JP2002100410A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2002100410A JP2002100410A JP2000339498A JP2000339498A JP2002100410A JP 2002100410 A JP2002100410 A JP 2002100410A JP 2000339498 A JP2000339498 A JP 2000339498A JP 2000339498 A JP2000339498 A JP 2000339498A JP 2002100410 A JP2002100410 A JP 2002100410A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- aqueous electrolyte
- negative electrode
- electrolyte secondary
- positive 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 74
- 239000007773 negative electrode material Substances 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims description 41
- 229910002804 graphite Inorganic materials 0.000 claims description 41
- 239000000835 fiber Substances 0.000 claims description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011301 petroleum pitch Substances 0.000 claims description 5
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 229930188620 butyrolactone Natural products 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000004321 preservation Methods 0.000 abstract 1
- 239000006255 coating slurry Substances 0.000 description 45
- 239000000203 mixture Substances 0.000 description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 34
- 229910001416 lithium ion Inorganic materials 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 22
- 239000011889 copper foil Substances 0.000 description 21
- 238000003825 pressing Methods 0.000 description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 239000002174 Styrene-butadiene Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 229920000126 latex Polymers 0.000 description 14
- 239000004816 latex Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- -1 LiCoO2 Chemical class 0.000 description 10
- 230000002950 deficient Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 150000001786 chalcogen compounds Chemical class 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011302 mesophase pitch Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101150000715 DA18 gene Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910014135 LiMn2 O4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水系電解液二次
電池に関し、特に負極を改良した非水系電解液二次電池
に係わる。The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly, to a non-aqueous electrolyte secondary battery having an improved negative electrode.
【０００２】[0002]
【従来の技術】近年、ＶＴＲ、携帯電話、パソコンなど
の各種電子機器、コードレスの携帯型電子機器の小型、
軽量化に伴ない、それら機器用電源の高エネルギー密度
の要求が高まり、負極活物質に金属リチウムを使用した
リチウム二次電池に代表される非水系電解液二次電池が
提案されている。しかしながら、負極活物質として金属
リチウムを用いたリチウム二次電池は、放電時にリチウ
ムイオンとして電解液中に溶解したリチウムが電解液中
の非水溶媒と反応して一部不活性になる。このため、充
放電を繰り返すと負極の表面の凸部にリチウムが電析し
てデンドライト状（樹枝状）に析出し、このデンドライ
ト状リチウムがセパレータを貫通して正極と接すること
により内部短絡を生じる問題があった。2. Description of the Related Art In recent years, various types of electronic devices such as VTRs, mobile phones, and personal computers, and small-sized cordless portable electronic devices have been developed.
Along with the weight reduction, the demand for a high energy density of the power supply for such devices has been increased, and non-aqueous electrolyte secondary batteries represented by lithium secondary batteries using metallic lithium as a negative electrode active material have been proposed. However, in a lithium secondary battery using metallic lithium as the negative electrode active material, lithium dissolved in the electrolyte as lithium ions at the time of discharge reacts with the nonaqueous solvent in the electrolyte to become partially inactive. Therefore, when charge and discharge are repeated, lithium is electrodeposited on the convex portion on the surface of the negative electrode and precipitates in a dendrite shape (dendritic shape), and this dendrite-like lithium penetrates the separator and comes into contact with the positive electrode, thereby causing an internal short circuit. There was a problem.
【０００３】このようなことから、特開昭６３−１２１
２６０号公報には負極にカーボンを用いた軽量の二次電
池が開示されている。その後、負極活物質としてコーク
ス、グラファイト、樹脂焼成体、熱分解気相炭素等、種
々の炭素質材料を用いる、いわゆるリチウムイオン二次
電池が提案され、実用化されている。In view of the above, Japanese Patent Application Laid-Open No. 63-121
No. 260 discloses a lightweight secondary battery using carbon for the negative electrode. After that, a so-called lithium ion secondary battery using various carbonaceous materials such as coke, graphite, a resin fired body, and pyrolysis gas phase carbon as a negative electrode active material has been proposed and put into practical use.
【０００４】前記リチウムイオン二次電池としては、正
極にＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4等のカル
コゲン化合物を用い、負極に前記炭素質材料を用いたも
のが知られており、前記炭素質材料の素材によって種々
の特徴を有する。例えば、特開平５−８９８７９号公報
のように繊維径の断面方向にラメラ構造を持つ炭素繊維
を負極活物質として含むリチウムイオン二次電池は優れ
た充放電特性を有する。また、黒鉛度の高いグラファイ
トを負極活物質として含むリチウムイオン二次電池は高
い充電エネルギーを有する。As the lithium ion secondary battery, there is known a lithium ion secondary battery in which a chalcogen compound such as LiCoO2, LiNiO2, and LiMn2 O4 is used for a positive electrode and the carbonaceous material is used for a negative electrode. It has the characteristics of For example, a lithium ion secondary battery containing carbon fibers having a lamellar structure in the cross-sectional direction of the fiber diameter as a negative electrode active material as disclosed in JP-A-5-89879 has excellent charge / discharge characteristics. Further, a lithium ion secondary battery containing graphite having a high degree of graphite as a negative electrode active material has high charging energy.
【０００５】前記リチウムイオン二次電池は、金属リチ
ウムを負極として用いた二次電池に比べて安全性が高
く、各種の携帯端末の電源として広く利用されている。
特に、携帯端末用の二次電池の需要が多くなると、多岐
にわたる使用環境やトラブルを想定した特性の維持の要
求が多くなる。例えば、夏場に携帯電話機を自動車内に
放置する等、過酷な環境におかれた場合でも正常に作動
する、充放電特性を有することが要求されている。The lithium ion secondary battery has higher safety than a secondary battery using metallic lithium as a negative electrode, and is widely used as a power source for various portable terminals.
In particular, when the demand for a secondary battery for a portable terminal increases, there is an increasing demand for maintaining characteristics that assume a wide variety of use environments and troubles. For example, it is required to have a charge / discharge characteristic that can operate normally even in a harsh environment such as leaving a mobile phone in a car in summer.
【０００６】[0006]
【発明が解決しようとする課題】従来のリチウムイオン
二次電池では、通常の環境を想定して設計がなされ、特
殊仕様として寒冷地環境を採用することが行われてい
た。しかしながら、従来のリチウム二次電池では前述し
たような過酷な環境での使用に対応することが困難であ
った。The conventional lithium ion secondary battery was designed on the assumption of a normal environment, and a cold environment was adopted as a special specification. However, it has been difficult for conventional lithium secondary batteries to cope with use in the harsh environment as described above.
【０００７】本発明は、負極を改良することによって高
温の充放電サイクル寿命が向上され、さらに高温保存回
復特性を改善した非水系電解液二次電池を提供しようと
するものである。An object of the present invention is to provide a nonaqueous electrolyte secondary battery in which the high-temperature charge / discharge cycle life is improved by improving the negative electrode, and the high-temperature storage recovery characteristics are further improved.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水系電解液二次電池は、リチウムを吸
蔵・放出可能な正極、リチウムを吸蔵・放出可能な負
極、セパレータおよび非水系電解液を備え、前記正極お
よび前記負極は、集電体にそれぞれ正極材料および負極
材料を塗布した構造を有し、かつ前記負極材料は、低温
焼成炭素を含む２種以上の炭素質材を含有することを特
徴とするものである。A non-aqueous electrolyte secondary battery according to the present invention for achieving the above object has a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator and a non-aqueous electrolyte. An aqueous electrolyte is provided, the positive electrode and the negative electrode have a structure in which a positive electrode material and a negative electrode material are applied to a current collector, respectively, and the negative electrode material includes two or more types of carbonaceous materials including low-temperature fired carbon. It is characterized by containing.
【０００９】本発明に係る別の非水系電解液二次電池
は、リチウムを吸蔵・放出可能な正極、リチウムを吸蔵
・放出可能な負極、セパレータおよび非水系電解液を備
え、前記正極および前記負極は、集電体にそれぞれ正極
材料および負極材料を塗布した構造を有し、かつ前記負
極材料は、球状のメソフェーズ低温焼成炭素を含む２種
以上の炭素質材を含有することを特徴とするものであ
る。Another non-aqueous electrolyte secondary battery according to the present invention comprises a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator and a non-aqueous electrolyte, wherein the positive electrode and the negative electrode are provided. Has a structure in which a positive electrode material and a negative electrode material are applied to a current collector, respectively, and the negative electrode material contains two or more types of carbonaceous materials including spherical mesophase low-temperature calcined carbon. It is.
【００１０】本発明に係るさらに別の非水系電解液二次
電池は、リチウムを吸蔵・放出可能な正極、リチウムを
吸蔵・放出可能な負極、セパレータおよび非水系電解液
を備え、前記正極および前記負極は、集電体にそれぞれ
正極材料および負極材料を塗布した構造を有し、かつ前
記負極材料は、メソフェーズ低温焼成炭素繊維を含む２
種以上の炭素質材を含有することを特徴とするものであ
る。[0010] Still another non-aqueous electrolyte secondary battery according to the present invention comprises a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator, and a non-aqueous electrolytic solution. The negative electrode has a structure in which a positive electrode material and a negative electrode material are applied to a current collector, respectively, and the negative electrode material includes a mesophase low-temperature fired carbon fiber.
It is characterized by containing more than one kind of carbonaceous material.
【００１１】[0011]
【発明の実施の形態】以下、本発明に係わる非水系電解
液二次電池を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a non-aqueous electrolyte secondary battery according to the present invention will be described in detail.
【００１２】この非水系電解液二次電池は、リチウムを
吸蔵・放出可能な正極、リチウムを吸蔵・放出可能な負
極、セパレータおよび非水系電解液を備える。This non-aqueous electrolyte secondary battery includes a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator, and a non-aqueous electrolyte.
【００１３】次に、前記負極、正極、セパレータおよび
非水系電解液を説明する。Next, the negative electrode, the positive electrode, the separator and the non-aqueous electrolyte will be described.
【００１４】１）負極 この負極は、集電体に負極材料を塗布した構造を有す
る。1) Negative Electrode This negative electrode has a structure in which a current collector is coated with a negative electrode material.
【００１５】前記集電体としては、例えば銅板、銅メッ
シュ材等を挙げることができる。Examples of the current collector include a copper plate and a copper mesh material.
【００１６】前記負極材料は、低温焼成炭素を含む２種
以上の炭素質材と、結着剤を含有する。The negative electrode material contains two or more carbonaceous materials including low-temperature fired carbon and a binder.
【００１７】前記低温焼成炭素は、負極容量の増大に寄
与する。この低温焼成炭素としては、石炭、石油ピッチ
などから得られた揮発性有機物、溶融溶解性有機物、不
融性繊維状有機物、フェノール樹脂、フルフラール樹脂
等を原料として、１０００℃以下の温度で焼成されたカ
ーボン材料を挙げることができる。好ましい低温焼成炭
素としては、石油系ピッチから得られ、１０００℃以下
（より好ましくは９００℃以下）の低温で焼成されるメ
ソフェーズ系低温焼成炭素を用いることができる。この
メソフェーズ系低温焼成炭素としては、例えば球状のメ
ソフェーズ系低温焼成炭素またはメソフェーズ系低温焼
成炭素繊維を挙げることができる。The low-temperature fired carbon contributes to an increase in the capacity of the negative electrode. As the low-temperature fired carbon, volatile organic matter obtained from coal, petroleum pitch, etc., melt-soluble organic matter, infusible fibrous organic matter, phenol resin, furfural resin and the like are used as raw materials and fired at a temperature of 1000 ° C. or less. Carbon materials. As preferred low-temperature fired carbon, mesophase low-temperature fired carbon obtained from petroleum pitch and fired at a low temperature of 1000 ° C. or less (more preferably 900 ° C. or less) can be used. Examples of the mesophase low-temperature fired carbon include spherical mesophase low-temperature fired carbon or mesophase low-temperature fired carbon fibers.
【００１８】前記球状のメソフェーズ低温焼成炭素は、
平均粒径８〜２０μｍ、真密度１．５０〜１．７５ｇ／
ｃｃであることが好ましい。The spherical mesophase low-temperature calcined carbon is as follows:
Average particle size 8-20 μm, true density 1.50-1.75 g /
cc is preferred.
【００１９】前記メソフェーズ低温焼成炭素繊維は、比
較的低温で焼成することにより得られ、平均繊維径８〜
１８μｍ、平均繊維長８〜２０μｍ、真密度１．５０〜
１．７５ｇ／ｃｃであることが好ましい。The mesophase low-temperature fired carbon fiber is obtained by firing at a relatively low temperature, and has an average fiber diameter of 8 to
18 μm, average fiber length 8-20 μm, true density 1.50
It is preferably 1.75 g / cc.
【００２０】前記炭素質材は、例えば次のような組成を
有することが好ましい。The carbonaceous material preferably has, for example, the following composition.
【００２１】（１）繊維状炭素質材と低温焼成炭素とを
混合した炭素質材。(1) A carbonaceous material obtained by mixing a fibrous carbonaceous material and low-temperature fired carbon.
【００２２】（２）鱗片状、球状、球塊状または疑球状
の黒鉛と低温焼成炭素を混合した炭素質材。(2) A carbonaceous material obtained by mixing flaky, spherical, spherical or spheroidal graphite and low-temperature calcined carbon.
【００２３】（３）繊維状炭素材と低温焼成炭素と鱗片
状、球状、球塊状または擬球状の黒鉛とを混合した炭素
質材。(3) A carbonaceous material obtained by mixing a fibrous carbon material, low-temperature fired carbon, and flaky, spherical, spherical or pseudo-spherical graphite.
【００２４】前記繊維状炭素質材は、１０００℃以上
（好ましくは２５００℃以上）の高温で焼成された炭素
質材であり、放電サイクル特性の向上に寄与する。繊維
状炭素質材としては、例えばメソフェーズピッチ系カー
ボン繊維、ＰＡＮ系炭素繊維、またはフェノール樹脂、
ポリイミドからなる繊維状をなす炭素質材、繊維状の気
相成長炭素体等を挙げることができる。特に、メソフェ
ーズピッチ系カーボン繊維が好ましい。The fibrous carbonaceous material is a carbonaceous material fired at a high temperature of 1000 ° C. or higher (preferably 2500 ° C. or higher) and contributes to improvement of discharge cycle characteristics. Examples of the fibrous carbonaceous material include mesophase pitch-based carbon fiber, PAN-based carbon fiber, or phenol resin,
Examples thereof include a fibrous carbonaceous material made of polyimide and a fibrous vapor-grown carbon body. Particularly, mesophase pitch-based carbon fibers are preferable.
【００２５】前記繊維状炭素質材は、平均繊維径８〜１
８μｍ、平均繊維長１０〜５０μｍ、真密度２．２２ｇ
／ｃｃ以上、面間隔（ｄ002）０．３３５６〜０．３３
６８ｎｍ（より好ましくは０．３３５４〜０．３３５
９）、ｃ軸方向の結晶子の大きさ（Ｌｃ）が４０ｎｍ以
上であることが望ましい。特に、平均繊維長を１０μｍ
未満にすると、繊維としての性質が低下して、むしろ微
粉末状態になって充放電効率が低下する恐れがある。一
方、平均繊維長が５０μｍを超えると、集電体に対する
負極材料の密着性の低下、負極の欠けのような負極物性
が低下する恐れがある。また、前記繊維状炭素質材はａ
軸方向の結晶子の大きさ（Ｌａ）が４０ｎｍ以上で、Ｃ
ｕ−ＫαによるＸ線回折法での（１０１）回折ピークＰ
101と（１００）回折ピークＰ100の強度比（Ｐ101／Ｐ
100）が１．０〜２．２であることが好ましい。The fibrous carbonaceous material has an average fiber diameter of 8 to 1
8 μm, average fiber length 10-50 μm, true density 2.22 g
/ Cc or more, spacing (d 002 ) 0.3356-0.33
68 nm (more preferably 0.3354 to 0.335
9) It is desirable that the crystallite size (Lc) in the c-axis direction is 40 nm or more. In particular, the average fiber length is 10 μm
If it is less than the above, there is a possibility that the properties as a fiber are lowered, and rather, the powder becomes a fine powder state and the charge / discharge efficiency is lowered. On the other hand, if the average fiber length exceeds 50 μm, the physical properties of the negative electrode, such as a decrease in the adhesion of the negative electrode material to the current collector and the chipping of the negative electrode, may be reduced. The fibrous carbonaceous material is a
When the size (La) of the crystallite in the axial direction is 40 nm or more,
(101) diffraction peak P in X-ray diffraction method by u-Kα
The intensity ratio between the 101 and (100) diffraction peaks P 100 (P 101 / P
100 ) is preferably from 1.0 to 2.2.
【００２６】前記繊維状炭素質材は、ホウ素添加により
黒鉛結晶の面間隔（ｄ002）を拡大する、つまり黒鉛化
度を高めることを許容する。The fibrous carbonaceous material allows boron to increase the interplanar spacing (d 002 ) of graphite crystals, that is, to increase the degree of graphitization.
【００２７】前記鱗片状または球塊状の黒鉛は天然系、
人造系は問わなく、繊維状炭素質材間の結着剤を高め
て、前記負極材料の密度の向上に寄与する。この黒鉛
は、平均粒径２〜５０μｍ、比表面積２〜２０ｍ2／
ｇ、真密度２．２３〜２．２８ｇ／ｃｃ、面間隔（ｄ
002）０．３５４〜０．３３５８ｎｍであることが好ま
しい。特に、前記黒鉛の平均粒径を２μｍ未満にする
と、比表面積、吸油量が大きくなって負極材料を集電体
に塗布する際の固形分比率が低下すると共に、負極の不
可逆容量が大きくなる恐れがある。一方、前記黒鉛の平
均粒径が５０μｍを超えると、集電体に対する負極材料
の密着性が低下する等の物性劣化とプレス成形に際して
必要とする圧下線圧が増大する恐れがある。The flaky or spherical graphite is a natural type,
Regardless of the artificial system, the binder between the fibrous carbonaceous materials is increased to contribute to the improvement of the density of the negative electrode material. This graphite has an average particle size of 2 to 50 μm and a specific surface area of 2 to 20 m 2 /
g, true density 2.23 to 2.28 g / cc, face spacing (d
002 ) It is preferably from 0.354 to 0.3358 nm. In particular, when the average particle size of the graphite is less than 2 μm, the specific surface area and the oil absorption increase, the solid content ratio when the negative electrode material is applied to the current collector decreases, and the irreversible capacity of the negative electrode may increase. There is. On the other hand, when the average particle size of the graphite exceeds 50 μm, there is a possibility that physical properties such as a decrease in the adhesion of the negative electrode material to the current collector and the reduction linear pressure required in press molding may increase.
【００２８】前記（１），（２）、（３）の炭素質材に
おいて、前記低温焼成炭素は１〜１０重量％の割合で含
有されることが好ましい。前記低温焼成炭素の含有割合
を１重量％未満にすると、高温保存回復特性を改善する
ことが困難になる虞がある。一方、前記低温焼成炭素の
含有割合が１０重量％を超えると負極の不可逆容量が大
きくなって二次電池の容量が低下する虞がある。In the carbonaceous materials (1), (2) and (3), the low-temperature fired carbon is preferably contained in a ratio of 1 to 10% by weight. If the content of the low-temperature fired carbon is less than 1% by weight, it may be difficult to improve the high-temperature storage recovery characteristics. On the other hand, if the content ratio of the low-temperature fired carbon exceeds 10% by weight, the irreversible capacity of the negative electrode increases, and the capacity of the secondary battery may decrease.
【００２９】前記（３）の炭素質材において、前記鱗片
状、球塊状または擬球状の黒鉛は、１０〜６０重量％の
割合で含有されることが好ましい。この黒鉛の含有割合
を１０重量％未満にすると、この黒鉛の配合による効
果、つまり繊維状炭素質材間の結着剤を高めて、前記負
極材料の密度の向上させる効果を十分に図ることが困難
になる。一方、前記黒鉛の含有割合が６０重量％を超え
るとこの黒鉛を含む負極塗料スラリーを調製した際に固
形分比率が低下する虞がある。In the carbonaceous material of (3), it is preferable that the flaky, spherical or pseudospherical graphite is contained in a ratio of 10 to 60% by weight. When the content of the graphite is less than 10% by weight, the effect of the blending of the graphite, that is, the effect of increasing the binder between the fibrous carbonaceous materials and improving the density of the negative electrode material can be sufficiently achieved. It becomes difficult. On the other hand, if the content ratio of the graphite exceeds 60% by weight, the solid content ratio may decrease when a negative electrode coating slurry containing the graphite is prepared.
【００３０】前記結着剤は、ＰＶｄＦに代表される有機
溶媒に溶解性を持つ高分子材料、ＣＭＣ、ＳＢＲに代表
される水に分散し易い高分子材料等を用いることができ
るが、これらの高分子材料は一例に過ぎず特に制約を受
けない。ただし、今後の環境の点も考慮すると水に分散
し易い高分子材料が好ましい。As the binder, a polymer material having solubility in an organic solvent represented by PVdF, a polymer material easily dispersed in water represented by CMC and SBR, and the like can be used. The polymer material is merely an example and is not particularly limited. However, in consideration of the environment in the future, a polymer material that is easily dispersed in water is preferable.
【００３１】前記結着剤は、負極材料に対して１．０〜
６．０重量％配合されることが好ましい。結着剤利配合
量を１．０重量％未満にすると、容量向上等の電極性能
の点で好ましいものの、集電体に対する負極材料の密着
性が低下して負極の加工時（特に裁断時）において欠け
や剥離を生じ、また例えば正負極間にセパレータを介在
した帯状物を捲回して電極群を作製する際にその電極群
に微細な欠損物が混入して正負極の短絡等を招く虞があ
る。一方、前記結着剤の配合量が６．０重量％を超える
と、負極中に占める結着剤量が増大して容量の低下を招
く。The binder is used in an amount of 1.0 to 1.0 with respect to the negative electrode material.
It is preferred to be blended at 6.0% by weight. When the amount of the binder is less than 1.0% by weight, although it is preferable in terms of electrode performance such as capacity improvement, the adhesiveness of the negative electrode material to the current collector is reduced and the negative electrode is processed (particularly during cutting). Chipping or peeling, and, for example, when winding a belt-like material having a separator interposed between the positive and negative electrodes to produce an electrode group, minute defects may be mixed into the electrode group to cause a short circuit between the positive and negative electrodes. There is. On the other hand, when the compounding amount of the binder exceeds 6.0% by weight, the amount of the binder occupying in the negative electrode increases and the capacity is reduced.
【００３２】２）正極 この正極は、集電体に正極材料を塗布した構造を有す
る。2) Positive electrode This positive electrode has a structure in which a positive electrode material is applied to a current collector.
【００３３】前記集電体としては、例えばアルミニウム
板、アルミニウムメッシュ材等を挙げることができる。Examples of the current collector include an aluminum plate and an aluminum mesh material.
【００３４】前記正極材料は、例えば活物質と結着剤と
を含有する。前記活物質としては、例えば二酸化マンガ
ン、二硫化モリブデン、ＬｉＣｏＯ2、ＬｉＮｉＯ2、Ｌ
ｉＭｎ2Ｏ4等のカルコゲン化合物を挙げることができ
る。これらのカルコゲン化合物は、１種または２種以上
の混合物で用いることができる。The positive electrode material contains, for example, an active material and a binder. Examples of the active material include manganese dioxide, molybdenum disulfide, LiCoO 2 , LiNiO 2 , L
Chalcogen compounds such as iMn 2 O 4 can be mentioned. These chalcogen compounds can be used alone or in a mixture of two or more.
【００３５】前記結着剤としては、例えばフッ素系樹
脂、ポリオレフィン樹脂、スチレン系樹脂、アクリル系
樹脂のような熱可塑性エラストマー系樹脂、またはフッ
素ゴムのようなゴム系樹脂を用いることができる。具体
的には、ポリテトラフルオロエチレン、ポリフッ化ビニ
リデン、ポリフッ化ビニル、ポリエチレン、ポリアクリ
ロニトリル、ニトリルゴム、ポリブタジエン、ブチルゴ
ム、ポリスチレン、スチレン−ブタジエンゴム、水添ス
チレン−ブタジエンゴム、多硫化ゴム、ニトロセルロー
ス、シアノエチルセルロース、カルボキシメチルセルロ
ース等が挙げられる。これらの結着剤の中でエラストマ
ー、ゴム架橋体または極性基を導入した変成体は、前記
集電体と前記正極材料との密着性の向上および過充電時
における抵抗増大効果の向上の観点から好適である。As the binder, for example, a thermoplastic elastomer resin such as a fluorine resin, a polyolefin resin, a styrene resin, an acrylic resin, or a rubber resin such as a fluorine rubber can be used. Specifically, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyethylene, polyacrylonitrile, nitrile rubber, polybutadiene, butyl rubber, polystyrene, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, polysulfide rubber, nitrocellulose , Cyanoethylcellulose, carboxymethylcellulose and the like. Among these binders, elastomers, cross-linked rubbers or modified compounds having polar groups introduced are preferably used in view of improving the adhesion between the current collector and the positive electrode material and improving the resistance increasing effect during overcharge. It is suitable.
【００３６】前記正極材料には、導電補助材としてアセ
チレンブラック、粉末状膨張黒鉛などのグラファイト
類、炭素繊維粉砕物、黒鉛化炭素繊維粉砕物、等をさら
に含有することを許容する。The cathode material is allowed to further contain, as a conductive auxiliary material, acetylene black, graphite such as powdered expanded graphite, pulverized carbon fiber, pulverized graphitized carbon fiber, and the like.
【００３７】３）セパレータ このセパレータとしては、例えば１０〜３０μｍの厚さ
を有するポリエチレン多孔質フィルム、ポリプロピレン
多孔質フィルム等を用いることができる。3) Separator As the separator, for example, a porous polyethylene film or a porous polypropylene film having a thickness of 10 to 30 μm can be used.
【００３８】４）非水系電解液 この非水系電解液は、例えばエチレンカーボネート、ジ
メチルカーボネート、メチルエチルカーボネート、ジエ
チルカーボネート、γ−ブチロラクトンから選ばれる少
なくとも１種からなる非水溶媒に、過塩素酸リチウム
（ＬｉＣｌＯ4）、六フッ化リン酸リチウム（ＬｉＰ
Ｆ6）、ホウフッ化リチウム（ＬｉＢＦ4）、六フッ化砒
素リチウム（ＬｉＡｓＦ6）を溶解した組成のもの等を
用いることができる。4) Non-aqueous Electrolyte This non-aqueous electrolyte is prepared, for example, by adding lithium perchlorate to a non-aqueous solvent comprising at least one selected from ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and γ-butyrolactone. (LiClO 4 ), lithium hexafluorophosphate (LiP
F 6), lithium borofluoride (LiBF 4), or the like can be used as the composition prepared by dissolving lithium hexafluoroarsenate (LiAsF 6).
【００３９】前記非水溶媒は、液体粘性との関係から単
独で使用するよりも２〜３種類を混合して使用すること
が好ましく、この非水溶媒に溶解する電解質の濃度は
０．５〜１．５モル／Ｌの範囲にすることが好ましい。
特に、中間にアルミニウム箔を介在させたラミネートフ
ィルムからなる外装フィルムを用いる薄型非水系電解液
二次電池では、前記非水溶媒中にはγ−ブチロラクトン
が１０〜８０重量％（より好ましくは４５〜７０重量
％）含有することが望ましい。The non-aqueous solvent is preferably used in combination of two or three types rather than used alone in view of the viscosity of the liquid. The concentration of the electrolyte dissolved in this non-aqueous solvent is 0.5 to 0.5. It is preferred to be in the range of 1.5 mol / L.
In particular, in a thin non-aqueous electrolyte secondary battery using an exterior film made of a laminate film with an aluminum foil interposed therebetween, γ-butyrolactone is contained in the non-aqueous solvent in an amount of 10 to 80% by weight (more preferably 45 to 50% by weight). 70% by weight).
【００４０】前記電解質は、単独でも混合物の形態でも
使用することができる。The above-mentioned electrolytes can be used alone or in the form of a mixture.
【００４１】本発明に係る非水系電解液二次電池として
は、次に説明する図１に示す円筒型、図２に示す角型、
図３，図４に示す薄型の構造のものが挙げられる。The non-aqueous electrolyte secondary battery according to the present invention includes a cylindrical type shown in FIG. 1 and a rectangular type shown in FIG.
3 and 4 have a thin structure.
【００４２】（１）円筒型非水系電解液二次電池 図１に示すように有底円筒状をなす金属製外装缶１は、
例えば負極端子を兼ね、底部内面に下部絶縁板２が配置
されている。発電要素である電極体３は、前記外装缶１
内に収納されている。前記電極体３は、負極４とセパレ
ータ５と正極６とを前記セパレータ５が最外周に位置す
るように渦巻き状に捲回することにより作製したもので
ある。前記負極４の下端面には、負極リードタブ７が接
続され、かつこのリードタブ７の他端は前記外装缶１の
底部内面に接続されている。中心付近に正極リードタブ
取出穴を有する上部絶縁板８は、前記外装缶１内の前記
電極体３上に配置されている。(1) Cylindrical Nonaqueous Electrolyte Secondary Battery As shown in FIG. 1, a metal outer can 1 having a bottomed cylindrical shape is
For example, the lower insulating plate 2 is disposed on the inner surface of the bottom portion also serving as a negative electrode terminal. The electrode body 3 as a power generating element is provided with the outer can 1
Is housed inside. The electrode body 3 is manufactured by spirally winding the negative electrode 4, the separator 5, and the positive electrode 6 such that the separator 5 is located at the outermost periphery. A negative electrode lead tab 7 is connected to a lower end surface of the negative electrode 4, and the other end of the lead tab 7 is connected to a bottom inner surface of the outer can 1. An upper insulating plate 8 having a positive electrode lead tab extraction hole near the center is disposed on the electrode body 3 in the outer can 1.
【００４３】茫漠気孔を有する封口部材９は、正極端子
を兼ね、前記外装缶１の上端開口部に絶縁ガスケット１
０を介してかしめ固定されている。この封口部材９は、
中央付近にガス抜き穴１１が開口された皿形封口板１２
と、この封口板１２に前記ガス抜き穴１１を覆うように
固定された例えばアルミニウムからなる弁膜ラブチャ１
３と、前記封口板１２の周縁に配置されたリング状のＰ
ＴＣ（Positive temperature Coefficient）１４と、複
数のガス抜き孔１５が開口された帽子形の正極端子１６
とから構成されている。前記封口板１２の下面には、正
極リードタブ１７が接続され、かつこのリードタブ１７
の他端は前記上部絶縁板８のリード取出穴を通して前記
電極３の正極６に接続されている。A sealing member 9 having a stunning pore also serves as a positive electrode terminal, and an insulating gasket 1 is provided at an upper end opening of the outer can 1.
It is swaged and fixed through 0. This sealing member 9
Dish-shaped sealing plate 12 with vent hole 11 opened near the center
And a valve membrane latch 1 made of, for example, aluminum fixed to the sealing plate 12 so as to cover the gas vent hole 11.
3 and a ring-shaped P disposed on the periphery of the sealing plate 12.
TC (Positive Temperature Coefficient) 14 and hat-shaped positive electrode terminal 16 having a plurality of vent holes 15
It is composed of A positive electrode lead tab 17 is connected to the lower surface of the sealing plate 12 and
Is connected to the positive electrode 6 of the electrode 3 through a lead extraction hole of the upper insulating plate 8.
【００４４】（２）角型非水系電解液二次電池 図２に示す有底矩形筒状をなす金属、例えばアルミニウ
ムから作られる外装缶２１は、例えば正極端子を兼ね、
底部内面に絶縁フィルム２２が配置されている。発電要
素である電極体２３は、前記外装缶２１内に収納されて
いる。なお、外装缶がステンレスまたは鉄からなる場合
には負極端子を兼ねる。前記電極体２３は、負極２４と
セパレータ２５と正極２６とを前記正極２６が最外周に
位置するように渦巻状に捲回した後、扁平状にプレス成
形することにより作製したものである。中心付近にリー
ド取出穴を有する例えば合成樹脂からなるスペーサ２７
は、前記外装缶２１内の前記電極体２３上に配置されて
いる。(2) Prismatic Nonaqueous Electrolyte Secondary Battery An outer can 21 made of metal having a bottomed rectangular cylindrical shape, for example, aluminum as shown in FIG. 2 also serves as a positive electrode terminal, for example.
An insulating film 22 is disposed on the inner surface of the bottom. The electrode body 23 as a power generation element is housed in the outer can 21. When the outer can is made of stainless steel or iron, it also serves as the negative electrode terminal. The electrode body 23 is formed by spirally winding the negative electrode 24, the separator 25, and the positive electrode 26 such that the positive electrode 26 is located at the outermost periphery, and then press-molding the flat electrode into a flat shape. Spacer 27 made of, for example, synthetic resin and having a lead extraction hole near the center
Is disposed on the electrode body 23 in the outer can 21.
【００４５】金属製蓋体２８は、前記外装缶１の上端開
口部に例えばレーザ溶接により気密に接合されている。
前記蓋体２８の中心付近には、負極端子の取出穴２９が
開口されている。負極端子３０は、前記蓋体２８の穴２
９にガラス製または樹脂製の絶縁材３１を介してハーメ
ティックシールされている。前記負極端子３０の下端面
には、リード３２が接続され、かつこのリード３２の他
端は前記電極体２３の負極２４に接続されている。The metal lid 28 is hermetically joined to the upper end opening of the outer can 1 by, for example, laser welding.
In the vicinity of the center of the lid 28, an extraction hole 29 for a negative electrode terminal is opened. The negative electrode terminal 30 is connected to the hole 2 of the lid 28.
9 is hermetically sealed via an insulating material 31 made of glass or resin. A lead 32 is connected to the lower end surface of the negative electrode terminal 30, and the other end of the lead 32 is connected to the negative electrode 24 of the electrode body 23.
【００４６】上部側絶縁紙３３は、前記蓋体２８の外表
面全体に被覆されている。スリット３４を有する下部側
絶縁紙３５は、前記外装缶２１の底面に配置されてい
る。二つ折りされたＰＴＣ素子（Positive Temperatur
e Coefficient）３６は、一方の面が前記外装缶２１の
底面と前記下部側絶縁紙３５の間に介装され、かつ他方
の面が前記スリット３４を通して前記絶縁紙３５の外側
に延出されている。外装チューブ３７は、前記外装缶２
１の側面から上下面の絶縁紙３３、３５の周辺まで延出
するように配置され、前記上部側絶縁紙３３および下部
側絶縁紙３５を前記外装缶２１に固定している。このよ
うな外装チューブ３７の配置により、外部に延出された
前記ＰＴＣ素子３６の他方の面が前記下部側絶縁紙３５
の底面に向けて折り曲げられる。The upper insulating paper 33 covers the entire outer surface of the lid 28. The lower insulating paper 35 having the slit 34 is disposed on the bottom surface of the outer can 21. PTC element (Positive Temperatur)
e Coefficient) 36, one surface is interposed between the bottom surface of the outer can 21 and the lower insulating paper 35, and the other surface is extended outside the insulating paper 35 through the slit 34. I have. The outer tube 37 is made of the outer can 2.
The upper insulating paper 33 and the lower insulating paper 35 are fixed to the outer can 21 so as to extend from the side surface 1 to the periphery of the insulating papers 33 and 35 on the upper and lower surfaces. Due to such an arrangement of the outer tube 37, the other surface of the PTC element 36 extended to the outside is connected to the lower insulating paper 35.
It is bent toward the bottom of.
【００４７】（３）薄型非水系電解液二次電池 図３，図４に示すように発電要素４１は、例えば活物質
および結着剤を含む正極材料である正極活物質層４２が
集電体４３の両面に担持された正極４４とセパレータ４
５と活物質および結着剤を含む負極材料である負極活物
質層４６が集電体４７の両面に担持された負極４８とセ
パレータ４５とを渦巻状に捲回し、さらに成形した扁平
で矩形状をなす。前記正極４４，負極４８に接続された
外部リード端子４９，５０は、それぞれ前記発電要素４
１の同一側面から外部に延出されている。(3) Thin Non-Aqueous Electrolyte Secondary Battery As shown in FIGS. 3 and 4, the power generating element 41 is formed by a positive electrode active material layer 42 which is a positive electrode material containing, for example, an active material and a binder. The positive electrode 44 and the separator 4 supported on both surfaces of the negative electrode 43
5, a negative electrode active material layer 46, which is a negative electrode material containing an active material and a binder, spirally winds a negative electrode 48 supported on both surfaces of a current collector 47 and a separator 45, and further forms a flat and rectangular shape. Make External lead terminals 49 and 50 connected to the positive electrode 44 and the negative electrode 48 are connected to the power generating element 4 respectively.
1 extend outside from the same side.
【００４８】前記発電要素４１は、図３に示すように例
えば２つ折りのカップ型外装フィルム５１のカップ５２
内にその折曲げ部が前記発電要素４１の前記外部リード
端子４９，５０が延出された側面と反対側の側面側に位
置するように包み込まれている。この外装フィルム５１
は、図４に示すように内面側に位置するシーラントフィ
ルム５３、アルミニウムまたはアルミニウム合金の箔５
４および剛性を有する有機樹脂フィルム５５をこの順序
で積層した構造を有する。前記外装フィルム５１におけ
る前記折り曲げ部を除く前記発電要素１の２つの長側面
および１つの短側面に対応する３つの側部は、前記シー
ラントフィルム５３同士を熱シールして水平方向に延出
したシール部５６ａ，５６ｂ,５６ｃが形成され、これ
らのシール部５６ａ,５６ｂ,５６ｃにより前記発電要素
４１を封口している。前記発電要素４１の正極４４、負
極４８に接続された外部端子４９，５０は、前記折り曲
げ部と反対側のシール部５６ｂを通して外部に延出され
ている。前記発電要素４１内部および前記シール部５６
ａ,５６ｂ,５６ｃで封口された前記外装フィルム５１内
には、非水系電解液が含浸・収容されている。As shown in FIG. 3, the power generating element 41 includes a cup 52 of a two-fold cup-shaped exterior film 51, for example.
The bent portion is enclosed so as to be located on the side surface opposite to the side surface on which the external lead terminals 49 and 50 of the power generation element 41 extend. This exterior film 51
Is a sealant film 53 located on the inner side as shown in FIG.
4 and a rigid organic resin film 55 laminated in this order. Three side portions corresponding to two long side surfaces and one short side surface of the power generation element 1 excluding the bent portion in the exterior film 51 are seals extending in the horizontal direction by heat sealing the sealant films 53 to each other. Parts 56a, 56b, 56c are formed, and the power generating element 41 is sealed by these seal parts 56a, 56b, 56c. External terminals 49 and 50 connected to the positive electrode 44 and the negative electrode 48 of the power generation element 41 extend to the outside through a seal portion 56b on the opposite side to the bent portion. Inside the power generating element 41 and the seal portion 56
A non-aqueous electrolytic solution is impregnated and contained in the exterior film 51 sealed by a, 56b, and 56c.
【００４９】なお、前記薄型非水系電解液二次電池にお
いて外装フィルムはカップ型に限らず、ピロー型、パウ
チ型にしてもよい。In the thin non-aqueous electrolyte secondary battery, the outer film is not limited to the cup type, but may be a pillow type or a pouch type.
【００５０】以上説明したように本発明に係る非水系電
解液二次電池は、リチウムを吸蔵・放出可能な正極、リ
チウムを吸蔵・放出可能な負極、セパレータおよび非水
系電解液を備え、前記正極および前記負極が集電体にそ
れぞれ正極材料および負極材料を塗布した構造を有し、
かつ前記負極材料が低温焼成炭素を含む２種以上の炭素
質材を含有した構造を有する。As described above, the non-aqueous electrolyte secondary battery according to the present invention comprises a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator, and a non-aqueous electrolyte. And the negative electrode has a structure in which a positive electrode material and a negative electrode material are applied to a current collector, respectively.
In addition, the negative electrode material has a structure containing two or more carbonaceous materials including low-temperature fired carbon.
【００５１】このような低温焼成炭素を含む２種以上の
炭素質材を含有した負極材料を集電体に塗布した改良さ
れた負極を備えることによって、高温充放電サイクル特
性が向上され、かつ高温保存回復特性を改善した非水電
解二次電池を得ることができる。By providing an improved negative electrode in which a current collector is coated with a negative electrode material containing two or more kinds of carbonaceous materials including such low-temperature fired carbon, high-temperature charge / discharge cycle characteristics are improved, and A non-aqueous electrolytic secondary battery with improved storage recovery characteristics can be obtained.
【００５２】特に、前記低温焼成炭素として、例えば石
油系ピッチから得られ、平均粒径８〜２０μｍ、真密度
１．５０〜１．７５ｇ／ｃｃの球状のメソフェーズ系低
温焼成炭素、または平均繊維径８〜１８μｍ、平均繊維
長８〜２０μｍ、真密度１．５０〜１．７５ｇ／ｃｃの
メソフェーズ低温焼成炭素繊維を用いることによって、
より高温保存回復特性を改善した非水系電解液二次電池
を得ることができる。In particular, as the low-temperature fired carbon, a spherical mesophase low-temperature fired carbon obtained from, for example, petroleum pitch and having an average particle diameter of 8 to 20 μm and a true density of 1.50 to 1.75 g / cc, or an average fiber diameter By using mesophase low-temperature-fired carbon fibers having an average fiber length of 8 to 18 μm, an average fiber length of 8 to 20 μm, and a true density of 1.50 to 1.75 g / cc,
A non-aqueous electrolyte secondary battery with improved high-temperature storage recovery characteristics can be obtained.
【００５３】また、前記低温焼成炭素以外の炭素質材と
して繊維状炭素材（好ましくは平均繊維径８〜１８μ
ｍ、平均繊維長１０〜５０μｍ、真密度２．２２ｇ／ｃ
ｃ以上、面間隔（ｄ002）０．３３５６〜０．３３６８
ｎｍ、ｃ軸方向の結晶子の大きさ（Ｌｃ）が４０ｎｍ以
上である繊維状炭素質材）を用いることによって、高温
保存回復特性を改善され、かつ充放電サイクル寿命を向
上した非水電解二次電池を得ることができる。As a carbonaceous material other than the low-temperature fired carbon, a fibrous carbon material (preferably having an average fiber diameter of 8 to 18 μm) is used.
m, average fiber length 10 to 50 μm, true density 2.22 g / c
c or more, surface interval (d 002 ) 0.3356 to 0.3368
The use of a fibrous carbonaceous material having a crystallite size (Lc) of at least 40 nm in the nm and c-axis directions) improves the high-temperature storage recovery characteristics and improves the charge / discharge cycle life. The following battery can be obtained.
【００５４】さらに、前記低温焼成炭素以外の炭素質材
として繊維状炭素材（好ましくは平均繊維径８〜１８μ
ｍ、平均繊維長１０〜５０μｍ、真密度２．２２ｇ／ｃ
ｃ以上、面間隔（ｄ002）０．３３５６〜０．３３６８
ｎｍ、ｃ軸方向の結晶子の大きさ（Ｌｃ）が４０ｎｍ以
上である繊維状炭素質材）と鱗片状、球状、球塊状また
は擬球状の黒鉛（好ましくは平均粒径２〜５０μｍ、比
表面積２〜２０ｍ2／ｇ、真密度２．２３〜２．２８ｇ
／ｃｃ、面間隔（ｄ002）０．３３５４〜０．３３５８
ｎｍである黒鉛）との２種を用いることによって、より
高温保存回復特性を改善され、かつ充放電サイクル寿命
を向上した非水電解二次電池を得ることができる。Further, as a carbonaceous material other than the low-temperature fired carbon, a fibrous carbon material (preferably having an average fiber diameter of 8 to 18 μm) is used.
m, average fiber length 10 to 50 μm, true density 2.22 g / c
c or more, surface interval (d 002 ) 0.3356 to 0.3368
fibrous carbonaceous material having a crystallite size (Lc) of 40 nm or more in the nm and c-axis directions) and scaly, spherical, spherical or massive graphite (preferably having an average particle size of 2 to 50 μm, specific surface area) 2 to 20 m 2 / g, true density 2.23 to 2.28 g
/ Cc, spacing (d 002 ) 0.3354-0.3358
By using the two types of graphite described above, it is possible to obtain a nonaqueous electrolytic secondary battery having improved high-temperature storage / recovery characteristics and improved charge / discharge cycle life.
【００５５】[0055]
【実施例】以下、本発明の好ましい実施例を詳細に説明
する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail.
【００５６】「メソフェーズ低温焼成炭素繊維」黒鉛化
温度８３０℃で焼成した平均繊維径１３．８μｍ、平均
繊維長１７μｍ、真密度１．５５ｇ／ｃｃのメソフェー
ズ低温焼成炭素繊維を用意した。"Mesophase Low-Temperature Carbon Fiber" A mesophase low-temperature-fired carbon fiber having an average fiber diameter of 13.8 μm, an average fiber length of 17 μm, and a true density of 1.55 g / cc, which was fired at a graphitization temperature of 830 ° C., was prepared.
【００５７】「フルフラール樹脂からの低温焼成炭素
（擬球状低温焼成体）」焼成温度８４０℃で焼成した平
均粒径１０μｍ、真密度１．６０ｇ／ｃｃの低温焼成炭
素材を準備した。"Low-temperature fired carbon from furfural resin (pseudo spherical low-temperature fired body)" A low-temperature fired carbon material fired at a firing temperature of 840 ° C and having an average particle diameter of 10 µm and a true density of 1.60 g / cc was prepared.
【００５８】「球状メソフェーズ低温焼成炭素」黒鉛化
温度８５０℃で焼成した平均粒径１７μｍ、真密度１．
６３ｇ／ｃｃの球状メソフェーズ低温焼成炭素を用意し
た。"Spherical mesophase low-temperature calcined carbon" calcined at a graphitization temperature of 850 ° C, average particle diameter 17 µm, true density 1.
63 g / cc spherical mesophase low-temperature calcined carbon was prepared.
【００５９】「繊維状炭素質材の作製」メソフェーズピ
ッチを紡糸、不融化し、アルゴン雰囲気下、６８０℃で
炭化し、適度に粉砕した後、窒素雰囲気下で３０００℃
にて黒鉛化することにより繊維状炭素質材を得た。[Preparation of fibrous carbonaceous material] A mesophase pitch was spun, made infusible, carbonized at 680 ° C in an argon atmosphere, pulverized appropriately, and then 3,000 ° C in a nitrogen atmosphere.
To obtain a fibrous carbonaceous material.
【００６０】得られた繊維状炭素質材は、ｃ軸方向の結
晶子（Ｌｃ）の大きさ６０ｎｍ、平均繊維径８．５μ
ｍ、平均繊維長１８．５μｍ、真密度２．２４ｇ／ｃ
ｃ、面間隔（ｄ002）０．３３５９ｎｍ、Ｃｕ−Ｋαに
よるＸ線回折法での（１０１）回折ピークＰ101と（１
００）回折ピークＰ100の強度比（Ｐ101／Ｐ100）が
１．４５であった。The obtained fibrous carbonaceous material had a crystallite (Lc) size of 60 nm in the c-axis direction and an average fiber diameter of 8.5 μm.
m, average fiber length 18.5 μm, true density 2.24 g / c
c, spacing (d 002 ) of 0.3359 nm, (101) diffraction peak P 101 and (1) by X-ray diffraction method using Cu-Kα
00) The intensity ratio (P 101 / P 100 ) of the diffraction peak P 100 was 1.45.
【００６１】「黒鉛の作製」天然系黒鉛を球塊状に解扮
した黒鉛を用意した。この黒鉛は、平均粒径８．５μ
ｍ、比表面積６．７ｍ2／ｇ、面間隔（ｄ002）０．３３
５８ｎｍであった。[Preparation of Graphite] Graphite prepared by dressing natural graphite in a spherical shape was prepared. This graphite has an average particle size of 8.5μ.
m, specific surface area 6.7 m 2 / g, spacing (d 002 ) 0.33
It was 58 nm.
【００６２】（実施例１） ＜正極の作製＞まず、１２重量％濃度のポリフッ化ビニ
リデン樹脂（ＰＶｄＦ）のＮ−メチルピロリドン溶液４
１．７重量部に活物質としてのＬｉＣｏＯ2粉末１００
重量部、導電フィラーとしてのグラファイト粉末（ロン
ザ社製商品名；ＫＳ４）５重量部を混合し、混練した。
つづいて、この混合物にＮ−メチルピロリドン１５重量
部をさらに添加し、ビーズミルを用いて前記固形物を分
散させて正極塗工スラリーを調製した。Example 1 <Preparation of Positive Electrode> First, a 12% by weight solution of polyvinylidene fluoride resin (PVdF) in N-methylpyrrolidone 4
1.7 parts by weight of LiCoO 2 powder 100 as an active material
5 parts by weight of graphite powder (trade name: KS4, manufactured by Lonza) as a conductive filler was mixed and kneaded.
Subsequently, 15 parts by weight of N-methylpyrrolidone was further added to the mixture, and the solid was dispersed using a bead mill to prepare a positive electrode coating slurry.
【００６３】次いで、前記正極塗工スラリーを厚さ１５
μｍのアルミニウム箔（集電体）の両面にそれそれ２５
５ｇ／ｍ2になるように塗工し、乾燥した後、プレス、
スリット加工を施すことにより厚さ１６７μｍ、幅４
２．００ｍｍの帯状正極を作製した。Next, the positive electrode coating slurry was applied to a thickness of 15
25 μm on both sides of aluminum foil (current collector)
After coating to 5 g / m 2 and drying, press
167μm thickness, 4 width by slit processing
A band-shaped positive electrode of 2.00 mm was produced.
【００６４】＜負極の作製＞カルボキシメチルセルロー
スの０．６８重量％濃度の粘調水溶液１７７重量部に前
記繊維状炭素質材８９重量部、前記メソフェーズ低温焼
成炭素繊維１重量部を添加した後、せん断分散した。つ
づいて、この混合物にＳＢＲラテックス３．４重量部を
添加し、均一の混合攪拌して負極塗工スラリーを調製し
た。<Preparation of Negative Electrode> 89 parts by weight of the fibrous carbonaceous material and 1 part by weight of the mesophase low-temperature calcined carbon fiber were added to 177 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.68% by weight, and then shearing was performed. Dispersed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【００６５】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１５μｍの銅箔（集電体）の両面に１
０３ｇ／ｍ2になるように塗工し、乾燥した。この時の
銅箔上の負極材料の密度は、１．２３ｇ／ｃｃであっ
た。その後、プレス、スリット加工を施して厚さ１４９
μｍ（負極材料の密度；１．５ｇ／ｃｃ）、幅４３．２
５ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both sides of a copper foil (current collector) having a thickness of 15 μm using a knife edge coater.
Coating was performed so as to be 03 g / m 2 and drying was performed. At this time, the density of the negative electrode material on the copper foil was 1.23 g / cc. Then, press and slit to give a thickness of 149
μm (density of negative electrode material; 1.5 g / cc), width 43.2
A 5 mm strip-shaped negative electrode was produced.
【００６６】次いで、前記正負極の集電体にリードタブ
をそれぞれ接合し、自動捲回機を用いてポリエチレン製
多孔膜を２枚介してスパイラル状に巻き上げ、さらにプ
レスすることにより扁平状の電極体を作製した。得られ
た電極体に直流電源から１００Ｖの電圧を５秒間印加
し、１０μＶ以上流れるものを不良と判定して除外し
た。Next, lead tabs were respectively joined to the positive and negative electrode current collectors, spirally wound through two polyethylene porous membranes using an automatic winding machine, and further pressed to obtain a flat electrode body. Was prepared. A voltage of 100 V was applied from a DC power supply to the obtained electrode body for 5 seconds, and a current flowing at 10 μV or more was judged to be defective and excluded.
【００６７】次いで、良品として判定された電極体を厚
さ４．８ｍｍ、幅３０ｍｍ、高さ４７ｍｍの有底矩形筒
状をなすアルミニウム製外装缶内に挿入し、非水系電解
液を注入した後、前記外装缶の開口部にアルミニウム製
蓋体を気密に接合することにより前述した図２に示す角
型リチウムイオン二次電池を組立てた。なお、前記非水
系電解液はエチレンカーボネートとメチルエチルカーボ
ネートとジエチルカーボネートを３：２：５の重量比で
混合した混合非水溶媒に六フッ化リン酸リチウム（Ｌｉ
ＰＦ6）を１．０モル／Ｌの濃度で溶解した組成を有す
る。Next, the electrode assembly determined as a non-defective product was inserted into an aluminum outer can having a bottomed rectangular cylindrical shape having a thickness of 4.8 mm, a width of 30 mm, and a height of 47 mm. The above-mentioned prismatic lithium ion secondary battery shown in FIG. 2 was assembled by hermetically bonding an aluminum lid to the opening of the outer can. The non-aqueous electrolytic solution was prepared by mixing lithium hexafluorophosphate (Li) in a mixed non-aqueous solvent in which ethylene carbonate, methyl ethyl carbonate and diethyl carbonate were mixed at a weight ratio of 3: 2: 5.
PF 6 ) at a concentration of 1.0 mol / L.
【００６８】（実施例２）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Example 2 Example 1 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００６９】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２５８ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１６９μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at 258 g / m 2 and dried. A band-shaped positive electrode having a thickness of 169 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００７０】＜負極の作製＞カルボキシメチルセルロー
スの０．６７重量％濃度の粘調水溶液１８０重量部に前
記繊維状炭素質材７０重量部、前記メソフェーズ低温焼
成炭素繊維５重量部および前記球塊状黒鉛２５重量部を
添加した後、せん断分散した。つづいて、この混合物に
ＳＢＲラテックス３．４重量部を添加し、均一の混合攪
拌して負極塗工スラリーを調製した。<Preparation of negative electrode> 70 parts by weight of the fibrous carbonaceous material, 5 parts by weight of the mesophase low-temperature calcined carbon fiber, and 25 parts of the spheroidal graphite 25 were added to 180 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.67% by weight. After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【００７１】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１５μｍの銅箔（集電体）の両面にそ
れぞれ１０１ｇ／ｍ2になるように塗工し、乾燥した。
この時、の銅箔上の負極材料の密度は１．２３ｇ／ｃｃ
であった。その後、プレス、スリット加工を施して厚さ
１４７μｍ（負極材料の密度；１．５ｇ／ｃｃ）、幅４
３．２５ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 15 μm to a thickness of 101 g / m 2 by a knife edge coater and dried.
At this time, the density of the negative electrode material on the copper foil was 1.23 g / cc.
Met. After that, it is pressed and slit to a thickness of 147 μm (density of the negative electrode material; 1.5 g / cc) and a width of 4 μm.
A 3.25 mm strip-shaped negative electrode was produced.
【００７２】（実施例３）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Example 3 Example 1 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００７３】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２６２ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１７１μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 262 g / m 2 and dried. A band-shaped positive electrode having a thickness of 171 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００７４】＜負極の作製＞カルボキシメチルセルロー
スの０．６４重量％濃度の粘調水溶液１９０重量部に前
記繊維状炭素質材５６重量部、前記球状メソフェーズ低
温焼成炭素９重量部および前記球塊状黒鉛３５重量部を
添加した後、せん断分散した。つづいて、この混合物に
ＳＢＲラテックス３．４重量部を添加し、均一の混合攪
拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> In 190 parts by weight of a 0.64% by weight viscous aqueous solution of carboxymethyl cellulose, 56 parts by weight of the fibrous carbonaceous material, 9 parts by weight of the spherical mesophase low-temperature calcined carbon, and 35 parts of the spheroidal graphite 35 After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【００７５】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１５μｍの銅箔（集電体）の両面にそ
れぞれ１００ｇ／ｍ2になるように塗工し、乾燥した。
この時、の銅箔上の負極材料の密度は１．２３ｇ／ｃｃ
であった。その後、プレス、スリット加工を施して厚さ
１４５μｍ（負極材料の密度；１．５ｇ／ｃｃ）、幅４
３．２５ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 15 μm by a knife edge coater so as to have a thickness of 100 g / m 2 and dried.
At this time, the density of the negative electrode material on the copper foil was 1.23 g / cc.
Met. After that, it is pressed and slit to give a thickness of 145 μm (density of the negative electrode material; 1.5 g / cc) and a width of 4 μm.
A 3.25 mm strip-shaped negative electrode was produced.
【００７６】（実施例４）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Example 4 Example 1 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００７７】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２６４ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１６９μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 264 g / m 2 and dried. A band-shaped positive electrode having a thickness of 169 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００７８】＜負極の作製＞カルボキシメチルセルロー
スの０．６４重量％濃度の粘調水溶液１９０重量部に前
記繊維状炭素質材４５重量部、前記球状メソフェーズ低
温焼成炭素１０重量部および前記球塊状黒鉛４５重量部
を添加した後、せん断分散した。つづいて、この混合物
にＳＢＲラテックス３．４重量部を添加し、均一の混合
攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 45 parts by weight of the fibrous carbonaceous material, 10 parts by weight of the spherical mesophase low-temperature calcined carbon and 190 parts by weight of the viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.64% by weight were prepared. After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【００７９】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１５μｍの銅箔（集電体）の両面にそ
れぞれ９０ｇ／ｍ2になるように塗工し、乾燥した。こ
の時、の銅箔上の負極材料の密度は１．２２ｇ／ｃｃで
あった。その後、プレス、スリット加工を施して厚さ１
４４μｍ（負極材料の密度；１．５ｇ／ｃｃ）、幅４
３．２５ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a 15 μm-thick copper foil (current collector) at 90 g / m 2 by a knife edge coater and dried. At this time, the density of the negative electrode material on the copper foil was 1.22 g / cc. After that, press and slit processing is performed to make the thickness 1
44 μm (density of negative electrode material; 1.5 g / cc), width 4
A 3.25 mm strip-shaped negative electrode was produced.
【００８０】（実施例５）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Example 5 Example 1 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００８１】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２７０ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１６９μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at 270 g / m 2 and dried. A band-shaped positive electrode having a thickness of 169 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００８２】＜負極の作製＞カルボキシメチルセルロー
スの０．６２重量％濃度の粘調水溶液１９４重量部に前
記繊維状炭素質材４３重量部、前記擬球状低温焼成炭素
１５重量部および前記球塊状黒鉛４２重量部を添加した
後、せん断分散した。つづいて、この混合物にＳＢＲラ
テックス３．４重量部を添加し、均一の混合攪拌して負
極塗工スラリーを調製した。次いで、前記塗工スラリー
をナイフエッジコータにより厚さ１５μｍの銅箔（集電
体）の両面にそれぞれ９４ｇ／ｍ2になるように塗工
し、乾燥した。この時、銅箔上の負極材料の密度は、
１．２２ｇ／ｃｃであった。その後、プレス、スリット
加工を施して厚さ１３７μｍ（負極材料の密度；１．５
ｇ／ｃｃ）、幅４３．２５ｍｍの帯状負極を作製した。<Preparation of negative electrode> 43 parts by weight of the fibrous carbonaceous material, 15 parts by weight of the pseudo-spherical low-temperature calcined carbon and spheroidal graphite 42 were added to 194 parts by weight of a carboxymethyl cellulose viscosified aqueous solution having a concentration of 0.62% by weight. After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry. Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 15 μm at a thickness of 94 g / m 2 by a knife edge coater, and dried. At this time, the density of the negative electrode material on the copper foil is
1.22 g / cc. After that, it is pressed and slit to a thickness of 137 μm (density of negative electrode material: 1.5
g / cc) and a band-shaped negative electrode having a width of 43.25 mm was produced.
【００８３】（比較例１）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Comparative Example 1 Example 1 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００８４】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２５５ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１６７μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at a rate of 255 g / m 2 and dried. A band-shaped positive electrode having a thickness of 167 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００８５】＜負極の作製＞カルボキシメチルセルロー
スの０．６８重量％濃度の粘調水溶液１７７重量部に前
記繊維状炭素質材８０重量部および前記球塊状黒鉛２０
重量部を添加した後、せん断分散した。つづいて、この
混合物にＳＢＲラテックス３．４重量部を添加し、均一
の混合攪拌して負極塗工スラリーを調製した。次いで、
前記塗工スラリーをナイフエッジコータにより厚さ１５
μｍの銅箔（集電体）の両面にそれぞれ１０４ｇ／ｍ2
になるように塗工し、乾燥した。この時、銅箔上の負極
材料の密度は、１．２４ｇ／ｃｃであった。その後、プ
レス、スリット加工を施して厚さ１５１μｍ（負極材料
の密度；１．５ｇ／ｃｃ）、幅４３．２５ｍｍの帯状負
極を作製した。<Preparation of Negative Electrode> 80 parts by weight of the fibrous carbonaceous material and spheroidal graphite 20 were added to 177 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.68% by weight.
After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry. Then
The coating slurry was applied to a thickness of 15 using a knife edge coater.
104 g / m 2 on both sides of a copper foil (current collector) of μm
And dried. At this time, the density of the negative electrode material on the copper foil was 1.24 g / cc. Then, pressing and slitting were performed to produce a strip-shaped negative electrode having a thickness of 151 μm (density of negative electrode material; 1.5 g / cc) and a width of 43.25 mm.
【００８６】（比較例２）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例１
と同様な構造の角型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する電極体の作製後
は、実施例１と同様な良・不良の判定を行ない、良品と
して判定された電極体のみを使用した。Comparative Example 2 Example 1 was repeated except that the positive electrode and the negative electrode were manufactured by the method described below.
A prismatic lithium ion secondary battery having the same structure as that of was assembled. After the fabrication of the electrode body having the positive and negative electrodes and the separator, the same good / bad determination as in Example 1 was performed, and only the electrode body determined to be non-defective was used.
【００８７】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ２５７ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１６８μｍ、幅４２．００ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 257 g / m 2 and dried. A band-shaped positive electrode having a thickness of 168 μm and a width of 42.00 mm was prepared by pressing and slitting.
【００８８】＜負極の作製＞カルボキシメチルセルロー
スの０．６２重量％濃度の粘調水溶液１９４重量部に前
記繊維状炭素質材５０重量部および前記球塊状黒鉛５０
重量部を添加した後、せん断分散した。つづいて、この
混合物にＳＢＲラテックス３．４重量部を添加し、均一
の混合攪拌して負極塗工スラリーを調製した。次いで、
前記塗工スラリーをナイフエッジコータにより厚さ１５
μｍの銅箔（集電体）の両面にそれぞれ１０４ｇ／ｍ2
になるように塗工し、乾燥した。この時、銅箔上の負極
材料の密度は、１．２４ｇ／ｃｃであった。その後、プ
レス、スリット加工を施して厚さ１５１μｍ（負極材料
の密度；１．５ｇ／ｃｃ）、幅４３．２５ｍｍの帯状負
極を作製した。<Preparation of Negative Electrode> 50 parts by weight of the fibrous carbonaceous material and spheroidal graphite 50 were added to 194 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.62% by weight.
After adding parts by weight, shear dispersion was performed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry. Then
The coating slurry was applied to a thickness of 15 using a knife edge coater.
104 g / m 2 on both sides of a copper foil (current collector) of μm
And dried. At this time, the density of the negative electrode material on the copper foil was 1.24 g / cc. Then, pressing and slitting were performed to produce a strip-shaped negative electrode having a thickness of 151 μm (density of negative electrode material; 1.5 g / cc) and a width of 43.25 mm.
【００８９】得られた実施例１〜５および比較例１，２
の角型リチウムイオン二次電池について、７００ｍＡｈ
で６時間初充電し、エージングを１２時間施した後、２
０℃で０．２Ｃ相当で放電した時の初期容量を測定し
た。The obtained Examples 1 to 5 and Comparative Examples 1 and 2
700 mAh for the prismatic lithium ion secondary battery of
After charging for 6 hours and aging for 12 hours,
The initial capacity at the time of discharging at 0.2 ° C. at 0 ° C. was measured.
【００９０】また、前記各二次電池について２０℃にお
いて１Ｃで満充電し、８５℃の環境下に４８時間放置と
９０℃の環境下に２４時間放置した後、１Ｃ（カットオ
フ電圧３．０Ｖ）で放電したときの容量を測定し、得ら
れた容量から初期容量に対する容量維持率を求めた。Each of the secondary batteries was fully charged at 1 ° C. at 20 ° C., left for 48 hours in an environment of 85 ° C. and 24 hours in an environment of 90 ° C., and then charged at 1 C (cutoff voltage of 3.0 V). ), The capacity at the time of discharging was measured, and the capacity retention ratio with respect to the initial capacity was determined from the obtained capacity.
【００９１】さらに、放電後の各二次電池を２０℃にお
いて１Ｃで追充電し、１Ｃ（カットオフ電圧３．０Ｖ）
で放電させたときの容量を測定し、得られた容量から初
期容量に対する容量回復率を求めた。Further, each secondary battery after discharging was additionally charged at 20 ° C. at 1 C, and was charged at 1 C (cutoff voltage 3.0 V).
The capacity at the time of discharging was measured, and the capacity recovery rate with respect to the initial capacity was determined from the obtained capacity.
【００９２】さらに、前記各二次電池について２０℃お
よび６０℃の環境下において１Ｃで充電し、１Ｃ（カッ
トオフ電圧３．０Ｖ）で放電する充放電を繰り返し、５
００サイクル目の放電容量を測定し、得られた放電容量
から初期容量に対する容量維持率を求めた。Further, each of the secondary batteries was repeatedly charged and discharged at 1 C under an environment of 20 ° C. and 60 ° C. and discharged at 1 C (cutoff voltage 3.0 V).
The discharge capacity at the 00th cycle was measured, and the capacity retention ratio with respect to the initial capacity was determined from the obtained discharge capacity.
【００９３】これらの結果を下記表１に示す。The results are shown in Table 1 below.
【００９４】[0094]
【表１】 [Table 1]
【００９５】前記表１から明らかなように、実施例１〜
４の角型リチウムイオン二次電池と比較例１，２の角型
リチウムイオン二次電池とは初期容量の点で大きな差異
がないものの、特定の炭素材料を含む負極を備えた実施
例１〜４の二次電池は比較例１，２の二次電池に比べて
８５℃の環境下に２４時間放置後の容量維持率および容
量回復率がいずれも優れていることがわかる。As apparent from Table 1 above, Examples 1 to
Although the square lithium ion secondary battery of Comparative Example 4 and the prismatic lithium ion secondary batteries of Comparative Examples 1 and 2 have no significant difference in the initial capacity, Examples 1 to 3 provided with the negative electrode containing a specific carbon material It can be seen that the secondary battery of No. 4 is superior to the secondary batteries of Comparative Examples 1 and 2 both in the capacity retention ratio and the capacity recovery ratio after being left for 24 hours in an environment of 85 ° C.
【００９６】一方、実施例５の角型リチウムイオン二次
電池は初期容量が比較例１，２の二次電池に比べて若干
劣るものの、８５℃の環境下に２４時間放置後の容量維
持率および容量回復率数いずれも優れていることがわか
る。On the other hand, although the initial capacity of the prismatic lithium ion secondary battery of Example 5 was slightly inferior to that of the secondary batteries of Comparative Examples 1 and 2, the capacity retention rate after being left for 24 hours in an environment of 85 ° C. It can be seen that both the capacity recovery rate numbers are excellent.
【００９７】（実施例６） ＜正極の作製＞まず、１２重量％濃度のポリフッ化ビニ
リデン樹脂（ＰＶｄＦ）のＮ−メチルピロリドン溶液４
１．７重量部に活物質としてのＬｉＣｏＯ2粉末１００
重量部、導電フィラーとしてのグラファイト粉末（ロン
ザ社製商品名；ＫＳ４）５重量部を混合し、混練した。
つづいて、この混合物にＮ−メチルピロリドン１５重量
部をさらに添加し、ビーズミルを用いて前記固形物を分
散させて正極塗工スラリーを調製した。Example 6 <Preparation of Positive Electrode> First, a 12% by weight solution of polyvinylidene fluoride (PVdF) in N-methylpyrrolidone 4
1.7 parts by weight of LiCoO 2 powder 100 as an active material
5 parts by weight of graphite powder (trade name: KS4, manufactured by Lonza) as a conductive filler was mixed and kneaded.
Subsequently, 15 parts by weight of N-methylpyrrolidone was further added to the mixture, and the solid was dispersed using a bead mill to prepare a positive electrode coating slurry.
【００９８】次いで、前記正極塗工スラリーを厚さ１５
μｍのアルミニウム箔（集電体）の両面にそれそれ１９
４ｇ／ｍ2になるように塗工し、乾燥した後、プレス、
スリット加工を施すことにより厚さ１３０μｍ、幅４
９．５ｍｍの帯状正極を作製した。Next, the positive electrode coating slurry was applied to a thickness of 15
μm on both sides of aluminum foil (collector) 19
After coating and drying to 4g / m2, press,
130μm thickness, 4 width by slit processing
A 9.5 mm strip-shaped positive electrode was produced.
【００９９】＜負極の作製＞カルボキシメチルセルロー
スの０．６８重量％濃度の粘調水溶液１７７重量部に前
記繊維状炭素材７２重量部、前記球状メソフェーズ低温
焼成炭素１重量部および前記球塊状黒鉛２７重量部をそ
れぞれ添加した後、せん断分散した。つづいて、この混
合物にＳＢＲラテックス３．４重量部を添加し、均一の
混合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 72 parts by weight of the fibrous carbon material, 1 part by weight of the spherical mesophase low-temperature calcined carbon and 27 parts by weight of the spheroidal graphite were added to 177 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.68% by weight. After adding each part, it was sheared and dispersed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１００】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面に７
６ｇ／ｍ2になるように塗工し、乾燥した。その後、プ
レス、スリット加工を施して厚さ１１３μｍ、幅５１．
０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both sides of a copper foil (current collector) having a thickness of 12 μm using a knife edge coater.
Coating was performed to 6 g / m 2 and drying was performed. After that, pressing and slitting are performed to make the thickness 113 μm and the width 51.
A band-shaped negative electrode of 0 mm was produced.
【０１０１】次いで、前記正負極の集電体にリードタブ
をそれぞれ接合し、自動捲回機を用いてポリエチレン製
多孔膜を２枚介してスパイラル状に巻き上げ、さらにプ
レスすることにより扁平状の発電要素を作製した。得ら
れた発電要素に直流電源から１００Ｖの電圧を５秒間印
加し、１０μＶ以上流れるものを不良と判定して除外し
た。Next, lead tabs were respectively joined to the positive and negative electrode current collectors, spirally wound through two polyethylene porous membranes using an automatic winding machine, and further pressed to obtain a flat power generating element. Was prepared. A voltage of 100 V was applied from the DC power supply to the obtained power generating element for 5 seconds, and a current flowing at 10 μV or more was judged to be defective and excluded.
【０１０２】次いで、厚さ２５μｍの延伸ナイロンフィ
ルムと厚さ４０μｍのアルミニウムシートと厚さ３０μ
ｍの直鎖状低密度ポリエチレン（ＬＬＤＰＥ）フィルム
とをこの順序でウレタン系接着剤を介して積層・接着し
た厚さ３．６ｍｍの外装材用フィルム素材を二つ折りに
し、一方の面にカップ部（長さ３６ｍｍ、幅３５ｍｍ、
高さ６２ｍｍ）を絞り加工し、このカップ部に良品とし
て判定された発電要素を挿入し、他方の面を前記カップ
部を有する面の周辺に注液口を除いて熱シールし、非水
系電解液を注入した後、前記注液口を熱シールして封口
することによって、前述した図３，図４に示す薄型リチ
ウムイオン二次電池を組立てた。なお、前記非水系電解
液はエチレンカーボネートとγ−ブチロラクトンを１：
３の重量比で混合した混合非水溶媒にホウフッ化リチウ
ム（ＬｉＢＦ4）を１．５モル／Ｌの濃度で溶解した組
成を有する。Next, a stretched nylon film having a thickness of 25 μm, an aluminum sheet having a thickness of 40 μm, and a
m and a low-density linear low-density polyethylene (LLDPE) film are laminated and bonded in this order via a urethane-based adhesive, and a 3.6 mm-thick film material for an exterior material is folded in two. (Length 36mm, width 35mm,
(The height of 62 mm) is drawn, a power generating element determined as a non-defective product is inserted into the cup portion, and the other surface is heat-sealed around the surface having the cup portion except for a liquid injection port, and the non-aqueous electrolytic solution is formed. After the liquid was injected, the injection port was heat-sealed and sealed to assemble the thin lithium ion secondary battery shown in FIGS. The non-aqueous electrolyte solution was prepared by mixing ethylene carbonate and γ-butyrolactone in a ratio of 1:
The composition has a composition in which lithium borofluoride (LiBF 4 ) is dissolved at a concentration of 1.5 mol / L in a mixed nonaqueous solvent mixed at a weight ratio of 3.
【０１０３】（実施例７）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例６
と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。Example 7 Example 6 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A thin lithium-ion secondary battery having the same structure as that of was assembled. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１０４】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９４ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３０μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 194 g / m 2 and dried. A band-shaped positive electrode having a thickness of 130 μm and a width of 49.5 mm was produced by pressing and slitting.
【０１０５】＜負極の作製＞カルボキシメチルセルロー
スの０．５８重量％濃度の粘調水溶液１７３重量部に前
記繊維状炭素材９０重量部、前記球状メソフェーズ低温
焼成炭素３重量部および前記球塊状黒鉛７重量部をそれ
ぞれ添加した後、せん断分散した。つづいて、この混合
物にＳＢＲラテックス３．４重量部を添加し、均一の混
合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 90 parts by weight of the fibrous carbon material, 3 parts by weight of the spherical mesophase low-temperature calcined carbon and 7 parts by weight of the spheroidal graphite were added to 173 parts by weight of a 0.58% by weight viscous aqueous solution of carboxymethyl cellulose. After adding each part, it was sheared and dispersed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１０６】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７６ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１１３μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 12 μm by a knife edge coater so as to have a thickness of 76 g / m 2 , respectively, and dried. After that, it is pressed and slit to a thickness of 113 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１０７】（実施例８）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例６
と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。Example 8 Example 6 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A thin lithium-ion secondary battery having the same structure as that of was assembled. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１０８】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９６ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３２μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at 196 g / m 2 and dried. A band-shaped positive electrode having a thickness of 132 μm and a width of 49.5 mm was produced by performing pressing and slitting.
【０１０９】＜負極の作製＞カルボキシメチルセルロー
スの１．１６重量％濃度の粘調水溶液２０６重量部に前
記繊維状炭素材５重量部、前記メソフェーズ低温焼成炭
素繊維７重量部および前記球塊状黒鉛８８重量部をそれ
ぞれ添加した後、せん断分散した。つづいて、この混合
物にＳＢＲラテックス３．４重量部を添加し、均一の混
合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 5 parts by weight of the fibrous carbon material, 7 parts by weight of the mesophase low-temperature calcined carbon fiber, and 88 parts by weight of the spheroidal graphite were added to 206 parts by weight of a 1.16% by weight viscous aqueous solution of carboxymethyl cellulose. After adding each part, it was sheared and dispersed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１１０】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７３ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１１０μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied on both surfaces of a copper foil (current collector) having a thickness of 12 μm by a knife edge coater so as to be 73 g / m 2 , and dried. After that, pressing and slitting are performed to a thickness of 110 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１１１】（実施例９）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例６
と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。Example 9 Example 6 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A thin lithium-ion secondary battery having the same structure as that of was assembled. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１１２】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９６ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３２μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at 196 g / m 2 and dried. A band-shaped positive electrode having a thickness of 132 μm and a width of 49.5 mm was produced by performing pressing and slitting.
【０１１３】＜負極の作製＞カルボキシメチルセルロー
スの０．７４重量％濃度の粘調水溶液１９１重量部に前
記繊維状炭素材４５重量部、前記メソフェーズ低温焼成
炭素繊維１０重量部および前記球塊状黒鉛４５重量部を
それぞれ添加した後、せん断分散した。つづいて、この
混合物にＳＢＲラテックス３．４重量部を添加し、均一
の混合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 45 parts by weight of the fibrous carbon material, 10 parts by weight of the mesophase low-temperature calcined carbon fiber, and 45 parts by weight of the spheroidal graphite were added to 191 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.74% by weight. After adding each part, it was sheared and dispersed. Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１１４】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７３ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１１０μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 12 μm to a thickness of 73 g / m 2 by a knife edge coater and dried. After that, pressing and slitting are performed to a thickness of 110 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１１５】（実施例１０）正極および負極として、以
下に説明する方法で作製したものを用いた以外、実施例
６と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。(Example 10) A thin lithium ion secondary battery having the same structure as in Example 6 was assembled except that the positive electrode and the negative electrode were manufactured by the method described below. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１１６】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９６ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３２μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 196 g / m 2 and dried. A band-shaped positive electrode having a thickness of 132 μm and a width of 49.5 mm was produced by performing pressing and slitting.
【０１１７】＜負極の作製＞カルボキシメチルセルロー
スの０．６４重量％濃度の粘調水溶液１９０重量部に前
記繊維状炭素材５０重量部、前記擬球状低温焼成炭素１
５重量部および前記球塊状黒鉛３５重量部をそれぞれ添
加した後、せん断分散した。つづいて、この混合物にＳ
ＢＲラテックス３．４重量部を添加し、均一の混合攪拌
して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 50 parts by weight of the fibrous carbon material and 190 parts by weight of a viscous aqueous solution of carboxymethyl cellulose having a concentration of 0.64% by weight,
After 5 parts by weight and 35 parts by weight of the spheroidal graphite were added, they were shear-dispersed. Subsequently, S
3.4 parts by weight of BR latex were added, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１１８】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７１ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１０７μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 12 μm by a knife edge coater so as to be 71 g / m 2 , and dried. After that, it is pressed and slitted to a thickness of 107 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１１９】（比較例３）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例６
と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。Comparative Example 3 Example 6 was repeated except that the positive electrode and the negative electrode were manufactured by the method described below.
A thin lithium-ion secondary battery having the same structure as that of was assembled. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１２０】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９４ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３０μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both surfaces of a 15 μm-thick aluminum foil (current collector) at 194 g / m 2 and dried. A band-shaped positive electrode having a thickness of 130 μm and a width of 49.5 mm was produced by pressing and slitting.
【０１２１】＜負極の作製＞カルボキシメチルセルロー
スの０．６７重量％濃度の粘調水溶液１８０重量部に前
記繊維状炭素材７５重量部および前記球塊状黒鉛２５重
量部をそれぞれ添加した後、せん断分散した。つづい
て、この混合物にＳＢＲラテックス３．４重量部を添加
し、均一の混合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 75 parts by weight of the fibrous carbon material and 25 parts by weight of the spheroidal graphite were added to 180 parts by weight of a viscous aqueous solution of carboxymethylcellulose having a concentration of 0.67% by weight, followed by shear dispersion. . Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１２２】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７８ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１１６μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both sides of a copper foil (current collector) having a thickness of 12 μm by a knife edge coater so as to have a thickness of 78 g / m 2 , and dried. After that, it is pressed and slit to a thickness of 116 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１２３】（比較例４）正極および負極として、以下
に説明する方法で作製したものを用いた以外、実施例６
と同様な構造の薄型リチウムイオン二次電池を組立て
た。なお、正負極、セパレータを有する発電要素の作製
後は、実施例６と同様な良・不良の判定を行ない、良品
として判定された発電要素のみを使用した。Comparative Example 4 Example 6 was repeated except that a positive electrode and a negative electrode were manufactured by the method described below.
A thin lithium-ion secondary battery having the same structure as that of was assembled. After the production of the power generating element having the positive and negative electrodes and the separator, the same good / bad judgment as in Example 6 was performed, and only the power generating element judged as good was used.
【０１２４】＜正極の作製＞実施例１と同様な正極塗工
スラリーを厚さ１５μｍのアルミニウム箔（集電体）の
両面にそれぞれ１９４ｇ／ｍ2になるように塗工し、乾
燥した後、プレス、スリット加工を施すことにより厚さ
１３０μｍ、幅４９．５ｍｍの帯状正極を作製した。<Preparation of Positive Electrode> The same positive electrode coating slurry as in Example 1 was applied to both sides of a 15 μm-thick aluminum foil (current collector) at 194 g / m 2 and dried. A band-shaped positive electrode having a thickness of 130 μm and a width of 49.5 mm was produced by pressing and slitting.
【０１２５】＜負極の作製＞カルボキシメチルセルロー
スの０．７４重量％濃度の粘調水溶液１９１重量部に前
記繊維状炭素材５０重量部および前記球塊状黒鉛５０重
量部をそれぞれ添加した後、せん断分散した。つづい
て、この混合物にＳＢＲラテックス３．４重量部を添加
し、均一の混合攪拌して負極塗工スラリーを調製した。<Preparation of Negative Electrode> 50 parts by weight of the fibrous carbon material and 50 parts by weight of the spheroidal graphite were added to 191 parts by weight of a viscous aqueous solution of carboxymethylcellulose having a concentration of 0.74% by weight, and then dispersed by shearing. . Subsequently, 3.4 parts by weight of SBR latex was added to the mixture, and the mixture was uniformly mixed and stirred to prepare a negative electrode coating slurry.
【０１２６】次いで、前記塗工スラリーをナイフエッジ
コータにより厚さ１２μｍの銅箔（集電体）の両面にそ
れぞれ７８ｇ／ｍ2になるように塗工し、乾燥した。そ
の後、プレス、スリット加工を施して厚さ１１６μｍ、
幅５１．０ｍｍの帯状負極を作製した。Next, the coating slurry was applied to both surfaces of a copper foil (current collector) having a thickness of 12 μm by a knife edge coater so as to be 78 g / m 2 , and dried. After that, it is pressed and slit to a thickness of 116 μm,
A strip-shaped negative electrode having a width of 51.0 mm was produced.
【０１２７】得られた実施例６〜１０および比較例３，
４の薄型リチウムイオン二次電池について、実施例１と
同様に初期容量、８５℃の環境下に４８時間放置した後
における容量維持率および容量回復率、９０℃の環境下
に２４時間放置した後における容量維持率および容量回
復率、２０℃および６０℃の環境下における５００サイ
クル後の容量維持率をそれぞれ求めた。これらの結果を
下記表２に示す。The obtained Examples 6 to 10 and Comparative Example 3,
As for the thin lithium ion secondary battery of No. 4, the initial capacity was the same as in Example 1, the capacity retention rate and capacity recovery rate after being left for 48 hours in an environment of 85 ° C., and after being left for 24 hours in an environment of 90 ° C. , And the capacity retention rate after 500 cycles in an environment of 20 ° C. and 60 ° C., respectively. The results are shown in Table 2 below.
【０１２８】[0128]
【表２】 [Table 2]
【０１２９】前記表２から明らかなように、実施例６〜
９の薄型リチウムイオン二次電池と比較例３，４の薄型
リチウムイオン二次電池とは、初期容量および２０℃の
環境下での５００サイクル目の容量維持率の点で大きな
差異がないものの、特定の炭素材料を含む負極を備えた
実施例６〜９の二次電池は６０℃の環境下での５００サ
イクル目の容量維持率および９０℃の環境下に４８時間
放置後の容量回復率数が比較例３，４の二次電池に比べ
て著しく優れていることがわかる。As is clear from Table 2 above, Examples 6 to
Although the thin lithium ion secondary battery of No. 9 and the thin lithium ion secondary batteries of Comparative Examples 3 and 4 have no significant difference in the initial capacity and the capacity retention ratio at the 500th cycle in an environment of 20 ° C., The secondary batteries of Examples 6 to 9 provided with the negative electrode containing the specific carbon material had the capacity retention rate at the 500th cycle in a 60 ° C environment and the capacity recovery rate after being left in a 90 ° C environment for 48 hours. It can be seen that is significantly superior to the secondary batteries of Comparative Examples 3 and 4.
【０１３０】一方、実施例１０の二次電池は初期容量が
比較例３，４の二次電池に比べて若干劣るものの、６０
℃の環境下での５００サイクル目の容量維持率および９
０℃の環境下に４８時間放置後の容量回復率数がいずれ
も優れていることがわかる。On the other hand, although the secondary battery of Example 10 had a slightly lower initial capacity than the secondary batteries of Comparative Examples 3 and 4,
500% cycle capacity retention rate in an environment of
It can be seen that all the capacity recovery rates after being left for 48 hours in an environment of 0 ° C. are excellent.
【０１３１】なお、前述した実施例１〜１０では角型、
薄型のリチウムイオン二次電池について説明したが、本
発明は前述した図１の円筒型リチウムイオン二次電池に
適用しても同様な優れた高温充放電サイクル特性および
高温保存回復特性を有する。It should be noted that in Examples 1 to 10 described above, a square
Although the thin lithium-ion secondary battery has been described, the present invention has the same excellent high-temperature charge / discharge cycle characteristics and high-temperature storage / recovery characteristics even when applied to the above-described cylindrical lithium-ion secondary battery of FIG.
【０１３２】[0132]
【発明の効果】以上詳述したように、本発明によれば負
極を改良することによって高温充放電サイクル特性の向
上および高温保存回復特性の改善を図ることができ、例
えば夏場に携帯電話機を自動車内に放置する等、過酷な
環境におかれた場合でも正常に作動する高信頼性、高性
能の非水系電解液二次電池を提供することができる。As described above in detail, according to the present invention, by improving the negative electrode, the high-temperature charge / discharge cycle characteristics and the high-temperature storage recovery characteristics can be improved. It is possible to provide a highly reliable and high-performance non-aqueous electrolyte secondary battery that normally operates even in a harsh environment such as being left inside.
【図１】本発明に係る非水系電解液二次電池の一形態あ
る円筒型非水系電解液二次電池（円筒型リチウムイオン
二次電池）を示す部分断面図。FIG. 1 is a partial cross-sectional view showing a cylindrical non-aqueous electrolyte secondary battery (cylindrical lithium ion secondary battery) as one embodiment of the non-aqueous electrolyte secondary battery according to the present invention.
【図２】本発明に係る非水系電解液二次電池の他の形態
ある角型非水系電解液二次電池（角型リチウムイオン二
次電池）を示す部分切欠斜視図。FIG. 2 is a partially cutaway perspective view showing a prismatic nonaqueous electrolyte secondary battery (square lithium ion secondary battery) as another embodiment of the nonaqueous electrolyte secondary battery according to the present invention.
【図３】本発明に係る非水系電解液二次電池のさらに他
の形態ある薄型非水系電解液二次電池（薄型リチウムイ
オン二次電池）を示す斜視図。FIG. 3 is a perspective view showing a thin non-aqueous electrolyte secondary battery (thin lithium ion secondary battery) as still another embodiment of the non-aqueous electrolyte secondary battery according to the present invention.
【図４】図３のIV−IV線に沿う断面図。FIG. 4 is a sectional view taken along the line IV-IV in FIG. 3;
１、２１…外装缶、 ３，２３電極体、 ４，２４，４８…負極、 ５，２５，４５…セパレータ、 ６，２６，４４…正極、 １２…封口板、 ２８…蓋体、 ４１…発電要素、 ４３，４６…集電体、 ５１…外装フィルム。 1, 21: exterior can, 3,23 electrode body, 4, 24, 48 ... negative electrode, 5, 25, 45 ... separator, 6, 26, 44 ... positive electrode, 12 ... sealing plate, 28 ... lid, 41 ... power generation Elements, 43, 46: current collector, 51: exterior film.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中島 孝之 東京都品川区南品川３丁目４番10号 株式 会社エイ・ティーバッテリー内 (72)発明者 松本 浩一 東京都品川区南品川３丁目４番10号 株式 会社エイ・ティーバッテリー内 (72)発明者 上林 信一 神奈川県横浜市磯子区新杉田町８番地 東 芝電子エンジニアリング株式会社内 Ｆターム(参考） 5H029 AJ05 AK02 AK03 AK04 AK18 AL06 AL07 AL08 AL19 AM03 AM04 AM05 AM06 CJ02 DJ15 DJ16 DJ17 HJ01 HJ04 HJ05 HJ07 HJ08 HJ13 HJ14 5H050 AA05 AA07 AA10 BA17 CB07 CB08 CB09 CB30 DA18 FA16 FA17 FA19 GA02 HA01 HA04 HA05 HA07 HA08 HA13 HA14 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayuki Nakajima 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside AT Battery Inc. (72) Inventor Koichi Matsumoto 3-4-1 Minamishinagawa, Shinagawa-ku, Tokyo No. 10 Inside AT Battery Co., Ltd. (72) Inventor Shinichi Kamibayashi F-term (reference) 5H029 AJ05 AK02 AK03 AK04 AK18 AL06 AL07 AL08 AL19 in Shin-Sugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture AM03 AM04 AM05 AM06 CJ02 DJ15 DJ16 DJ17 HJ01 HJ04 HJ05 HJ07 HJ08 HJ13 HJ14 5H050 AA05 AA07 AA10 BA17 CB07 CB08 CB09 CB30 DA18 FA16 FA17 FA19 GA02 HA01 HA04 HA05 HA07 HA08 HA13 HA14
Claims (25)
ウムを吸蔵・放出可能な負極、セパレータおよび非水系
電解液を備え、 前記正極および前記負極は、集電体にそれぞれ正極材料
および負極材料を塗布した構造を有し、かつ前記負極材
料は、低温焼成炭素を含む２種以上の炭素質材を含有す
ることを特徴とする非水系電解液二次電池。1. A positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator, and a non-aqueous electrolyte. The positive electrode and the negative electrode each include a positive electrode material and a negative electrode material as a current collector. A non-aqueous electrolyte secondary battery having a structure coated, and wherein the negative electrode material contains two or more types of carbonaceous materials including low-temperature fired carbon.
チから得られた揮発性有機物、溶融溶解性有機物、不融
性繊維状有機物、フェノール樹脂、フルフラール樹脂を
原料として、１０００℃以下の温度で焼成されたカーボ
ン材料であることを特徴とする請求項１記載の非水系電
解液二次電池。2. The low-temperature calcined carbon is made of a volatile organic substance obtained from coal, petroleum pitch, a melt-soluble organic substance, an infusible fibrous organic substance, a phenol resin, a furfural resin, and has a temperature of 1000 ° C. or less. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte secondary battery is a carbon material fired in the above.
からメソフェーズを経由して得られたメソフェーズ系低
温焼成炭素であることを特徴とする請求項２記載の非水
系電解液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 2, wherein the low-temperature fired carbon is a mesophase-based low-temperature fired carbon obtained from the petroleum pitch via a mesophase.
維状炭素質材であることを特徴とする請求項１記載の非
水系電解液二次電池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbonaceous material other than the low-temperature fired carbon is a fibrous carbonaceous material.
１８μｍ、平均繊維長１０〜５０μｍ、真密度２．２４
ｇ／ｃｃ以上、面間隔（ｄ002）０．３３５６〜０．３
３６８ｎｍ、ｃ軸方向の結晶子の大きさ（Ｌｃ）が４０
ｎｍ以上であることを特徴とする請求項４記載の非水系
電解液二次電池。5. The fibrous carbonaceous material has an average fiber diameter of 8 to 8.
18 μm, average fiber length 10-50 μm, true density 2.24
g / cc or more, surface spacing (d 002 ) 0.3356-0.3
368 nm, crystallite size (Lc) in the c-axis direction is 40
The non-aqueous electrolyte secondary battery according to claim 4, wherein
片状、球状、球塊状または擬球状の黒鉛であることを特
徴とする請求項１記載の非水系電解液二次電池。6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbonaceous material other than the low-temperature fired carbon is flaky, spherical, spherical, or pseudospherical graphite.
の黒鉛は、平均粒径２〜５０μｍ、比表面積２〜２０ｍ
2／ｇ、真密度２．２３〜２．２８ｇ／ｃｃ、面間隔
（ｄ002）０．３３５４〜０．３３５８ｎｍであること
を特徴とする請求項６記載の非水系電解液二次電池。7. The flaky, spherical, spherical or pseudo-spherical graphite has an average particle size of 2 to 50 μm and a specific surface area of 2 to 20 m.
2 / g, a true density 2.23~2.28g / cc, the nonaqueous electrolyte secondary battery according to claim 6, characterized in that the plane spacing (d 002) 0.3354~0.3358nm.
１〜１０重量％の割合で含有されることを特徴とする請
求項１ないし７いずれか記載の非水系電解液二次電池。8. The non-aqueous electrolyte secondary battery according to claim 1, wherein the low-temperature fired carbon is contained in the carbonaceous material at a ratio of 1 to 10% by weight.
の黒鉛は、炭素質材中に１０〜６０重量％の割合で含有
されることを特徴とする請求項１ないし８記載の非水系
電解液二次電池。9. The non-aqueous system according to claim 1, wherein said flaky, spherical, spherical or pseudo-spherical graphite is contained in the carbonaceous material at a ratio of 10 to 60% by weight. Electrolyte secondary battery.
チウムを吸蔵・放出可能な負極、セパレータおよび非水
系電解液を備え、 前記正極および前記負極は、集電体にそれぞれ正極材料
および負極材料を塗布した構造を有し、かつ前記負極材
料は、球状のメソフェーズ低温焼成炭素を含む２種以上
の炭素質材を含有することを特徴とする非水系電解液二
次電池。10. A positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, a separator, and a non-aqueous electrolyte. The positive electrode and the negative electrode each include a positive electrode material and a negative electrode material as a current collector. A non-aqueous electrolyte secondary battery having a coated structure, wherein the negative electrode material contains two or more kinds of carbonaceous materials including spherical mesophase low-temperature fired carbon.
は、平均粒径８〜２０μｍ、真密度１．５０〜１．７５
ｇ／ｃｃであることを特徴とする請求項１０記載の非水
系電解液二次電池。11. The spherical mesophase low-temperature calcined carbon has an average particle size of 8 to 20 μm and a true density of 1.50 to 1.75.
The non-aqueous electrolyte secondary battery according to claim 10, wherein the secondary battery is g / cc.
以外の炭素質材は、繊維状炭素質材であることを特徴と
する請求項１０記載の非水系電解液二次電池。12. The non-aqueous electrolyte secondary battery according to claim 10, wherein the carbonaceous material other than the spherical mesophase low-temperature fired carbon is a fibrous carbonaceous material.
〜１８μｍ、平均繊維長１０〜５０μｍ、真密度２．２
４ｇ／ｃｃ以上、面間隔（ｄ002）０．３３５６〜０．
３３６８ｎｍ、ｃ軸方向の結晶子の大きさ（Ｌｃ）が４
０ｎｍ以上であることを特徴とする請求項１２記載の非
水系電解液二次電池。13. The fibrous carbonaceous material has an average fiber diameter of 8
１８18 μm, average fiber length 10-50 μm, true density 2.2
4 g / cc or more, face spacing (d 002 ) 0.3356-0.
3368 nm, the crystallite size (Lc) in the c-axis direction is 4
The non-aqueous electrolyte secondary battery according to claim 12, wherein the thickness is 0 nm or more.
球塊状の黒鉛を含有することを特徴とする請求項１０記
載の非水系電解液二次電池。14. The non-aqueous electrolyte secondary battery according to claim 10, wherein the carbonaceous material further contains flaky or spherical graphite.
均粒径２〜５０μｍ、比表面積２〜２０ｍ2／ｇ、真密
度２．２３〜２．２８ｇ／ｃｃ、面間隔（ｄ0 02）０．
３３５４〜０．３３５８ｎｍであることを特徴とする請
求項１４記載の非水系電解液二次電池。15. The flaky or spherical graphite has an average particle size of 2 to 50 μm, a specific surface area of 2 to 20 m 2 / g, a true density of 2.23 to 2.28 g / cc, and a spacing (d 0 02 ). 0.
The non-aqueous electrolyte secondary battery according to claim 14, wherein the thickness is 3354 to 0.3358 nm.
は、前記炭素質材中に１〜１０重量％の割合で含有され
ることを特徴とする請求項９ないし１５いずれか記載の
非水系電解液二次電池。16. The non-aqueous electrolyte solution according to claim 9, wherein the spherical mesophase low-temperature calcined carbon is contained in the carbonaceous material at a ratio of 1 to 10% by weight. Next battery.
記炭素質材中に１０〜６０重量％の割合で含有されるこ
とを特徴とする請求項１４記載の非水系電解液二次電
池。17. The non-aqueous electrolyte secondary battery according to claim 14, wherein the flaky or spherical graphite is contained in the carbonaceous material at a ratio of 10 to 60% by weight.
チウムを吸蔵・放出可能な負極、セパレータおよび非水
系電解液を備え、 前記正極および前記負極は、集電体にそれぞれ正極材料
および負極材料を塗布した構造を有し、かつ前記負極材
料は、メソフェーズ低温焼成炭素繊維を含む２種以上の
炭素質材を含有することを特徴とする非水系電解液二次
電池。18. A positive electrode capable of storing and releasing lithium, a negative electrode capable of storing and releasing lithium, a separator, and a non-aqueous electrolyte. The positive electrode and the negative electrode each include a positive electrode material and a negative electrode material as a current collector. A non-aqueous electrolyte secondary battery having a structure coated, and wherein the negative electrode material contains two or more types of carbonaceous materials including mesophase low-temperature fired carbon fibers.
は、平均繊維径８〜１８μｍ、平均繊維長８〜２０μ
ｍ、真密度１．５０〜１．７５ｇ／ｃｃであることを特
徴とする請求項１８記載の非水系電解液二次電池。19. The mesophase low-temperature fired carbon fiber has an average fiber diameter of 8 to 18 μm and an average fiber length of 8 to 20 μm.
19. The non-aqueous electrolyte secondary battery according to claim 18, wherein the true density is 1.50 to 1.75 g / cc.
外の炭素質材は、繊維状炭素材であることを特徴とする
請求項１８記載の非水系電解液二次電池。20. The non-aqueous electrolyte secondary battery according to claim 18, wherein the carbonaceous material other than the mesophase low-temperature fired carbon fiber is a fibrous carbon material.
１８μｍ、平均繊維長１０〜５０μｍ、真密度２．２４
ｇ／ｃｃ以上であることを特徴とする請求項２０記載の
非水系電解液二次電池。21. The fibrous carbon material has an average fiber diameter of 8 to
18 μm, average fiber length 10-50 μm, true density 2.24
21. The non-aqueous electrolyte secondary battery according to claim 20, which is at least g / cc.
外の炭素質材は、鱗片状、球塊状または擬球状の黒鉛を
含有することを特徴とする請求項１８記載の非水系電解
液二次電池。22. The non-aqueous electrolyte secondary battery according to claim 18, wherein the carbonaceous material other than the mesophase low-temperature fired carbon fibers contains flaky, spherical or spheroidal graphite.
は、前記炭素質材中に１〜１０重量％の割合で含有され
ることを特徴とする請求項１８ないし２２いずれか記載
の非水系電解液二次電池。23. The non-aqueous electrolyte secondary solution according to claim 18, wherein the mesophase low-temperature fired carbon fibers are contained in the carbonaceous material at a ratio of 1 to 10% by weight. battery.
ブチロラクトンを１０〜８０重量％含有することを特徴
とする請求項１８ないし２３いずれか記載の非水系電解
液二次電池。24. The non-aqueous solvent of the non-aqueous electrolyte solution is γ-
The non-aqueous electrolyte secondary battery according to any one of claims 18 to 23, comprising 10 to 80% by weight of butyrolactone.
ブチロラクトンを４５〜７０重量％含有することを特徴
とする請求項１８ないし２４いずれか記載の非水系電解
液二次電池。25. The non-aqueous solvent of the non-aqueous electrolyte solution is γ-
The non-aqueous electrolyte secondary battery according to any one of claims 18 to 24, comprising 45 to 70% by weight of butyrolactone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000339498A JP2002100410A (en) | 2000-07-21 | 2000-11-07 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-220944 | 2000-07-21 | ||
| JP2000220945 | 2000-07-21 | ||
| JP2000220944 | 2000-07-21 | ||
| JP2000-220945 | 2000-07-21 | ||
| JP2000339498A JP2002100410A (en) | 2000-07-21 | 2000-11-07 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002100410A true JP2002100410A (en) | 2002-04-05 |
Family
ID=27344129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000339498A Pending JP2002100410A (en) | 2000-07-21 | 2000-11-07 | Nonaqueous electrolyte secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP2002100410A (en) |
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|---|---|---|---|---|
| JP2005135826A (en) * | 2003-10-31 | 2005-05-26 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| US9190661B2 (en) | 2011-05-10 | 2015-11-17 | Toyota Jidosha Kabushiki Kaisha | Secondary battery and method for producing secondary battery |
| US9997768B2 (en) | 2010-12-06 | 2018-06-12 | Toyota Jidosha Kabushiki Kaisha | Lithium ion secondary battery and method for manufacturing lithium ion secondary battery |
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| JPH11111297A (en) * | 1993-03-10 | 1999-04-23 | Toshiba Corp | Lithium secondary battery |
| JP2000138061A (en) * | 1998-08-27 | 2000-05-16 | Nec Corp | Nonaqueous electrolyte secondary battery, and its manufacture and carbon material composition |
| JP2000156230A (en) * | 1998-11-18 | 2000-06-06 | Samsung Sdi Co Ltd | Carbonic active material for lithium ion secondary battery |
| JP2000200624A (en) * | 1999-01-06 | 2000-07-18 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte secondary battery |
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| JPH11111297A (en) * | 1993-03-10 | 1999-04-23 | Toshiba Corp | Lithium secondary battery |
| JPH087885A (en) * | 1994-06-15 | 1996-01-12 | Toshiba Corp | Lithium secondary battery |
| JP2000138061A (en) * | 1998-08-27 | 2000-05-16 | Nec Corp | Nonaqueous electrolyte secondary battery, and its manufacture and carbon material composition |
| JP2000156230A (en) * | 1998-11-18 | 2000-06-06 | Samsung Sdi Co Ltd | Carbonic active material for lithium ion secondary battery |
| JP2000200624A (en) * | 1999-01-06 | 2000-07-18 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte secondary battery |
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|---|---|---|---|---|
| JP2005135826A (en) * | 2003-10-31 | 2005-05-26 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| US9997768B2 (en) | 2010-12-06 | 2018-06-12 | Toyota Jidosha Kabushiki Kaisha | Lithium ion secondary battery and method for manufacturing lithium ion secondary battery |
| US9190661B2 (en) | 2011-05-10 | 2015-11-17 | Toyota Jidosha Kabushiki Kaisha | Secondary battery and method for producing secondary battery |
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