JP2003346798A - Secondary battery and battery pack using the same and method of use of secondary battery - Google Patents
Secondary battery and battery pack using the same and method of use of secondary batteryInfo
- Publication number
- JP2003346798A JP2003346798A JP2002150701A JP2002150701A JP2003346798A JP 2003346798 A JP2003346798 A JP 2003346798A JP 2002150701 A JP2002150701 A JP 2002150701A JP 2002150701 A JP2002150701 A JP 2002150701A JP 2003346798 A JP2003346798 A JP 2003346798A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- positive electrode
- active material
- battery
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 28
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 11
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000006182 cathode active material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract 2
- 238000006731 degradation reaction Methods 0.000 abstract 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 18
- -1 LiMn 2 O 4 Chemical class 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 13
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 12
- 239000011149 active material Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 239000000779 smoke Substances 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 102100031083 Uteroglobin Human genes 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical class COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- CZLVPINBLDRZCJ-UHFFFAOYSA-N 2,3,4,4,5,5,6,6-octachlorocyclohex-2-en-1-one Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1=O CZLVPINBLDRZCJ-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000777301 Homo sapiens Uteroglobin Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013454 LiC4 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012096 LiSb Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical class CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Chemical class COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OMYOBDYSDXYBAL-UHFFFAOYSA-N carbonic acid;diethyl carbonate Chemical compound OC(O)=O.CCOC(=O)OCC OMYOBDYSDXYBAL-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- UOALEFQKAOQICC-UHFFFAOYSA-N chloroborane Chemical compound ClB UOALEFQKAOQICC-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- JPKDSLBROREYTM-UHFFFAOYSA-N n-(dimethylcarbamoyl)acetamide Chemical compound CN(C)C(=O)NC(C)=O JPKDSLBROREYTM-UHFFFAOYSA-N 0.000 description 1
- 238000009782 nail-penetration test Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Mounting, Suspending (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、二次電池およびそ
れを用いた組電池、および二次電池の使用方法に関す
る。The present invention relates to a secondary battery, an assembled battery using the same, and a method of using the secondary battery.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池をはじめとする
二次電池は、自動車用の電池や電力貯蔵用電池などの用
途において、大型化、大容量化が求められている。その
際、エネルギー密度の高いセルを組電池化し、大容量化
する必要がある。2. Description of the Related Art A secondary battery such as a lithium ion secondary battery is required to have a large size and a large capacity in applications such as a battery for an automobile and a battery for power storage. At that time, it is necessary to make a cell having a high energy density into a battery pack to increase the capacity.
【０００３】リチウムイオン二次電池のエネルギー密度
を高める方法として、電池の動作電位を上昇させること
が有効である。従来のＬｉＣｏＯ２やＬｉＮｉＯ２、Ｌ
ｉＭｎＯ４を正極活物質として用いたリチウムイオン二
次電池では、動作電位はいずれも４Ｖ級（平均動作電位
＝３．６〜３．８Ｖ：対リチウム電位）となる。これ
は、ＣｏイオンもしくはＭｎイオンの酸化還元反応（Ｃ
ｏ３＋←→Ｃｏ４＋、Ｎｉ３＋←→Ｎｉ４＋、もしくは
Ｍｎ３＋←→Ｍｎ４＋）によって発現電位が規定される
ためである。As a method for increasing the energy density of a lithium ion secondary battery, it is effective to increase the operating potential of the battery. Conventional LiCoO 2 , LiNiO 2 , L
In a lithium ion secondary battery using iMnO 4 as a positive electrode active material, the operating potential is 4 V class (average operating potential = 3.6 to 3.8 V: potential with respect to lithium). This is due to the oxidation-reduction reaction (C
This is because the expression potential is defined by o 3+ ← → Co 4+ , Ni 3+ ← → Ni 4+ or Mn 3+ ← → Mn 4+ .
【０００４】これらの４Ｖ級正極活物質のうち、ＬｉＣ
ｏＯ２やＬｉＮｉＯ２は、層状岩塩構造（α-ＮａＦｅ
Ｏ２構造）を有しているため、充電時のリチウム離脱に
より、電気陰性度の大きい酸素層が隣接することにな
る。そのため、過充電状態などリチウムの引き抜き量が
多すぎる場合、酸素層間の静電反発力のため構造変化を
起こし発熱する。Among these 4V class positive electrode active materials, LiC
oO 2 and LiNiO 2 have a layered rock salt structure (α-NaFe
Because it has an O 2 structure), by lithium withdrawal during charging, high-oxygen layer electronegativity will be adjacent. Therefore, if the amount of extracted lithium is too large, such as in an overcharged state, a structural change occurs due to electrostatic repulsion between oxygen layers, and heat is generated.
【０００５】４Ｖ級正極活物質のうち、ＬｉＣｏＯ２は
電位平坦性、容量、放電電位、サイクル特性のそれぞれ
が、ある程度良好な特性を示すため、リチウムイオン二
次電池の正極活物質として広く用いられている。しかし
ながら、コバルトは可採埋蔵量が少なく高価な化合物で
ある。またＬｉＮｉＯ２はＬｉＣｏＯ２以上の容量を有
しているものの、ＬｉＣｏＯ２よりも酸素脱離温度が低
く安全性確保はより困難な化合物である。[0005] Among the 4V-class positive electrode active materials, LiCoO 2 is widely used as a positive electrode active material for lithium ion secondary batteries because each of the electric potential flatness, capacity, discharge potential, and cycle characteristics shows somewhat favorable characteristics. ing. However, cobalt is an expensive compound with small recoverable reserves. Also although LiNiO 2 has a LiCoO 2 or more capacity, oxygen desorption temperature safety lower than LiCoO 2 is more difficult compounds.
【０００６】また、ＬｉｘＮｉｙＭｎ１−ｙＯ２型の化
合物を正極活物質として用いることも研究されているも
のの、従来の報告では、Ｍｎ置換量の大きくなるにつれ
層状化が低下したり、容量が低下するという問題があ
り、化合物ｙの値が小さく高容量で安全性の高い物質を
得ることは困難である。Although the use of a Li x Ni y Mn 1-y O 2 type compound as a positive electrode active material has been studied, according to a conventional report, layering is reduced as the Mn substitution amount is increased. However, there is a problem that the capacity is reduced, and it is difficult to obtain a compound having a small value of the compound y, a high capacity and a high safety.
【０００７】一方、ＬｉＭｎ２Ｏ４はスピネル構造を有
している。安価なマンガンを原料としており、過充電時
にのみ使用される余分なリチウムをほとんど含んでいな
いためＬｉＣｏＯ２と比較し高い安全性を示す。しか
し、エネルギー密度はＬｉＮｉＯ２、ＬｉＣｏＯ２に比
べて小さい。また、ＬｉＭｎ２Ｏ４等のスピネル化合物
の場合も、サイクルに伴う容量低下や、高温での結晶構
造の劣化が起こることがある。On the other hand, LiMn 2 O 4 has a spinel structure. Since it is made of inexpensive manganese and contains almost no extra lithium used only at the time of overcharging, it exhibits higher safety than LiCoO 2 . However, the energy density is smaller than LiNiO 2 and LiCoO 2 . Also, in the case of a spinel compound such as LiMn 2 O 4 , the capacity may decrease with the cycle and the crystal structure may be deteriorated at a high temperature.
【０００８】また、これらのリチウムイオン二次電池を
組電池化した際にも、正極活物質の熱安定性が組電池の
安全性に大きく影響を与える。[0008] Also, when these lithium ion secondary batteries are assembled into a battery pack, the thermal stability of the positive electrode active material greatly affects the safety of the battery pack.
【０００９】さらに、組電池化する際には、巻回型の二
次電池では電極が長く、電極中の抵抗のばらつきは大き
くなり、安全性に影響を与える。Further, when the battery is assembled, the wound secondary battery has a long electrode, and the resistance in the electrode greatly varies, which affects safety.
【００１０】ここで、ラミネート外装体に収納された構
成を用いることにより、二次電池やそれを用いた組電池
の軽量化や自由な形状が可能となる。しかし、ラミネー
ト型の場合、円筒型と比べて、電池素子にかかる圧力が
低いことなどから、構成材料の熱安定性などの影響を大
きく受ける性質を有する。[0010] Here, by using the configuration accommodated in the laminate outer package, it is possible to reduce the weight of the secondary battery and the assembled battery using the secondary battery and to achieve a free shape. However, in the case of the laminate type, the pressure applied to the battery element is lower than that of the cylindrical type, so that the laminate type is greatly affected by the thermal stability of the constituent materials.
【００１１】[0011]
【発明が解決しようとする課題】こうした状況に鑑み、
本発明は、サイクル数に伴う容量低下や、高温での安全
性の低下が抑制され、大容量かつ高安全性を実現する二
次電池およびそれを用いた組電池、および二次電池の使
用方法を提供することを目的とする。In view of these circumstances,
The present invention is directed to a secondary battery that achieves a large capacity and high safety by suppressing a decrease in capacity due to the number of cycles and a decrease in safety at a high temperature, a battery pack using the same, and a method of using the secondary battery The purpose is to provide.
【００１２】[0012]
【課題を解決するための手段】本発明によれば、正極、
負極、およびこれらに挟持された電解質を備える二次電
池であって、正極活物質として下記式（Ｉ）で表される
化合物を含むことを特徴とする特徴とする二次電池が提
供される。
ＬｉｘＮｉｙＭｎ１−ｙＯ２ （Ｉ）
（ただし、ｘ、ｙは、０．９≦ｘ≦１．１、０．４５≦
ｙ≦０．５５を満たす。)According to the present invention, a positive electrode,
A secondary battery including a negative electrode and an electrolyte sandwiched therebetween is provided, which comprises a compound represented by the following formula (I) as a positive electrode active material. Li x Ni y Mn 1-y O 2 (I) (where x and y are 0.9 ≦ x ≦ 1.1, 0.45 ≦
Satisfies y ≦ 0.55. )
【００１３】上記式（Ｉ）で示される正極活物質は、安
全性の高いＬｉＣｏＯ２以上の容量を有し、かつ容量が
高いが酸素脱離温度が低いＬｉＮｉＯ２より安全性が高
い化合物である。The positive electrode active material represented by the above formula (I) is a compound having a capacity higher than that of LiCoO 2 with high safety, and having higher capacity but higher safety than LiNiO 2 with low oxygen desorption temperature. .
【００１４】したがって、上記式（Ｉ）で示される化合
物を正極活物質として含むことにより、サイクルに伴う
容量低下や、高温での発煙、発火などの安全性の低下を
抑えつつ、大容量を実現する二次電池が提供される。Therefore, by including the compound represented by the formula (I) as a positive electrode active material, a large capacity can be realized while suppressing a decrease in capacity due to a cycle and a decrease in safety such as smoke and ignition at a high temperature. Is provided.
【００１５】本発明の二次電池において、０．９≦ｘ≦
１．１とすることにより、好ましい電池特性が発揮され
る。さらに、ｘ＝１とすることにより、より好ましい電
池特性が発揮される。また、ｙの値は０．４５≦ｙ≦
０．５５とすることができる。０．４５≦ｙとすること
により、二次電池の高い容量が確保される。In the secondary battery of the present invention, 0.9 ≦ x ≦
By setting it to 1.1, preferable battery characteristics are exhibited. Further, by setting x = 1, more preferable battery characteristics are exhibited. The value of y is 0.45 ≦ y ≦
0.55. By setting 0.45 ≦ y, a high capacity of the secondary battery is secured.
【００１６】本発明の二次電池において、前記式（Ｉ）
において、０．５≦ｙ≦０．５５とすることができる。
こうすることにより、さらに高い容量が得られる。一
方、ｙ≦０．５５とすることにより、電池の安全性が維
持される。In the secondary battery of the present invention, the above formula (I)
In the formula, 0.5 ≦ y ≦ 0.55 may be satisfied.
In this way, a higher capacity can be obtained. On the other hand, by setting y ≦ 0.55, the safety of the battery is maintained.
【００１７】本発明の二次電池において、前記正極活物
質のＤ５０粒径（メジアン径）を１μｍ以上１００μｍ
以下とすることができる。Ｄ５０粒径を１μｍ以上とす
ることにより、正極活物質の比表面積を適度に小さくす
ることができるため、結着剤の必要量を減少することが
できる。したがって、正極活物質の含量を高めることが
でき、正極の容量密度を増加させることができる。ま
た、Ｄ５０粒径を１００μｍ以下とすることにより、反
応の均一性が保たれ、スラリー作製の容易さ、安全性な
どが確保される。[0017] In the secondary battery of the present invention, the D 50 particle size (median diameter) of the positive electrode active material 1μm or 100μm
It can be: By D 50 particle size greater than or equal to 1 [mu] m, it is possible to appropriately reduce the specific surface area of the cathode active material, it is possible to reduce the required amount of the binder. Therefore, the content of the positive electrode active material can be increased, and the capacity density of the positive electrode can be increased. Further, with the 100μm or less D 50 particle size, uniformity of the reaction is maintained, the slurry ease of fabrication, and safety is ensured.
【００１８】本発明の二次電池において、電池容量を
１．０Ａｈ以上１０Ａｈ以下とすることができる。こう
することにより、電池の発火、発煙が抑制され、電池の
安全性を確保することができる。In the secondary battery of the present invention, the battery capacity can be set to 1.0 Ah or more and 10 Ah or less. By doing so, ignition and smoking of the battery are suppressed, and the safety of the battery can be ensured.
【００１９】本発明の二次電池において、正極活物質と
して前記式（Ｉ）で示される化合物に加え、さらにスピ
ネル型リチウムマンガン酸化物を５重量％以上含む構成
とすることができる。５重量％以上とすることにより、
高温における電池の安全性をさらに向上させることがで
きる。また、９５重量％以下とすることにより、前記二
次電池のエネルギー密度を高めることができる。さら
に、８０重量％以下とすることにより、前記二次電池の
エネルギー密度をより高めることができる。In the secondary battery of the present invention, the cathode active material may be configured to further contain 5% by weight or more of a spinel-type lithium manganese oxide in addition to the compound represented by the formula (I). By making it 5% by weight or more,
The safety of the battery at a high temperature can be further improved. Further, when the content is 95% by weight or less, the energy density of the secondary battery can be increased. Further, by setting the content to 80% by weight or less, the energy density of the secondary battery can be further increased.
【００２０】本発明の二次電池において、前記スピネル
型リチウムマンガン酸化物は、Ｌｉ １＋ｘＭｎ２Ｏ
４（０．０２≦ｘ≦０．５）とすることができる。In the secondary battery according to the present invention, the spinel
Type lithium manganese oxide is Li 1 + xMn2O
4(0.02 ≦ x ≦ 0.5).
【００２１】本発明の二次電池において、電池容量を
１．０Ａｈ以上２０Ａｈ以下とすることができる。こう
することにより、電池の発火、発煙が抑制され、安全性
を確保することができる。In the secondary battery of the present invention, the battery capacity can be set to 1.0 Ah or more and 20 Ah or less. By doing so, ignition and smoking of the battery are suppressed, and safety can be ensured.
【００２２】本発明の二次電池において、前記正極およ
び前記負極が矩形であって、前記正極および前記負極の
それぞれについて、一辺に電極端子取付部が設けられ、
下記式（ＩＩ）を満たす構成とすることができる。
０＜Ｂ／Ａ≦３０ （ＩＩ）
（ただし、Ａは矩形である電極の一辺で、電極端子取付
部となる辺の長さ、Ｂは矩形である電極の一辺で、Ａに
垂直方向における活物質領域の最長幅を表す。）In the secondary battery of the present invention, the positive electrode and the negative electrode are rectangular, and each of the positive electrode and the negative electrode is provided with an electrode terminal attaching portion on one side,
A configuration satisfying the following formula (II) can be adopted. 0 <B / A ≦ 30 (II) (where A is one side of the rectangular electrode, the length of the side to be the electrode terminal attachment portion, B is one side of the rectangular electrode, and A Indicates the longest width of the material area.)
【００２３】こうすることにより、電極の抵抗による発
熱が抑制されるため、電池の安全性をさらに高めること
ができる。By doing so, heat generation due to the resistance of the electrodes is suppressed, so that the safety of the battery can be further improved.
【００２４】本発明の二次電池は、ラミネート外装体を
有する構成とすることができる。こうすることにより、
二次電池やそれを用いた組電池の軽量化が可能となり、
また二次電池や組電池を自由な形状に容易に構成するこ
とができる。[0024] The secondary battery of the present invention may be configured to have a laminate outer package. By doing this,
It is possible to reduce the weight of secondary batteries and assembled batteries using them,
Also, the secondary battery and the assembled battery can be easily formed in any shape.
【００２５】本発明によれば、前記二次電池が、前記正
極および前記負極それぞれに設けられた電極端子取付部
を介して複数個組み合わせてなる組電池が提供される。According to the present invention, there is provided an assembled battery in which a plurality of the secondary batteries are combined via electrode terminal attachment portions provided on each of the positive electrode and the negative electrode.
【００２６】本発明に係る組電池は、正極活物質として
前記式（Ｉ）で示される化合物を含む。こうすることに
より、組電池エネルギー密度および安全性の高い大型電
池へ展開することができる。したがって、組電池におい
ても電池の発火、発煙が抑制され、電池の安全性を確保
することができる。The battery pack according to the present invention contains the compound represented by the above formula (I) as a positive electrode active material. By doing so, it is possible to develop the battery into a large battery with high energy density and safety. Therefore, also in the assembled battery, the ignition and smoke of the battery are suppressed, and the safety of the battery can be secured.
【００２７】また、発明によれば、二次電池の使用方法
であって、放電深度（ＤＯＤ）５％以上１００％以下の
範囲で使用することを特徴とする二次電池の使用方法が
提供される。こうすることにより、サイクル数に伴う容
量低下が抑制することができる。なお、放電深度（ＤＯ
Ｄ）は、容量に対する放電した容量の百分率である。According to the invention, there is provided a method of using a secondary battery, wherein the secondary battery is used in a depth of discharge (DOD) of 5% or more and 100% or less. You. By doing so, capacity reduction due to the number of cycles can be suppressed. The depth of discharge (DO
D) is the percentage of discharged capacity to capacity.
【００２８】[0028]
【発明の実施の形態】本発明に係る二次電池は、正極、
負極、およびこれらに挟持された電解質とを備える。DESCRIPTION OF THE PREFERRED EMBODIMENTS A secondary battery according to the present invention comprises a positive electrode,
A negative electrode and an electrolyte interposed therebetween.
【００２９】たとえば、本発明に係る二次電池は、リチ
ウム含有金属複合酸化物を正極活物質とした正極と、リ
チウムを吸蔵放出可能な負極活物質を持つ負極を主要成
分とすることができる。正極と負極の間に電気的接続を
起こさないようなセパレータが挟まれ、正極と負極はリ
チウムイオン伝導性の電解液に浸った状態であり、これ
らが外装体の中に密閉された状態となっている。For example, the secondary battery according to the present invention can have, as main components, a positive electrode using a lithium-containing metal composite oxide as a positive electrode active material and a negative electrode having a negative electrode active material capable of inserting and extracting lithium. A separator that does not cause electrical connection is sandwiched between the positive electrode and the negative electrode, and the positive electrode and the negative electrode are immersed in a lithium ion conductive electrolyte, and these are sealed in the outer package. ing.
【００３０】図１は、本発明に係る二次電池の斜視図で
あり、図２は図１の電池の電池要素の分解斜視図であ
り、図３は当該電池要素の断面図である。図３に示すよ
うに、セパレータ３で区切られた空間に負極１と正極２
を交互に配置され、それぞれの負極１の末端から延出さ
れた負極集電部７を介して負極端子４が設けられる。同
様に、それぞれの正極２の末端から延出された正極集電
部８を介して正極端子５が設けられている。また、図３
では、負極集電部７と正極集電部８、負極端子４と正極
端子５は互いに反対方向に延出させている。FIG. 1 is a perspective view of a secondary battery according to the present invention, FIG. 2 is an exploded perspective view of a battery element of the battery of FIG. 1, and FIG. 3 is a sectional view of the battery element. As shown in FIG. 3, a negative electrode 1 and a positive electrode
Are alternately arranged, and a negative electrode terminal 4 is provided via a negative electrode current collector 7 extending from an end of each negative electrode 1. Similarly, a positive electrode terminal 5 is provided via a positive electrode current collector 8 extending from an end of each positive electrode 2. FIG.
Here, the negative electrode current collector 7 and the positive electrode current collector 8 and the negative electrode terminal 4 and the positive electrode terminal 5 extend in opposite directions.
【００３１】また、図５は、本発明に係る二次電池の電
極の積層構造の例を示した断面図である。正極板１００
上に正極活物質層１０２が形成され、正極１１０を構成
している。また、負極板１０８上に負極活物質層１０６
が形成され、負極１１２を構成している。正極１１０と
負極１１２は、電解液に浸漬した状態のセパレータ１０
４を介して対向配置されている。FIG. 5 is a sectional view showing an example of a laminated structure of the electrodes of the secondary battery according to the present invention. Positive electrode plate 100
The positive electrode active material layer 102 is formed thereon, and constitutes the positive electrode 110. Further, the negative electrode active material layer 106 is formed on the negative electrode plate 108.
Are formed to constitute the negative electrode 112. The positive electrode 110 and the negative electrode 112 are connected to the separator 10 immersed in the electrolytic solution.
4 are disposed opposite to each other.
【００３２】正極と負極に電圧を印加することにより正
極活物質からリチウムイオンが脱離し、負極活物質にリ
チウムイオンが吸蔵され、充電状態となる。また、正極
と負極の電気的接触を電池外部で起こすことにより、充
電時と逆に、負極活物質からリチウムイオンが放出さ
れ、正極活物質にリチウムイオンが吸蔵されることによ
り、放電が起こる。When a voltage is applied to the positive electrode and the negative electrode, lithium ions are desorbed from the positive electrode active material, lithium ions are occluded in the negative electrode active material, and the battery is charged. In addition, by causing electrical contact between the positive electrode and the negative electrode outside the battery, lithium ions are released from the negative electrode active material, and lithium ions are occluded in the positive electrode active material, thereby causing discharge, as opposed to charging.
【００３３】本発明の二次電池は、正極活物質として下
記式（Ｉ）で示される化合物を含む。The secondary battery of the present invention contains a compound represented by the following formula (I) as a positive electrode active material.
【００３４】ＬｉｘＮｉｙＭｎ１−ｙＯ２ （Ｉ）
（ただし、ｘ、ｙは、０．９≦ｘ≦１．１、０．４５≦
ｙ≦０．５５を満たす。) Li x Ni y Mn 1-y O 2 (I) (where x and y are 0.9 ≦ x ≦ 1.1, 0.45 ≦
Satisfies y ≦ 0.55. )
【００３５】式（Ｉ）で示される化合物は、ＬｉＮｉＯ
２やＬｉＣｏＯ２に比べ熱的に安定で、安全性に優れて
いる。かつＬｉＣｏＯ２と同等のエネルギー密度を有し
ている。The compound represented by the formula (I) is LiNiO
2 and LiCoO 2 are more thermally stable and have higher safety. And it has an energy density equivalent to that of LiCoO 2 .
【００３６】本発明では、Ｌｉ原料と、ＭｎおよびＬｉ
原料としてニッケルマンガン酸化物を用いることによ
り、式（Ｉ）におけるｙの値が０．４５≦ｙ≦０．５５
と従来の正極活物質より小さい範囲となる化合物を得る
ことができる。In the present invention, Li raw material, Mn and Li
By using nickel manganese oxide as a raw material, the value of y in the formula (I) is 0.45 ≦ y ≦ 0.55
And a compound having a range smaller than that of the conventional positive electrode active material can be obtained.
【００３７】したがって、式（Ｉ）で示される化合物を
積層ラミネート型リチウムイオン二次電池に用いること
により、従来の正極活物質では安全性を確保するのが困
難であった容量領域においても、電池の作製、使用が可
能であるため、エネルギー密度を落とさずに大型電池へ
展開することができる。Therefore, by using the compound represented by the formula (I) for a laminated lithium ion secondary battery, even in a capacity region where it is difficult to secure safety with the conventional cathode active material, Since it can be manufactured and used, it can be applied to a large battery without lowering the energy density.
【００３８】式（Ｉ）において、ｘの値はプロセス上の
変動を伴うが、たとえば０．９≦ｘ≦１．１とすること
ができる。また、ｘ＝１とすることにより、さらに優れ
た電池特性が発揮される。また、ｙの値は０．４５≦ｙ
≦０．５５とすることができる。０．４５≦ｙとするこ
とにより、二次電池の高い容量が確保される。また、
０．５≦ｙとすることにより、さらに高い容量が得られ
る。一方、ｙ≦０．５５とすることにより、電池の安全
性が維持される。In the formula (I), the value of x involves a variation in the process, but can be, for example, 0.9 ≦ x ≦ 1.1. Further, by setting x = 1, more excellent battery characteristics are exhibited. The value of y is 0.45 ≦ y
≤0.55. By setting 0.45 ≦ y, a high capacity of the secondary battery is secured. Also,
By setting 0.5 ≦ y, a higher capacity can be obtained. On the other hand, by setting y ≦ 0.55, the safety of the battery is maintained.
【００３９】本発明において、式（Ｉ）で示される化合
物は、たとえば以下のようにして作製することができ
る。In the present invention, the compound represented by the formula (I) can be prepared, for example, as follows.
【００４０】正極活物質として用いられる式（Ｉ）で示
される化合物の作製原料として、Ｌｉ原料には、Ｌｉ２
ＣＯ３、ＬｉＯＨ、Ｌｉ２Ｏ、Ｌｉ２ＳＯ４などを用い
ることができるが、Ｌｉ２ＣＯ３、ＬｉＯＨなどが適し
ている。また、ＭｎおよびＮｉ原料には、たとえばＭｎ
とＮｉの複合酸化物、たとえば（Ｍｎ０．５Ｎ
ｉ０． ５）３Ｏ２を用いることができる。As a raw material for producing the compound represented by the formula (I) used as a positive electrode active material, Li 2
CO 3 , LiOH, Li 2 O, Li 2 SO 4 and the like can be used, but Li 2 CO 3 and LiOH are suitable. The Mn and Ni raw materials include, for example, Mn
And a composite oxide of Ni and, for example, (Mn 0.5 N
i 0. 5 ) 3 O 2 can be used.
【００４１】原料の粒径は、できるだけ分散の幅が小さ
いことが望ましい。また、式（Ｉ）で示される化合物の
粒径は、原料の粒径に依存する。たとえば出発原料とし
てＬｉ２ＣＯ３と（Ｍｎ０．５Ｎｉ０．５）３Ｏ２を用
いる場合、Ｌｉ２ＣＯ３は、粉砕などの方法によってＤ
５０粒径５μｍ以下とすることにより、反応の均一性を
より確実なものとすることができる。また、（Ｍｎ
０．５Ｎｉ０．５）３Ｏ２は分級などの方法により、Ｄ
５０粒径を、５μｍ以上２０μｍ以下とすることによ
り、反応の均一性をより確実なものとすることができ
る。As for the particle size of the raw material, it is desirable that the width of dispersion is as small as possible. Further, the particle size of the compound represented by the formula (I) depends on the particle size of the raw material. For example, when Li 2 CO 3 and (Mn 0.5 Ni 0.5 ) 3 O 2 are used as starting materials, Li 2 CO 3 is converted into D 2 by a method such as pulverization.
By setting the 50 particle size to 5 μm or less, the uniformity of the reaction can be further ensured. In addition, (Mn
0.5 Ni 0.5 ) 3 O 2 is obtained by a method such as classification.
By setting the 50 particle size to 5 μm or more and 20 μm or less, the uniformity of the reaction can be further ensured.
【００４２】こうして粒径が揃えられたＬｉ２ＣＯ３お
よび（Ｍｎ０．５Ｎｉ０．５）３Ｏ ２を、所定の割合で
混合し、混合紛を空気中または酸素中で、６００℃以上
９５０℃以下で焼成することにより、目的の正極活物質
を得る。焼成温度は、それぞれの元素の拡散させるため
には高温である方が望ましいが、焼成温度が高すぎると
酸素欠損を生じ、電池特性に悪影響がある。このことか
ら、７００℃から８５０℃程度であることが望ましい。The Li particles having a uniform particle size in this way2CO3You
And (Mn0.5Ni0.5)3O 2At a given rate
Mix and mix powder in air or oxygen at 600 ° C or higher
By firing at 950 ° C or lower, the desired positive electrode active material
Get. The firing temperature is set to allow each element to diffuse.
It is desirable that the temperature is high, but if the firing temperature is too high
Oxygen deficiency occurs, adversely affecting battery characteristics. This thing
Therefore, it is desirable that the temperature is about 700 ° C. to 850 ° C.
【００４３】得られた正極活物質は、たとえば空気分級
機などを用いて、粒径を揃えることができる。たとえ
ば、ＬｉＮｉ０．５Ｍｎ０．５Ｏ２を正極活物質として
用いる場合、たとえばＬｉＮｉ０．５Ｍｎ０．５Ｏ２の
Ｄ５０粒径を１μｍ以上とすることができる。こうする
ことにより、正極活物質の比表面積を適度に小さくする
ことができるため、結着剤の必要量を減少することがで
きる。したがって、正極活物質の含量を高めることがで
き、正極の容量密度を増加させることができる。さら
に、Ｄ５０粒径を５μｍ以上とすることにより、より一
層正極活物質の含量を高めることができ、正極の容量密
度を増加させることができる。また、得られた正極活物
質の比表面積は３ｍ２／ｇ以下であることが望ましく、
好ましくは１ｍ２／ｇ以下である。比表面積が大きいほ
ど、結着剤が多く必要であり、正極の容量密度の点で不
利になるからである。The particle size of the obtained positive electrode active material can be uniformed by using, for example, an air classifier. For example, when using LiNi 0.5 Mn 0.5 O 2 as the positive electrode active material may be, for example, LiNi 0.5 Mn 0.5 O 2 of the D 50 particle size of 1μm or more. By doing so, the specific surface area of the positive electrode active material can be appropriately reduced, so that the required amount of the binder can be reduced. Therefore, the content of the positive electrode active material can be increased, and the capacity density of the positive electrode can be increased. Further, by the above 5μm a D 50 particle size, it is possible to increase the content of more positive electrode active material, thereby increasing the capacity density of the positive electrode. The specific surface area of the obtained positive electrode active material is desirably 3 m 2 / g or less,
It is preferably at most 1 m 2 / g. This is because the larger the specific surface area, the more binder is required, which is disadvantageous in terms of the capacity density of the positive electrode.
【００４４】また、ＬｉＮｉ０．５Ｍｎ０．５Ｏ２のＤ
５０粒径を１００μｍ以下とすることができる。こうす
ることにより、反応の均一性が保たれ、スラリー作製の
容易さ、安全性などが確保される。さらに、Ｄ５０粒径
を２０μｍ以下とすることにより、一層反応の均一性が
より高められ、スラリー作製の容易さ、安全性が向上す
る。In addition, the D of LiNi 0.5 Mn 0.5 O 2
The 50 particle size can be 100 μm or less. By doing so, the uniformity of the reaction is maintained, and the ease of preparation of the slurry, safety and the like are ensured. Furthermore, by less 20μm a D 50 particle size, it increased more uniformity of the reaction, the slurry ease of fabrication, safety is improved.
【００４５】本発明の正極活物質は、式（Ｉ）で示され
る化合物に加え、さらに適宜スピネル型リチウムマンガ
ン酸化物を含むことができる。スピネル型リチウムマン
ガン酸化物は、正極活物質中５重量％以上含むことがで
き、これにより高温における電池の安全性をさらに向上
させることができる。また正極活物質中のスピネル型リ
チウムマンガン酸化物を８０重量％以下とすることによ
り、エネルギー密度をより高めることができる。スピネ
ル型リチウムマンガン酸化物として、たとえばＬｉ
１＋ｘＭｎ２Ｏ４（０．０２≦ｘ≦０．５）などを用い
ることができる。The positive electrode active material of the present invention may further contain a spinel-type lithium manganese oxide in addition to the compound represented by the formula (I). The spinel-type lithium manganese oxide can be contained in the positive electrode active material in an amount of 5% by weight or more, whereby the safety of the battery at a high temperature can be further improved. Further, by setting the content of the spinel-type lithium manganese oxide in the positive electrode active material to 80% by weight or less, the energy density can be further increased. As a spinel type lithium manganese oxide, for example, Li
1 + x Mn 2 O 4 (0.02 ≦ x ≦ 0.5) or the like can be used.
【００４６】なお、本発明の積層ラミネート型リチウム
イオン二次電池用正極活物質において、スラリー調整、
安全性に大きく影響しない範囲内であれば、式（Ｉ）で
示す化合物に他の活物質、例えばＬｉＮｉＯ２やＬｉＣ
ｏＯ２等を少量混合することができる。In the positive electrode active material for a laminate type lithium ion secondary battery according to the present invention, slurry preparation,
The compound represented by the formula (I) may be added to another active material such as LiNiO 2 or LiC within a range that does not significantly affect safety.
oO 2 and the like can be mixed in a small amount.
【００４７】得られた正極活物質を用いて、以下のよう
にして正極を作製することができる。正極活物質を導電
性付与剤と混合し、結着剤によって集電体上に形成す
る。導電付与剤の例としては、炭素材料の他、導電性酸
化物の粉末などを使用することができる。結着剤として
はポリフッ化ビニリデンなどが用いられる。集電体とし
てはＡｌなどを主体とする金属薄膜を用いる。Using the obtained positive electrode active material, a positive electrode can be produced as follows. A positive electrode active material is mixed with a conductivity-imparting agent, and formed on a current collector with a binder. Examples of the conductivity-imparting agent include, in addition to a carbon material, a powder of a conductive oxide. Polyvinylidene fluoride or the like is used as the binder. As the current collector, a metal thin film mainly composed of Al or the like is used.
【００４８】導電付与剤の添加量は、たとえば１〜１０
重量％程度とすることができ、結着剤の添加量は１〜１
０重量％程度とすることができる。活物質重量の割合が
大きい方が重量あたりの容量が大きくなる。導電付与剤
と結着剤の割合が小さすぎると、導電性が保てなくなっ
たり、電極剥離の問題が生じる。The amount of the conductive agent is, for example, 1 to 10
% By weight, and the amount of the binder added is 1 to 1
It can be about 0% by weight. The larger the proportion of the active material weight, the larger the capacity per weight. If the ratio between the conductivity-imparting agent and the binder is too small, the conductivity cannot be maintained or the problem of electrode peeling occurs.
【００４９】また、本発明のリチウム二次電池において
用いることのできるセパレータとしては、ポリプロピレ
ン、ポリエチレン等のポリオレフィン、フッ素樹脂等の
多孔性フィルムを用いることができる。As a separator that can be used in the lithium secondary battery of the present invention, a porous film such as a polyolefin such as polypropylene or polyethylene, or a fluororesin can be used.
【００５０】本発明に係る二次電池に用いられる電解液
としては、プロピレンカーボネート（ＰＣ）、エチレン
カーボネート（ＥＣ）、ブチレンカーボネート（Ｂ
Ｃ）、ビニレンカーボネート（ＶＣ）等の環状カーボネ
ート類、ジメチルカーボネート（ＤＭＣ）、ジエチルカ
ーボネート（ＤＥＣ）、エチルメチルカーボネート（Ｅ
ＭＣ）、ジプロピルカーボネート（ＤＰＣ）等の鎖状カ
ーボネート類、ギ酸メチル、酢酸メチル、プロピオン酸
エチル等の脂肪族カルボン酸エステル類、γ−ブチロラ
クトン等のγ−ラクトン類、１，２−エトキシエタン
（ＤＥＥ）、エトキシメトキシエタン（ＥＭＥ）等の鎖
状エーテル類、テトラヒドロフラン、２−メチルテトラ
ヒドロフラン等の環状エーテル類、ジメチルスルホキシ
ド、１，３−ジオキソラン、ホルムアミド、アセトアミ
ド、ジメチルホルムアミド、ジオキソラン、アセトニト
リル、プロピルニトリル、ニトロメタン、エチルモノグ
ライム、リン酸トリエステル、トリメトキシメタン、ジ
オキソラン誘導体、スルホラン、メチルスルホラン、
１，３−ジメチル−２−イミダゾリジノン、３−メチル
−２−オキサゾリジノン、プロピレンカーボネート誘導
体、テトラヒドロフラン誘導体、エチルエーテル、１，
３−プロパンサルトン、アニソール、Ｎ−メチルピロリ
ドン、フッ素化カルボン酸エステルなどの非プロトン性
有機溶媒を一種又は二種以上を混合して使用し、これら
の有機溶媒に溶解するリチウム塩を溶解させる。リチウ
ム塩としては、例えばＬｉＰＦ６、ＬｉＡｓＦ６、Ｌｉ
ＡｌＣｌ４、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＳｂ
Ｆ６、ＬｉＣＦ３ＳＯ３、ＬｉＣ４Ｆ９ＣＯ ３、ＬｉＣ
（ＣＦ３ＳＯ２）２、ＬｉＮ（ＣＦ３ＳＯ２）２、Ｌｉ
Ｎ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＢ１０Ｃｌ１０、低級脂
肪族カルボン酸カルボン酸リチウム、クロロボランリチ
ウム、四フェニルホウ酸リチウム、ＬｉＢｒ、ＬｉＩ、
ＬｉＳＣＮ、ＬｉＣｌ、イミド類などがあげられる。ま
た、電解液に代えてポリマー電解質を用いてもよい。Electrolyte used for secondary battery according to the present invention
Propylene carbonate (PC), ethylene
Carbonate (EC), butylene carbonate (B
C), cyclic carbonates such as vinylene carbonate (VC)
Dimethyl carbonate (DMC), diethyl carbonate
-Carbonate (DEC), ethyl methyl carbonate (E
MC), dipropyl carbonate (DPC), etc.
-Carbonates, methyl formate, methyl acetate, propionic acid
Aliphatic carboxylic acid esters such as ethyl, γ-butyrol
Γ-lactones such as octone, 1,2-ethoxyethane
Chains such as (DEE) and ethoxymethoxyethane (EME)
Ethers, tetrahydrofuran, 2-methyltetra
Cyclic ethers such as hydrofuran, dimethyl sulfoxy
Do, 1,3-dioxolan, formamide, acetoamido
, Dimethylformamide, dioxolan, acetonitrile
Ryl, propyl nitrile, nitromethane, ethyl monog
Lime, phosphate triester, trimethoxymethane, di
Oxolane derivatives, sulfolane, methylsulfolane,
1,3-dimethyl-2-imidazolidinone, 3-methyl
-2-oxazolidinone, propylene carbonate derived
Body, tetrahydrofuran derivative, ethyl ether, 1,
3-propane sultone, anisole, N-methylpyrroli
Aprotic, such as carboxylic acid esters
Use one or a mixture of two or more organic solvents.
Is dissolved in the organic solvent. Lichiu
As the salt, for example, LiPF6, LiAsF6, Li
AlCl4, LiClO4, LiBF4, LiSb
F6, LiCF3SO3, LiC4F9CO 3, LiC
(CF3SO2)2, LiN (CF3SO2)2, Li
N (C2F5SO2)2, LiB10Cl10, Low grade fat
Lithium aliphatic carboxylate, chloroborane lich
, Lithium tetraphenylborate, LiBr, LiI,
LiSCN, LiCl, imides and the like can be mentioned. Ma
Further, a polymer electrolyte may be used instead of the electrolytic solution.
【００５１】電解質としては、ＬｉＢＦ４、ＬｉＰ
Ｆ６、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、Ｌ
ｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）Ｎ、ＬｉＣ４Ｆ
９ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、Ｌｉ（Ｃ２Ｆ５
ＳＯ２）２Ｎなどを単独もしくは混合して用いることが
できる。電解質濃度はたとえば０．５ｍｏｌ／ｌ〜１．
５ｍｏｌ／ｌとすることができる。濃度が高すぎると密
度と粘度が増加することがあり、濃度が低すぎると電気
電導率が低下することがある。As the electrolyte, LiBF 4 , LiP
F 6, LiClO 4, LiAsF 6 , LiSbF 6, L
iCF 3 SO 3 , Li (CF 3 SO 2 ) N, LiC 4 F
9 SO 3 , Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5
SO 2 ) 2 N or the like can be used alone or in combination. The electrolyte concentration is, for example, 0.5 mol / l to 1.
It can be 5 mol / l. If the concentration is too high, the density and the viscosity may increase, and if the concentration is too low, the electric conductivity may decrease.
【００５２】負極活物質としてはリチウムを吸蔵放出可
能な材料が用いられ、グラファイトまたは非晶質炭素等
の炭素材料、Ｌｉ金属、Ｓｉ、Ｓｎ、Ａｌ、ＳｉＯ、Ｓ
ｎＯなどを単独または混合して用いることができる。As the negative electrode active material, a material capable of inserting and extracting lithium is used, and a carbon material such as graphite or amorphous carbon, Li metal, Si, Sn, Al, SiO, S
nO or the like can be used alone or as a mixture.
【００５３】負極活物質は導電性付与剤と結着剤によっ
て集電体上に形成させる。導電付与剤の例としては、炭
素材料の他、導電性酸化物の粉末などを使用することが
できる。結着剤としてはポリフッカビニリデンなどが用
いられる。集電体としてはＡｌ、Ｃｕなどを主体とする
金属薄膜を用いることができる。The negative electrode active material is formed on a current collector by using a conductivity-imparting agent and a binder. Examples of the conductivity-imparting agent include, in addition to a carbon material, a powder of a conductive oxide. As the binder, polyfukkavinylidene or the like is used. As the current collector, a metal thin film mainly composed of Al, Cu, or the like can be used.
【００５４】作製された正極と負極はセパレータによっ
て電気的接触がない状態で対向させる。セパレータとし
てはポリエチレン、ポリプロピレンなどからなる微多孔
質膜を用いることができる。The produced positive electrode and negative electrode are opposed to each other by a separator without electrical contact. As the separator, a microporous membrane made of polyethylene, polypropylene, or the like can be used.
【００５５】その際、たとえば図１、図５に示すような
積層型の構造とすることができる。積層型にすることに
より、巻回型の二次電池よりも電極の長さを短くするこ
とがきるため、電極中の抵抗のばらつきを低減すること
ができる。このため、積層型形状とすることにより、抵
抗のばらつきによる発熱が抑制されるため、大容量の電
池においても安全性を確保することができる。At this time, for example, a laminated structure as shown in FIGS. 1 and 5 can be obtained. With the stacked type, the length of the electrode can be shorter than that of the wound secondary battery, so that the variation in resistance in the electrode can be reduced. For this reason, heat generation due to variations in resistance is suppressed by adopting a stacked shape, so that safety can be ensured even in a large-capacity battery.
【００５６】ここで、図５においては２組の正極−セパ
レータ−負極積層体１１４を、セパレータ１０４を介し
て積層する例を示したが、３組以上の積層体について
も、同様に作製することができる。Here, FIG. 5 shows an example in which two sets of the positive electrode-separator-negative electrode stack 114 are stacked with the separator 104 interposed therebetween. Can be.
【００５７】この正極と負極がセパレータを挟んで対向
したものを、外装体に収納する。The cathode and the anode facing each other with a separator interposed therebetween are housed in an exterior body.
【００５８】外装体として、たとえばラミネートフィル
ムを用いることができる。図１では、図３の電池要素が
フィルム外装体６に収納されている。外装体にラミネー
トフィルムを用いる場合、セパレータを挟んで対向した
正極、負極を積層型の形態でラミネートパックし、正極
活物質、負極活物質の両方が電解液に接するような状態
となるように電解液に浸す。正極、負極それぞれと電気
的接触を保った電極端子を接続しておき、その電極端子
を電極ケース外部に通ずるように接続しておき、ラミネ
ートパックを密閉して二次電池が完成する。As the outer package, for example, a laminate film can be used. In FIG. 1, the battery element of FIG. When a laminate film is used for the outer package, the positive electrode and the negative electrode facing each other with a separator interposed between them are laminated and packed in a laminated form, and electrolysis is performed so that both the positive electrode active material and the negative electrode active material come into contact with the electrolytic solution. Soak in liquid. Electrode terminals that maintain electrical contact with each of the positive electrode and the negative electrode are connected, and the electrode terminals are connected so as to pass outside the electrode case, and the laminate pack is sealed to complete the secondary battery.
【００５９】また、図１、図２、図３の積層形態では、
正極および負極の電極端子取付部は対向して設けられて
いるが、必要に応じて同じ辺側に設けることもできる
し、隣り合う辺に設けることもできる。Further, in the lamination form of FIGS. 1, 2 and 3,
The electrode terminal mounting portions for the positive electrode and the negative electrode are provided facing each other, but may be provided on the same side or on adjacent sides as necessary.
【００６０】本実施形態に係る二次電池において、正極
および負極が矩形である場合、正極および負極はそれぞ
れについて、一辺に電極端子取付部、たとえば正極活物
質および負極活物質の未塗布部が設けられ（図４、図
６）、０＜Ｂ／Ａ≦３０ （ＩＩ）（ただし、Ａは
矩形である電極の一辺で、電極端子取付部となる辺の長
さ、Ｂは矩形である電極の一辺で、Ａに垂直方向におけ
る活物質領域の最長幅を表す。）とした場合、電池の安
全性がより確実なものとなる。In the secondary battery according to this embodiment, when the positive electrode and the negative electrode are rectangular, each of the positive electrode and the negative electrode is provided with an electrode terminal mounting portion on one side, for example, a non-coated portion of the positive electrode active material and the negative electrode active material. (FIG. 4 and FIG. 6), 0 <B / A ≦ 30 (II) (where A is one side of the rectangular electrode, the length of the side serving as the electrode terminal attachment portion, and B is the length of the rectangular electrode. When one side represents the longest width of the active material region in the direction perpendicular to A.), the safety of the battery becomes more reliable.
【００６１】図４は本実施形態の電極の上面図、図６は
正極を例にした場合の電極の斜視図である。図４では、
活物質領域１３は集電体上の活物質が塗布された領域で
あり、電極端子取付部１５は活物質が塗布されていない
領域である。また、電極端子１４は電極端子取付部１５
上に取り付けられている。図４中のＡは、活物質領域の
幅を表し、Ｂは活物質領域の長さを表し、Ｃは電極端子
幅を表す。電極端子幅Ｃは、電池形態に応じて所定の長
さに設定することができる。また、図６では、電極端子
取付部の一例として、正極活物質未塗布部１１６が設け
られている。FIG. 4 is a top view of the electrode of this embodiment, and FIG. 6 is a perspective view of the electrode in the case of taking a positive electrode as an example. In FIG.
The active material region 13 is a region on the current collector where the active material is applied, and the electrode terminal mounting portion 15 is a region where the active material is not applied. Further, the electrode terminal 14 is connected to the electrode terminal mounting portion 15.
Mounted on top. A in FIG. 4 represents the width of the active material region, B represents the length of the active material region, and C represents the electrode terminal width. The electrode terminal width C can be set to a predetermined length according to the form of the battery. In FIG. 6, a positive electrode active material uncoated portion 116 is provided as an example of the electrode terminal attachment portion.
【００６２】ここで、式（ＩＩ）におけるＢ／Ａの値が
大きいほど、電極板の長さが電極端子取付部に対して大
きくなるため、電極板の抵抗は大きくなる。抵抗値と発
熱量は比例関係にあるため、電極板の抵抗が大きいほど
発熱の原因となり、電池の安全性を低下させる要因にな
る。本実施形態においては、正極活物質に式（Ｉ）で示
される化合物を用いることにより、電極が式（ＩＩ）を
満たす範囲で、電極板の抵抗による発熱が抑制され、電
池の安全性をさらに高めることができる。Here, as the value of B / A in the formula (II) becomes larger, the length of the electrode plate becomes larger with respect to the electrode terminal mounting portion, so that the resistance of the electrode plate becomes larger. Since the resistance value and the calorific value are in a proportional relationship, the greater the resistance of the electrode plate, the more heat is generated, and the lower the safety of the battery. In this embodiment, by using the compound represented by the formula (I) as the positive electrode active material, heat generation due to the resistance of the electrode plate is suppressed within a range where the electrode satisfies the formula (II), and the safety of the battery is further improved. Can be enhanced.
【００６３】以上のようにして作製された二次電池は、
容量が１．０Ａｈ以上１０Ａｈ以下で安全性が確保され
る。特に、正極活物質として、式（Ｉ）で示される化合
物およびスピネル型リチウムマンガン酸化物を含む二次
電池電池では、容量が１．０Ａｈ以上２０Ａｈ以下で安
全性が確保される。The secondary battery manufactured as described above is
When the capacity is 1.0 Ah or more and 10 Ah or less, safety is ensured. In particular, in a secondary battery containing the compound represented by the formula (I) and the spinel-type lithium manganese oxide as the positive electrode active material, safety is ensured at a capacity of 1.0 Ah to 20 Ah.
【００６４】また、本発明の二次電池は、放電深度（Ｄ
ＯＤ）０％以上１００％以下の範囲で使用することがで
きる。特に、ＤＯＤ５％以上１００％以下で使用するこ
とにより、充放電サイクルの増加による容量低下を好ま
しく防ぐことができる。The secondary battery of the present invention has a depth of discharge (D
OD) It can be used in the range of 0% to 100%. In particular, by using the DOD at 5% or more and 100% or less, it is possible to preferably prevent a decrease in capacity due to an increase in charge / discharge cycles.
【００６５】本発明の二次電池を単電池として、複数の
単電池を接続して所望の電圧、容量の組電池を構成する
ことができる。例えば、正、負極を揃えて積層し接続す
ることによって並列接続による組電池が得られる。ま
た、積層する際に正、負極を交互に接続すれば直列接続
による組電池が得られる。さらに、並列接続と直列接続
を併用して組電池を構成することも可能であり、自由な
レイアウトでかつ空間を有効利用した、直列、並列、直
並列型組電池を得ることができる。By using the secondary battery of the present invention as a unit cell, a plurality of unit cells can be connected to form an assembled battery having a desired voltage and capacity. For example, an assembled battery by parallel connection can be obtained by stacking and connecting the positive and negative electrodes. When the positive electrode and the negative electrode are alternately connected at the time of stacking, an assembled battery by series connection can be obtained. Furthermore, it is possible to configure a battery pack by using both parallel connection and series connection, and it is possible to obtain a series, parallel, and series-parallel battery pack with a free layout and effective use of space.
【００６６】[0066]
【実施例】〔実施例１〕本実施例では、正極活物質にＬ
ｉＮｉ０．５Ｍｎ０．５Ｏ２を用いた積層ラミネート型
リチウムイオン二次電池を作製し、正極活物質をＬｉＣ
ｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４とした場合と電
池特性の比較を行った。[Embodiment 1] In this embodiment, the positive electrode active material is L
A laminated laminated lithium ion secondary battery using iNi 0.5 Mn 0.5 O 2 was prepared, and the positive electrode active material was LiC
The battery characteristics were compared with those of oO 2 , LiNiO 2 , and LiMn 2 O 4 .
【００６７】Ｌｉ２ＣＯ３と（Ｍｎ０．５Ｎｉ０．５）
３Ｏ２を出発原料として、ＬｉＮｉ ０．５Ｍｎ０．５Ｏ
２合成した。Ｌｉ２ＣＯ３は粉砕し、Ｄ５０粒径が１．
４μｍとなったものを用いた。（Ｍｎ０．５Ｎ
ｉ０．５）３Ｏ２（田中化学社製）は分級により、Ｄ
５０粒径が１０μｍとなったものを用いた。Li2CO3And (Mn0.5Ni0.5)
3O2Starting material, LiNi 0.5Mn0.5O
2Synthesized. Li2CO3Is crushed and D50Particle size is 1.
Those having a thickness of 4 μm were used. (Mn0.5N
i0.5)3O2(Manufactured by Tanaka Chemical Co., Ltd.)
50The one having a particle size of 10 μm was used.
【００６８】こうして粒径が揃えられたＬｉ２ＣＯ３お
よび（Ｍｎ０．５Ｎｉ０．５）３Ｏ ２を、［Ｌｉ］：
［Ｍｎ］=１．０：０．５の割合で混合した。The Li particles having a uniform particle size in this way2CO3You
And (Mn0.5Ni0.5)3O 2To [Li]:
[Mn] = 1.0: 0.5.
【００６９】この混合紛を酸素フローの雰囲気下、７５
０℃で焼成し、ＬｉＮｉ０．５Ｍｎ ０．５Ｏ２を得た。
次いで、ＬｉＮｉ０．５Ｍｎ０．５Ｏ２粒子の中で、粒
径が1μｍ以下のものを空気分級器により除去した。こ
うして得られたＬｉＮｉ０． ５Ｍｎ０．５Ｏ２の各種粉
体測定を測定したところ、粉体特性は、比表面積が０．
９ｍ２/ｇ、タップ密度が２．３９ｇ/ｍｌ、真密度が
４．４２ｇ/ｍｌ、Ｄ５ ０粒径が１３μｍ、格子定数が
０．８１７５ｎｍであった。ここで、真密度は気体置換
法により求め、Ｄ５０粒径測定にはレーザー回折法を用
い、比表面積はガス吸着法により算出した。また、格子
定数はＸ線回折により測定した。This mixed powder was placed in an atmosphere of oxygen flow at 75
Baking at 0 ° C, LiNi0.5Mn 0.5O2I got
Then, LiNi0.5Mn0.5O2Among the particles, the particles
Those having a diameter of 1 μm or less were removed by an air classifier. This
LiNi thus obtained0. 5Mn0.5O2Various powders
As a result of body measurement, the powder had a specific surface area of 0.3.
9m2/ g, tap density 2.39g / ml, true density
4.42 g / ml, D5 0Particle size 13μm, lattice constant
0.8175 nm. Where the true density is gas displacement
By the method, D50Laser diffraction method is used for particle size measurement
The specific surface area was calculated by a gas adsorption method. Also the grid
The constant was measured by X-ray diffraction.
【００７０】このようにして得られたＬｉＮｉ０．５Ｍ
ｎ０．５Ｏ２を正極活物質として用いて、積層ラミネー
ト型リチウムイオン二次電池を作製した。The thus obtained LiNi 0.5 M
Using n 0.5 O 2 as a positive electrode active material, a laminated laminate type lithium ion secondary battery was manufactured.
【００７１】正極の作製は以下のように行った。ＬｉＮ
ｉ０．５Ｍｎ０．５Ｏ２および導電性付与剤を乾式混合
し、バインダーであるポリビニリデンフルオライド（Ｐ
ＶｄＦ）を溶解させたＮ−メチル―２−ピロリドン（Ｎ
ＭＰ）中に超音波分散機を用いて均一に分散させ、スラ
リーを作製した。導電性付与剤としては平均粒径４μｍ
のグラファイト（ロンザジャパン社製）を用い、正極中
の固形分は重量比でＬｉＮｉ０．５Ｍｎ０．５Ｏ２：導
電性付与剤：ＰＶｄＦ＝８０:１０:１０となるよう混合
した。得られたスラリーを、厚さ２５μｍのアルミ金属
箔上に塗布し、１００℃〜１４０℃にてＮＭＰを蒸発さ
せた後、１００ｍｍ×１５０ｍｍに切断し、正極シート
とした。The preparation of the positive electrode was performed as follows. LiN
i 0.5 Mn 0.5 O 2 and a conductivity-imparting agent are dry-mixed, and polyvinylidene fluoride (P
VdF) dissolved in N-methyl-2-pyrrolidone (N
MP) using an ultrasonic disperser to uniformly disperse the slurry to prepare a slurry. The average particle size is 4 μm as the conductivity-imparting agent.
Was mixed so that the solid content in the positive electrode was LiNi 0.5 Mn 0.5 O 2 : conductivity imparting agent: PVdF = 80: 10: 10 in weight ratio. The obtained slurry was applied on a 25-μm-thick aluminum metal foil, NMP was evaporated at 100 ° C. to 140 ° C., and then cut into 100 mm × 150 mm to obtain a positive electrode sheet.
【００７２】一方、負極の作製は以下のように行った。
重量比でハードカーボン：ＰＶｄＦ＝９０:１０となる
ように混合し、ＮＭＰに分散させた。これを厚さ２０μ
ｍの銅箔上に塗布し、１００℃〜１４０℃にてＮＭＰを
蒸発させた後１１５ｍｍ×１５５ｍｍに切断し、負極シ
ートとした。On the other hand, the production of the negative electrode was performed as follows.
Hard carbon: PVdF was mixed at a weight ratio of 90:10 and dispersed in NMP. This has a thickness of 20μ
m, and NMP was evaporated at 100 ° C. to 140 ° C., and then cut into 115 mm × 155 mm to obtain a negative electrode sheet.
【００７３】以上のようにして得られた正極シートおよ
び負極シートを、厚さ２５μｍ、大きさ１２０ｍｍ×１
６０ｍｍのポリエチレン多孔膜セパレータを介して積層
した。ここで、１０Ａｈおよび１０．５Ａｈの積層ラミ
ネート型リチウムイオン二次電池二次電池を作製するた
めに、その積層数を変更させた。The positive electrode sheet and the negative electrode sheet obtained as described above were separated by a thickness of 25 μm and a size of 120 mm × 1.
They were laminated via a 60 mm polyethylene porous membrane separator. Here, in order to produce a 10 Ah and 10.5 Ah laminated laminate type lithium ion secondary battery, the number of layers was changed.
【００７４】次に、セパレータを介して積層した電極板
の電極端子取付部と、正極リード端子としてアルミニウ
ム板とを一括して超音波溶接した。同様に、負極の電極
端子取付部と、負極リード端子としてニッケル板とを一
括して超音波溶接した。これを、電池素子とした。Next, the electrode terminal mounting portion of the electrode plate laminated with the separator interposed therebetween and the aluminum plate as the positive electrode lead terminal were ultrasonically welded together. Similarly, the electrode terminal mounting portion of the negative electrode and the nickel plate as the negative electrode lead terminal were collectively ultrasonically welded. This was used as a battery element.
【００７５】上で得られた電池素子を、電極リード端子
のみがラミネート外装体から突出するようにして、ラミ
ネートフィルムで被い、熱融着によって外装体の周囲三
辺を溶接した。ここで、ラミネートフィルムには、ナイ
ロン／アルミニウム／ポリプロピレンの三層構造を持つ
アルミラミネートフィルムを用いた。The battery element obtained above was covered with a laminate film such that only the electrode lead terminals protruded from the laminate outer package, and three sides around the outer package were welded by heat fusion. Here, an aluminum laminated film having a three-layer structure of nylon / aluminum / polypropylene was used as the laminated film.
【００７６】次に、接合してない残りの一辺から、上記
電池素子に電解液を注液した。電解液は１ＭのＬｉＰＦ
６を支持塩とし、プロピレンカーボネート（ＰＣ）とエ
チレンカーボネート（ＥＣ）とジエチルカーボネート
（ＤＥＣ）の混合溶液を溶媒とした。混合比は体積比で
ＰＣ：ＥＣ：ＤＥＣ＝２０:３０:５０とした。電解液注
液後、真空中にて外装体を封口し、１０Ａｈおよび１
０．５Ａｈの積層ラミネート型リチウムイオン二次電池
を得た。Next, an electrolytic solution was injected into the above-mentioned battery element from the other side not joined. The electrolyte is 1M LiPF
6 was used as a supporting salt, and a mixed solution of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) was used as a solvent. The mixing ratio was PC: EC: DEC = 20: 30: 50 by volume. After injecting the electrolyte solution, the exterior body was sealed in a vacuum, and 10 Ah and 1
A 0.5 Ah laminated laminate type lithium ion secondary battery was obtained.
【００７７】さらに、上と同様にして、正極活物質にＬ
ｉＣｏＯ２、ＬｉＮｉＯ２、およびＬｉＭｎ２Ｏ４をそ
れぞれ用いた１０Ａｈおよび１０．５Ａｈの積層ラミネ
ート型二次電池を作製した。Further, in the same manner as above, L
Laminated secondary batteries of 10 Ah and 10.5 Ah using iCoO 2 , LiNiO 2 , and LiMn 2 O 4 respectively were produced.
【００７８】これらの積層ラミネート型リチウムイオン
二次電池を、１６０℃のホットボックス試験に供した。
電池温度を３時間で１６０℃まで昇温した後１６０℃で
３時間保持し、その後降温した。結果を表１に示す。These laminated lithium ion secondary batteries were subjected to a hot box test at 160 ° C.
The battery temperature was raised to 160 ° C. in 3 hours, kept at 160 ° C. for 3 hours, and then lowered. Table 1 shows the results.
【００７９】表１より、正極活物質にＬｉＮｉ０．５Ｍ
ｎ０．５Ｏ２を用いた場合、１０Ａｈの積層ラミネート
型リチウムイオン二次電池では、発煙・発火が認められ
ず、１０．５Ａｈではわずかな蒸気が確認された。一
方、正極活物質にＬｉＣｏＯ２またはＬｉＮｉＯ２を用
いた場合、１０Ａｈであっても発煙・発火が認められ
た。またＬｉＭｎ２Ｏ４を正極活物質とした場合は、発
煙・発火は認められなかったものの、重量が他に比べ極
めて重かった。As shown in Table 1, the positive electrode active material was LiNi 0.5 M
In the case of using n 0.5 O 2 , no smoke or ignition was observed in the laminated lithium ion secondary battery of 10 Ah, and slight vapor was confirmed at 10.5 Ah. On the other hand, when LiCoO 2 or LiNiO 2 was used as the positive electrode active material, smoking and ignition were observed even at 10 Ah. When LiMn 2 O 4 was used as the positive electrode active material, no smoke or ignition was recognized, but the weight was extremely heavy as compared with the others.
【００８０】従って、ＬｉＮｉ０．５Ｍｎ０．５Ｏ２を
正極活物質とした積層ラミネート型リチウムイオン二次
電池は軽量で、かつ１６０℃にて安全に用いられること
が確認され、１０Ａｈ以下での使用がより好ましいこと
が確かめられた。Therefore, it was confirmed that the laminated laminated lithium ion secondary battery using LiNi 0.5 Mn 0.5 O 2 as the positive electrode active material was lightweight and could be safely used at 160 ° C. Has been found to be more preferred.
【００８１】また、正極活物質にＬｉＮｉ０．５Ｍｎ
０．５Ｏ２を用いた１０Ａｈの積層ラミネート型リチウ
ムイオン二次電池を、６０℃で１Ｃの定電流定電圧試験
に供し、放電深度（ＤＯＤ）０％〜ＤＯＤ１００％、お
よびＤＯＤ５％〜ＤＯＤ１００％でのサイクル特性の評
価を行った。サイクル特性は、１０サイクル目の容量を
基準とした。結果を表２に示す。Further, LiNi 0.5 Mn was used as the positive electrode active material.
A 10 Ah laminated laminated lithium ion secondary battery using 0.5 O 2 was subjected to a constant current constant voltage test of 1 C at 60 ° C., and a depth of discharge (DOD) of 0% to 100% and a DOD of 5% to 100%. Was evaluated for cycle characteristics. The cycle characteristics were based on the capacity at the tenth cycle. Table 2 shows the results.
【００８２】表２より、本実施例の正極活物質にＬｉＮ
ｉ０．５Ｍｎ０．５Ｏ２を用いた積層ラミネート型リチ
ウムイオン二次電池二次電池は、ＤＯＤ０％〜ＤＯＤ１
００％の使用においても、６００サイクル目の容量変化
率が低かった。さらに、上限ＤＯＤが５％以下で使用を
すれば、信頼性がより一層向上することが確かめられ
た。As shown in Table 2, LiN was used as the positive electrode active material in this example.
The laminated battery of lithium ion secondary battery using i 0.5 Mn 0.5 O 2 is DOD0% to DOD1.
Even at the use of 00%, the capacity change rate at the 600th cycle was low. Further, it was confirmed that the reliability was further improved if the upper limit DOD was used at 5% or less.
【００８３】[0083]
【表１】 [Table 1]
【００８４】[0084]
【表２】 [Table 2]
【００８５】〔実施例２〕実施例1と同様の方法によ
り、正極活物質にＬｉＮｉ０．５Ｍｎ０．５Ｏ２を用い
て０．９Ａｈおよび１．０Ａｈの積層ラミネート型リチ
ウムイオン二次電池を作製し、得られたセルを４本並列
に接続した組電池を作製した。さらに、比較としてＬｉ
ＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４を用いた組電
池を作製した。これらの組電池に対し、釘刺し試験を行
った。釘刺しスピードは５ｍｍ/ｍｉｎとした。試験結
果を表３に示す。Example 2 In the same manner as in Example 1, a laminated laminated lithium ion secondary battery of 0.9 Ah and 1.0 Ah using LiNi 0.5 Mn 0.5 O 2 as the positive electrode active material. And an assembled battery in which four cells were connected in parallel was produced. Further, for comparison, Li
An assembled battery using CoO 2 , LiNiO 2, and LiMn 2 O 4 was produced. A nail penetration test was performed on these assembled batteries. The nail penetration speed was 5 mm / min. Table 3 shows the test results.
【００８６】表３より、正極活物質にＬｉＮｉ０．５Ｍ
ｎ０．５Ｏ２を用いた場合、組電池の容量が３．６Ａ
ｈ、４Ａｈいずれの場合も発煙・発火が認められず、組
電池とした際の安全が確保されていることが確かめられ
た。これに対し、正極活物質にＬｉＣｏＯ２またはＬｉ
ＮｉＯ２を用いた場合、３．６Ａｈでは発煙、発火は生
じなかったものの、４Ａｈではあっても発煙・発火が認
められ、安全性確保が困難であった。またＬｉＭｎ２Ｏ
４を正極活物質とした場合は、発煙・発火は認められな
かったものの、同一容量での組電池の重量が大きかっ
た。As shown in Table 3, LiNi 0.5 M was used for the positive electrode active material.
When n 0.5 O 2 is used, the capacity of the assembled battery is 3.6 A
h and 4Ah, no smoke or ignition was observed, and it was confirmed that the safety of the assembled battery was ensured. On the other hand, LiCoO 2 or LiCoO 2
When NiO 2 was used, smoke and ignition did not occur at 3.6 Ah, but smoke and ignition were observed even at 4 Ah, making it difficult to ensure safety. LiMn 2 O
When No. 4 was used as the positive electrode active material, smoke and ignition were not recognized, but the weight of the assembled battery with the same capacity was large.
【００８７】したがって、本実施例より、正極活物質に
ＬｉＮｉ０．５Ｍｎ０．５Ｏ２を用い、特に１．０Ａｈ
以上の積層ラミネート型リチウムイオン二次電池組を組
電池化することにより、ＬｉＣｏＯ２やＬｉＮｉＯ２を
用いた場合よりも、より安全に用いることができ、また
ＬｉＭｎ２Ｏ４を用いた場合よりも、より高エネルギー
密度の電池が得られることが確かめられた。Therefore, according to this example, LiNi 0.5 Mn 0.5 O 2 was used as the positive electrode active material, and in particular, 1.0 Ah
By making the above-described laminated laminate type lithium ion secondary battery set into an assembled battery, it can be used more safely than when LiCoO 2 or LiNiO 2 is used, and also when LiMn 2 O 4 is used. It was confirmed that a battery with higher energy density could be obtained.
【００８８】[0088]
【表３】 [Table 3]
【００８９】〔実施例３〕本実施例では、正極活物質に
ＬｉＮｉ０．５Ｍｎ０．５Ｏ２およびＬｉ１＋ｘＭｎ２
Ｏ４（０．０２≦ｘ≦０．５）を用いた積層ラミネート
型リチウムイオン二次電池を作製し、正極活物質にＬｉ
Ｎｉ０．５Ｍｎ０．５Ｏ２のみを用いた場合との電池特
性の比較を行った。Example 3 In this example, LiNi 0.5 Mn 0.5 O 2 and Li 1 + x Mn 2 were used as the positive electrode active material.
A laminated laminate type lithium ion secondary battery using O 4 (0.02 ≦ x ≦ 0.5) was manufactured, and Li was used as a positive electrode active material.
The battery characteristics were compared with those using only Ni 0.5 Mn 0.5 O 2 .
【００９０】ＬｉＮｉ０．５Ｍｎ０．５Ｏ２は、実施例
1と同様の方法により調製した。ＬｉＮｉ０．５Ｍｎ
０．５Ｏ２、Ｌｉ１＋ｘＭｎ２Ｏ４、および導電性付与
剤を乾式混合した。これを、バインダーであるＰＶｄＦ
を溶解させたＮ―メチル―２−ピロリドン（ＮＭＰ）中
に超音波分散機を用いて均一に分散させ、スラリーを作
製した。導電性付与剤としては平均粒径４μｍのグラフ
ァイト（ロンザジャパン社製）を用いた。正極中の固形
分は、重量比でＬｉＮｉ０．５Ｍｎ０．５Ｏ２：Ｌｉ
１＋ｘＭｎ２Ｏ４：導電性付与剤：ＰＶｄＦ＝（１００
−α）×８０：α×８０：１０:１０となるよう混合し
た。得られたスラリーを、厚さ２５μｍのアルミ金属箔
上に塗布し、１００℃〜１４０℃にてＮＭＰを蒸発させ
た後、１００ｍｍ×１５０ｍｍに切断し、正極シートと
した。LiNi 0.5 Mn 0.5 O 2 was prepared according to the example
Prepared by a method similar to 1. LiNi 0.5 Mn
0.5 O 2 , Li 1 + x Mn 2 O 4 , and a conductivity-imparting agent were dry-mixed. This is used as the binder PVdF
Was dispersed uniformly in N-methyl-2-pyrrolidone (NMP) using an ultrasonic disperser to prepare a slurry. Graphite (manufactured by Lonza Japan) having an average particle size of 4 μm was used as the conductivity-imparting agent. The solid content in the positive electrode was LiNi 0.5 Mn 0.5 O 2 : Li in weight ratio.
1 + x Mn 2 O 4 : conductivity imparting agent: PVdF = (100
-Α) × 80: α × 80: 10: 10. The obtained slurry was applied on a 25-μm-thick aluminum metal foil, NMP was evaporated at 100 ° C. to 140 ° C., and then cut into 100 mm × 150 mm to obtain a positive electrode sheet.
【００９１】負極の作製は実施例１と同様に行い、負極
シートを得た。The production of the negative electrode was performed in the same manner as in Example 1, and a negative electrode sheet was obtained.
【００９２】以上のようにして得られた正極シートおよ
び負極シートを、厚さ２５μｍ、大きさ１２０ｍｍ×１
６０ｍｍのポリエチレン多孔膜セパレータを介して積層
し、その積層数を変更させることにより、実施例１と同
様にして２０Ａｈの積層ラミネート型リチウムイオン二
次電池を得た。ここで、電解液は実施例１と同様、１Ｍ
のＬｉＰＦ６を支持塩とし、プロピレンカーボネート
（ＰＣ）とエチレンカーボネート（ＥＣ）とジエチルカ
ーボネート（ＤＥＣ）の混合溶液を溶媒とした。混合比
は体積比でＰＣ：ＥＣ：ＤＥＣ＝２０:３０:５０とし
た。The positive electrode sheet and the negative electrode sheet obtained as described above were put in a thickness of 25 μm and a size of 120 mm × 1.
By laminating through a 60 mm polyethylene porous membrane separator, and changing the number of laminations, a laminated laminated lithium ion secondary battery of 20 Ah was obtained in the same manner as in Example 1. Here, the electrolytic solution was 1M as in Example 1.
The LiPF 6 as a supporting salt was propylene carbonate (PC) and ethylene carbonate (EC) mixed solution of diethyl carbonate (DEC) as a solvent. The mixing ratio was PC: EC: DEC = 20: 30: 50 by volume.
【００９３】また、正極活物質にＬｉＮｉ０．５Ｍｎ
０．５Ｏ２のみを用いた２０Ａｈの積層ラミネート型リ
チウムイオン二次電池を上と同様にして作製した。Also, LiNi 0.5 Mn was used as the positive electrode active material.
A 20 Ah laminated laminate type lithium ion secondary battery using only 0.5 O 2 was produced in the same manner as above.
【００９４】これらの二次電池セルを、１６０℃のホッ
トボックス試験に供した。電池温度を３時間で１６０℃
まで昇温した後１６０℃で３時間保持し、その後降温し
た。結果を表４に示す。[0094] These secondary battery cells were subjected to a hot box test at 160 ° C. Battery temperature 160 ℃ in 3 hours
Then, the temperature was maintained at 160 ° C. for 3 hours, and then the temperature was lowered. Table 4 shows the results.
【００９５】表４より、正極活物質にＬｉ１＋ｘＭｎ２
Ｏ４を５％以上混合することにより、２０Ａｈの電池容
量であっても発煙・発火が認められず、より安全に用い
ることができることが確かめられた。また、Ｌｉ１＋ｘ
Ｍｎ２Ｏ４の混合量を８０％以下とすることにより、よ
り高いエネルギー密度の二次電池が得られることが確か
められた。As shown in Table 4, Li 1 + x Mn 2 was used as the positive electrode active material.
By mixing O 4 at 5% or more, no smoke or ignition was recognized even with a battery capacity of 20 Ah, and it was confirmed that the battery could be used more safely. Also, Li 1 + x
It has been confirmed that a secondary battery with a higher energy density can be obtained by setting the mixing amount of Mn 2 O 4 to 80% or less.
【００９６】[0096]
【表４】 [Table 4]
【００９７】〔実施例４〕本実施例においては、正極活
物質にＬｉＮｉ０．５Ｍｎ０．５Ｏ２を用いた。正極お
よび負極に、正極、負極を長方形の板状の電極とし、正
極、負極それぞれについて、電極端子取付部として活物
質の未塗布部を設け、電極端子取付部となる辺の長さ
と、これに垂直な辺の長さとの比を変化させた際の電池
特性の評価を行った。Example 4 In this example, LiNi 0.5 Mn 0.5 O 2 was used as the positive electrode active material. For the positive electrode and the negative electrode, the positive electrode and the negative electrode are rectangular plate-shaped electrodes, and for each of the positive electrode and the negative electrode, an uncoated portion of the active material is provided as an electrode terminal mounting portion. The battery characteristics when the ratio to the length of the vertical side was changed were evaluated.
【００９８】実施例１と同様に、正極を作製した。Ｌｉ
Ｎｉ０．５Ｍｎ０．５Ｏ２および導電性付与剤を乾式混
合し、バインダーであるポリビニリデンフルオライド
（ＰＶｄＦ）を溶解させたＮ−メチル―２−ピロリドン
（ＮＭＰ）中に超音波装置を用いて均一に分散させ、ス
ラリーを作製した。導電性付与剤としては平均粒径４μ
ｍのグラファイト（ロンザジャパン社製）を用い、正極
中の固形分は重量比でＬｉＮｉ０．５Ｍｎ０．５Ｏ２：
導電性付与剤：ＰＶｄＦ＝８０:１０:１０となるよう混
合した。得られたスラリーを、厚さ２５μｍのアルミ金
属箔上に塗布し、１００℃〜１４０℃にてＮＭＰを蒸発
させた。A positive electrode was manufactured in the same manner as in Example 1. Li
Ni 0.5 Mn 0.5 O 2 and a conductivity-imparting agent are dry-mixed, and an ultrasonic device is placed in N-methyl-2-pyrrolidone (NMP) in which polyvinylidene fluoride (PVdF) as a binder is dissolved. To obtain a slurry. Average particle size 4μ as conductivity imparting agent
m of graphite (manufactured by Lonza Japan Co., Ltd.), and the solid content in the positive electrode is LiNi 0.5 Mn 0.5 O 2 :
The conductivity-imparting agent was mixed so that PVdF = 80: 10: 10. The obtained slurry was applied on a 25-μm-thick aluminum metal foil, and NMP was evaporated at 100 ° C to 140 ° C.
【００９９】得られた正極は、（辺Ａ（５ｍｍ））×
（辺Ｂ（１５０ｍｍ））に切断し、正極シートとした。
ここで、辺Ａには電極端子取付部として、正極活物質の
未塗布部を設けた（図６）。The obtained positive electrode was (side A (5 mm)) ×
(Side B (150 mm)) to obtain a positive electrode sheet.
Here, on the side A, an uncoated portion of the positive electrode active material was provided as an electrode terminal attachment portion (FIG. 6).
【０１００】負極の作製も、実施例１と同様以下のよう
に行った。重量比でハードカーボン：ＰＶｄＦ＝９０:
１０となるように混合し、ＮＭＰに分散させた。これを
厚さ２０μｍの銅箔上に塗布し、１００℃〜１４０℃に
てＮＭＰを蒸発させた。The production of the negative electrode was performed in the same manner as in Example 1 as follows. Hard carbon: PVdF = 90 by weight ratio:
The mixture was mixed so as to be 10 and dispersed in NMP. This was applied on a copper foil having a thickness of 20 μm, and NMP was evaporated at 100 ° C. to 140 ° C.
【０１０１】得られた負極は、（辺Ａ（６ｍｍ））×
（辺Ｂ（１５２ｍｍ））に切断し、負極シートとした。
正極同様、辺Ａには電極端子取付部として、負正極活物
質の未塗布部を設けた。The obtained negative electrode was (side A (6 mm)) ×
(Side B (152 mm)) to obtain a negative electrode sheet.
Similarly to the positive electrode, an uncoated portion of the negative positive electrode active material was provided on the side A as an electrode terminal mounting portion.
【０１０２】以上のようにして得られた正極シートおよ
び負極シートを、厚さ２５μｍ、大きさ８ｍｍ×１５５
ｍｍのポリエチレン多孔膜セパレータを介して積層し、
その積層数を変更させることにより、実施例１と同様に
して２．０Ａｈの積層ラミネート型リチウムイオン二次
電池を作製した。ここで、電解液は実施例１同様、１Ｍ
のＬｉＰＦ６を支持塩とし、プロピレンカーボネート
（ＰＣ）とエチレンカーボネート（ＥＣ）とジエチルカ
ーボネート（ＤＥＣ）の混合溶液を溶媒とした。混合比
は体積比でＰＣ：ＥＣ：ＤＥＣ＝２０:３０:５０とし
た。The positive electrode sheet and the negative electrode sheet obtained as described above were put in a thickness of 25 μm and a size of 8 mm × 155.
mm polyethylene porous membrane separator laminated,
By changing the number of layers, a 2.0 Ah laminated laminate type lithium ion secondary battery was produced in the same manner as in Example 1. Here, the electrolytic solution was 1M as in Example 1.
The LiPF 6 as a supporting salt was propylene carbonate (PC) and ethylene carbonate (EC) mixed solution of diethyl carbonate (DEC) as a solvent. The mixing ratio was PC: EC: DEC = 20: 30: 50 by volume.
【０１０３】また、同様にして、正極活物質にＬｉＮｉ
０．５Ｍｎ０．５Ｏ２を用い、電極シートの大きさが異
なる２．０Ａｈの積層ラミネート型リチウムイオン二次
電池を作製した。ここで、正極および負極の電極シート
はそれぞれ、（辺Ａ（５ｍｍ））×（辺Ｂ（１６０ｍ
ｍ））および（辺Ａ（６ｍｍ））×（辺Ｂ（１６４ｍ
ｍ））に切断した。正極、負極とも辺Ａには電極端子取
付部として、活物質の未塗布部を設けた。また、ポリエ
チレン多孔膜セパレータの大きさは、８ｍｍ×１６６ｍ
ｍとした。Similarly, LiNi was used as the positive electrode active material.
Using 0.5 Mn 0.5 O 2 , a 2.0 Ah laminated laminate type lithium ion secondary battery having different electrode sheet sizes was produced. Here, each of the positive electrode sheet and the negative electrode sheet is (side A (5 mm)) × (side B (160 m
m)) and (side A (6 mm)) × (side B (164 m
m)). On both sides of the positive electrode and the negative electrode, an uncoated portion of the active material was provided as an electrode terminal mounting portion. The size of the polyethylene porous membrane separator is 8 mm x 166 m.
m.
【０１０４】さらに、同様にして、正極活物質にＬｉＣ
ｏＯ２を用いた２．０Ａｈの積層ラミネート型リチウム
イオン二次電池を作製した。ここで、正極および負極の
電極シートはそれぞれ、（辺Ａ（５ｍｍ））×（辺Ｂ
（１５０ｍｍ））および（辺Ａ（６ｍｍ））×（辺Ｂ
（１５２ｍｍ））に切断した。正極、負極とも辺Ａには
電極端子取付部として、活物質の未塗布部を設けた。ま
た、ポリエチレン多孔膜セパレータの大きさは、８ｍｍ
×１５５ｍｍとした。Further, similarly, LiC was used as the positive electrode active material.
A 2.0 Ah laminated laminated lithium ion secondary battery using oO 2 was produced. Here, the positive electrode sheet and the negative electrode sheet are respectively (side A (5 mm)) × (side B
(150 mm)) and (Side A (6 mm)) × (Side B
(152 mm)). On both sides of the positive electrode and the negative electrode, an uncoated portion of the active material was provided as an electrode terminal mounting portion. The size of the polyethylene porous membrane separator is 8 mm.
× 155 mm.
【０１０５】これらの二次電池の過充電試験を行った。
セル過充電条件は１２Ｖ―３Ｃとした。結果を表５に示
す。An overcharge test was performed on these secondary batteries.
The cell overcharge condition was 12V-3C. Table 5 shows the results.
【０１０６】表５より、正極活物質にＬｉＮｉ０．５Ｍ
ｎ０．５Ｏ２を用い、電極端子取付部となる辺Ａと、こ
れに垂直な辺Ｂとの長さとした際に
０＜Ｂ／Ａ≦３０ （ＩＩ）
とした場合は、過充電時の発煙・発火が生じなかった。From Table 5, it was found that the positive electrode active material was LiNi 0.5 M
When 0 <B / A ≦ 30 (II) when n 0.5 O 2 is used and the length of the side A serving as the electrode terminal mounting portion and the side B perpendicular to the side A are overcharged, No smoke or ignition occurred.
【０１０７】したがって、本実施例において、正極活物
質にＬｉＮｉ０．５Ｍｎ０．５Ｏ２を用い、式（ＩＩ）
で示される電極形状を採用することにより、より安全に
用いることができる二次電池が提供されることが確かめ
られた。Therefore, in this example, LiNi 0.5 Mn 0.5 O 2 was used as the positive electrode active material and the formula (II)
It was confirmed that a secondary battery that can be used more safely was provided by adopting the electrode shape represented by.
【０１０８】以上の実施例より、本発明に係る正極活物
質にＬｉＮｉ０．５Ｍｎ０．５Ｏ２を用いた積層ラミネ
ート型リチウムイオン二次電池およびそれを用いた組電
池は、安全性が高く、かつエネルギー密度が高いことが
明らかになった。From the above examples, the laminated laminated lithium-ion secondary battery using LiNi 0.5 Mn 0.5 O 2 as the positive electrode active material according to the present invention and the assembled battery using the same have high safety. It was clear that the energy density was high.
【０１０９】[0109]
【表５】 [Table 5]
【０１１０】[0110]
【発明の効果】本発明によれば、サイクル数に伴う容量
低下や、高温での安全性の低下が抑制され、大容量かつ
高安全性を実現する二次電池およびそれを用いた組電
池、および二次電池の使用方法が実現される。According to the present invention, a secondary battery which achieves a large capacity and high safety by suppressing a decrease in capacity due to the number of cycles and a decrease in safety at a high temperature, and an assembled battery using the same, And the method of using the secondary battery is realized.
【図１】本発明の積層ラミネート型リチウムイオン二次
電池の斜視図である。FIG. 1 is a perspective view of a laminated lithium ion secondary battery of the present invention.
【図２】本発明の積層ラミネート型リチウムイオン二次
電池の電池要素の分解斜視図である。FIG. 2 is an exploded perspective view of a battery element of the laminate type lithium ion secondary battery of the present invention.
【図３】本発明のフィルム外装電池の電池要素の断面図
である。FIG. 3 is a sectional view of a battery element of the film-covered battery of the present invention.
【図４】本発明の二次電池の正極または負極と電極端子
との寸法比を説明するための上面図である。FIG. 4 is a top view for explaining a dimensional ratio between a positive electrode or a negative electrode and an electrode terminal of the secondary battery of the present invention.
【図５】本発明に係る二次電池の電極の積層構造を模式
的に示す断面図である。FIG. 5 is a cross-sectional view schematically showing a laminated structure of electrodes of a secondary battery according to the present invention.
【図６】本発明に係る二次電池の正極を示す斜視図であ
る。FIG. 6 is a perspective view showing a positive electrode of a secondary battery according to the present invention.
１ 負極 ２ 正極 ３ セパレータ ４ 負極端子 ５ 正極端子 ６ フィルム外装体 ７ 負極集電部 ８ 正極集電部 １３ 活物質領域 １４ 電極端子 １５ 電極端子取付部 １００ 正極板 １０２ 正極活物質層 １０４ セパレータ １０６ 負極活物質層 １０８ 負極板 １１０ 正極 １１２ 負極 １１４ 正極−セパレータ−負極積層体 １１６ 正極活物質未塗布部 1 negative electrode 2 Positive electrode 3 separator 4 Negative electrode terminal 5 Positive terminal 6 Film exterior 7 Negative electrode current collector 8 Positive current collector 13 Active material area 14 electrode terminals 15 Electrode terminal mounting part 100 positive plate 102 Positive electrode active material layer 104 separator 106 Negative electrode active material layer 108 Negative electrode plate 110 positive electrode 112 negative electrode 114 Positive electrode-separator-negative electrode laminate 116 Positive electrode active material uncoated area
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ ５Ｈ０５０ 10/44 10/44 Ｚ Ｆターム(参考） 5H011 AA13 BB04 CC02 CC06 CC10 EE04 5H022 AA09 AA19 CC02 CC16 5H029 AJ05 AJ12 AK03 AL02 AL06 AL07 AL11 AL12 AM03 AM04 AM05 AM07 BJ04 BJ12 DJ02 DJ05 DJ17 EJ01 EJ12 HJ02 HJ04 HJ05 HJ19 5H030 AA06 AA10 AS03 AS08 BB21 FF41 5H040 AS01 AS06 AS07 AT04 AY01 DD03 DD05 5H050 AA07 AA15 BA16 BA17 CA08 CA09 CB02 CB08 CB11 CB12 FA02 FA19 HA01 HA02 HA05 HA19 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01M 10/40 H01M 10/40 Z 5H050 10/44 10/44 Z F term (Reference) 5H011 AA13 BB04 CC02 CC06 CC10 EE04 5H022 AA09 AA19 CC02 CC16 5H029 AJ05 AJ12 AK03 AL02 AL06 AL07 AL11 AL12 AM03 AM04 AM05 AM07 BJ04 BJ12 DJ02 DJ05 DJ17 EJ01 EJ12 HJ02 HJ04 HJ05 HJ19 5H030 AA06 AA10 AS03 AS01 AS05 AS04 AS05 BB21 DD01 BA17 CA08 CA09 CB02 CB08 CB11 CB12 FA02 FA19 HA01 HA02 HA05 HA19
Claims (12)
電解質を備える二次電池であって、正極活物質として下
記式（Ｉ）で表される化合物を含むことを特徴とする特
徴とする二次電池。 ＬｉｘＮｉｙＭｎ１−ｙＯ２ （Ｉ） （ただし、ｘ、ｙは、０．９≦ｘ≦１．１、０．４５≦
ｙ≦０．５５を満たす。）1. A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte sandwiched therebetween, comprising a compound represented by the following formula (I) as a positive electrode active material. Next battery. Li x Ni y Mn 1-y O 2 (I) (where x and y are 0.9 ≦ x ≦ 1.1, 0.45 ≦
Satisfies y ≦ 0.55. )
記式（Ｉ）において、０．５≦ｙ≦０．５５であること
を特徴とする二次電池。2. The secondary battery according to claim 1, wherein in the formula (I), 0.5 ≦ y ≦ 0.55.
いて、前記正極活物質が粒子の形態であって、そのメジ
アン径（Ｄ５０粒径）が１μｍ以上１００μｍ以下であ
ることを特徴とする二次電池。3. A secondary battery according to claim 1 or 2, wherein the positive electrode active material is in the form of particles, and characterized in that the median diameter (D 50 particle size) is 1μm or more 100μm or less Rechargeable battery.
池において、電池容量が１．０Ａｈ以上１０Ａｈ以下で
あることを特徴とする二次電池。4. The secondary battery according to claim 1, wherein the battery capacity is 1.0 Ah or more and 10 Ah or less.
池において、正極活物質として前記式（Ｉ）で示される
化合物に加え、さらにスピネル型リチウムマンガン酸化
物を含み、前記正極活物質全体に対する前記スピネル型
リチウムマンガン酸化物の含有量が５重量％以上である
ことを特徴とする二次電池。5. The secondary battery according to claim 1, wherein the cathode active material further comprises a spinel-type lithium manganese oxide in addition to the compound represented by the formula (I) as the cathode active material. A secondary battery, wherein the content of the spinel-type lithium manganese oxide is 5% by weight or more based on the whole.
記正極活物質全体に対する前記スピネル型リチウムマン
ガン酸化物の含有率が５重量％以上９５重量％以下であ
ることを特徴とする二次電池。6. The secondary battery according to claim 5, wherein the content of the spinel-type lithium manganese oxide is 5% by weight or more and 95% by weight or less based on the whole positive electrode active material. battery.
いて、前記スピネル型リチウムマンガン酸化物がＬｉ
１＋ｘＭｎ２Ｏ４（０．０２≦ｘ≦０．５）であること
を特徴とする二次電池。7. The secondary battery according to claim 5, wherein the spinel-type lithium manganese oxide is Li
A secondary battery, wherein 1 + x Mn 2 O 4 (0.02 ≦ x ≦ 0.5).
池において、電池容量が１．０Ａｈ以上２０Ａｈ以下で
あることを特徴とする二次電池。8. The secondary battery according to claim 5, wherein a battery capacity is 1.0 Ah or more and 20 Ah or less.
池において、前記正極および前記負極が矩形であって、
前記正極および前記負極のそれぞれについて、一辺に電
極端子取付部が設けられ、下記式（ＩＩ）を満たすこと
を特徴とする二次電池。 ０＜Ｂ／Ａ≦３０ （ＩＩ） （ただし、Ａは矩形である電極の一辺で、電極端子取付
部となる辺の長さ、Ｂは矩形である電極の一辺で、Ａに
垂直方向における活物質領域の最長幅を表す。）9. The secondary battery according to claim 1, wherein the positive electrode and the negative electrode are rectangular,
A secondary battery, wherein each of the positive electrode and the negative electrode is provided with an electrode terminal attachment portion on one side, and satisfies the following formula (II). 0 <B / A ≦ 30 (II) (where A is one side of the rectangular electrode, the length of the side to be the electrode terminal attachment portion, B is one side of the rectangular electrode, and A Indicates the longest width of the material area.)
電池において、ラミネート外装体を有することを特徴と
する二次電池。10. The secondary battery according to claim 1, further comprising a laminate exterior body.
次電池が、前記正極および前記負極それぞれに設けられ
た電極端子取付部を介して複数個組み合わせてなる組電
池。11. An assembled battery comprising a plurality of the secondary batteries according to claim 1 combined with each other via an electrode terminal mounting portion provided on each of the positive electrode and the negative electrode.
次電池の使用方法であって、放電深度５％以上〜放電深
度１００％以下の範囲で使用することを特徴とする二次
電池の使用方法。12. The method of using a secondary battery according to claim 1, wherein the secondary battery is used in a range from a depth of discharge of 5% or more to a depth of discharge of 100% or less. how to use.
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| JP2002150701A Pending JP2003346798A (en) | 2002-05-24 | 2002-05-24 | Secondary battery and battery pack using the same and method of use of secondary battery |
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