JP5150080B2 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
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- JP5150080B2 JP5150080B2 JP2006265615A JP2006265615A JP5150080B2 JP 5150080 B2 JP5150080 B2 JP 5150080B2 JP 2006265615 A JP2006265615 A JP 2006265615A JP 2006265615 A JP2006265615 A JP 2006265615A JP 5150080 B2 JP5150080 B2 JP 5150080B2
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- 229910052744 lithium Inorganic materials 0.000 title claims description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000005486 organic electrolyte Substances 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 208000028659 discharge Diseases 0.000 description 90
- 210000004027 cell Anatomy 0.000 description 42
- 238000007600 charging Methods 0.000 description 27
- 238000007599 discharging Methods 0.000 description 27
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 23
- 239000012046 mixed solvent Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 230000007423 decrease Effects 0.000 description 15
- 239000007770 graphite material Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 13
- -1 fluoroethyl methyl carbonate Chemical compound 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003780 insertion Methods 0.000 description 7
- 230000037431 insertion Effects 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
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- 239000000758 substrate Substances 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
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- 150000001768 cations Chemical class 0.000 description 3
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- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- QOARFWDBTJVWJG-UHFFFAOYSA-N 2,2-difluoroethyl methyl carbonate Chemical compound COC(=O)OCC(F)F QOARFWDBTJVWJG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 2
- 239000011331 needle coke Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000006253 pitch coke Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013841 LiP0.4B0.6O2.9 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 101150004907 litaf gene Proteins 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
正極:(放電)Cx + A− = CxA + e−(充電) 式1
負極:(放電)Cy + Li+ + e− = LiCy(充電) 式2
従って、この種の二次電池における正極は、充放電により電解質アニオンの黒鉛層問化合物が可逆的に形成される反応を、負極は充放電により電解質カチオンの炭素層問化合物が可逆的に形成される反応を、各々利用したものであると表現することができる。
式中、X1、X2及びX3は、それぞれ独立に水素またはフッ素原子から選ばれ、かつ、少なくとも一つはフッ素原子である。
本発明に係るリチウム二次電池は、電解質アニオンの吸蔵・放出を行うことにより充放電を行う黒鉛粉末を正極材料として含有する正極と、リチウム金属又はリチウムイオンの吸蔵・放出を行うことにより充放電を行う負極材料と、リチウム塩を含有する有機溶媒からなる有機電解液を備え、前記有機電解液は、一般式(1)で示される化合物を含むことを特徴とする。
式中、X1、X2及びX3は、それぞれ独立に水素またはフッ素原子から選ばれ、かつ、少なくとも一つはフッ素原子である。
(式中、X1、X2及びX3は、それぞれ独立に水素またはフッ素原子から選ばれ、かつ、少なくとも一つはフッ素原子である。)即ち、上記化合物は、FEMC,DFEMCTFEMC、またはそれらの複数を含有する。他に含有されてもよい有機溶媒は、プロピレンカーボネート(PC)、エチレンカーボネート(EC)、1,2−ブチレンカーボネート(BC)、γ−ブチロラクトン(GBL)、ビニレンカーボネート(VC)、アセトニトリル(AN)、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(EMC)及びこれらの誘導体、若しくはそれらの混合溶媒等である。
黒鉛粉末を正極に使用したリチウム二次電池の低温特性問題について、18650型セル(直径φ18mm,高さ65mm)での実施例に基づき詳述する。
次に、前述と同仕様の18650型セルA〜Eを試作し、25℃及び0℃で充放電を行った。充放電の方法は、温度が一定に保たれた恒温槽内に電池を設置し、電流を1A、電圧を4.2V、時間を30分としたとした定電流/定電圧充電を行い、2時間休止させた後、セル電圧が2.0Vに達するまで0.5A又は0.1Aの定電流で放電させ、その放電容量を測定した。放電と充電の温度が異なる場合は、充電終了後、直ちに恒温槽で放電温度の設定を行い、2時間の休止の間に電池温度を放電温度に馴染ませた。
低温において放電容量が減少する理由について考察するために、3極式の18650型テストセルを作製し、正・負極挙動を観察した。図5に3極式の18650型テストセルの断面図と正・負極電位の測定法(模式図)を示す。このセルは、帯状に成形された正極部48と、同じく帯状に成形された負極部49とが、セパレータ50を介して渦巻状に捲回され、その捲回電極体がステンレス製容器41に収納された構造になっている。この容器41は、円柱状のステンレス製ブロックに直径φ18mm、深さ65mmの円柱状の穴が切削されたもので、この穴に電極捲回体が収納される。容器の開口部にはステンレス製の蓋42が、2枚のエチレンプロピレンゴム(EPDM)製パッキング51を介し、ネジ43で容器41と固定され、この2枚のゴムパッキング51の間から、アルミニウム製の正極リード板44、及びニッケル製の負極リード板45がセルの外部に取り出されている。参照電極は、帯状ニッケル基板52の両側に帯状リチウム金属箔53が貼り付けられたものを使用し、捲回により生じた円柱状の空間部に挿入され、ニッケル基板部分が2枚のゴムパッキング51の間からセルの外部に取り出されている。
(1)テストセルの作製
黒鉛粉末(Timcal社製のSFG−44)及びCMC(カルボキシメチルセルロース)(第1工業製薬(株)セロゲン4H)の2重量%水溶液を、重量比で97:3となるように混合し、蒸留水を加えてスラリーを得た。なお前記重量比のCMC割合は固形分の割合である。得られたスラリーを、単位面積当たりの黒鉛材料の量が約12mg/cm2となるように、ドクタープレード法でアルミニウム箔(厚さ20μm)の片面に塗布し、60℃で20分間乾燥してシート状電極を作成した。その後ダイセットに当該シートを挟み込み、正極合剤の見かけ密度が約1.0g/cm3となるようにプレス機でシート全体を圧縮・成形した。得られたシート電極を打ち抜きプレスでφ9mmに打ち抜き、テストセルの作用極とした。
各テストセルに使用した電解液は、図8に示した通りである。図8中の電解液の表記方法であるが、例えば2M LiPF6/PC+DMC(75:25 by vol.)と表記された場合、PCとDMCが体積比で75:25に混合された溶媒へ、LiPF6が2mol/Lの濃度で溶解されたものを表現したものとする。なお、図8中に示した溶媒の略号と化学構造式は以下の表2の通りである。
[0℃での放電容量維持率] = B/A×100(%) 式3
図8に、使用した電解液と第10サイクル目の放電容量(25℃での放電容量)、第10サイクル目の充電終止時点に到達した作用極の電位(25℃での作用極の電位)、第11サイクル目の放電容量(0℃での放電容量)、第11サイクル目の充電終止時点に到達した作用極の電位(0℃での作用極の電位)、0℃での放電容量維持率をまとめた。
13 負極部 14 正極リード板
15 負極リード板 21 電池ケース
23 絶縁底板 25 ガスケット
26 正極端子板 27 中間感圧板
28 突部 29 基部
30 接続部 41 容器
42 蓋 43 ネジ
44 正極リード板 45 負極リード板
48 正極部 49 負極部
50 セパレータ 51 ゴムパッキング
52 ニッケル基板 53 帯状リチウム金属箔
64 作用極 66 対極
68 バネ 70 参照極
72 パラフィルム 74 セパレータ
80 ステンレス固定板(80a,80b) 82 挿間ブロック
84 ボルト 86 ナット
88 固定用ボルト 90 アルミニウム板
92 ポリプロピレン板 94 ステンレスディスク
Claims (1)
- 電解質アニオンの吸蔵・放出を行うことにより充放電を行う黒鉛粉末を正極材料として含有する正極と、
リチウム金属又はリチウムイオンの吸蔵・放出を行うことにより充放電を行う負極材料と、
リチウム塩を含有する有機溶媒からなる有機電解液と
を備えるリチウム二次電池であって、
前記有機溶媒は、下記一般式(1)で表される化合物を含むことを特徴とする、
リチウム二次電池。
(式中、X1、X2及びX3は、それぞれ独立に水素またはフッ素原子から選ばれ、かつ、少なくとも一つはフッ素原子である。)
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