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 15 ⁇ .
- the charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiBF 2 (PO 2 F 2 ) 2 and its addition concentration was 1.0% by mass. .
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 92%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 8 ⁇ .
- Example 5 A charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiB (PO 2 F 2 ) 4 and its addition concentration was 2.0% by mass. The results are shown in Table 1. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 88%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is It was 12 ⁇ .
- the charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiPF 4 (PO 2 F 2 ) 2 and its addition concentration was 2.0% by mass. .
- the results are shown in Table 1.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 90%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 9 ⁇ .
- the charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiPF 3 (PO 2 F 2 ) 3 and its addition concentration was 2.0% by mass. .
- the results are shown in Table 1.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 93%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is 10 ⁇ .
- Example 5 A charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was changed to LiPF (PO 2 F 2 ) 5 and its addition concentration was 2.0% by mass. The results are shown in Table 1. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 85%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is 7 ⁇ .
- Example 5 The compound of the general formula (1) used in Example 5 was changed to LiB (C 6 F 5 ) 3 (PO 2 F 2 ) and the addition concentration was 2.0% by mass in the same manner. A discharge test was performed. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 94%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is 6 ⁇ .
- Example 5 The compound of the general formula (1) used in Example 5 was changed to LiB (C 6 H 5 ) 3 (PO 2 F 2 ) and the addition concentration was 2.0% by mass in the same manner. A discharge test was performed. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 84%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is 18 ⁇ .
- the charge / discharge test was carried out in the same manner except that the compound of the general formula (1) used in Example 5 was LiB (CF 3 ) 3 (PO 2 F 2 ) and the addition concentration was 2.0% by mass. Carried out.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 87%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 8 ⁇ .
- the compound of general formula (1) used in Example 5 was changed to KBF 3 (PO 2 F 2 ), the solute was changed to LiBF 4 , and the solvents were ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate in volume.
- a charge / discharge test was carried out in the same manner except that the mixed solvent had a ratio of 1: 1: 1: 1.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 82%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 17 ⁇ .
- Example 5 The compound of the general formula (1) used in Example 5 was changed to NaBF 3 (PO 2 F 2 ), and the volume ratio of ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate was 1: 1: 1: 1.
- a charge / discharge test was conducted in the same manner except that the mixed solvent was used. The results are shown in Table 1.
- Table 1 the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 85%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is It was 12 ⁇ .
- the compound of the general formula (1) used in Example 5 was (C 2 H 5 ) 4 NBF 3 (PO 2 F 2 ), and the solvent was a volume ratio of ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate.
- a charge / discharge test was conducted in the same manner except that the mixed solvent was 1: 1: 1: 1.
- the results are shown in Table 1.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 90%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is 10 ⁇ .
- An electrolyte solution having a concentration of 1.0 mol / L was prepared using LiPF 6 as an electrolyte.
- Example 2 Using this electrolytic solution, a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material in the same manner as in Example 2, and a battery charge / discharge test was actually performed.
- a charge / discharge test was conducted at an environmental temperature of 25 ° C. using the produced cell. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated. The initial discharge capacity was 340 mAh / g based on the mass of the negative electrode. And the discharge capacity maintenance factor after 500 cycles represented by the percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity was 71%.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- Example 2 Using this electrolytic solution, a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material in the same manner as in Example 2, and a battery charge / discharge test was actually performed.
- a charge / discharge test was conducted at an environmental temperature of 25 ° C. using the produced cell. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated. The initial discharge capacity was 310 mAh / g based on the mass of the negative electrode. And the discharge capacity maintenance factor after 500 cycles represented by the percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity was 50%.
- Example 2 Using this electrolytic solution, a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material in the same manner as in Example 2, and a battery charge / discharge test was actually performed.
- a charge / discharge test was conducted at an environmental temperature of 25 ° C. using the produced cell. Both charging and discharging were performed at a current density of 0.35 mA / cm 2. After charging reached 4.2 V, 4.2 V was maintained for 1 hour, and discharging was performed up to 3.0 V, and the charge / discharge cycle was repeated. The initial discharge capacity was 280 mAh / g based on the mass of the negative electrode. The discharge capacity retention rate after 500 cycles, expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity, was 23%. [Comparative Example 4] A charge / discharge test was conducted in the same manner as in Example 5 except that the compound of the general formula (1) was not used.
- the post-cycle capacity retention ratio expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity is 41%
- the post-cycle resistance value which is the cell resistance value at room temperature after 500 cycles, is It was 36 ⁇ .
- a charge / discharge test was conducted in the same manner as in Example 16 except that the compound of the general formula (1) was not used.
- the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 30%
- Example 6 A charge / discharge test was conducted in the same manner as in Example 17 except that the compound of the general formula (1) was not used. As shown in Table 1, the post-cycle capacity retention rate expressed as a percentage of the discharge capacity after 500 cycles to the initial discharge capacity is 38%, and the post-cycle resistance value, which is the cell resistance value at room temperature after 500 cycles, is 40 ⁇ .
- the electrolyte for an electrochemical device of the present invention is used as an electrolyte for an electrochemical device such as a lithium battery, a lithium ion battery, or an electric double layer capacitor as described above, and is particularly useful for an electrolyte for a non-aqueous electrolyte battery.
- Other applications include organic synthesis reaction catalysts, polymer polymerization catalysts, olefin polymerization promoters, and the like.
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Abstract
Description
)3]-、[B(PO2F2)4]-、[PF5(PO2F2)]-、[PF4(PO2F2)2]-、[PF3(PO2F2)3]-、[PF2(PO2F2)4]-、[PF(PO2F2)5]-、[P(PO2F2)6]-、[B(C6H5)3(PO2F2)]-、[B(C6F5)3(PO2F2)]-からなる群から選ばれた少なくとも一の化合物であることを特
徴とする電気化学ディバイス用電解質を提供するものである。
LiBF3(PO2F2)、LiBF2(PO2F2)2、LiBF(PO2F2)3、LiB(PO2F2)4、LiB(CF3)3(PO2F2)、LiB(C2F5)3(PO2F2)、LiB(C6H5)3(PO2F2)、LiB(C6F5)3(PO2F2)、LiPF5(PO2F2)、LiPF4(PO2F2)2、LiPF3(PO2F2)3、LiPF2(PO2F2)4、LiPF(PO2F2)5、LiP(PO2F2)6、LiP(CF3)3F2(PO2F2)等が挙げられる。
例えば、LiB(C6H5)3(PO2F2)の化学構造式は、次式
また、Rの中で使用されるハロゲンは特にフッ素が好ましく、その強い電子吸引性による電解質の解離度の向上とサイズが小さくなることによる移動度の向上の効果により、イオン伝導度が非常に高くなる。
LiBF2(PO2F2)2の場合、非水溶媒中でBF3と2倍モルのLiPO2F2を反応させる方法やLiBF4と2倍モルのLiPO2F2を反応させて、LiFを除去する方法により合成できる。
LiPF5(PO2F2)の場合、非水溶媒中でPF5と等モルのLiPO2F2を反応させる方法により合成できる。
得られた生成物はLiBF3(PO2F2)であり、NMRスペクトルにより確認された。
NMRスペクトルについて以下に示す。
19F-NMR(トリクロロフルオロメタン基準、溶媒CD3CN)
-83.1ppm(1F,d,J=961.3Hz)
-85.6ppm(1F,d,J=961.3Hz)
-146.7ppm(3F,s)
11B-NMR(B(OCH3)3基準、溶媒CD3CN)
-19.9ppm(s)
[比較例1]
LiPF6を電解質として用いて、濃度1.0mol/Lの電解液を調製した。このとき溶媒としてはエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)の混合溶媒(体積比EC:EMC=1:2)を使用した。
LiBF4を電解質として用いて、濃度1.0mol/Lの電解液を調製した。このとき溶媒としてはエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)の混合溶媒(体積比EC:EMC=1:2)を使用した。
LiN(SO2CF3)2を電解質として用いて、濃度1.0mol/Lの電解液を調製した。このとき溶媒としてはエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)の混合溶媒(体積比EC:EMC=1:2)を使用した。
前記実施例5において一般式(1)の化合物を使用しなかったこと以外は同様にして充放電試験を実施した。結果は表1に示すとおり、初期の放電容量に対する500サイクル後の放電容量の百分率で表されるサイクル後容量維持率は41%、500サイクル後の室温におけるセル抵抗値であるサイクル後抵抗値は36Ωであった。
[比較例5]
前記実施例16において一般式(1)の化合物を使用しなかったこと以外は同様にして充放電試験を実施した。結果は表1に示すとおり、初期の放電容量に対する500サイクル後の放電容量の百分率で表されるサイクル後容量維持率は30%、500サイクル後の室温におけるセル抵抗値であるサイクル後抵抗値は52Ωであった。
[比較例6]
前記実施例17において一般式(1)の化合物を使用しなかったこと以外は同様にして充放電試験を実施した。結果は表1に示すとおり、初期の放電容量に対する500サイクル後の放電容量の百分率で表されるサイクル後容量維持率は38%、500サイクル後の室温におけるセル抵抗値であるサイクル後抵抗値は40Ωであった。
Claims (11)
- 一般式(1)で示される化学構造式よりなる電気化学ディバイス用電解質。
A+は、アルカリ金属イオンまたはオニウムイオン、
mは、Mが、13族の場合は1~4、15族の場合は1~6、
nは、Mが、13族の場合は0~3、15族の場合は0~5、
Rは、ハロゲン、C1~C10のハロゲン化アルキル、C6~C20のアリール、またはC6~C20のハロゲン化アリール、あるいは、これらの構造中の、水素の代わりに、ハロゲン、鎖状又は環状のアルキル基、アリール基、アルケニル基、アルコキシ基、アリーロキシ基、スルホニル基、アミノ基、シアノ基、カルボニル基、アシル基、アミド基、または水酸基、あるいは、炭素の代わりに、窒素、イオウ、または酸素が導入された構造でもよく、n個あるRはそれぞれ独立で、別の種類のものでも同じものでもよいことを表す。 - Mが、BまたはPのいずれかである、請求項1に記載の電気化学ディバイス用電解質。
- A+が、Liイオン、Naイオン、Kイオン、または4級アルキルアンモニウムイオンからなる群から選ばれたいずれか一つのカチオンである、請求項1に記載の電気化学ディバイス用電解質。
- Rが、フッ素、フェニル基、またはペンタフルオロフェニル基の官能基である、請求項1に記載の電気化学ディバイス用電解質。
- 一般式(1)のアニオン部分が、 [BF3(PO2F2)]-、[BF2(PO2F2)2]-、[BF(PO2F2)3]-、[B(PO2F2)4]-、[PF5(PO2F2)]-
、[PF4(PO2F2)2]-、[PF3(PO2F2)3]-、[PF2(PO2F2)
4]-、[PF(PO2F2)5]-、[P(PO2F2)6]-、[B(C6H5)3(PO2F2)]-、[B(C6F5)3(PO2F2)]-からなる群から選ばれたいずれか一
つの化合物である、請求項1に記載の電気化学ディバイス用電解質。 - 非水有機溶媒に、請求項1~5のいずれか1項に記載の電気化学ディバイス用電解質を含有することを特徴とする非水電解液電池用電解液。
- 非水有機溶媒と溶質とからなる非水電池用電解液において、添加剤として請求項1~5のいずれか1項に記載の電気化学ディバイス用電解質を含有する、非水電解液電池用電解液。
- 非水有機溶媒が、エチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、またはエチルメチルカーボネートである、請求項6または7に記載の非水電解液電池用電解液。
- 請求項1~5のいずれか1項に記載の電気化学ディバイス用電解質の添加濃度が、非水電解液電池用電解液に対して0.01~10.0質量%の範囲である、請求項7または8に記載の非水電解液電池用電解液。
- 溶質が、LiPF6、LiBF4、(CF3SO2)2NLi、または(C2F5SO2)2NLiである、請求項7または8に記載の非水電解液電池用電解液。
- 少なくとも正極と、リチウムまたはリチウムの吸蔵放出の可能な負極材料からなる負極と、電解液と、を備えた非水電解液電池において、電解液に請求項6~10のいずれか1項に記載の非水電解液電池用電解液を含む、非水電解液電池。
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Cited By (5)
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WO2016088773A1 (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 |
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 |
WO2019013140A1 (ja) * | 2017-07-14 | 2019-01-17 | 三井化学株式会社 | フルオロリン酸ホウ素リチウム錯化合物、フルオロリン酸ホウ素リチウム含有組成物、フルオロリン酸ホウ素リチウム、リチウム二次電池用添加剤、電池用非水電解液、及びリチウム二次電池 |
JPWO2019013140A1 (ja) * | 2017-07-14 | 2020-03-26 | 三井化学株式会社 | フルオロリン酸ホウ素リチウム錯化合物、フルオロリン酸ホウ素リチウム含有組成物、フルオロリン酸ホウ素リチウム、リチウム二次電池用添加剤、電池用非水電解液、及びリチウム二次電池 |
US11597736B2 (en) | 2017-07-14 | 2023-03-07 | Mitsui Chemicals, Inc. | Lithium boron fluorophosphate complex compound, lithium boron fluorophosphate-containing composition, lithium boron fluorophosphate, additive for lithium secondary battery, non-aqueous electrolytic solution for battery, and lithium secondary battery |
Also Published As
Publication number | Publication date |
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EP2408051A4 (en) | 2012-09-19 |
EP2408051A1 (en) | 2012-01-18 |
CN102414902A (zh) | 2012-04-11 |
US20120028132A1 (en) | 2012-02-02 |
EP2408051B1 (en) | 2015-05-13 |
JP5544748B2 (ja) | 2014-07-09 |
KR101363442B1 (ko) | 2014-02-14 |
JP2010257616A (ja) | 2010-11-11 |
US8841034B2 (en) | 2014-09-23 |
KR20110131264A (ko) | 2011-12-06 |
CN102414902B (zh) | 2014-10-15 |
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