WO2015022792A1 - リチウムイオン二次電池、充放電システムおよび充電方法 - Google Patents
リチウムイオン二次電池、充放電システムおよび充電方法 Download PDFInfo
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Definitions
- the present invention relates to a lithium ion secondary battery, and more particularly to a lithium ion secondary battery suitable for charging and discharging at a high rate.
- non-aqueous electrolyte secondary batteries have been increasing as high-energy density batteries capable of storing electrical energy.
- non-aqueous electrolyte secondary batteries research on lithium ion secondary batteries using an organic solvent such as ethylene carbonate in which a lithium salt such as LiPF 6 or LiBF 4 is dissolved as an electrolyte is active.
- a molten salt battery using a flame retardant molten salt electrolyte having excellent thermal stability is promising.
- a molten salt electrolyte for example, an ionic liquid that is a salt of an organic cation and an anion has been reported (see Patent Document 1).
- lithium ion secondary batteries has expanded and is also used as a storage battery for electric vehicles. Due to such diversification of applications, improvement in charge / discharge characteristics at a high rate of lithium ion secondary batteries is required. However, it is known that the capacity of a lithium ion secondary battery decreases when operating at a high rate.
- a lithium ion secondary battery is a lithium ion secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
- the negative electrode active material is selected from the group consisting of lithium metal, lithium alloy, carbon material, lithium-containing titanium compound, silicon oxide, silicon alloy, zinc, zinc alloy, tin oxide and tin alloy.
- the non-aqueous electrolyte includes at least one kind, and includes a first salt of an organic cation and a first anion, and a second salt of a lithium ion and a second anion.
- the proportion of the lithium ions in the total is 20 mol% or more, and the total content of the first salt and the second salt in the nonaqueous electrolyte is 90 mass% or more. is there.
- charge and discharge system controls a lithium ion secondary battery, a temperature measuring unit for detecting the temperature of the lithium ion secondary battery, the charging current I in the lithium ion secondary battery charging A control device and a discharge control device for controlling a discharge current I out of the lithium ion secondary battery, the charge control device according to the temperature of the lithium ion secondary battery detected by the temperature measurement unit , it sets the charging current I in, is a charge-discharge system.
- the lithium ion secondary battery According to the lithium ion secondary battery, a high capacity can be obtained even when charging and discharging at a high rate.
- FIG. 2 is a sectional view taken along line II-II in FIG. It is a front view of the negative electrode which concerns on one Embodiment of this invention.
- FIG. 4 is a sectional view taken along line IV-IV in FIG. 3. It is the perspective view which notched a part of battery case of the molten salt battery which concerns on one Embodiment of this invention.
- FIG. 6 is a longitudinal sectional view schematically showing a section taken along line VI-VI in FIG. 5. It is a block diagram which shows the outline
- a first aspect of the present invention is a lithium ion secondary battery including (1) a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
- a positive electrode active material held by the positive electrode current collector contains a lithium-containing transition metal oxide
- a negative electrode is a negative electrode current collector and a negative electrode held by the negative electrode current collector
- the negative electrode active material includes at least one selected from the group consisting of lithium metal, lithium alloy, carbon material, lithium-containing titanium compound, silicon oxide, silicon alloy, zinc, zinc alloy, tin oxide, and tin alloy.
- the non-aqueous electrolyte includes a first salt of an organic cation and a first anion and a second salt of a lithium ion and a second anion, and the lithium ion occupies a total of the organic cation and the lithium ion. Ratio of Ion is not less than 20 mol% total content of the second salt and the first salt in the nonaqueous electrolyte is 90 mass% or more, a lithium ion secondary battery.
- the non-aqueous electrolyte used in one embodiment of the present invention is a molten salt electrolyte. Since the molten salt occupies 90% by mass or more of the nonaqueous electrolyte, and lithium ions occupy 20 mol% or more of the cation contained in the nonaqueous electrolyte, the lithium ion secondary battery is operated at a high temperature. Excellent rate characteristics can be obtained. Such an effect is a characteristic effect when a molten salt electrolyte having a high ion concentration is used.
- the upper limit of the lithium ion concentration in the electrolyte is considered to be about 2.0 mol / L. This is because there is a concern that harmful effects such as precipitation of lithium salt may occur.
- At least one selected from the first anion and the second anion is preferably a fluorine-containing amide anion. This is because the fluorine-containing amide anion has high heat resistance and ionic conductivity.
- the nonaqueous electrolyte contains a carbonate compound.
- the nonaqueous electrolyte preferably contains a fluorine-containing carbonate compound.
- the positive electrode current collector is a first metal porous body having a three-dimensional network shape and a hollow skeleton, and the first metal preferably contains aluminum.
- the negative electrode current collector is a porous body of a second metal having a three-dimensional network shape and a hollow skeleton, and the second metal preferably contains copper. This is because in the negative electrode or the positive electrode, the fillability, retention, and current collection of the active material are improved. Thereby, the further improvement of a rate characteristic can be anticipated.
- the second aspect of the present invention is the lithium ion secondary battery according to the first aspect, a temperature measuring unit for detecting the temperature of the lithium ion secondary battery, and the charging current of the lithium ion secondary battery.
- the present invention relates to a charge / discharge system for a lithium ion secondary battery in which a charging current I in is set according to the temperature of the battery. According to this system, it is possible to charge at a current corresponding to the temperature of the battery.
- the discharge control device sets a discharge current Iout according to the temperature of the lithium ion secondary battery detected by the temperature measurement unit. According to this system, it is possible to discharge at a current corresponding to the temperature of the battery.
- the temperature of the lithium ion secondary battery does not reach a temperature suitable for charging / discharging, the temperature can be adjusted to an appropriate temperature by heating with a heater.
- the fourth aspect of the present invention includes a step of detecting the temperature of the lithium ion secondary battery in the first aspect, and the discharge current Iout is increased as the detected temperature is higher.
- a step of selecting the current I out from at least two set discharge currents I out-k (k 1, 2,...), And discharging the lithium ion secondary battery with the selected set discharge current I out-k And a discharging method for a lithium ion secondary battery.
- the detected temperature is lower than a predetermined target temperature, it is preferable to include a step of heating the lithium ion secondary battery until the detected temperature (detected temperature) reaches the target temperature. This is because the temperature of the lithium ion secondary battery lithium is set to a temperature suitable for the lithium ion secondary battery to charge and discharge.
- the non-aqueous electrolyte is a molten salt electrolyte containing a first salt of an organic cation and a first anion and a second salt of a lithium ion and a second anion.
- the non-aqueous electrolyte may be a liquid in the operating temperature range of the lithium ion secondary battery.
- the total content of the first salt and the second salt ie, the molten salt
- the molten salt may occupy 100% by mass of the non-aqueous electrolyte, but as an additive, an organic solvent may be contained in an amount of 10% by mass or less, preferably 8% by mass or less.
- an organic solvent a carbonate compound is preferable.
- the carbonate compound include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), chain carbonates such as diethyl carbonate (DEC) and dimethyl carbonate (DMC), and fluorine-containing carbonate compounds such as fluoroethylene carbonate. It is done. By containing a carbonate compound or a fluorine-containing carbonate compound, good SEI is easily formed on the negative electrode.
- SEI is essential for a negative electrode using graphite, but it is known that lithium ion secondary batteries using an organic electrolyte deteriorate at a temperature of, for example, 40 ° C. or higher. When the SEI deteriorates, the capacity greatly decreases. Therefore, measures are often taken to suppress the temperature rise of the lithium ion secondary battery. On the other hand, in this embodiment, although a reason is not certain, a big capacity
- fluorine-containing carbonate compound examples include mono-, di- or trifluoroethylene carbonate (FEC), fluoromethyl methyl carbonate, 1,1-difluoromethyl methyl carbonate, 1,2-difluoromethyl methyl carbonate, and the like.
- FEC is preferable in that good SEI can be formed.
- the first salt preferably contains a salt of an organic cation and a fluorine-containing amide anion.
- the second salt preferably contains a salt of lithium ion and fluorine-containing amide anion. These are because of high heat resistance and low viscosity.
- the fluorine-containing amide anion has a bis (sulfonyl) amide skeleton and has a structure having a fluorine atom in the sulfonyl group, to obtain a nonaqueous electrolyte with high heat resistance and high ion conductivity. It is preferable in that it can be performed.
- the lithium ion concentration is 20 mol% or more with respect to the cation contained in the nonaqueous electrolyte, that is, the total of the organic cation and the lithium cation.
- the lithium ion concentration is preferably 25 mol% or more, and more preferably 30 mol% or more.
- the lithium ion concentration is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 45 mol% or less of the cation contained in the nonaqueous electrolyte.
- Such a non-aqueous electrolyte has a low viscosity, and even when charging / discharging at a higher rate of current, it is easy to achieve a high capacity.
- the preferable upper limit and the lower limit of the lithium ion concentration can be arbitrarily combined to set a preferable range.
- Examples of organic cations include nitrogen-containing cations; sulfur-containing cations; and phosphorus-containing cations.
- Nitrogen-containing cations include cations derived from aliphatic amines, alicyclic amines, and aromatic amines (for example, quaternary ammonium cations), and organic cations having nitrogen-containing heterocycles (that is, cyclic amines). Examples thereof include derived cations).
- Examples of the quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation (TEA + : tetraethylammonium cation), ethyltrimethylammonium cation, hexyltrimethylammonium cation, ethyltrimethylammonium cation, and methyltriethylammonium cation (TEMA + : methyltriethylammonium cation).
- tetraalkylammonium cations such as tetra-C 1-10 alkylammonium cations).
- sulfur-containing cation examples include tertiary sulfonium cations such as trialkylsulfonium cations such as trimethylsulfonium cation, trihexylsulfonium cation, and dibutylethylsulfonium cation (for example, tri-C 1-10 alkylsulfonium cation). .
- tertiary sulfonium cations such as trialkylsulfonium cations such as trimethylsulfonium cation, trihexylsulfonium cation, and dibutylethylsulfonium cation (for example, tri-C 1-10 alkylsulfonium cation).
- Phosphorus-containing cations include quaternary phosphonium cations, for example, tetraalkylphosphonium cations such as tetramethylphosphonium cation, tetraethylphosphonium cation, tetraoctylphosphonium cation (for example, tetra C 1-10 alkylphosphonium cation); triethyl (methoxymethyl) ) Alkyl (alkoxyalkyl) phosphonium cations such as phosphonium cation, diethylmethyl (methoxymethyl) phosphonium cation, trihexyl (methoxyethyl) phosphonium cation (for example, tri-C 1-10 alkyl (C 1-5 alkoxy C 1-5 alkyl)) Phosphonium cation, etc.).
- tetraalkylphosphonium cations such as tetramethylphosphonium cation, te
- the total number of alkyl groups and alkoxyalkyl groups bonded to the phosphorus atom is 4, and the number of alkoxyalkyl groups is preferably 1 or 2.
- the number of carbon atoms of the alkyl group bonded to the nitrogen atom of the quaternary ammonium cation, the sulfur atom of the tertiary sulfonium cation, or the phosphorus atom of the quaternary phosphonium cation is preferably 1 to 8, more preferably 1 to 4. 1, 2, or 3 is particularly preferable.
- the organic cation is preferably an organic cation having a nitrogen-containing heterocycle.
- An ionic liquid having an organic cation having a nitrogen-containing heterocycle is promising as a molten salt electrolyte because of its high heat resistance and low viscosity.
- the nitrogen-containing heterocyclic skeleton of the organic cation include pyrrolidine, imidazoline, imidazole, pyridine, piperidine, and the like, 5- to 8-membered heterocycles having 1 or 2 nitrogen atoms as ring constituent atoms; Examples thereof include 5- to 8-membered heterocycles having 1 or 2 nitrogen atoms and other heteroatoms (oxygen atoms, sulfur atoms, etc.).
- the nitrogen atom which is a constituent atom of the ring may have an organic group such as an alkyl group as a substituent.
- alkyl group examples include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
- the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1, 2 or 3.
- organic cations having a pyrrolidine skeleton are particularly promising as non-aqueous electrolytes because of their high heat resistance and low production costs.
- the organic cation having a pyrrolidine skeleton preferably has two of the above alkyl groups on one nitrogen atom constituting the pyrrolidine ring.
- the organic cation having a pyridine skeleton preferably has one alkyl group on one nitrogen atom constituting the pyridine ring.
- the organic cation which has an imidazole skeleton has one said alkyl group respectively in two nitrogen atoms which comprise an imidazole ring.
- organic cation having a pyrrolidine skeleton examples include 1,1-dimethylpyrrolidinium cation, 1,1-diethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1- Propylpyrrolidinium cation (MPPY + : 1-methyl-1-propylpyrrolidinium cation), 1-methyl-1-butylpyrrolidinium cation (MBPY + ), 1-ethyl-1- And propylpyrrolidinium cation.
- pyrrolidinium cations having a methyl group and an alkyl group having 2 to 4 carbon atoms such as MPPY + and MBPY +, are preferable because of particularly high electrochemical stability.
- organic cation having a pyridine skeleton examples include 1-alkylpyridinium cations such as 1-methylpyridinium cation, 1-ethylpyridinium cation, and 1-propylpyridinium cation. Of these, pyridinium cations having an alkyl group having 1 to 4 carbon atoms are preferred.
- organic cation having an imidazole skeleton examples include 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation (EMI + : 1-ethyl-3-methylimidazolium cation), and 1-methyl-3.
- EMI + 1-ethyl-3-methylimidazolium cation
- BMI + 1-butyl-3-methylimidazolium cation
- imidazolium cations having a methyl group and an alkyl group having 2 to 4 carbon atoms such as EMI + and BMI + are preferable.
- the first anion or the second anion is a fluorine-containing amide anion.
- the fluorine-containing amide anion include an anion having a bis (sulfonyl) amide skeleton and a fluorine atom in the sulfonyl group.
- the sulfonyl group having a fluorine atom include a sulfonyl group having a fluoroalkyl group in addition to a fluorosulfonyl group.
- the fluoroalkyl group may be a perfluoroalkyl group in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, or all of the hydrogen atoms are replaced with fluorine atoms.
- the sulfonyl group having a fluorine atom is preferably a fluorosulfonyl group or a perfluoroalkylsulfonyl group.
- the bis (sulfonyl) amide anion specifically, bis (fluorosulfonyl) amide anion [(N (SO 2 F) 2 -)], ( fluorosulfonyl) (perfluoroalkyl sulfonyl) amide anion [(fluorosulfonyl ) (Trifluoromethylsulfonyl) amide anion ((FSO 2 ) (CF 3 SO 2 ) N ⁇ ) and the like], bis (perfluoroalkylsulfonyl) amide anion [bis (trifluoromethylsulfonyl) amide anion (N (SO 2 CF 3 ) 2 ⁇ ), bis (pentafluoroethylsulfonyl) amide anion (N (SO 2 C 2 F 5 ) 2 ⁇ ) and the like] and the like.
- the carbon number of the perfluoroalkyl group is, for example, 1 to 10, preferably 1 to
- an anion of a fluorine-containing acid [anion of fluorine-containing phosphate such as hexafluorophosphate ion (PF 6 ⁇ ); tetrafluoroborate ion (BF 4 -), such as an anion of a fluorine-containing boric acid, etc.], chloride anion containing acid [perchlorate ion (ClO 4 -, etc.), anions of oxygen acids having oxalate group [lithium bis (oxalato) borate ion (B ( Oxalatoborate ions such as C 2 O 4 ) 2 ⁇ ); Oxalatoborate ions such as lithium tris (oxalato) phosphate ions (P (C 2 O 4 ) 3 ⁇ ) and the like], anion of fluoroalkanesulfonic acid [trifluoro Romethanesulfonate
- the first anion and the second anion may be the same or different.
- the nonaqueous electrolyte may contain a salt of a metal cation other than lithium ions such as sodium, potassium, rubidium and cesium and an anion. That is, the type of salt constituting the nonaqueous electrolyte is not limited to one or two.
- the nonaqueous electrolyte may contain three or more kinds of salts, or may be a mixture of four or more kinds of salts.
- molten salt As a specific example of the combination of the first salt and the second salt (molten salt), (I) a molten salt containing a salt of lithium ion and FSA ⁇ (Li ⁇ FSA) and a salt of MPPY + and FSA ⁇ (MPPY ⁇ FSA), (Ii) a molten salt containing a salt of lithium ion and TFSA ⁇ (Li ⁇ TFSA) and a salt of MPPY + and TFSA ⁇ (MPPY ⁇ TFSA); (Iii) a molten salt containing a salt of lithium ion and FSA ⁇ (Li ⁇ FSA) and a salt of EMI + and FSA ⁇ (EMI ⁇ FSA), (Iv) Salts of lithium ions and TFSA ⁇ (Li ⁇ TFSA) and molten salts containing a salt of EMI + and TFSA ⁇ (EMI ⁇ TFSA).
- FIG. 1 is a front view of a positive electrode according to an embodiment of the present invention
- FIG. 2 is a cross-sectional view taken along the line II-II in FIG.
- the positive electrode 2 includes a positive electrode current collector 2a and a positive electrode active material layer 2b held by the positive electrode current collector 2a.
- the positive electrode active material layer 2b includes a positive electrode active material as an essential component, and may include a conductive carbon material, a binder, and the like as optional components.
- the positive electrode active material may be any material that electrochemically occludes and releases lithium ions, but here, a lithium-containing transition metal oxide is used.
- a lithium-containing transition metal oxide may be used alone, or a plurality of lithium-containing transition metal oxides may be used in combination.
- the average particle size of the lithium-containing transition metal oxide particles is preferably 2 ⁇ m or more and 20 ⁇ m or less.
- lithium-containing transition metal oxide examples include, for example, lithium cobaltate, lithium nickelate, nickel cobaltate (such as LiCo 0.3 Ni 0.7 O 2 ), lithium manganate (LiMn 2 O 4 ), lithium titanate ( Li 4 Ti 5 O 12 ) and the like. Some of these oxide transition metals may be substituted with other elements.
- iron phosphate having an olivine structure can also be used.
- the iron phosphate include LiFePO 4 and other compounds in which a part of iron is substituted with a transition metal element and / or a typical metal element (LiFe 0.5 Mn 0.5 PO 4 or the like).
- Examples of the conductive carbon material included in the positive electrode include graphite, carbon black, and carbon fiber.
- carbon black is particularly preferable because it can easily form a sufficient conductive path when used in a small amount.
- Examples of carbon black include acetylene black, ketjen black, and thermal black.
- the amount of the conductive carbon material is preferably 2 to 15 parts by mass and more preferably 3 to 8 parts by mass per 100 parts by mass of the positive electrode active material.
- the binder serves to bond the positive electrode active materials to each other and fix the positive electrode active material to the positive electrode current collector.
- fluororesin polyamide, polyimide, polyamideimide and the like can be used.
- fluororesin polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and the like can be used.
- the amount of the binder is preferably 1 to 10 parts by weight and more preferably 3 to 5 parts by weight per 100 parts by weight of the positive electrode active material.
- the positive electrode current collector 2a a metal foil, a non-woven fabric made of metal fibers, a porous metal sheet, or the like is used.
- the metal constituting the positive electrode current collector is preferably aluminum or an aluminum alloy because it is stable at the positive electrode potential, but is not particularly limited. When using an aluminum alloy, it is preferable that metal components (for example, Fe, Si, Ni, Mn, etc.) other than aluminum are 0.5 mass% or less.
- the thickness of the metal foil serving as the positive electrode current collector is, for example, 10 to 50 ⁇ m, and the thickness of the metal fiber non-woven fabric or metal porous sheet is, for example, 100 to 800 ⁇ m, preferably 100 to 600 ⁇ m.
- the positive electrode current collector 2a is preferably a porous body of a first metal having a three-dimensional network shape and a hollow skeleton in terms of filling property, retention property, and current collecting property of the positive electrode active material. It is preferable that the single metal contains aluminum.
- the porous body preferably has communication holes, and the porosity is preferably 30% or more and 98% or less, and more preferably 90 to 98%.
- “Aluminum Celmet” (registered trademark) manufactured by Sumitomo Electric Industries, Ltd. can be used.
- a porous body containing aluminum can be obtained by forming a coating layer of aluminum or an aluminum alloy on the surface of a foamed resin or a nonwoven fabric serving as a base material and then removing the base material.
- the foamed resin is not particularly limited as long as it is a porous resin molded body.
- foamed urethane polyurethane foam
- foamed styrene polystyrene foam
- urethane foam is preferable in terms of high porosity, high cell diameter uniformity, and excellent thermal decomposability.
- urethane foam is used, a porous body containing aluminum that is less likely to cause variations in thickness and has excellent surface flatness can be obtained.
- a current collecting lead piece 2c may be formed on the positive electrode current collector 2a. As shown in FIG. 1, the lead piece 2 c may be formed integrally with the positive electrode current collector, or a separately formed lead piece may be connected to the positive electrode current collector by welding or the like.
- FIG. 3 is a front view of a negative electrode according to an embodiment of the present invention
- FIG. 4 is a cross-sectional view taken along line IV-IV in FIG.
- the negative electrode 3 includes a negative electrode current collector 3a and a negative electrode active material layer 3b attached to the negative electrode current collector 3a.
- a metal that forms an alloy with lithium or a material that electrochemically occludes and releases lithium ions can be used as the negative electrode active material.
- at least one selected from the group consisting of lithium metal, lithium alloy, carbon material, lithium-containing titanium compound, silicon oxide, silicon alloy, zinc, zinc alloy, tin oxide and tin alloy is used.
- the negative electrode active material layer 3b can be obtained, for example, by attaching a metal sheet to the negative electrode current collector 3a or by pressure bonding. Further, the negative electrode active material may be gasified and attached to the negative electrode current collector by a vapor phase method such as vacuum deposition or sputtering, or metal fine particles may be deposited by an electrochemical method such as plating. You may make it adhere to a negative electrode electrical power collector. According to the vapor phase method or the plating method, a thin and uniform negative electrode active material layer can be formed.
- lithium titanate is preferable. Specifically, it is preferable to use at least one selected from the group consisting of Li 2 Ti 3 O 7 and Li 4 Ti 5 O 12 . Moreover, you may substitute a part of Ti or Na of lithium titanate with another element.
- Li 2-x M 5 x Ti 3-y M 6 y O 7 (0 ⁇ x ⁇ 3/2, 0 ⁇ y ⁇ 8/3, M 5 and M 6 are each independently of Ti and Na
- a metal element for example, at least one selected from the group consisting of Ni, Co, Mn, Fe, Al and Cr
- Li 4-x M 7 x Ti 5-y M 8 y O 12 ( 0 ⁇ x ⁇ 11/3, 0 ⁇ y ⁇ 14/3, M 7 and M 8 are each independently a metal element other than Ti and Na, for example, from Ni, Co, Mn, Fe, Al and Cr
- a lithium-containing titanium compound may be used individually by 1 type, and may be used in combination of multiple types.
- the lithium-containing titanium compound may be used in combination with non-graphitizable carbon.
- M 5 and M 7 are Na sites
- M 6 and M 8 are elements occupying Ti sites.
- Examples of the carbon material include graphite, graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), and the like. These carbonaceous materials can be used singly or in combination of two or more. Of these, graphite is preferable from the viewpoint of thermal stability and electrochemical stability. Examples of graphite include natural graphite (such as flake graphite), artificial graphite, and graphitized mesocarbon microspheres.
- Graphite is a layered structure in which planar six-membered rings of carbon are two-dimensionally connected, and has a hexagonal crystal structure. Lithium ions can easily move between the layers of graphite and are reversibly inserted into and desorbed from the graphite.
- the negative electrode active material layer 3b may be a mixture layer that includes the negative electrode active material active material as an essential component and includes a binder, a conductive carbon material, and the like as optional components.
- the binder and the conductive carbon material used for the negative electrode the materials exemplified as the constituent elements of the positive electrode can be used.
- the amount of the binder is preferably 1 to 10 parts by mass and more preferably 3 to 5 parts by mass per 100 parts by mass of the negative electrode active material.
- the amount of the conductive carbon material is preferably 5 to 15 parts by mass and more preferably 5 to 10 parts by mass per 100 parts by mass of the negative electrode active material.
- the negative electrode current collector 3a a metal foil, a non-woven fabric made of metal fibers, a porous metal sheet, or the like is used.
- the metal a metal that is not alloyed with lithium can be used. Of these, copper, copper alloy, nickel, nickel alloy, and the like are preferable because they are stable at the negative electrode potential.
- the copper alloy preferably contains less than 50% by mass of elements other than copper, and the nickel alloy preferably contains less than 50% by mass of elements other than nickel.
- the thickness of the metal foil serving as the negative electrode current collector is, for example, 10 to 50 ⁇ m, and the thickness of the metal fiber non-woven fabric or metal porous body sheet is, for example, 100 to 600 ⁇ m.
- the negative electrode current collector 3a is preferably a porous body of a second metal having a three-dimensional network shape and a hollow skeleton in terms of filling property, retention property, and current collecting property of the negative electrode active material.
- the bimetal is preferably copper.
- the porous body preferably has communication holes, and the porosity is preferably 30% or more and 98% or less, more preferably 80 to 98%, and particularly preferably 90 to 98%.
- a copper porous body can be obtained by forming a copper coating layer on the surface of a foamed resin or a nonwoven fabric serving as a base material and then removing the base material. Again, it is preferable to use urethane foam as the foamed resin.
- the copper coating layer may be a vapor phase method such as vapor deposition, sputtering, or plasma CVD, as well as an aluminum coating layer, and an electrolytic plating method. Of these, electrolytic plating is preferred.
- a current collecting lead piece 3c may be formed on the negative electrode current collector 3a. As shown in FIG. 3, the lead piece 3c may be formed integrally with the negative electrode current collector, or a separately formed lead piece may be connected to the negative electrode current collector by welding or the like.
- a separator can be disposed between the positive electrode and the negative electrode.
- the material of the separator may be selected in consideration of the operating temperature of the battery, but from the viewpoint of suppressing side reactions with the nonaqueous electrolyte, glass fiber, silica-containing polyolefin, fluororesin, alumina, polyphenylene sulfide (PPS) Etc. are preferably used.
- a glass fiber nonwoven fabric is preferable because it is inexpensive and has high heat resistance.
- Silica-containing polyolefin and alumina are preferable in terms of excellent heat resistance.
- a fluororesin and PPS are preferable in terms of heat resistance and corrosion resistance. In particular, PPS has excellent resistance to fluorine contained in the molten salt.
- the thickness of the separator is preferably 10 ⁇ m to 500 ⁇ m, more preferably 20 to 50 ⁇ m. If the thickness is within this range, an internal short circuit can be effectively prevented, and the volume occupancy of the separator in the electrode group can be kept low, so that a high capacity density can be obtained.
- the lithium ion secondary battery is used in a state where the electrode group including the positive electrode and the negative electrode and the molten salt electrolyte are accommodated in a battery case.
- the electrode group is formed by laminating or winding a positive electrode and a negative electrode with a separator interposed therebetween.
- a metal battery case by making one of the positive electrode and the negative electrode conductive with the battery case, a part of the battery case can be used as the first external terminal.
- the other of the positive electrode and the negative electrode is connected to a second external terminal led out of the battery case in a state insulated from the battery case, using a lead piece or the like.
- FIG. 5 is a perspective view of the lithium ion secondary battery 100 with a part of the battery case cut out
- FIG. 6 is a longitudinal sectional view schematically showing a cross section taken along line VI-VI in FIG.
- the lithium ion secondary battery 100 includes a stacked electrode group 11, an electrolyte (not shown), and a rectangular aluminum battery case 10 that accommodates them.
- the battery case 10 includes a bottomed container body 12 having an upper opening and a lid 13 that closes the upper opening.
- a step of injecting a molten salt electrolyte into the container body 12 and impregnating the molten salt electrolyte into the gaps of the separator 1, the positive electrode 2 and the negative electrode 3 constituting the electrode group 11 is performed.
- the molten salt electrolyte may be impregnated with the electrode group, and then the electrode group including the molten salt electrolyte may be accommodated in the container body 12.
- An external positive terminal 14 that penetrates the lid 13 while being insulated from the battery case 10 is provided near one side of the lid 13, and is electrically connected to the battery case 10 at a position near the other side of the lid 13. In this state, an external negative electrode terminal 15 that penetrates the lid portion 13 is provided. In the center of the lid portion 13, a safety valve 16 is provided for releasing gas generated inside when the internal pressure of the electronic case 10 rises.
- the stacked electrode group 11 is composed of a plurality of positive electrodes 2, a plurality of negative electrodes 3, and a plurality of separators 1 interposed between them, each having a rectangular sheet shape.
- the separator 1 is formed in a bag shape so as to surround the positive electrode 2, but the form of the separator is not particularly limited.
- the plurality of positive electrodes 2 and the plurality of negative electrodes 3 are alternately arranged in the stacking direction in the electrode group 11.
- a positive electrode lead piece 2 c may be formed at one end of each positive electrode 2.
- the plurality of positive electrodes 2 are connected in parallel by bundling the positive electrode lead pieces 2 c of the plurality of positive electrodes 2 and connecting them to the external positive terminal 14 provided on the lid portion 13 of the battery case 10.
- a negative electrode lead piece 3 c may be formed at one end of each negative electrode 3.
- the plurality of negative electrodes 3 are connected in parallel by bundling the negative electrode lead pieces 3 c of the plurality of negative electrodes 3 and connecting them to the external negative terminal 15 provided on the lid portion 13 of the battery case 10.
- the bundle of the positive electrode lead pieces 2c and the bundle of the negative electrode lead pieces 3c are desirably arranged on the left and right sides of one end face of the electrode group 11 so as to avoid mutual contact.
- the external positive terminal 14 and the external negative terminal 15 are both columnar, and at least a portion exposed to the outside has a screw groove.
- a nut 7 is fitted in the screw groove of each terminal, and the nut 7 is fixed to the lid portion 13 by rotating the nut 7.
- a flange portion 8 is provided in a portion of each terminal accommodated in the battery case, and the flange portion 8 is fixed to the inner surface of the lid portion 13 via a washer 9 by the rotation of the nut 7.
- the charging / discharging of the lithium ion secondary battery can be performed by, for example, a charging / discharging system as shown in FIG.
- Discharge system includes a lithium-ion secondary battery 100, temperature measuring unit for detecting the temperature of the lithium ion secondary battery 100 (the temperature sensor) 101, charge control for controlling the charging current I in the lithium ion secondary cell 100
- a control unit 107 including a device (charging circuit) 102 and a discharge control device (discharge circuit) 103 that controls the discharge current I out of the lithium ion secondary battery 100.
- the charging control device sets the charging current I in supplied from the power source 104 according to the temperature of the lithium ion secondary battery 100 detected by the temperature measuring unit 101.
- the charge / discharge system may include a heater 105 or a cooling device (not shown) as necessary.
- the heater 105 preferably includes a heating control device 106 that controls the amount of heat supplied to the lithium ion secondary battery 100.
- the lithium ion secondary battery 100 is used as a battery for an external load 108 such as an electric vehicle.
- FIG. 8 shows an embodiment of a flow relating to the charging current I in control.
- the charging start temperature Tp1 is set in advance, and when the detected temperature T of the lithium ion secondary battery is higher than Tp1, charging of the lithium ion secondary battery is started.
- the charging current I in is set according to the difference between the detected temperature T and the charging start temperature Tp1.
- the temperature measuring unit (temperature sensor) 101 detects the temperature of the lithium ion secondary battery 100 (S1). Next, it is determined whether or not the temperature T has reached the charging start temperature Tp1 (S2).
- the charging current I in is the current I in-k (> I in-2 ) when the difference between the detected temperature T and the charging start temperature Tp1 is from ⁇ ° C. (> ⁇ ) to ⁇ ° C. (> ⁇ ). (S5k).
- the voltage V of the battery 100 After charging for a certain period of time, it is determined whether or not the voltage V of the battery 100 has reached the upper limit voltage Vmax (S6). If the voltage V has reached the upper limit voltage Vmax, the power is turned off (S7), and charging is completed. When the voltage V has not reached the upper limit voltage Vmax, S5 is started again and charging is started. Steps 5 and 6 are repeated until the voltage V reaches the upper limit voltage Vmax.
- ⁇ is set to a sufficiently large value so that the difference between the detected temperature T and the target temperature Tp1 does not exceed ⁇ .
- the heater 105 When it is determined that the detected temperature T has not reached the charging start temperature Tp1, the heater 105 is switched on and the lithium ion secondary battery 100 is heated (S3). After heating, the flow is started again from S1, and if the lithium ion secondary battery 100 has reached the charging start temperature Tp1, the steps after S4 are performed.
- the target temperature Tp2 is set in advance, and charging of the lithium ion secondary battery is started while heating until the detected temperature T of the lithium ion secondary battery reaches Tp2.
- the charging current I in is set according to the difference between the detected temperature T and the target temperature Tp2.
- the temperature measurement unit (temperature sensor) 101 detects the temperature of the lithium ion secondary battery 100 (s1). Next, it is determined whether or not the detected temperature T has reached a preset target temperature Tp2 (s2).
- charging of the lithium ion secondary battery is started at a preset current value Iin-k (s5k). After charging for a certain period of time, it is determined whether or not the voltage V of the battery 100 has reached the upper limit voltage Vmax (s6k). If the voltage V has reached the upper limit voltage Vmax, the power is turned off (s7), and charging is completed. When the voltage V has not reached the upper limit voltage Vmax, s5k is started again and charging is started. Step 5 (s5k) and step 6 (s6k) are repeated until the voltage V reaches the upper limit voltage Vmax.
- the difference between the detected temperature T and the target temperature Tp2 is determined, and the charging current I in corresponding to the difference is set, so Charging of the next battery is started. That is, when the difference between the target temperature Tp2 and the detected temperature T is ⁇ ° C. to ⁇ ° C. ( ⁇ > ⁇ ) (s4a), charging is started by the current I in-1 (s5a), and the difference is ⁇ ° C. In the following case (s4b), charging is started by the current Iin -2 (> Iin -1 ) (s5b). In the present embodiment, heating by the heater is started simultaneously with the start of charging. Note that ⁇ is set to a sufficiently large value so that the difference between the detected temperature T and the target temperature Tp2 does not exceed ⁇ .
- the difference between the target temperature Tp2 and the detected temperature T is from ⁇ ° C. to ⁇ ° C. ( ⁇ > ⁇ ) (s4a)
- charging is started by the current I in-1 and lithium ion is applied by the heater.
- the secondary battery is heated (s5a).
- the temperature is detected again (s8a). If the difference between the target temperature Tp2 and the temperature T is less than ⁇ ° C, the current value is switched to a larger I in-2 and charging is started. To do. During this time, heating by the heater continues.
- the temperature is detected again (s8b), and when the detected temperature T has reached the target temperature Tp2, the current value I in-k (> I in-2 ) is obtained in step 5 (s5k).
- the temperature is periodically detected, and charging is performed while switching to a current value corresponding to the detected temperature T.
- the charging time can be further shortened.
- the lithium ion secondary battery according to an embodiment of the present invention contains a high concentration of lithium ions in a specific nonaqueous electrolyte, it is charged at a high rate charge / discharge, for example, 2 C or higher (specifically, 2 to 5 C). In this case, a large capacity can be obtained. In addition, the capacity can be improved as the temperature during charging increases. Note that charging / discharging at a rate of 2C means charging / discharging a battery having a nominal capacity at a current value at which charging / discharging is completed in 0.5 hours after rated charging / discharging.
- the steps of detecting the temperature of the lithium ion secondary battery, as the detected temperature is high, so that the charging current I in increases And a step of selecting the charging current I in from at least two set charging currents I in-k (k 1, 2,...), And a lithium ion secondary battery with the selected setting charging current I in-k And a step of charging.
- a step of heating the lithium ion secondary battery until the target temperature is reached may be included.
- the upper limit of the target temperature is preferably 100 ° C.
- the discharge of the lithium ion secondary battery includes, for example, a step of detecting the temperature of the lithium ion secondary battery, and the discharge current Iout increases as the detected temperature increases.
- a step of selecting the discharge current Iout from at least two set discharge currents Iout-k (k 1, 2,...), And discharging the lithium ion secondary battery with the selected set discharge current Iout-k.
- a process including the steps when the measured temperature is lower than the target temperature, the lithium ion secondary battery may be heated until the target temperature is reached.
- the battery temperature is the temperature of the battery surface.
- Example 1 (Preparation of positive electrode) 96 parts by mass of LiCoO 2 (positive electrode active material) having an average particle size of 5 ⁇ m, 2 parts by mass of acetylene black (conductive carbon material) and 2 parts by mass of polyvinylidene fluoride (binder) were added to N-methyl-2-pyrrolidone (NMP). ) To prepare a positive electrode slurry. A positive electrode slurry was filled in a porous aluminum body (manufactured by Sumitomo Electric Industries, Ltd., aluminum cermet, thickness 1 mm, porosity 90%), dried, and rolled with a roller press to obtain a positive electrode having a thickness of 700 ⁇ m.
- a porous aluminum body manufactured by Sumitomo Electric Industries, Ltd., aluminum cermet, thickness 1 mm, porosity 90%
- the positive electrode was cut into a rectangle of size 100 ⁇ 100 mm to prepare 10 positive electrodes. However, a lead piece for current collection was formed at one end of one side of the positive electrode.
- a negative electrode slurry was prepared by dispersing 97 parts by mass of graphite powder having an average particle size of about 3 ⁇ m and 3 parts by mass of polyvinylidene fluoride (binder) in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- a negative electrode slurry was filled in a copper porous body (manufactured by Sumitomo Electric Industries, Ltd., copper cermet, thickness 1 mm, porosity 85%), dried, and rolled with a roller press to obtain a negative electrode having a thickness of 500 ⁇ m.
- the negative electrode was cut into a rectangle of size 105 ⁇ 105 mm to prepare 10 negative electrodes. However, a current collecting lead piece was formed at one end of one side of the negative electrode.
- Separator A separator made of silica-containing polyolefin having a thickness of 50 ⁇ m was prepared. The average pore diameter is 0.1 ⁇ m, and the porosity is 70%. The separator was cut into a size of 110 ⁇ 110 mm to prepare 21 separators.
- the positive electrode, the negative electrode, and the separator were sufficiently dried by heating at 90 ° C. or higher under a reduced pressure of 0.3 Pa. Thereafter, a separator is interposed between the positive electrode and the negative electrode so that the positive electrode lead pieces and the negative electrode lead pieces overlap each other, and the bundle of the positive electrode lead pieces and the bundle of the negative electrode lead pieces are arranged at right and left target positions.
- the electrode group was produced by stacking. Thereafter, separators were also arranged outside both ends of the electrode group, and the electrode group and separator were housed in the battery case together with the molten salt electrolyte.
- a lithium ion secondary battery A having a nominal capacity of 1.8 Ah and having a structure as shown in FIGS. 5 and 6 was completed.
- Example 2 A lithium ion secondary salt battery B was produced in the same manner as in Example 1 except that Li ⁇ FSA and EMI ⁇ FSA were mixed as the electrolyte and a mixture having a lithium ion concentration of 40 mol% was used. .
- Example 3 A lithium ion secondary salt battery C was produced in the same manner as in Example 1, except that an electrolyte containing 5% by mass of FEC and the balance being the molten salt prepared in Example 1 was used.
- Comparative Example 1 Except that LiPF 6 was blended in a solvent composed of EC (50 mass%) and DEC (50 mass%) as an electrolyte so that the lithium ion concentration would be 1 mol / L, the same as in Example 1.
- a lithium ion secondary salt battery a was prepared.
- Comparative Example 2 A lithium ion secondary salt battery b was produced in the same manner as in Comparative Example 1 except that LiPF 6 was blended so that the lithium ion concentration was 2.5 mol / L.
- a lithium ion secondary salt battery was prepared in the same manner as in Example 1, except that an electrolyte was prepared by mixing Li ⁇ FSA and MPPY ⁇ FSA so that the lithium ion concentration in all cations was 10 mol%. c was produced.
- the rate characteristics of a lithium ion secondary battery decrease as the charge / discharge temperature increases (see battery a).
- the rate characteristics of a lithium ion secondary battery decrease as the charge / discharge temperature increases (see battery a).
- the rate characteristics were improved as the temperature increased.
- the discharge rate increases, the discharge capacity decreases due to polarization, but a contrasting result is obtained.
- the lithium ion concentration of the battery b was almost the same as that of the battery A, but the rate characteristics were particularly inferior at high temperatures.
- the battery c exhibited rate characteristics equivalent to those of the batteries A to C when the discharge rate was small, but the rate characteristics decreased as the discharge rate increased.
- the lithium ion secondary battery according to the present invention is excellent in rate characteristics at high temperatures and at high rate charge / discharge, so that it is used outdoors, for example, a large-scale electric power storage device for home use or industrial use, an electric vehicle, and a hybrid vehicle. It is useful as a power source.
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Abstract
Description
最初に発明の実施形態の内容を列記して説明する。
本発明の第一の局面は、(1)正極、負極、前記正極と前記負極との間に介在するセパレータ、および非水電解質を含むリチウムイオン二次電池であって、正極は、正極集電体および前記正極集電体に保持された正極活物質を含み、前記正極活物質は、リチウム含有遷移金属酸化物を含み、負極は、負極集電体および前記負極集電体に保持された負極活物質を含み、負極活物質は、リチウム金属、リチウム合金、炭素材料、リチウム含有チタン化合物、ケイ素酸化物、ケイ素合金、亜鉛、亜鉛合金、錫酸化物および錫合金よりなる群から選ばれる少なくとも1種を含み、非水電解質は、有機カチオンと第一アニオンとの第一塩と、リチウムイオンと第二アニオンとの第二塩とを含み、有機カチオンとリチウムイオンとの合計に占める前記リチウムイオンの割合が、20モル%以上であり、非水電解質における前記第一塩と前記第二塩との合計含有量が、90質量%以上である、リチウムイオン二次電池に関する。
本発明の実施形態を具体的に以下に説明する。なお、本発明は、以下の内容に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
非水電解質は、有機カチオンと第一アニオンとの第一塩と、リチウムイオンと第二アニオンとの第二塩とを含む溶融塩電解質である。非水電解質は、リチウムイオン二次電池の作動温度域で液体であればよい。第一塩と第二塩との合計(すなわち溶融塩)の含有量は、非水電解質の90質量%以上であり、92質量%以上であることが好ましい。溶融塩の含有量が、非水電解質の90質量%以上であれば、耐熱性および不燃性がより向上する。また、高温下での充放電におけるレート特性が向上する。
オン(MBPY+:1-methyl-1- butylpyrrolidinium cation)、1-エチル-1-プロピルピロリジニウムカチオンなどが挙げられる。これらのうちでは、特に電気化学的安定性が高いことから、MPPY+、MBPY+などの、メチル基と、炭素数2~4のアルキル基とを有するピロリジニウムカチオンが好ましい。
(i)リチウムイオンとFSA-との塩(Li・FSA)およびMPPY+とFSA-との塩(MPPY・FSA)を含む溶融塩、
(ii)リチウムイオンとTFSA-との塩(Li・TFSA)およびMPPY+とTFSA-との塩(MPPY・TFSA)を含む溶融塩、
(iii)リチウムイオンとFSA-との塩(Li・FSA)およびEMI+とFSA-との塩(EMI・FSA)を含む溶融塩、
(iv)リチウムイオンとTFSA-との塩(Li・TFSA)およびEMI+とTFSA-との塩(EMI・TFSA)を含む溶融塩などが挙げられる。
図1は、本発明の一実施形態に係る正極の正面図であり、図2は図1のII-II線断面図である。
正極2は、正極集電体2aおよび正極集電体2aに保持された正極活物質層2bを含む。正極活物質層2bは、正極活物質を必須成分として含み、任意成分として導電性炭素材料、結着剤等を含んでもよい。
図3は、本発明の一実施形態に係る負極の正面図であり、図4は図3のIV-IV線断面図である。
負極3は、負極集電体3aおよび負極集電体3aに付着した負極活物質層3bを含む。
なお、M5およびM7はNaサイト、M6およびM8はTiサイトを占める元素である。
銅の多孔体は、基材となる発泡樹脂又は不織布の表面に銅被覆層を形成した後、基材を除去することにより得ることができる。ここでも、発泡樹脂としては、発泡ウレタンを用いることが好ましい。銅被覆層は、アルミニウム被覆層と同様、蒸着、スパッタ、プラズマCVD等の気相法のほか、電解めっき法等が挙げられる。これらのうちでは、電解めっきが好ましい。
正極と負極との間には、セパレータを配置することができる。セパレータの材質は、電池の使用温度を考慮して選択すればよいが、非水電解質との副反応を抑制する観点からは、ガラス繊維、シリカ含有ポリオレフィン、フッ素樹脂、アルミナ、ポリフェニレンサルファイド(PPS)などを用いることが好ましい。なかでもガラス繊維の不織布は、安価であり、耐熱性も高い点で好ましい。また、シリカ含有ポリオレフィンやアルミナは、耐熱性に優れる点で好ましい。また、フッ素樹脂やPPSは、耐熱性と耐腐食性の点で好ましい。特にPPSは、溶融塩に含まれるフッ素に対する耐性に優れている。
リチウムイオン二次電池は、上記の正極と負極を含む電極群および溶融塩電解質を、電池ケースに収容した状態で用いられる。電極群は、正極と負極とを、これらの間にセパレータを介在させて積層または捲回することにより形成される。このとき、金属製の電池ケースを用いるとともに、正極および負極の一方を電池ケースと導通させることにより、電池ケースの一部を第1外部端子として利用することができる。一方、正極および負極の他方は、電池ケースと絶縁された状態で電池ケース外に導出された第2外部端子と、リード片などを用いて接続される。
図5は、電池ケースの一部を切り欠いたリチウムイオン二次電池100の斜視図であり、図6は、図5におけるVI-VI線断面を概略的に示す縦断面図である。
なお、図8は、充電電流Iin制御に関するフローの一実施形態を示す。本実施形態では、充電開始温度Tp1を予め設定し、検知されたリチウムイオン二次電池の温度Tが、Tp1より大きい場合には、リチウムイオン二次電池の充電を開始する。充電電流Iinは、検知温度Tと充電開始温度Tp1との差に応じて設定されている。
時間経過後、再び温度検知を行い(s8b)、検知温度Tが目標温度Tp2に達している場合には、ステップ5(s5k)により、電流値Iin-k(>Iin-2)で充電が開始される。つまり、検知温度Tが目標温度Tp2以上となるまで加熱を継続しながら、定期的に温度検知を行って、検知温度Tに応じた電流値に切り替えながら充電する。これにより、より充電時間を短くすることができる。
本発明の一実施形態に係るリチウムイオン二次電池は、特定の非水電解質に高濃度のリチウムイオンを含むため、高レート充放電、例えば2C以上(具体的には、2~5C)で充電した場合において、大きな容量を得ることができる。また、充電時の温度が高くなるほど、容量を向上させることができる。なお、レート2Cで充放電するとは、公称容量の電池を定格充放電して0.5時間で充放電が終了となる電流値で充放電する、ということである。
また、本発明の一実施形態に係るリチウムイオン二次電池の放電は、例えば、リチウムイオン二次電池の温度を検知する工程と、前記検知された温度が高いほど、放電電流Ioutが大きくなるように、放電電流Ioutを少なくとも2つの設定放電電流Iout-k(k=1、2、・・・)から選択する工程と、選択された設定放電電流Iout-kでリチウムイオン二次電池を放電する工程と、を含む方法により行われる。この場合にも、測定された温度が、目標温度より低い場合に、目標温度に達するまで、前記リチウムイオン二次電池を加熱する工程を有していてもよい。
以上において、電池の温度とは、電池表面の温度である。
次に、実施例に基づいて、本発明の実施形態をより具体的に説明する。ただし、以下の実施例は、本発明を限定するものではない。
(正極の作製)
平均粒子径5μmのLiCoO2(正極活物質)96質量部、アセチレンブラック(導電性炭素材料)2質量部およびポリフッ化ビニリデン(結着剤)2質量部を、N-メチル-2-ピロリドン(NMP)に分散させて、正極スラリーを調製した。アルミニウム多孔体(住友電気工業株式会社製、アルミセルメット、厚み1mm、気孔率90%)に、正極スラリーを充填し、乾燥させ、ローラープレスで圧延して、厚み700μmの正極とした。
平均粒径約3μmのグラファイト粉末97質量部およびポリフッ化ビニリデン(結着剤)3質量部を、N-メチル-2-ピロリドン(NMP)に分散させて、負極スラリーを調製した。銅多孔体(住友電気工業株式会社製、銅セルメット、厚み1mm、気孔率85%)に、負極スラリーを充填し、乾燥させ、ローラープレスで圧延して、厚み500μmの負極とした。
厚さ50μmのシリカ含有ポリオレフィン製のセパレータを準備した。平均細孔径は0.1μmであり、空隙率は70%である。セパレータは、サイズ110×110mmに裁断し、21枚のセパレータを準備した。
全カチオンに占めるリチウムイオン濃度が40モル%となるように、Li・FSAと、MPPY・FSAとを混合し、溶融塩電解質を調製した。
正極、負極およびセパレータを、0.3Paの減圧下で、90℃以上で加熱して十分に乾燥させた。その後、正極と負極との間にセパレータを介在させ、正極リード片同士および負極リード片同士が重なり、かつ正極リード片の束と負極リード片の束とが左右対象な位置に配置されるように積層し、電極群を作製した。その後、電極群の両端部の外側にもセパレータを配置し、その電極群とセパレータを溶融塩電解質とともに前記電池ケースに収容した。こうして、図5、6に示すような構造の公称容量1.8Ahのリチウムイオン二次電池Aを完成させた。
電解質として、Li・FSAと、EMI・FSAとを混合し、リチウムイオン濃度が40モル%である混合物を使用した以外は、実施例1と同様にして、リチウムイオン二次塩電池Bを作製した。
FECを5質量%含み、残部が実施例1で調製した溶融塩である電解質を使用したこと以外は、実施例1と同様にして、リチウムイオン二次塩電池Cを作製した。
電解質として、EC(50質量%)とDEC(50質量%)とからなる溶媒に、LiPF6をリチウムイオン濃度が1モル/Lとなるように配合したこと以外は、実施例1と同様にして、リチウムイオン二次塩電池aを作製した。
LiPF6をリチウムイオン濃度が2.5モル/Lとなるように配合したこと以外は、比較例1と同様にして、リチウムイオン二次塩電池bを作製した。
全カチオンに占めるリチウムイオン濃度が10モル%となるように、Li・FSAとMPPY・FSAとを混合して電解質を調製したこと以外は、実施例1と同様にして、リチウムイオン二次塩電池cを作製した。
各リチウムイオン二次電池A、B、C、a、bおよびcを恒温室内で、25℃になるまで加熱し、温度が安定した状態で、以下の(1)および(2)の条件を1サイクルとして充放電を行った。各リチウムイオン二次電池の放電容量を、それぞれ表1~6に示す。
(2)放電電流0.5Cで、放電終止電圧2.5Vまで放電
電解質として有機溶媒のみを使用した電池aでは、高温下で充放電することができなかった。電池bのリチウムイオン濃度は、電池Aとほぼ同じであるが、特に高温下におけるレート特性に劣っていた。電池cは、小さい放電レートの場合は、電池A~Cと同等のレート特性を示したが、放電レートが大きくなるとレート特性が低下した。
また、60℃、充放電レート1Cの条件で、前記(1)および(2)の充放電を1000サイクル行った。1サイクル目の放電容量に対する1000サイクル目の放電容量の割合(容量維持率)を求めた。
その結果、リチウムイオン二次電池Aは90%、電池Bは86%、電池Cは88%、電池aは31%、電池bは40%、電池cは63%であった。
Claims (14)
- 正極、負極、前記正極と前記負極との間に介在するセパレータ、および非水電解質を含むリチウムイオン二次電池であって、
前記正極は、正極集電体および前記正極集電体に保持された正極活物質を含み、前記正極活物質は、リチウム含有遷移金属酸化物を含み、
前記負極は、負極集電体および前記負極集電体に保持された負極活物質を含み、前記負極活物質は、リチウム金属、リチウム合金、炭素材料、リチウム含有チタン化合物、ケイ素酸化物、ケイ素合金、亜鉛、亜鉛合金、錫酸化物および錫合金よりなる群から選ばれる少なくとも1種を含み、
前記非水電解質は、有機カチオンと第一アニオンとの第一塩と、リチウムイオンと第二アニオンとの第二塩とを含み、
前記有機カチオンとリチウムイオンとの合計に占める前記リチウムイオンの割合が、20モル%以上であり、
前記非水電解質における前記第一塩と前記第二塩との合計含有量が、90質量%以上である、リチウムイオン二次電池。 - 前記第一アニオンおよび前記第二アニオンより選ばれる少なくとも一方が、フッ素含有アミドアニオンである、請求項1に記載のリチウムイオン二次電池。
- 前記非水電解質が、カーボネート化合物を含む、請求項1または請求項2に記載のリチウムイオン二次電池。
- 前記カーボネート化合物が、フッ素含有カーボネート化合物である、請求項3に記載のリチウムイオン二次電池。
- 前記正極集電体が、三次元網目状で中空の骨格を有する第一金属の多孔体であり、前記第一金属がアルミニウムを含む、請求項1~請求項4のいずれか1項に記載のリチウムイオン二次電池。
- 前記負極集電体が、三次元網目状で中空の骨格を有する第二金属の多孔体であり、前記第二金属が銅を含む、請求項1~請求項5のいずれか1項に記載のリチウムイオン二次電池。
- 請求項1に記載のリチウムイオン二次電池と、
前記リチウムイオン二次電池の温度を検知する温度測定部と、
前記リチウムイオン二次電池の充電電流Iinを制御する充電制御装置と、
前記リチウムイオン二次電池の放電電流Ioutを制御する放電制御装置と、を具備し、 前記充電制御装置は、前記温度測定部により検知された前記リチウムイオン二次電池の温度に応じて、前記充電電流Iinを設定する、充放電システム。 - 前記放電制御装置は、前記温度測定部により検知された前記リチウムイオン二次電池の温度に応じて、前記放電電流Ioutを設定する、請求項7に記載の充放電システム。
- 前記検知された温度が高いほど、前記充電電流Iinが大きくなるように、前記充電電流Iinが少なくとも2つの設定充電電流Iin-k(k=1、2、・・・)から選択される、請求項7または請求項8に記載の充放電システム。
- 前記検知された温度が高いほど、前記放電電流Ioutが大きくなるように、前記放電電流Ioutが少なくとも2つの設定放電電流Iout-k(k=1、2、・・・)から選択される、請求項8または請求項9に記載の充放電システム。
- 更に、前記リチウムイオン二次電池を加熱するヒータと、
前記ヒータが前記リチウムイオン二次電池に供給する熱量を制御する加熱制御装置と、を具備する、請求項7~請求項10のいずれか1項に記載の充放電システム。 - 請求項1に記載のリチウムイオン二次電池の温度を検知する工程と、
前記検知された温度が高いほど、充電電流Iinが大きくなるように、前記充電電流Iinを少なくとも2つの設定充電電流Iin-k(k=1、2、・・・)から選択する工程と、
前記選択された設定充電電流Iin-kで前記リチウムイオン二次電池を充電する工程と、を有するリチウムイオン二次電池の充電方法。 - 請求項1に記載のリチウムイオン二次電池の温度を検知する工程と、
前記検知された温度が高いほど、放電電流Ioutが大きくなるように、前記放電電流Ioutを少なくとも2つの設定放電電流Iout-k(k=1、2、・・・)から選択する工程と、
前記選択された設定放電電流Iout-kで前記リチウムイオン二次電池を放電する工程と、を有するリチウムイオン二次電池の放電方法。 - 更に、前記検知された温度が、予め定めた目標温度より低い場合には、前記検知された温度が前記目標温度に達するまで、前記リチウムイオン二次電池を加熱する工程を有する、請求項12または請求項13に記載のリチウムイオン二次電池の充電方法。
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JP (1) | JP2015037024A (ja) |
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Cited By (2)
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JP2019046746A (ja) * | 2017-09-06 | 2019-03-22 | 学校法人 関西大学 | 電解液および当該電解液を用いた蓄電デバイス |
CN110534697A (zh) * | 2019-09-11 | 2019-12-03 | 中国工程物理研究院电子工程研究所 | 一种热电池单体电池及其制备方法 |
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GB201604133D0 (en) * | 2016-03-10 | 2016-04-27 | Zapgocharger Ltd | Supercapacitor with integrated heater |
JP6740928B2 (ja) * | 2017-02-17 | 2020-08-19 | 株式会社村田製作所 | リチウムイオン二次電池用電解液、リチウムイオン二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 |
KR102227308B1 (ko) * | 2017-05-02 | 2021-03-15 | 주식회사 엘지화학 | 전지셀의 충방전장치 및 방법 |
DE102018206383A1 (de) * | 2018-04-25 | 2019-10-31 | Bayerische Motoren Werke Aktiengesellschaft | Verfahren zum Betreiben einer Lithiumionenbatterie, Lithiumionenbatterie und Kraftfahrzeug |
US11949111B2 (en) | 2018-05-17 | 2024-04-02 | Honda Motor Co., Ltd. | Lithium ion secondary battery |
ES2903545T3 (es) * | 2018-08-08 | 2022-04-04 | Prologium Tech Co Ltd | Grupo de elementos de suministro eléctrico compuestos horizontales |
JP2022504837A (ja) * | 2018-10-09 | 2022-01-13 | ザ リージェンツ オブ ザ ユニバーシティ オブ コロラド,ア ボディー コーポレイト | リチウムイオン電池におけるイオン液体電解質の性能向上方法 |
KR102144571B1 (ko) * | 2018-10-24 | 2020-08-14 | 울산과학기술원 | 전극 구조체, 이의 제조 방법 및 이를 포함하는 이차 전지 |
WO2022009025A1 (ja) * | 2020-07-10 | 2022-01-13 | 株式会社半導体エネルギー研究所 | 非水溶媒、二次電池および二次電池を搭載した車両 |
JP7490617B2 (ja) | 2021-02-03 | 2024-05-27 | 株式会社東芝 | 非水電解質、二次電池、電池パック、車両及び定置用電源 |
US20220255133A1 (en) * | 2021-02-03 | 2022-08-11 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte, secondary battery, battery pack, vehicle, and stationary power supply |
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- 2014-04-28 US US14/911,553 patent/US20160190642A1/en not_active Abandoned
- 2014-04-28 KR KR1020167001643A patent/KR20160041902A/ko not_active Application Discontinuation
- 2014-04-28 WO PCT/JP2014/061846 patent/WO2015022792A1/ja active Application Filing
- 2014-04-28 CN CN201480044224.0A patent/CN105556733A/zh active Pending
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JP2019046746A (ja) * | 2017-09-06 | 2019-03-22 | 学校法人 関西大学 | 電解液および当該電解液を用いた蓄電デバイス |
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CN110534697B (zh) * | 2019-09-11 | 2022-03-01 | 中国工程物理研究院电子工程研究所 | 一种热电池单体电池及其制备方法 |
Also Published As
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JP2015037024A (ja) | 2015-02-23 |
US20160190642A1 (en) | 2016-06-30 |
KR20160041902A (ko) | 2016-04-18 |
CN105556733A (zh) | 2016-05-04 |
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