WO2019212040A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
- Publication number
- WO2019212040A1 WO2019212040A1 PCT/JP2019/017864 JP2019017864W WO2019212040A1 WO 2019212040 A1 WO2019212040 A1 WO 2019212040A1 JP 2019017864 W JP2019017864 W JP 2019017864W WO 2019212040 A1 WO2019212040 A1 WO 2019212040A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium ion
- active material
- negative electrode
- electrode active
- positive electrode
- Prior art date
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 208
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 239000007773 negative electrode material Substances 0.000 claims abstract description 85
- 239000007774 positive electrode material Substances 0.000 claims abstract description 57
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 54
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 150000003949 imides Chemical class 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- -1 imide lithium salt Chemical class 0.000 abstract description 23
- 238000012360 testing method Methods 0.000 description 45
- 238000000034 method Methods 0.000 description 34
- 239000011888 foil Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
- 229940021013 electrolyte solution Drugs 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 239000011572 manganese Substances 0.000 description 6
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
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- 238000002848 electrochemical method Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
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- 230000036962 time dependent Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
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- 229910018871 CoO 2 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
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- 150000005678 chain carbonates Chemical class 0.000 description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 150000002596 lactones Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
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- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
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- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 description 1
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- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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Definitions
- This disclosure relates to a lithium ion secondary battery.
- Lithium ion secondary batteries are widely used because they exhibit excellent characteristics such as excellent energy density. And since the use of a lithium ion secondary battery increases as the heat resistance increases, various techniques for improving the heat resistance of the lithium ion secondary battery have been proposed. For example, Japanese Patent Application Laid-Open No. 2014-160638 discloses a lithium ion secondary battery having heat resistance of about 60 ° C.
- the heat resistance of the lithium ion secondary battery described in JP-A-2014-160638 is about 60 ° C., and a lithium ion secondary battery that can withstand higher temperatures is demanded.
- heat resistance of about 85 ° C. is required. Therefore, a more improved lithium ion secondary battery is required.
- One feature of the present disclosure is that a positive electrode active material capable of occluding and releasing lithium ions, a positive electrode binder binding the positive electrode active material, a negative electrode active material capable of occluding and releasing lithium ions, and the negative electrode A negative electrode binder for binding the active material; and an electrolytic solution containing an organic solvent and an imide-based lithium salt, the negative electrode active material is pre-doped with the lithium ions, and the positive electrode binder is a Hansen solubility parameter for the electrolytic solution.
- This is a lithium ion secondary battery having a RED value based on 1 greater than 1.
- the lithium ion secondary battery can have a heat resistance of about 85 ° C.
- that the lithium ion secondary battery has heat resistance means that the lithium ion secondary battery has a performance operable in a high temperature environment.
- FIG. 1 is a schematic exploded perspective view of a lithium ion secondary battery according to an embodiment.
- 1 is a perspective view of a lithium ion secondary battery according to an embodiment.
- FIG. 3 is a schematic diagram of a III-III cross section in the lithium ion secondary battery of FIG. 2. It is a figure explaining the example of the external appearance of the positive electrode plate shown in FIG.
- FIG. 5 is a VV sectional view of the positive electrode plate of FIG. 4. It is a figure explaining the example of the external appearance of the negative electrode plate shown in FIG.
- FIG. 7 is a VII-VII sectional view of the negative electrode plate of FIG. It is a figure explaining the positional relationship of the positive electrode plate of a positive electrode shown in FIG.
- Test Example 1 the negative electrode plate of a negative electrode, a separator, and electrolyte solution. It is a figure explaining the upper limit of the amount of pre dope of a negative electrode.
- Test Example 1 it is a graph showing a change with time of internal resistance (m ⁇ ) at 85 ° C. of a lithium ion secondary battery.
- Test Example 1 it is a graph showing the change over time of the discharge capacity (mAh) at 85 ° C. of the lithium ion secondary battery.
- Test Example 2 it is a graph showing the change over time of the internal resistance (m ⁇ ) at 85 ° C. of the lithium ion secondary battery.
- FIG. 6 is a graph which shows a time-dependent change of the discharge capacity (mAh) in 85 degreeC of a lithium ion secondary battery.
- FIG. 6 is a graph showing changes over time in internal resistance of lithium ion secondary batteries at 85 ° C. in Test Examples 3 to 5.
- FIG. 6 is a graph showing changes with time in discharge capacity of a lithium ion secondary battery at 85 ° C. in Test Examples 3 to 5.
- the lithium ion secondary battery 1 includes a plurality of plate-like positive electrode plates 11 and a plurality of plate-like negative electrode plates 21, which are alternately stacked. Yes.
- Each positive electrode plate 11 includes an electrode terminal connection portion 12b protruding in one direction.
- Each negative electrode plate 21 also includes an electrode terminal connection portion 22b protruding in the same direction as the direction in which the electrode terminal connection portion 12b of the positive electrode plate 11 protrudes.
- the direction in which the electrode terminal connecting portion 12b of the positive electrode plate 11 protrudes is the X-axis direction
- the stacked direction is the Z-axis direction
- the direction orthogonal to the X-axis and the Z-axis is the Y-axis.
- These X axis, Y axis, and Z axis are orthogonal to each other.
- these axial directions indicate the same direction, and in the following description, descriptions regarding directions may be based on these axial directions. In the following description, illustration and detailed description of the incidental configuration are omitted.
- the lithium ion secondary battery 1 includes a plurality of positive plates 11, a plurality of negative plates 21, a plurality of separators 30, an electrolytic solution 40, and a laminate member 50.
- the positive plates 11 and the negative plates 21 are alternately stacked, and the separators 30 are sandwiched between the positive plates 11 and the negative plates 21.
- the electrolyte solution 40 is wrapped and sealed in two laminate members 50 together with a part of the plurality of positive electrode plates 11, a part of the plurality of negative electrode plates 21, and the plurality of separators 30 laminated in this manner. Yes.
- the electrode terminal connection portions 12 b of the plurality of positive electrode plates 11 protrude in the same direction and are electrically connected to the positive electrode terminal 14.
- Conductive members constituting the positive terminal side such as the positive terminal 14 and the plurality of positive plates 11 connected thereto can be collectively referred to as the positive electrode 10.
- the electrode terminal connecting portions 22b of the plurality of negative electrode plates 21 and the negative electrode terminals 24 are electrically connected, and the negative electrode terminals such as the negative electrode terminals 24 and the plurality of negative electrode plates 21 connected thereto are configured.
- the conductor members can be collectively referred to as the negative electrode 20.
- the lithium ion secondary battery 1 has the above-described configuration inside, and the appearance is shown in FIG.
- FIG. 3 schematically shows a III-III cross section of the lithium ion secondary battery 1 shown in FIG.
- each member in the lithium ion secondary battery 1 is illustrated with an interval.
- the positive electrode plate 11, the negative electrode plate 21, and the separator 30 are stacked with almost no gap.
- the positive electrode plate 11 includes a thin plate-like positive electrode current collector 12 and a positive electrode active material layer 13 coated on the positive electrode current collector 12.
- the positive electrode active material layer 13 is provided on both surfaces of the positive electrode current collector 12, but may be provided on either side of the positive electrode current collector 12. Then, at the time of manufacture, the positive electrode active material layer 13 is coated on the positive electrode current collector 12 so that the lithium ion secondary battery 1 does not contain excessive moisture, and then the coated positive electrode active material layer 13 is sufficiently dried. It is necessary to let
- the positive electrode current collector 12 is a metal foil having a plurality of holes 12c penetrating in the Z direction (see FIGS. 4 and 5), a rectangular current collector 12a (see FIG. 4), and a current collector 12a.
- a metal foil having a plurality of holes 12c penetrating in the Z direction (see FIGS. 4 and 5), a rectangular current collector 12a (see FIG. 4), and a current collector 12a.
- the width in the Y-axis direction of the electrode terminal connecting portion 12b shown in FIGS. 1 and 4 can be changed as appropriate, and may be the same width as the current collecting portion 12a, for example.
- the current collector 12a has a plurality of holes 12c (see FIGS.
- the electrode terminal connector 12b has a plurality of holes similar to the holes 12c of the current collector 12a. It may not be formed and may be formed.
- the current collector 12a has a plurality of holes 12c, cations and anions contained in the electrolytic solution 40 can pass through the current collector 12a.
- the current collector 12a may not have a plurality of holes 12c, and the electrode terminal connecting portion 12b may not have a plurality of holes similar to the holes 12c.
- a metal foil made of aluminum, stainless steel, copper, or nickel can be used for example.
- the positive electrode active material layer 13 includes a positive electrode active material capable of occluding and releasing lithium ions, a positive electrode binder that binds the positive electrode active material, and the positive electrode active material and the current collector 12a of the positive electrode current collector 12. including.
- the positive electrode active material layer 13 includes the positive electrode active material, and is configured to be able to occlude and release lithium ions.
- the positive electrode active material layer 13 may further contain other components such as a conductive additive for increasing the electrical conductivity of the positive electrode active material layer 13 and a thickener for facilitating the creation of the positive electrode plate 11. .
- the conductive auxiliary agent for example, ketjen black, acetylene black, graphite fine particles, and graphite fine fibers can be used.
- the thickener for example, carboxymethyl cellulose [CMC] can be used.
- the positive electrode active material a positive electrode active material capable of occluding and releasing lithium ions, which is used in a conventional lithium ion secondary battery, can be used.
- the positive electrode active material include manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (for example, Li x Mn 2 O 4 or Li x MnO 2 ), and lithium nickel composite oxide (for example, Li x NiO 2 ), lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel cobalt composite oxide (eg, LiNi 1-y Co y O 2 ), lithium nickel cobalt manganese composite oxide (NMC, ternary system, LiNi x Co y Mn 1-y -z O 2), spinel type lithium-manganese-nickel composite oxide (Li x Mn 2-y Ni y O 4), lithium polyanion compound (LiFePO 4, LiCoPO 4, LiVOPO 4, LiVPO 4 F, LiMnPO
- conductive polymer materials such as polyaniline and polypyrrole, disulfide-based polymer materials, organic materials such as sulfur (S) and carbon fluoride, and inorganic materials are also included. These may be used alone or in combination of two or more.
- the positive electrode active material is preferably a material whose upper limit of the operating potential based on Li is less than a predetermined value.
- the operating potential on the basis of Li is an operating potential with respect to the reference potential (Li / Li + ).
- the predetermined value of the operating potential on the basis of Li include 5.0V, 4.0V, 3.8V, and 3.6V.
- the predetermined value is 5.0 V
- spinel type lithium manganese nickel composite oxide Li x Mn 2-y Ni y O 4
- this predetermined value is 4.0 V
- lithium manganese composite oxide for example, Li x Mn 2 O 4 or Li x MnO 2
- the predetermined value is 3.8 V
- lithium cobalt composite oxide Li x CoO 2
- lithium nickel cobalt manganese etc. Examples thereof include composite oxides (NMC, ternary system, LiNi x Co y Mn 1-yz O 2 ).
- this predetermined value is 3.6 V
- LiFePO 4 can be mentioned.
- the positive electrode current collector 12 when the positive electrode current collector 12 is formed of aluminum, it is preferable to select a positive electrode active material in which the upper limit of the operating potential on the basis of Li is less than a predetermined value. If the operating potential of the positive electrode active material based on Li is 4.2 V or higher, the positive electrode current collector 12 formed of aluminum is relatively easily corroded in the charge / discharge process. In this case, for example, LiFePO 4 having an upper limit of the operating potential based on Li of less than 3.6 V can be selected as the positive electrode active material.
- a binder having a RED value (described later) based on the Hansen solubility parameter for the electrolytic solution 40 is larger than 1.
- a binder of positive and negative electrodes of a conventional lithium ion secondary battery for example, polyvinylidene fluoride [PVdF], polytetrafluoroethylene [PTFE], polyvinylpyrrolidone [PVP], polyvinyl chloride [PVC], polyethylene [PE ], Polypropylene [PP], ethylene-propylene copolymer, styrene butadiene rubber [SBR], acrylic resin, and polyacrylic acid.
- the positive electrode binder since the RED value based on the Hansen solubility parameter (HSP) with respect to the electrolytic solution 40 is larger than 1, the positive electrode binder exhibits poor solubility in the electrolytic solution 40.
- the Hansen solubility parameter was published by Charles M Hansen and is known as a solubility index indicating how much a certain substance is dissolved in a certain substance. For example, water and oil generally do not melt together because the “properties” of water and oil are different.
- the “property” of the substance relating to the solubility in the Hansen solubility parameter, three items of the dispersion term D, the polar term P, and the hydrogen bond term H are expressed numerically for each substance.
- the dispersion term D is a value representing the magnitude of van der Waals force
- the polar term P is a value representing the magnitude of the dipole moment
- the hydrogen bond term H is a value representing the magnitude of the hydrogen bond.
- Hansen solubility parameters are plotted in a three-dimensional orthogonal coordinate system (Hansen space, HSP space) in order to study solubility.
- the Hansen solubility parameter for each of the solution A and the solid B can be plotted on two coordinates (coordinate A and coordinate B) corresponding to the solution A and the solid B, respectively, in the Hansen space.
- Ra HSP distance, Ra
- the solutions A and the solids B have the above-mentioned “properties”, so the solid B is more likely to dissolve in the solution A. it can.
- the electrolytic solution 40 corresponds to the solution A here, and the positive electrode binder corresponds to the solid B. Since the positive electrode binder has a RED value based on the Hansen solubility parameter with respect to the electrolytic solution 40 larger than 1, the positive electrode binder is hardly soluble in the electrolytic solution 40. Conversely, if the RED value based on the Hansen solubility parameter with respect to the electrolytic solution 40 is a positive electrode binder that is hardly soluble in the electrolytic solution 40 to the extent that the RED value is greater than 1, the positive electrode binder also has a RED value based on the Hansen solubility parameter. Can be considered greater than 1.
- the Hansen solubility parameter and the interaction radius R0 can be calculated using the chemical structure and composition ratio of the components and experimental results. In that case, it can be obtained using software HSPiP developed by Hansen et al. (Hansen Solubility Parameters in Practice: Windows [registered trademark] software for efficiently handling HSP). This software HSPiP is available as of May 2, 2018 from http://www.hansen-solubility.com/. Also, the Hansen solubility parameters (D, P, H) can be calculated for a mixed solvent in which a plurality of solvents are mixed.
- the negative electrode plate 21 roughly has the same configuration as the positive electrode plate 11 described above, and includes a thin plate-like negative electrode current collector 22 and a negative electrode active material layer 23 coated on the negative electrode current collector 22. I have.
- the negative electrode active material layer 23 is coated on both surfaces of the negative electrode current collector 22, but the coated surface may be either one surface. Then, at the time of manufacture, the negative electrode active material layer 23 is coated on the negative electrode current collector 22 so that the lithium ion secondary battery 1 does not contain excessive moisture, and then the coated negative electrode active material layer 23 is sufficiently dried. It is necessary to let Further, as will be described later, the negative electrode active material layer 23 occludes lithium ions Li + during manufacturing (so-called pre-doping).
- the negative electrode current collector 22 is a metal foil in which a plurality of holes 22c penetrating in the Z direction are formed (see FIGS. 6 and 7), like the positive electrode current collector 12 of the positive electrode plate 11 described above.
- the current collector 22a and the electrode terminal connection 22b that protrudes outward from one end of the current collector 22a (the right end on the upper side in the example of FIG. 6) are integrally formed.
- the current collector 22a has a plurality of holes 22c (see FIGS. 6 and 7), but the electrode terminal connection 22b has a plurality of holes similar to the holes 22c of the current collector 22a. It may not be formed and may be formed.
- the current collector 22a has a plurality of holes 22c, cations and anions contained in the electrolytic solution 40 can pass through the current collector 12a.
- the current collector 22a may not have a plurality of holes 22c, and the electrode terminal connection portion 22b may not have a plurality of holes similar to the holes 22c.
- the positive electrode terminal connection portion 12 b and the electrode terminal connection portion 22 b of the negative electrode plate 21 are provided at positions spaced apart from each other in the surface direction of the negative electrode plate so as not to overlap. Yes.
- variety of the Y-axis direction of the electrode terminal connection part 22b shown in FIG. 1 and FIG. 6 can be changed suitably, for example, is good also as the same width as the current collection part 22a.
- a metal foil made of, for example, aluminum, stainless steel, or copper can be used in the same manner as the positive electrode current collector 12 of the positive electrode plate 11.
- the negative electrode active material layer 23 includes a negative electrode active material capable of occluding and releasing lithium ions, binding of the negative electrode active material, and collection of the negative electrode active material and the negative electrode current collector 22.
- the negative electrode active material layer 23 is comprised so that occlusion and discharge
- the negative electrode active material layer 23 may further contain other components such as a conductive additive for enhancing the electrical conductivity of the negative electrode active material layer 23 and a thickener for facilitating the creation of the negative electrode plate 21. .
- the same materials as those of the positive electrode plate 11 described above can be used. That is, for example, ketjen black, acetylene black, graphite fine particles, and graphite fine fibers can be used as the conductive assistant.
- the thickener for example, carboxymethyl cellulose [CMC] can be used.
- a negative electrode active material capable of occluding and releasing lithium ions, which is used in conventional lithium ion secondary batteries, can be used. That is, as a negative electrode active material, for example, carbonaceous materials such as graphite, metal oxides such as tin oxide and silicon oxide, and phosphorus and boron are added to these materials for the purpose of improving the negative electrode characteristics. What has been done can be used.
- lithium titanate represented by the chemical formula Li 4 + x Ti 5 O 12 (0 ⁇ x ⁇ 3) and having a spinel structure may be used.
- a material in which a part of Ti is substituted with an element such as Al or Mg may be used.
- silicon-based materials such as silicon, silicon alloy, SiO, and silicon composite material may be used. These may be used alone or in combination of two or more.
- positive and negative electrode binders used in conventional lithium ion secondary batteries can be used. That is, as a binder of a conventional lithium ion secondary battery, for example, polyvinylidene fluoride [PVdF], polytetrafluoroethylene [PTFE], polyvinylpyrrolidone [PVP], polyvinyl chloride [PVC], polyethylene [PE], polypropylene [ PP], ethylene-propylene copolymer, styrene butadiene rubber [SBR], acrylic resin, and polyacrylic acid.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PVP polyvinylpyrrolidone
- PVC polyvinyl chloride
- PE polyethylene
- PE polypropylene
- PP polypropylene
- SBR styrene butadiene rubber
- acrylic resin and polyacrylic acid.
- Such a binder can be used for the negative electrode binder of the lithium
- the negative electrode active material layer 23 is occluded (so-called pre-doped) with lithium ions Li + during manufacturing.
- pre-doping methods There are roughly two types of pre-doping methods. That is, in one method, as shown in FIG. 1, a plurality of positive plates 11, a plurality of negative plates 21, and a plurality of separators 30 are laminated, and these are put together with the electrolyte 40 inside the laminate member 50 (see FIG. 2). In this method, the pre-doping is performed after being housed in the laminate member 50. The other is a method of pre-doping outside the laminate member 50 in which lithium ion Li + is previously occluded in the negative electrode active material before the negative electrode plate 21 is formed.
- the method of pre-doping inside the laminate member 50 includes two methods, a chemical method and an electrochemical method.
- the method of pre-doping inside the laminate member 50 the plurality of positive plates 11, the plurality of negative plates 21, and the plurality of separators 30 are accommodated in the laminate member 50 (see FIG. 2) together with the electrolytic solution 40 and then pre-doped.
- the chemical method is a method in which lithium metal is dissolved in the electrolytic solution 40 to form lithium ion Li + and the lithium ion Li + is occluded in the negative electrode active material.
- the electrochemical method a voltage is applied to the lithium metal and the negative electrode plate 21 to convert the lithium metal to lithium ion Li + and to store the lithium ion Li + in the negative electrode active material.
- the current collector portion of the positive electrode current collector 12 of the positive electrode plate 11 so that the lithium ions Li + are easily diffused in the electrolytic solution 40. It is desirable that lithium ions Li + can pass through 12a (see FIG. 5) and the current collector 22a (see FIG. 7) of the negative electrode current collector 22 of the negative electrode plate 21. Therefore, when pre-doping is performed by a chemical method or an electrochemical method, the current collecting portion 12a of the positive electrode plate 11 has a plurality of holes 12c, and the current collecting portion 22a of the negative electrode plate 21 (see FIG. 7). ) Is preferably formed with a plurality of holes 22c.
- a lithium ion Li + in the electrolyte 40 to pre-dope It is not necessary to diffuse.
- the current collecting portion 12a of the positive electrode plate 11 does not need to have a plurality of holes 12c, and the current collecting portion 22a of the negative electrode plate 21 (FIG. 7). A plurality of holes 22c may not be formed.
- the method of pre-doping inside the laminate member 50 and the method of pre-doping outside the laminate member 50 may be appropriately combined. That is, in addition to the method of pre-doping outside the laminate member 50, the plurality of positive electrode plates 11, the plurality of negative electrode plates 21, and the plurality of separators 30 are accommodated inside the laminate member 50 (see FIG. 2) together with the electrolytic solution 40. Thereafter, pre-doping may be performed by a chemical method or an electrochemical method, which is a method of pre-doping inside the laminate member 50.
- the separator 30 is made of a porous material that separates the positive electrode plate 11 and the negative electrode plate 21 and can transmit the cation and anion of the electrolytic solution 40, and is formed in a rectangular sheet shape.
- the vertical and horizontal lengths of the separator 30 are the length of the current collector 12a of the positive electrode current collector 12 of the positive electrode plate 11 (see FIG. 4) and the negative electrode current collector of the negative electrode plate 21. It is set to be longer than the length of 22 current collectors 22a (see FIG. 6).
- a separator used in a conventional lithium ion secondary battery can be used. For example, papermaking such as viscose rayon or natural cellulose, or nonwoven fabric such as polyethylene or polypropylene can be used.
- the electrolytic solution 40 includes an organic solvent (nonaqueous solvent) and an imide-based lithium salt as an electrolyte. You may add an additive to the electrolyte solution 40 suitably.
- an additive for example, an additive that promotes the formation of a SEI film (Solid Electrolyte Interface film) on the negative electrode, such as vinylene carbonate [VC], fluoroethylene carbonate [FEC], or ethylene sulfite [ES], is used. Can do.
- organic solvent an organic solvent having a heat resistance of 85 ° C.
- An organic solvent can be illustrated.
- a solvent in which one or two or more of these organic solvents are mixed at an appropriate composition ratio can be used as the organic solvent.
- the carbonate organic solvent cyclic carbonates such as ethylene carbonate [EC], propylene carbonate [PC] and fluoroethylene carbonate [FEC], ethyl methyl carbonate [EMC], diethyl carbonate [DEC], dimethyl carbonate [DMC] and the like
- the chain carbonate can be illustrated.
- the organic solvent does not contain dimethyl carbonate [DMC] which is a kind of chain carbonate. Dimethyl carbonate [DMC] rarely causes deterioration of heat resistance.
- nitrile organic solvents include acetonitrile, acrylonitrile, adiponitrile, valeronitrile, and isobutyronitrile.
- lactone organic solvent include ⁇ -butyrolactone and ⁇ -valerolactone.
- ether organic solvents include cyclic ethers such as tetrahydrofuran and dioxane, and chain ethers such as 1,2-dimethoxyethane, dimethyl ether, and triglyme.
- the alcohol organic solvent include ethyl alcohol and ethylene glycol.
- ester organic solvent examples include phosphate esters such as methyl acetate, propyl acetate and trimethyl phosphate, sulfate esters such as dimethyl sulfate, and sulfite esters such as dimethyl sulfite.
- amide organic solvent examples include N-methyl-2-pyrrolidone and ethylenediamine.
- sulfone-based organic solvent examples include chain sulfones such as dimethyl sulfone and cyclic sulfones such as 3-sulfolene.
- ketone organic solvent examples include methyl ethyl ketone, and toluene as the aromatic organic solvent.
- the above-mentioned various organic solvents excluding the carbonate-based organic solvent are preferably used by mixing with cyclic carbonate, and in particular, mixed with ethylene carbonate [EC] capable of forming an SEI film (Solid Electrolyte Interface film) on the negative electrode. It is preferable to use it.
- the positive electrode binder and the negative electrode binder described above are preferably polyacrylic acid.
- the organic solvent preferably contains ethyl methyl carbonate [EMC] and diethyl carbonate [DEC].
- an imide-based lithium salt (a lithium salt having —SO 2 —N—SO 2 — in a partial structure) can be used.
- the imide-based lithium salt lithium bis (fluorosulfonyl) imide [LiN (FSO 2 ) 2 , LiFSI], lithium bis (trifluoromethanesulfonyl) imide [LiN (SO 2 CF 3 ) 2 , LiTFSI], lithium bis (Pentafluoroethanesulfonyl) imide [LiN (SO 2 CF 2 CF 3 ) 2 , LiBETI] can be exemplified.
- these imide-based lithium salts may be used alone or in combination of two or more. These imide-based lithium salts have a heat resistance of 85 ° C.
- an imide lithium salt having no trifluoromethane group (—CF 3 ), pentafluoroethane group (—CF 2 CF 3 ), or pentafluorophenyl group (—C 6 F 5 ) (for example, , Lithium bis (fluorosulfonyl) imide [LiN (FSO 2 ) 2 , LiFSI]) is preferable in the following points.
- the positive electrode binder and the negative electrode binder tend to have a RED value greater than 1 based on the Hansen solubility parameter. Further, even at high and low temperatures, the ionic conductivity of the electrolytic solution 40 hardly decreases, and the electrolytic solution 40 is stabilized.
- the concentration of the electrolyte in the electrolytic solution 40 is preferably 0.5 to 10.0 mol / L. From the viewpoint of an appropriate viscosity of the electrolytic solution 40 and ion conductivity, the concentration of the electrolyte in the electrolytic solution 40 is more preferably 0.5 to 2.0 mol / L. When the concentration of the electrolyte is less than 0.5 mol / L, it is not preferable because the ionic conductivity of the electrolytic solution 40 is too low due to a decrease in the concentration of ions from which the electrolyte is dissociated.
- the concentration of the electrolyte is higher than 10.0 mol / L because the ionic conductivity of the electrolytic solution 40 is too low due to an increase in the viscosity of the electrolytic solution 40.
- the positive electrode binder and negative electrode binder which were mentioned above are polyacrylic acid.
- the laminate member 50 includes a core material sheet 51, an outer sheet 52, and an inner sheet 53.
- the outer sheet 52 is bonded to the outer surface of the core material sheet 51
- the inner sheet 53 is bonded to the inner surface of the core material sheet 51.
- the core material sheet 51 can be an aluminum foil
- the outer sheet 52 can be a resin sheet such as a nylon pet film
- the inner sheet 53 can be a resin sheet such as polypropylene.
- FIG. 8 schematically shows the positional relationship (see FIG. 1) among the positive electrode plate 11 of the positive electrode 10, the negative electrode plate 21 of the negative electrode 20, the separator 30, and the electrolytic solution 40 of the lithium ion secondary battery 1.
- the lithium ion secondary battery 1 has a configuration in which a positive electrode plate 11 and a negative electrode plate 21 face each other with a separator 30 interposed therebetween.
- both the positive electrode active material layer 13 and the negative electrode active material layer 23 are configured to be able to occlude and release lithium ions Li + .
- lithium ions Li + move between the positive electrode active material layer 13 and the negative electrode active material layer 23 via the electrolytic solution 40 (see FIGS. 8 and 9). That is, lithium ion Li + moves from the positive electrode active material layer 13 to the negative electrode active material layer 23 during charging, and moves from the negative electrode active material layer 23 to the positive electrode active material layer 13 during discharging via the electrolytic solution 40 ( FIG. 8 and FIG. 9).
- the maximum amount of lithium ions Li + occluded in the negative electrode active material layer 23 is during full charge during the charge / discharge process.
- the amount of occluded lithium ion Li + in the positive electrode active material layer 13 and the negative electrode active material layer 23 is increased or decreased.
- the amount of lithium ion Li + may be a value proportional to the number of atoms of lithium ion Li +, for example, be a mol number.
- the negative electrode active material layer 23 is a lithium ion Li + is pre-doped
- the amount of lithium ion Li + to the pre-doping can also be an upper limit value as described below.
- the amount Pt of all lithium ions Li + occluded in the positive electrode active material layer 13 at the time of full discharge is the same as the amount Pt of lithium ions Li + , Occluded (see FIG. 9).
- the amount N of lithium ions Li + occluded in the negative electrode active material layer 23 at the time of full charge is the amount Pt of lithium ions Li + transferred from the positive electrode active material layer 13 to the negative electrode active material layer 23 and the pre-doped negative electrode This is the sum Np + Pt with the amount Np of lithium ions Li + occluded in the active material layer 23 (see FIG. 9).
- Pt is the amount of all the lithium ion Li + that was stored in the positive electrode active material layer 13 at the time of full discharge, the charge-discharge process in lithium ion Li + is also changed to inactive compounds, It is supplemented by lithium ions Li + occluded in the negative electrode active material layer 23 by pre-doping. For this reason, Pt is the same amount as the amount of lithium ion Li + occluded by the positive electrode active material layer 13 before the initial charge (that is, the amount of lithium ion Li + occluded by the positive electrode active material before manufacture). become.
- the amount of lithium ion Li + that can be occluded by the negative electrode active material layer 23 before pre-doping is Nt (see FIG. 9).
- Nt The amount of lithium ion Li + that can be occluded by the negative electrode active material layer 23 before pre-doping.
- Np + Pt the amount of lithium ions Li + occluded in the negative electrode active material layer 23
- Np + Pt ⁇ Nt is satisfied, and the negative electrode active material layer 23 can always occlude the lithium ion Li + released from the positive electrode active material layer 13, and the precipitation of lithium ion Li + can be suppressed.
- Npmax, Nt, and Pt can be represented by the number of moles.
- Nt is the amount of lithium ion Li + occluded by the positive electrode active material layer 13 before the initial charge (that is, lithium ion Li + occluded by the positive electrode active material before production). Amount). Therefore, the upper limit value Npmax of the amount of lithium ion Li + occluded in the negative electrode active material layer 23 by pre-doping is determined from the amount Nt of lithium ion Li + occluded by the negative electrode active material layer 23 before pre-doping before the positive electrode active This is the amount obtained by subtracting the amount (Pt) of lithium ions Li + stored by the substance. Nt and Pt can be calculated from, for example, theoretical values of the positive electrode active material and the negative electrode active material.
- the amount of the negative electrode active material before pre-doping can occlude lithium ions Li + and the positive electrode active material can be calculated. It is also possible to measure the amount of lithium ion Li + occluded by the substance and calculate from the measured value.
- Npmax is equal to 2 times Pt (ie, 2 ⁇ Pt) (see FIG. 9).
- Npmax varies depending on the value of Nt and the value of Pt (see FIG. 9). That is, the upper limit of the lithium ion Li + in an amount Np to be occluded in the negative electrode active material layer 23 in the pre-doping Npmax, the pre-doped prior to the negative electrode active material layer 23 is storable lithium ion Li + in an amount Nt, and before charge and discharge It varies depending on the amount Pt of lithium ion Li + stored in the positive electrode active material layer 13.
- the maximum amount of lithium ions Li + occluded in the negative electrode active material layer 23 is during full charge during the charge / discharge process.
- the amount N of lithium ions Li + stored in the negative electrode active material layer 23 at the time of full charge is the amount of all lithium ions Li + stored in the positive electrode active material layer 13 at the time of full discharge.
- N Np + Pt
- N Np + Pt
- the amount N of lithium ion Li + occluded in the negative electrode active material layer 23 during full charge is the amount Nt of lithium ion Li + occluded in the negative electrode active material layer 23 before pre-doping.
- N is expressed as% when N is 100%
- the dope rate of the negative electrode active material in a negative electrode active material layer is represented as follows.
- Doping rate (%) N / Nt ⁇ 100
- N Amount of lithium ion (mol) stored in the negative electrode active material (negative electrode active material layer) at full charge
- Nt Amount of lithium ion (mol) that can be occluded by the negative electrode active material (negative electrode active material layer) before pre-doping
- the lithium ion secondary battery described above is a stacked lithium ion secondary battery in which the positive electrode plate 11, the negative electrode plate 21, and the separator 30 are stacked.
- a wound lithium ion secondary battery in which a long negative electrode and a long separator are wound can be obtained.
- the lithium ion secondary battery may be a lithium polymer secondary battery.
- the lithium ion secondary battery 1 has a heat resistance of 85 ° C.
- the lithium ion Li + gradually changes into an inactive compound, so that the amount of lithium ion Li + that can participate in charging and discharging is reduced.
- the charge / discharge capacity may decrease gradually.
- Such a lithium ion secondary battery has a gradually reduced charge / discharge capacity at a high temperature, that is, poor high temperature durability.
- the high temperature durability means that the charge / discharge capacity of the lithium ion secondary battery is maintained at a sufficient amount even when the lithium ion secondary battery is kept at a high temperature.
- the lithium ion secondary battery 1 is pre-doped lithium ion Li + in the anode active material, lithium ion Li + is occluded in the negative electrode active substance in. For this reason, even if lithium ion Li + required for charge / discharge changes to an inactive compound, the lithium ion Li + occluded in the negative electrode active material by pre-doping compensates for the change, so that the lithium ion secondary battery 1 The decrease in charge / discharge capacity can be suppressed. For this reason, the lithium ion secondary battery 1 not only has a heat resistance of 85 ° C. but also a high temperature durability.
- the doping rate is preferably 50% to 100%, more preferably 80% to 100%, and still more preferably 90% to 100%.
- the lithium ion secondary battery of the present disclosure is not limited to the structure, configuration, appearance, shape, and the like described in the above embodiment, and various modifications and additions can be made by understanding the above embodiment. Can be deleted.
- the positive electrode slurry was prepared by the following procedure.
- a pre-slurry was prepared by mixing all materials and water with a mixer a (Shinky Co., Ltd. Awatori Nertaro ARE-310).
- the pre-slurry obtained in (1) was further mixed with a mixer b (Filmix 40-L manufactured by PRIMIX Co., Ltd.) to prepare an intermediate slurry.
- the intermediate slurry obtained in (2) was mixed again with the mixer a to prepare a positive electrode slurry.
- each positive electrode slurry was applied to the current collector foil and dried to prepare a positive electrode.
- the coating amount of the positive electrode slurry was adjusted so that the mass of the activated carbon after drying was 3 mg / cm 2 .
- a blade coater or a die coater was used for coating the positive electrode slurry on the current collector foil.
- a negative electrode slurry was prepared by the following procedure. (1) A material excluding the binder and water were mixed in a mixer a to prepare a pre-slurry. (2) The pre-slurry obtained in (1) was further mixed with a mixer b to prepare an intermediate slurry. (3) A binder was added to the intermediate slurry obtained in (2) and mixed by a mixer a to prepare a negative electrode slurry.
- a copper foil (porous foil) having a thickness of 10 ⁇ m was used as the current collector foil, and the negative electrode slurry was applied to the current collector foil and dried to prepare a negative electrode.
- the coating amount of the negative electrode slurry was adjusted so that the mass of graphite after drying was 3 mg / cm 2 .
- a blade coater was used for coating the negative electrode slurry on the current collector foil.
- Lithium bis (fluorosulfonyl) imide [LiN (FSO 2 ) 2 , LiFSI], which is an imide-based lithium salt, was added as an electrolyte.
- the electrolytic solution contains 1.0 mol / L of LiFSI.
- a lithium ion secondary battery was produced by the following procedure. (1) The positive electrode and the negative electrode are each punched out into a rectangle of 60 mm ⁇ 40 mm, and the current collecting tab is formed by stripping off the 20 mm ⁇ 40 mm region of the coating on the long side, leaving the 40 mm ⁇ 40 mm coating film. Attached. (2) A laminate was prepared by making the coating portions of the positive electrode and the negative electrode face each other with a cellulose separator having a thickness of 20 ⁇ m interposed therebetween.
- This lithium ion secondary battery was pre-doped to prepare a lithium ion secondary battery of Test Example 1.
- the number of moles of pre-doped lithium ion Li + is, according to literature values, the amount of lithium ion Li + occluded in the positive electrode active material of the positive electrode active material layer is 0.0010 mol, and the lithium ion that can be occluded by the negative electrode active material layer The amount of Li + is 0.0030 mol.
- 0.0102 g of metallic lithium was dissolved in the electrolytic solution, so that 0.0015 mol of lithium ion Li + was occluded in the negative electrode active material layer.
- the lithium ion secondary battery of Test Example 2 is different from the lithium ion secondary battery of Test Example 1 only in that it is not pre-doped.
- the internal resistance and discharge capacity of the lithium ion secondary battery were measured at room temperature (25 ° C.) with a cutoff voltage of 3.0 to 3.5 V, a measurement current of 5 mA, and 0.2 C.
- the internal resistance was measured by measuring the internal resistance (m ⁇ ) at 0 to 0.1 sec by the DC-IR method.
- the internal resistance (m ⁇ ) of the lithium ion secondary battery of Test Example 1 did not increase significantly even after 400 hours.
- the discharge capacity (mAh) of the lithium ion secondary battery of Test Example 1 was not significantly reduced even after 400 hours. This confirmed that the lithium ion secondary battery of Test Example 1 had heat resistance at 85 ° C. and high temperature durability.
- the internal resistance (m ⁇ ) did not increase significantly after 400 hours.
- the discharge capacity (mAh) of the lithium ion secondary battery of Test Example 2 decreased with time. Thereby, although the lithium ion secondary battery of Test Example 2 has heat resistance that can operate even in an environment of 85 ° C., it was revealed that the high-temperature durability is lower than that of Test Example 1.
- the rate of increase in internal resistance was less than 50% even after 1600 hours had elapsed. Further, as shown in FIG. 15, the capacity retention of the lithium ion secondary batteries of Test Examples 3 to 5 was 85% or more even after 1600 hours had elapsed. From these facts, it became clear that the lithium ion secondary batteries of Test Examples 3 to 5 have heat resistance at 85 ° C. and high temperature durability. Test Examples 4 and 5 were superior to Test Example 3 in the increase rate of internal resistance and the change in discharge capacity. From this, it became clear that the doping rate is preferably 90 to 100% rather than 80%.
- a mixed solvent of 30% by volume of ethylene carbonate (EC), 30% by volume of dimethyl carbonate (DMC) and 40% by volume of ethyl methyl carbonate (EMC) was used, and 1 mol / L of lithium bis (fluorosulfonylimide) (LiFSI) was used as the mixed solvent.
- the electrolyte solution I was adjusted by adding. Further, lithium hexafluorophosphate (LiPF 6 ) was added to the mixed solvent to prepare an electrolytic solution P.
- Electrolytic solution I2 was prepared by adding 1 mol / L of bis (fluorosulfonylimide) (LiFSI).
- the lithium ion secondary batteries of Test Examples 6 to 10 were subjected to lithium pre-doping, charge / discharge, and aging. Thereafter, the internal resistance and discharge capacity of each lithium ion secondary battery were measured at room temperature (25 ° C.) with a cut-off voltage of 2.2 to 3.8 V and a measurement current of 10 C, and the results were used as initial performance. The dope rate was adjusted to 80%.
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Abstract
Description
リチウムイオン二次電池1は、図1に示すように、複数の正極板11と、複数の負極板21と、複数のセパレータ30と、電解液40と、ラミネート部材50とを備えている。ここで、図1に示す様に、正極板11と負極板21とは交互に積層されており、正極板11と負極板21との間それぞれにセパレータ30が挟まれている。電解液40は、この様に積層された、複数の正極板11の一部と、複数の負極板21の一部と、複数のセパレータ30と共に、2つのラミネート部材50に包まれて密封されている。
<2-1.正極板11について(図1、図3~図5)>
図3~5に示すように、正極板11は、薄板状の正極集電体12と、正極集電体12に塗工されている正極活物質層13とを備えている。なお、正極活物質層13が設けられるのは、正極集電体12の両面であるが、正極集電体12のどちらかの片面であってもよい。そして、リチウムイオン二次電池1が過度に水分を含まない様に、製造時には、正極活物質層13を正極集電体12に塗工した後、塗工された正極活物質層13を十分乾燥させる必要がある。
負極板21は、大まかには上述した正極板11と同様の構成を備えており、薄板状の負極集電体22と、負極集電体22に塗工されている負極活物質層23とを備えている。負極活物質層23は、負極集電体22の両面に塗工されているが、塗工されている面はどちらかの片面であってもよい。そして、リチウムイオン二次電池1が過度に水分を含まない様に、製造時には、負極活物質層23を負極集電体22に塗工した後、塗工された負極活物質層23を十分乾燥させる必要がある。また、後述する様に、負極活物質層23は、製造時にリチウムイオンLi+が吸蔵される(いわゆるプレドープされる)。
セパレータ30は、図1に示す様に、正極板11と負極板21とを隔離し、かつ、電解液40の陽イオンおよび陰イオンが透過できる多孔質の材料からなり、矩形のシート状に形成されている。セパレータ30の縦横の長さ(図1および図3参照)は、正極板11の正極集電体12の集電部12aの長さ(図4参照)、および、負極板21の負極集電体22の集電部22aの長さ(図6参照)よりも長く設定されている。セパレータ30は、従来のリチウムイオン二次電池に使用されているようなセパレータを用いることができ、例えば、ビスコースレイヨンや天然セルロース等の抄紙、ポリエチレンやポリプロピレン等の不織布を用いることができる。
電解液40は、有機溶媒(非水溶媒)、および電解質としてイミド系リチウム塩を含む。電解液40には、適宜添加剤を添加してもよい。添加剤としては、例えば、ビニレンカーボネート[VC]や、フルオロエチレンカーボネート[FEC]や、エチレンサルファイト[ES]等、負極にSEI膜(Solid Electrolyte Interface 膜)の生成を促進させる添加剤を用いることができる。
ラミネート部材50は、図3に示すように、心材シート51、外側シート52、内側シート53を備えている。そして、心材シート51の外側となる面に外側シート52が接着され、心材シート51の内側となる面に内側シート53が接着されている。例えば、心材シート51をアルミニウム箔とし、外側シート52をナイロンペットフィルム等の樹脂シートとし、内側シート53をポリプロピレン等の樹脂シートとすることができる。
リチウムイオン二次電池1の、正極10の正極板11と、負極20の負極板21と、セパレータ30と、電解液40との位置関係(図1参照)を図8に模式的に示した。図8に示す様に、リチウムイオン二次電池1は、正極板11と負極板21とが、セパレータ30を間に挟んで向き合う構成となっている。上述した様に、正極活物質層13および負極活物質層23は、共にリチウムイオンLi+を吸蔵可能および放出可能に構成されている。
負極活物質層23にリチウムイオンLi+がプレドープされているが、このプレドープするリチウムイオンLi+の量は、以下で説明する様に上限値を設けることもできる。
ドープ率(%)=N/Nt×100
N:満充電時において負極活物質(負極活物質層)が吸蔵しているリチウムイオンの量(mol)
Nt:プレドープ前の負極活物質(負極活物質層)が吸蔵可能なリチウムイオンの量(mol)
その他の実施の形態として、例えば、上記のリチウムイオン二次電池は、正極板11と負極板21とセパレータ30とを積層した積層型のリチウムイオン二次電池であるが、長尺の正極と、長尺の負極と、長尺のセパレータとを捲回した捲回型のリチウムイオン二次電池とすることができる。
以上に説明した構成により、リチウムイオン二次電池1は、85℃の耐熱性をもつ。
[正極の作成]
まず、正極活物質としてLiFePO4を88質量部、バインダとしてポリアクリル酸(ポリアクリル酸のナトリウム中和塩)を6質量部、導電助剤としてカーボンブラックを15質量部、増粘剤としてカルボキシメチルセルロースを0.3質量部、溶媒として水を217質量部用いて正極活物質を含む正極用スラリーを調製した。
(1)全ての材料と水とを、ミキサーa(株式会社シンキー製あわとり練太郎ARE-310)にて混合してプレスラリーを調製した。
(2)(1)で得たプレスラリーを、ミキサーb(プライミクス株式会社製フィルミックス40-L)にて更に混合して中間スラリーを調製した。
(3)(2)で得た中間スラリーを再度ミキサーaで混合して正極用スラリーを調製した。
負極活物質としてのグラファイトを98質量部、バインダとしてのスチレンブタジエンゴム(SBR)を1.4質量部、増粘剤としてカルボキシメチルセルロース0.7質量部、溶媒として水を96質量部混合し、以下の手順にて負極用スラリーを調製した。
(1)バインダを除く材料と水とを、ミキサーaにて混合してプレスラリーを調製した。
(2)(1)で得たプレスラリーを、ミキサーbにて更に混合して中間スラリーを調製した。
(3)(2)で得た中間スラリーにバインダを添加し、ミキサーaにて混合して負極用スラリーを調製した。
エチレンカーボネート[EC]を20.0vol%、プロピレンカーボネート[PC]を10.0vol%、エチルメチルカーボネート[EMC]を46.7vol%、ジエチルカーボネート[DEC]を23.3vol%を含む混合溶媒に、電解質としてイミド系リチウム塩であるリチウムビス(フルオロスルホニル)イミド[LiN(FSO2)2、LiFSI]を加えた。電解液は、LiFSIを1.0mol/L含む。
リチウムイオン二次電池を、次の手順にて作製した。
(1)正極、負極をそれぞれ打ち抜き、60mm×40mmのサイズの長方形とし、40mm×40mmの塗膜を残して長辺の一端側の20mm×40mmの領域の塗膜を剥ぎ落として集電用タブを取り付けた。
(2)厚さ20μmのセルロース製セパレータを間に介した状態で正極と負極の塗膜部分を対向させて積層体を作製した。
(3)(2)で作製した積層体と、リチウムプレドープ用の金属リチウム箔をアルミラミネート箔に内包し、電解液を注入し、封止してリチウムイオン二次電池を作製した。
正極バインダの電解液に対するRED値を算出したところ、1より大きいことが確認された。
リチウムイオン二次電池を常温(25℃)にて、カットオフ電圧:3.0~3.5V、測定電流5mA、0.2Cで内部抵抗及び放電容量を測定した。ここで、内部抵抗の測定は、DC-IR法にて0~0.1secにおける内部抵抗(mΩ)を測定した。
外部電源を繋いで電圧を3.5に保持した状態のリチウムイオン二次電池を85℃の恒温槽内に放置した。その放置時間が、85℃,3.5Vフロート時間に相当する。所定時間経過後、リチウムイオン二次電池を恒温槽から取り出し、常温に戻した後上記の電池性能の測定を行った。
試験例1のリチウムイオン二次電池の内部抵抗(mΩ)の経時変化を図10に示し、放電容量(mAh)の経時変化を図11に示した。また、試験例2のリチウムイオン二次電池の内部抵抗(mΩ)の経時変化を図12に示し、放電容量(mAh)の経時変化を図13に示した。
次に、リチウムイオンのドープ率の影響を検討した。上述した作成方法で、試験例3~5のリチウムイオン二次電池を作成し、以下の試験を行った。但し、試験例3のドープ率は80%、試験例4のドープ率は90%、試験例5のドープ率は100%になるよう調整した。
リチウムイオン二次電池を常温(25℃)にて、カットオフ電圧:3.0~3.5V、測定電流5mA、0.2Cで内部抵抗及び放電容量を測定した。内部抵抗の測定は、DC-IR法にて0~0.1secにおける内部抵抗(mΩ)を測定した。続いて、外部電源を繋いで電圧を3.8Vに保持した状態のリチウムイオン二次電池を85℃の恒温槽内に放置した。所定時間経過後、リチウムイオン二次電池を恒温槽から取り出し、常温に戻した後上記の電池性能の測定を行った。図14には、試験例3~5の内部抵抗の増加率を示す。図15には、試験例3~5の放電容量の変化を示す。
次に、RED値の影響を検討した。なお、リチウムイオン二次電池の作成において、正極及び電解液のみを上述の方法から変更したため、これらの変更点についてのみ以下に説明し、重複する説明は省略する。
正極活物質としてLiFePO4、バインダとしてポリアクリル酸(ポリアクリル酸のナトリウム中和塩)、アクリル酸エステル又はスチレン-ブタジエンゴム〔SBR〕、導電助剤としてアセチレンブラック、増粘材としてカルボキシメチルセルロース〔CMC〕、溶媒として水を用いて、表1に示される組成にて正極活物質を含む正極用スラリーA~Cを上述の方法で調整した。なお、表1における「部」は質量部を示し、「%」は質量%を示す。
溶媒として、エチレンカーボネート(EC)30vol%、ジメチルカーボネート(DMC)30vol%及びエチルメチルカーボネート(EMC)40vol%の混合溶媒を用い、混合溶媒にリチウムビス(フルオロスルホニルイミド)(LiFSI)を1mol/L添加して電解液Iを調整した。また、混合溶媒にヘキサフルオロリン酸リチウム(LiPF6)を添加して電解液Pを調整した。また溶媒として、エチレンカーボネート(EC)30vol%、エチルメチルカーボネート(EMC)46.7vol%、ジエチルカーボネート(DEC)23.3vol%、プロピレンカーボネート(PC)10vol%の混合溶媒を用い、混合溶媒にリチウムビス(フルオロスルホニルイミド)(LiFSI)を1mol/L添加して電解液I2を調整した。
試験例6~10のリチウムイオン二次電池を、表2に示す正極及び電解液の組み合わせで作成した。また、それぞれの組み合わせにおけるRED値も表2に示す。
試験例6~10のリチウムイオン二次電池のリチウムプレドープ、充放電、エージングを行った。その後、常温(25℃)にて、カットオフ電圧:2.2~3.8V、測定電流10Cで各リチウムイオン二次電池の内部抵抗及び放電容量を測定し、その結果を初期性能とした。なお、ドープ率は80%に調整した。
試験例6~10のリチウムイオン二次電池を、外部電源を繋いで電圧を3.8Vに保持した状態で85℃の恒温槽内に放置した。その放置時間が、85℃,3.8Vフロート時間に相当する。所定時間経過後、リチウムイオン二次電池を恒温槽から取り出し、常温に戻した後上記初期性能の測定と同一条件で内部抵抗及び放電容量を測定し、容量維持率(初期の放電容量を100%としたときの放電容量の百分比)と、内部抵抗増加率(初期性能からの内部抵抗の増加率)を算出した。その結果を表3に示す。
Claims (5)
- リチウムイオン二次電池であって、
リチウムイオンを吸蔵可能および放出可能な正極活物質と、
前記正極活物質を結着させる正極バインダと、
リチウムイオンを吸蔵可能および放出可能な負極活物質と、
前記負極活物質を結着させる負極バインダと、
有機溶媒およびイミド系リチウム塩を含む電解液と、を備え、
前記負極活物質は前記リチウムイオンがプレドープされ、
前記正極バインダが、前記電解液に対するハンセン溶解度パラメータに基づくRED値が1より大きい、
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であって、
前記正極活物質は、Li基準における動作電位の上限が所定値未満である、
リチウムイオン二次電池。 - 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であって、
前記有機溶媒は、ジメチルカーボネートを含まない、
リチウムイオン二次電池。 - 請求項1から請求項3のいずれか1項に記載のリチウムイオン二次電池であって、
前記正極バインダおよび前記負極バインダの少なくとも一方はポリアクリル酸である、
リチウムイオン二次電池。 - 請求項1から請求項4のいずれか1項に記載のリチウムイオン二次電池であって、
前記負極活物質のドープ率が50%から100%である、
リチウムイオン二次電池。
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CN112074985A (zh) | 2020-12-11 |
EP3790096A4 (en) | 2022-01-26 |
JPWO2019212040A1 (ja) | 2021-05-13 |
KR20210003892A (ko) | 2021-01-12 |
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