JPH01161677A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH01161677A JPH01161677A JP62318692A JP31869287A JPH01161677A JP H01161677 A JPH01161677 A JP H01161677A JP 62318692 A JP62318692 A JP 62318692A JP 31869287 A JP31869287 A JP 31869287A JP H01161677 A JPH01161677 A JP H01161677A
- Authority
- JP
- Japan
- Prior art keywords
- electrode body
- positive electrode
- less
- negative electrode
- radius
- 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
- -1 transition metal chalcogen compound Chemical class 0.000 claims abstract description 37
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000002050 diffraction method Methods 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 68
- 230000001186 cumulative effect Effects 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910003092 TiS2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000005280 amorphization Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- GBROPGWFBFCKAG-UHFFFAOYSA-N picene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- 229910015028 LiAsF5 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000008360 acrylonitriles Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphene Chemical compound C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C=CC3=CC2=C1 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
【発明の詳細な説明】
（産業上の利用分野）
本発明は、二次電池に関し、更に詳しくは、エネルギー
密度が高く、充放電サイクル寿命が長く、信頼性が優れ
た二次電池に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a secondary battery, and more particularly to a secondary battery that has high energy density, long charge/discharge cycle life, and excellent reliability.
（従来の技術及び問題点）
近年、電子機器の発達に伴い、小型で軽量、かつエネル
ギー密度が高く、繰り返し充放電可能な二次電池の開発
に対する要望が高まってきた、 。(Prior Art and Problems) In recent years, with the development of electronic devices, there has been an increasing demand for the development of secondary batteries that are small, lightweight, have high energy density, and can be charged and discharged repeatedly.
そのような二次電池としては、例えばポリアセチレン等
の導電性高分子を正極や負極に使用したもの（特開昭５
６−１３６４１９号公報）が知られているが、導電性高
分子を正極に使用した場合には、電極容量が不充分とな
り、負極に使用した場合には自己放電が大きく、貯蔵後
特性が不安定になるという不都合を生じている。Such secondary batteries include, for example, those using conductive polymers such as polyacetylene for the positive and negative electrodes (Japanese Unexamined Patent Publication No. 5
6-136419) is known, but when a conductive polymer is used for the positive electrode, the electrode capacity is insufficient, and when used for the negative electrode, self-discharge is large and the characteristics after storage are poor. This causes the inconvenience of stability.
また、正極体の主要成分がＴｉＳ２．ＭｏＳ２のような
還移金属のカルコゲン化合物であり、負極体がＬｉ又は
Ｌｉを主体とするアルカリ金属である非水電解液二次電
池は、高エネルギー密度を有するので商品化の努力が払
われている。Moreover, the main component of the positive electrode body is TiS2. Efforts are being made to commercialize nonaqueous electrolyte secondary batteries, which are chalcogen compounds of reduced metals such as MoS2, and whose negative electrodes are Li or an alkali metal mainly composed of Li, because they have high energy density. There is.
このような二次電池の１例を第１図に示す０図はボタン
形非水電解液二次電池の縦断面図である。An example of such a secondary battery is shown in FIG. 1, and FIG. 0 is a longitudinal sectional view of a button-type non-aqueous electrolyte secondary battery.
図において、ｌが正極体である。正極体１は、上記した
ような遷移金属カルコゲン化合物の粉末とポリテトラフ
ルオロエチレンのような結着剤との混合物をペレット化
又はシート化したものである。In the figure, l is the positive electrode body. The positive electrode body 1 is made by pelletizing or sheeting a mixture of the above-mentioned transition metal chalcogen compound powder and a binder such as polytetrafluoroethylene.
２はセパレータで、例えば多孔質ポリプロピレン薄膜、
ポリプロピレン不織布のような保液性を有する材料で構
成され、正極体１の上に載置される。そして、このセパ
レータ２には、プロピレンカーボネート、１．２−ジメ
トキシエタン、１．３−ジオキソランのような非プロト
ン性有機溶媒に、Ｌｉ０文０４．ＬｉＡ又０４゜ＬｉＢ
Ｆ４ 、ＬｉＰＦ６ 、ＬｉＡｓＦ５のような電解質を
溶解せしめた所定濃度の非水電解液が含浸されている。2 is a separator, for example, a porous polypropylene thin film,
It is made of a liquid-retentive material such as polypropylene nonwoven fabric, and is placed on the positive electrode body 1 . Then, this separator 2 is prepared by adding Li0F04. LiA or 04°LiB
It is impregnated with a non-aqueous electrolyte of a predetermined concentration in which an electrolyte such as F4, LiPF6, or LiAsF5 is dissolved.
３は、セパレータ２を介して正極体ｌに載置されている
負極体で、Ｌｉ箔又はＬｉを主体とするアルカリ金属箔
で構成されている。Reference numeral 3 denotes a negative electrode body placed on the positive electrode body l via the separator 2, and is made of Li foil or an alkali metal foil containing Li as a main component.
これら正極体ｌ、セパレータ（非水電解液）２、及び負
極体３は全体として発電要素を構成する。そして、この
発電要素が正極缶４及び負極缶５から成る電池容器に内
蔵されて電池が組立てられる。６は絶縁バッキングであ
り、７は正極体１と正極缶４の間に介在せしめられた集
電体である。この集電体７は、通常、ニッケルネット、
ステンレス鋼製の金属金網、パンチトメタル、フオーム
メタルで構成され、ペレット化又はシート化された正極
体１の片面に圧着されている。These positive electrode body 1, separator (non-aqueous electrolyte) 2, and negative electrode body 3 constitute a power generation element as a whole. Then, this power generation element is housed in a battery container consisting of a positive electrode can 4 and a negative electrode can 5, and a battery is assembled. 6 is an insulating backing, and 7 is a current collector interposed between the positive electrode body 1 and the positive electrode can 4. This current collector 7 is usually made of nickel net,
It is composed of a stainless steel wire mesh, punched metal, or foam metal, and is crimped onto one side of the positive electrode body 1 which is formed into pellets or sheets.
上記したような従来構造の二次電池においては、次のよ
うな問題が生じており、その改善が求められている。In the secondary battery having the conventional structure as described above, the following problems have occurred, and improvement thereof is required.
それは、負極体がＬｉ箔又はＬｉを主体とするアルカリ
金属の箔そのものであることに基づく問題である。すな
わち、電池の放電時には負極体からＬｉがＬｉイオンと
なって電解液に移動し、充電時にはこのＬｉイオンが金
属Ｌｉとなって再び負極体に電析するが、この充放電サ
イクルを反復させるとそれに伴って電析する金属Ｌｉは
デンドライト状となりかつ成長していき、最後には、こ
のデンドライト形状の金属Ｌｉ電析物がセパレータを貫
通して正極体に達し、短絡現象を起すという問題である
。別言すれば、充放電サイクル寿命が短いという問題で
ある。This is a problem based on the fact that the negative electrode body is a Li foil or an alkali metal foil mainly composed of Li. In other words, when the battery is discharged, Li from the negative electrode body becomes Li ions and moves to the electrolyte, and during charging, these Li ions become metal Li and are deposited on the negative electrode body again, but if this charge-discharge cycle is repeated, Along with this, the metal Li deposited becomes dendrite-like and grows, and finally, this dendrite-shaped metal Li deposit penetrates the separator and reaches the positive electrode body, causing a short circuit phenomenon. . In other words, the problem is that the charge/discharge cycle life is short.
かかる現状に鑑み、本発明者らは、よりエネルギー密度
が高く、充放電サイクル寿命が長く、また消費電流の増
大に対応しうる二次電池を開発すべく鋭意検討を重ねた
結果、本発明に到達した。In view of the current situation, the present inventors have conducted intensive studies to develop a secondary battery that has higher energy density, longer charge/discharge cycle life, and can handle increased current consumption, and as a result, has developed the present invention. Reached.
（問題点を解決するための手段と作用）本発明の二次電
池は、正極体と、該正極体に載置されたセパレータと、
該セパレータに保持された電解質と、該セパレータに載
置された負極体と、該正極体及び／又は該負極体に包含
され充放電反応に対応して該正拳負極体間を移動する活
物質とから成る発電要素が内蔵された二次電池において
、
（ａ）正極体が、遷移金属カルコゲン化合物からなり、
（ｂ）負極体が、水素／炭素の原子比０．１０未満、Ｘ
線広角回折法による（００２）面の面間隔（ｄＱ０２）
３．３７Å以上３．７５Å以下、Ｃ軸方向の結晶子の大
きさ（Ｌｃ）５Å以上１５０Å以下、細孔半径が１０〜
２５０Ａである細孔の積算細孔容積が１ 、 ＯＸ Ｉ
Ｏ’ｍｌ／ｇ以上ならびに該積算細孔容積の分布が、
及び
である炭素質材料からなり、
（ｃ）活物質が、リチウム又はリチウムを主体とするア
ルカリ金属である
ことを特徴とする。(Means and effects for solving the problems) The secondary battery of the present invention includes a positive electrode body, a separator placed on the positive electrode body,
An electrolyte held in the separator, a negative electrode body placed on the separator, and an active material that is included in the positive electrode body and/or the negative electrode body and moves between the positive electrode bodies in response to charge/discharge reactions. (a) the positive electrode body is made of a transition metal chalcogen compound, (b) the negative electrode body has a hydrogen/carbon atomic ratio of less than 0.10,
Interplanar spacing (dQ02) of (002) plane by line wide-angle diffraction method
3.37 Å or more and 3.75 Å or less, crystallite size in the C-axis direction (Lc) of 5 Å or more and 150 Å or less, and pore radius of 10 to 150 Å
The integrated pore volume of a pore that is 250A is 1, OX I
O'ml/g or more and the integrated pore volume distribution is made of a carbonaceous material, and (c) the active material is lithium or an alkali metal mainly composed of lithium.
本発明の二次電池は、上記した（ａ）、（ｂ）、（ｃ）
、とりわけ（ｂ）を具備するところに特徴を有するもの
であり、その他の要素は従来の二次電池と同じであって
よい。The secondary battery of the present invention has the above-mentioned (a), (b), and (c).
, in particular, it is characterized by having (b), and other elements may be the same as conventional secondary batteries.
まず、本発明にかかる正極体は遷移金属カルコゲン化合
物からなるが、使用される遷移金属カルコゲン化合物と
しては、例えばＶ、Ｍｏ、Ｍｎ、Ｃｒ、Ｔｆ等の酸化物
や硫化物が挙げられ、■の酸化物、■の硫化物、Ｍｏの
酸化物、Ｍｏの硫化物、Ｍｎの酸化物、Ｃｒの酸化物、
Ｔｉの酸化物及びＴｉの硫化物が好ましい、さらに好ま
しくは、Ｖ２０ｓ ｔ Ｖ＠ ＯＢ、ＶＯ２、Ｖ２３５
、ＶＳ２ 、ＭｏＳ２ 、Ｍｏ５３．ＭｎＯ２、Ｃｒ
３０６ 、 Ｃｒ２０５ 、 ＴｉＳ２及びＴｉＯ２で
ある。First, the positive electrode body according to the present invention is made of a transition metal chalcogen compound, and examples of the transition metal chalcogen compound used include oxides and sulfides of V, Mo, Mn, Cr, Tf, etc. oxide, (■) sulfide, Mo oxide, Mo sulfide, Mn oxide, Cr oxide,
Ti oxides and Ti sulfides are preferred, more preferably V20s t V@OB, VO2, V235
, VS2, MoS2, Mo53. MnO2, Cr
306, Cr205, TiS2 and TiO2.
上記した遷移金属カルコゲン化合物が非晶質である場合
には、非晶質化は通常、溶融急冷法を用いて実施される
。また、非晶質の含水ゲルを調製して用いることもでき
る０本発明における非晶質物とは、Ｘ線回折を行なった
ときに、結晶に基づくピークが観察されない状態のもの
をいう、すなわち、非晶質化は、Ｘ線的に無定形なブロ
ードなハローを有する回折パターンより確認され、非晶
質物は長距離秩序が消滅した構造を有する。しかし、短
距離秩序は残存していることが各種分析の結果から確認
されている。When the transition metal chalcogen compound described above is amorphous, amorphization is usually carried out using a melt quenching method. In addition, an amorphous hydrogel can be prepared and used. The amorphous substance in the present invention refers to a substance in which no crystal-based peak is observed when X-ray diffraction is performed, that is, Amorphization is confirmed by an X-ray diffraction pattern having an amorphous broad halo, and the amorphous material has a structure in which long-range order has disappeared. However, various analyzes have confirmed that short-range order remains.
さらに、なお−層の充放電サイクル特性のレベルアップ
の目的で、上記の遷移金属カルコゲン化合物に、金属Ｌ
ｉまたは遷移金属を添加することができる。添加量は、
遷移金属カルコゲン化合物に対して、Ｌｉは５０モル％
未満、好ましくは３０モル％未満であり、遷移金属は２
０モル％未満、好ましくは１０モル％未満である。Furthermore, for the purpose of improving the charge-discharge cycle characteristics of the Na-layer, metal L is added to the above-mentioned transition metal chalcogen compound.
i or a transition metal can be added. The amount added is
Li is 50 mol% relative to the transition metal chalcogen compound
less than 30%, preferably less than 30% by mole, and the transition metal is less than 2% by mole.
It is less than 0 mol%, preferably less than 10 mol%.
本発明にかかる正極体は例えば次のようにして製造され
る。すなわち、まず、上記結晶質の遷移金属カルコゲン
化合物を粉砕して所定粒径の粉末にする。その体積平均
粒径は５００Ｑ以下、好ましくは２００％以下、さらに
好ましくは１００Ｑ以下、特に好ましくは５０−以下で
ある。また、その比表面積は好ましくは１ｍ″／ｇ以上
、さらに好ましくは１０ｍ’／ｇ以上、特に好ましくは
２０ｍ″／ｇ以上である。The positive electrode body according to the present invention is manufactured, for example, as follows. That is, first, the crystalline transition metal chalcogen compound is ground into powder with a predetermined particle size. The volume average particle size is 500Q or less, preferably 200% or less, more preferably 100Q or less, particularly preferably 50Q or less. Further, the specific surface area is preferably 1 m''/g or more, more preferably 10 m''/g or more, particularly preferably 20 m''/g or more.
遷移金属カルコゲン化合物粉末は、通常は所定量の結着
剤を添加して両者を充分に混練する。結着剤としそは、
ポリテトラフルオロエチレンのパウダーやディスバージ
ョン、ポリオレフィンのパウダー等が用いられ、好まし
い添加量は、遷移金属カルコゲン化合物に対し１〜１０
重量％である。Usually, a predetermined amount of a binder is added to the transition metal chalcogen compound powder, and the two are sufficiently kneaded. The binder and soo are
Polytetrafluoroethylene powder, dispersion, polyolefin powder, etc. are used, and the preferred amount added is 1 to 10% based on the transition metal chalcogen compound.
Weight%.
このとき、グラファイト、カーボンブラック等の導電材
料の粉末を、遷移金属カルコゲン化合物に対して５０重
量％未満添加することもでき、好ましくは３０重−量％
未満、さらに好ましくは１５重量％である。At this time, powder of a conductive material such as graphite or carbon black may be added in an amount of less than 50% by weight, preferably 30% by weight based on the transition metal chalcogen compound.
It is less than 15% by weight, more preferably 15% by weight.
得られた混練物を加圧成形し正極体とするが、遷移金属
カルコゲン化合物を単独で加圧成形して製造した箔を正
極体として使用することもできる。The obtained kneaded product is pressure-molded to form a positive electrode body, but a foil produced by pressure-molding a transition metal chalcogen compound alone can also be used as a positive electrode body.
次に負極体について説明する。Next, the negative electrode body will be explained.
負極体は後述する炭素質材料の粉末成形体である。この
炭素質材料は、Ｈ／Ｃ（原子比）が０．１０未満、ｄ
００２が３．３７Å以上３．７５Ａ以下、Ｌｃが５Å以
上１５０Å以下、細孔半径が１０〜２５０人である細孔
の積算細孔容積が１．０ＸｌＯ−”Ｊ／ｇ以上ならびに
該積算細孔容積の分布が、
細孔半径１０〜２５０人の細孔の積算細孔容積及び
のパラメータで特定される。The negative electrode body is a powder compact made of a carbonaceous material, which will be described later. This carbonaceous material has a H/C (atomic ratio) of less than 0.10, d
002 is 3.37 Å or more and 3.75 A or less, Lc is 5 Å or more and 150 Å or less, and the pore radius is 10 to 250 pores, and the cumulative pore volume is 1.0XlO-"J/g or more, and the cumulative pore The volume distribution is specified by the parameters of pore radius, integrated pore volume of pores of 10 to 250 people.
本発明にかかる負極体に用いる炭素質材料は、Ｈ／Ｃは
好ましくは０．０７未満、さらに好ましくは０．０５未
満である。この炭素質材料には、他の原子、例えば窒素
、酸素、ハロゲン等の原子が含まれていてもよいが、他
の原子／炭素原子（Ｗ子比）が、好ましくは０．１０未
満、さらに好ましくは０．０５未満、特に好ましくは０
．０３未満である。The H/C of the carbonaceous material used in the negative electrode body according to the present invention is preferably less than 0.07, more preferably less than 0.05. This carbonaceous material may contain other atoms such as nitrogen, oxygen, halogen, etc., but the ratio of other atoms/carbon atoms (W atom ratio) is preferably less than 0.10, and Preferably less than 0.05, particularly preferably 0
．． It is less than 03.
また、Ｘ線広角回折法により求めた（００２）面の面間
隔ｄ ００２は、好ましくは３．３９Ａ以上３．７０Ａ
以下、さらに好ましくは３．４１λ以上３．６８Ａ以下
であり、Ｃ軸方向の結晶子の大きさＬｃは、好ましくは
ＩＯＡ以上ｇＯＡ以下、さらに好ましくは１２Ａ以上７
０λ以下、特に好ましくは１５Ａ以上６０Å以下である
。In addition, the interplanar spacing d 002 of the (002) plane determined by X-ray wide-angle diffraction is preferably 3.39A or more and 3.70A.
The following is more preferably 3.41λ or more and 3.68A or less, and the crystallite size Lc in the C-axis direction is preferably IOA or more and gOA or less, and more preferably 12A or more and 7
It is 0 λ or less, particularly preferably 15 A or more and 60 Å or less.
Ｈ／Ｃ，ｄ００２およびＬｃのいずれかが上記範囲から
逸脱している場合は、負極体における充放電時の過電圧
が大きくなり、その結果、負極体からガスが発生して電
池の安全性が著しく損われる。If any of H/C, d002 and Lc deviate from the above ranges, the overvoltage at the negative electrode during charging and discharging will increase, and as a result, gas will be generated from the negative electrode, significantly reducing the safety of the battery. be damaged.
しかも充放電サイクル特性も不満足になる。Moreover, the charge/discharge cycle characteristics are also unsatisfactory.
さらに、本発明にかかる負極体に用いる炭素質材料は、
細孔半径が１０〜２５０人である細孔の積算細孔容積が
好ましくは１ 、５Ｘ １０’ａＪ／ｇ以上、さらに好
マシくは２ 、 ＯＸ １０＝ａＪ／ｇ以上、特に好ま
しくは３ 、 ＯＸ １０−３ａＪ／ｇ以上であり、そ
の分布は、好ましくは、
及び
である。Furthermore, the carbonaceous material used for the negative electrode body according to the present invention is
The cumulative pore volume of pores with a pore radius of 10 to 250 is preferably 1.5 x 10'aJ/g or more, more preferably 2.OX10 = aJ/g or more, particularly preferably 3. OX 10-3aJ/g or more, and its distribution is preferably: and.
本発明において、細孔半径に対する細孔容積の分布すな
わち細孔分布は、定容法を用いて平衡圧力下で試料に吸
着したガス量（または脱離したガス量）を測定すること
により求める。In the present invention, the distribution of pore volume with respect to pore radius, that is, the pore distribution, is determined by measuring the amount of gas adsorbed to the sample (or the amount of gas desorbed) under equilibrium pressure using a constant volume method.
すなわち１本発明において積算細孔容積およびその分布
は以下のようにして求めたものを意味する。That is, in the present invention, the cumulative pore volume and its distribution mean those determined as follows.
まず、細孔が円筒状であるとの仮定に基づき、次式
［式中、ｒには細孔のケルビン半径（入）；ｒは沸点に
おける吸着ガス液体の表面張力（Ｎ２の場合７７Ｋにお
いて８ 、８５ ｅｒｇ／ｃ＋ｍ２） ； Ｖ。First, based on the assumption that the pore is cylindrical, we use the following formula [where r is the Kelvin radius of the pore (in); r is the surface tension of the adsorbed gas liquid at the boiling point (8 , 85 erg/c+m2); V.
は吸着ガス液体の分子容量（Ｎ２の場合３４．７ｃｉ＋
３１モル）；Ｒはガス定数（８、３１４Ｘ１０’ ｅ
ｒｇ／に・モル）；Ｔは吸着ガスの沸点（Ｎ２の場合７
７Ｋ）；Ｐは吸着ガスの蒸気圧であり、Ｐ、、は冷却温
度での吸着ガスの飽和蒸気圧であり、Ｐ／Ｐｏは相対圧
力を表す］
で示されるケルビン式より、細孔のケルビン半径ｒＫを
求め、次いで真の細孔半径ｒｐを次式％式％
で求められる吸着したガス層の厚み（Ａ）である］
により求めた。is the molecular capacity of the adsorbed gas liquid (34.7ci+ for N2)
31 moles); R is the gas constant (8, 314X10' e
rg/mol); T is the boiling point of the adsorbed gas (7 for N2);
7K); P is the vapor pressure of the adsorbed gas, P is the saturated vapor pressure of the adsorbed gas at the cooling temperature, and P/Po is the relative pressure] From the Kelvin equation shown, the Kelvin of the pore is The radius rK was determined, and then the true pore radius rp was determined using the following formula: % is the thickness (A) of the adsorbed gas layer determined by the formula %.
さらに、これらの値を用いて積算細孔容積およびその分
布をＢａｒｒｅｔｔ、 Ｊｏｙｎｅｒ及びＨａｌｅｎｄ
ａにより提案されたＢ、Ｊ、Ｈ，法（Ｊ、 Ａ、 Ｃ，
Ｓ、。Furthermore, these values were used to calculate the integrated pore volume and its distribution according to Barrett, Joyner and Halend.
B, J, H, method (J, A, C,
S.
７３．３７３．１９５１）により求めた。すなわち、次
式、
（丹’ｎ−１に下げた時の脱離過程において蒸発がおき
る細孔の容積、
ｒ ｐｎ：同上の脱離過程において蒸発がおきる細孔の
真の細孔半径
ｒｋｎ ’同上の脱離過程において蒸発がおきる細孔の
ケルビン半径
Δｔ ：同上の脱離過程における物理吸着層の厚さの変
化量
■ ＝同上の脱離過程における脱離ガスの液体容積
Ａ 、二同上の脱離過程において物理吸着していたＪ
ガスが脱離した時に得られた空の細孔壁の表面積であり
、円筒状の細孔であるとして、細孔容積から求める］
で示した式を用いて、相対圧力Ｐ／Ｐ、を減少させて得
られる各脱離過程ごとのデータを使用して求めた。73.373.1951). That is, the following formula, (volume of the pore where evaporation occurs in the desorption process when lowered to 2'n-1, r pn: true pore radius of the pore where evaporation occurs in the above desorption process rkn' Kelvin radius Δt of the pore where evaporation occurs in the above desorption process: Amount of change in the thickness of the physical adsorption layer during the above desorption process ■ = Liquid volume A of the desorbed gas in the above same desorption process, 2 Same as above This is the surface area of the empty pore wall obtained when the J gas physically adsorbed during the desorption process is desorbed, and is calculated from the pore volume assuming that the pore is cylindrical. It was determined using data for each desorption process obtained by decreasing the relative pressure P/P.
さらに、本発明にかかる負極体に用いる炭素質材料にあ
っては、次に述べる特性を肴することが好ましい。Furthermore, the carbonaceous material used for the negative electrode body according to the present invention preferably has the following characteristics.
すなわち、Ｘ線広角回折分析における（１１０）面の面
間隔ｄｌｌＯの２倍の距離ａＱ （＝ ２ ｄ １１
０）が、好ましくは２．３８Ａ以上かつ２．４７Ａ以下
、さらに好ましくは２．３９Å以上かつ２．４６Ａ以下
、特に好ましくは２．４０Ａ以上かつ２．４５Ａ以下；
ａ軸方向の結晶子の大きさＬａが好ましくはＩＯＡ以上
、さらに好ましくは１５Ａ以上かつ１５０Å以下、とく
に好ましくは１９Ａ以上かつ７０λ以下である。That is, the distance aQ (= 2 d 11
0) is preferably 2.38A or more and 2.47A or less, more preferably 2.39A or more and 2.46A or less, particularly preferably 2.40A or more and 2.45A or less;
The crystallite size La in the a-axis direction is preferably IOA or more, more preferably 15 A or more and 150 Å or less, particularly preferably 19 A or more and 70 λ or less.
また、波長５１４５Ａのアルゴンイオンレーザ光を用い
たラマンスペクトル分析において、下記式：
１３８０±１００ｃｍの波数域におけるスペクトル強度
の積分値で定義されるＧ値が２．５未満であることが好
ましく、さらに好ましくは０．１〜１．５であり、特に
好ましくは０．２〜１．２である。Further, in Raman spectrum analysis using argon ion laser light with a wavelength of 5145 A, the following formula: It is preferable that the G value defined by the integral value of the spectral intensity in the wave number region of 1380 ± 100 cm is less than 2.5, and Preferably it is 0.1 to 1.5, particularly preferably 0.2 to 1.2.
さらに電子スピン共鳴スペクトル分析において、−次微
分吸収曲線のシグナルの線幅（ΔＨｐｐ）が１０ガウス
以上であるか、ｌＯガウス未満の線幅のシグナルを有し
ないことが好ましい。Furthermore, in electron spin resonance spectroscopy, it is preferable that the linewidth (ΔHpp) of the signal of the −th order differential absorption curve is 10 Gauss or more, or there is no signal with a linewidth less than 10 Gauss.
上述した本発明にかかる負極体に用いる炭素質材料は、
各種の形状をとりうるが、粒径１００ｍ以下の粒子であ
ることが好ましい、さらには比表面積が好ましくはｌｒ
ｎ”／’ｇ以上、さらに好ましくは２ｍ″／ｇ以上、特
に好ましくは４ｍ″／ｇ以上である。上述の範囲を逸脱
すると活物質の担持量が減少し、電池の容量が小さくな
る。The carbonaceous material used for the negative electrode body according to the present invention described above is
Although they can take various shapes, they are preferably particles with a particle size of 100 m or less, and more preferably a specific surface area of lr.
It is at least n''/'g, more preferably at least 2 m''/g, particularly preferably at least 4 m''/g. If it deviates from the above range, the amount of supported active material will decrease and the capacity of the battery will decrease.
このような炭素質材料は、例えば有機高分子化合物、縮
合多環炭化水素化合物、縮合多環炭化水素化合物、多環
複素環系化合物等の１種又は２種以上を焼成し、炭素化
することによって製造することができる。そのような出
発源としては、具体的には、例えばセルロース樹脂；フ
ェノール樹脂；ポリアクリロニトリル、ポリ（α−ハロ
ゲン化アクリロニトリル）などのアクリル樹脂；ポリ塩
化ビニル、ポリ塩化ビニリデン、ポリ塩素化塩化ビニル
などのハロゲン化ビニル樹脂；ポリアミドイミド樹脂；
ポリアミド樹脂；ポリアセチレン、ポリ（ｐ−フェニレ
ン）などの共役系樹脂のような任意の有機高分子化合物
；例えば、ナフタレン、フェナントレン、アントラセン
、トリフェニレン、ピレン、クリセン、ナフタセン、ピ
セン、ペリレン、ペンタフェン、ペンタセンのような３
員環以上の単環炭化水声化合物が互いに２個以上縮合し
てなる縮合多環炭化水素化合物、又は、上記化合物のカ
ルボン酸、カルボン酸無水物、カルボン酸イミドのよう
な誘導体、上記各化合物の混合物を主成分とする各種の
ピッチ；例えば、インドール、イソインドール、キノリ
ン、インキノリン、キノキサリン、フタラジン、カルバ
ゾール、アクリジン、フェナジン、フエナントロリンの
ような３員環以上の複素単環化合物が互いに少なくとも
２個以上結合するか、又は１個以上の３員環以上の単環
炭化水素化合物と結合してなる縮合複素環化合物、上記
各化合物のカルボン酸、カルボン酸無水物、カルボン酸
イミドのような誘導体、更にベンゼンの１．２，４．５
−テトラカルボン酸、その二無水物またはそのジイミド
；などをあげることができる。Such carbonaceous materials can be produced by carbonizing one or more of organic polymer compounds, condensed polycyclic hydrocarbon compounds, condensed polycyclic hydrocarbon compounds, polycyclic heterocyclic compounds, etc. by firing them. It can be manufactured by Examples of such starting sources include, for example, cellulose resins; phenolic resins; acrylic resins such as polyacrylonitrile and poly(α-halogenated acrylonitrile); polyvinyl chloride, polyvinylidene chloride, polychlorinated vinyl chloride, etc. halogenated vinyl resin; polyamideimide resin;
Polyamide resin; Any organic polymer compound such as conjugated resin such as polyacetylene, poly(p-phenylene); For example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentaphene, pentacene. like 3
A condensed polycyclic hydrocarbon compound formed by condensing two or more monocyclic hydrocarbon compounds with a member ring or more, or derivatives of the above compounds such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid imides, and each of the above compounds. Various pitches mainly composed of mixtures of Fused heterocyclic compounds formed by bonding at least two or more monocyclic hydrocarbon compounds of three or more members, such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid imides of each of the above compounds. derivatives, as well as benzene 1.2, 4.5
-tetracarboxylic acid, its dianhydride or its diimide; etc.
好ましくは、フェノール樹脂、セルロース樹脂、アクリ
ル樹脂、さらに好ましくはフェノール樹脂である。Preferred are phenolic resins, cellulose resins, and acrylic resins, and more preferred are phenolic resins.
次いで、上述の出発源を後述の条件で焼成する。すなわ
ち、不活性ガス流下または真空下に、３５０〜１０００
℃で焼成する。好ましくは不活性ガス流下に焼成し、そ
の際用いられる不活性ガスとしては、例えばＮ２ 、Ａ
ｒ、Ｈｅ等を用いることができるが、経済性等の点から
Ｎ２が好ましい、また、焼成温度は好ましくは４００〜
１０００℃、さらに好ましくは５００〜１０００℃、特
に好ましくは６００〜１０００℃である。Next, the above-mentioned starting material is fired under the conditions described below. That is, under an inert gas flow or under vacuum, 350 to 1000
Bake at ℃. Preferably, the firing is performed under an inert gas flow, and the inert gas used at that time includes, for example, N2, A
R, He, etc. can be used, but N2 is preferable from the point of view of economic efficiency, etc., and the firing temperature is preferably 400~400℃.
The temperature is 1000°C, more preferably 500 to 1000°C, particularly preferably 600 to 1000°C.
通常は２℃／時〜５００℃／分、好ましくは５℃／時〜
１００℃／分、さらに好ましくは１０℃／時〜５０℃／
分、特に好ましくは２０℃／時〜１０℃／分の昇温速度
で上述の焼成温度まで昇温し、さらにその温度で１分〜
１０時間、好ましくは５分〜８時間、さらに好ましくは
ｌＯ分〜５時間、特に好ましくは２０分〜３時間保持す
ることにより焼成を実施する。Usually 2°C/hour to 500°C/min, preferably 5°C/hour to
100°C/min, more preferably 10°C/hour to 50°C/
The temperature is increased to the above-mentioned firing temperature at a heating rate of 20°C/hour to 10°C/minute, particularly preferably 20°C/hour to 10°C/minute, and then maintained at that temperature for 1 minute to
Firing is carried out by holding for 10 hours, preferably 5 minutes to 8 hours, more preferably 10 minutes to 5 hours, particularly preferably 20 minutes to 3 hours.
さらに、焼成を経た材料を不活性ガス流下または真空下
に１０００℃を越え、かつ３０００℃以下の温度で炭素
化する。このとき、系内の０２濃度は好ましくは１１０
００ＰＰ以下、さらに好ましくは１００ ｐｐｍ以下、
特に好ましくは１ ｐｐｍ〜５０ｐｐｍである。０２濃
度がこの範囲を超えると良好な炭素化が行われない。Furthermore, the fired material is carbonized under an inert gas stream or under vacuum at a temperature of over 1000°C and below 3000°C. At this time, the 02 concentration in the system is preferably 110
00PP or less, more preferably 100 ppm or less,
Particularly preferably 1 ppm to 50 ppm. If the 02 concentration exceeds this range, good carbonization will not occur.
さらに、焼成・炭素化の工程の前、中間、後のいずれか
において粉砕工程を実施する。Furthermore, a pulverization step is performed either before, during, or after the firing/carbonization step.
粉砕は、次の条件により行う、すなわち、ｖ／ｖ０≧１
．５
［式中、■は粉砕後の、かつｖｏは粉砕前の試料の定容
法により求めた相対圧力Ｐ／ＰＧ（吸着ガスがＮ２の場
合０．９９５）において吸着したガスの全容量を表す］
となるべく粉砕を行う、この粉砕工程は２回以上実施す
ることもできる。粉砕工程は、好ましくは焼成争炭素化
の工程を経た後に実施する。Grinding is carried out under the following conditions: v/v0≧1
．． 5 [In the formula, ■ represents the total volume of gas adsorbed at the relative pressure P/PG (0.995 when the adsorbed gas is N2) determined by the constant volume method of the sample after pulverization and before pulverization. ] This pulverization process can be carried out two or more times. The pulverization step is preferably carried out after the calcination carbonization step.
さらに、上記の各工程に加えて、ＣＯ２等の酸化性ガス
雰囲気下に５００〜１５００℃の温度で加熱する賦活化
の工程を加えることもできる。Furthermore, in addition to the above-mentioned steps, an activation step of heating at a temperature of 500 to 1500° C. in an atmosphere of an oxidizing gas such as CO2 can also be added.
また、出発源としてカーボンブラックを用い、これを適
当な条件でさらに炭素化等の処理を施して炭素質材料と
してもよい。Alternatively, carbon black may be used as a starting source and subjected to further treatment such as carbonization under appropriate conditions to produce a carbonaceous material.
かくして得られた炭素質材料から本発明にかかる負極体
を製造するには１例えば次のようにして行う。To manufacture the negative electrode body according to the present invention from the carbonaceous material thus obtained, for example, it is carried out as follows.
上述の炭素質材料を単独で、または導電材、結着剤等と
混練した後、加圧成形して負極体とする。このとき使用
される導電材としてはアセチレンブラック、カーボンブ
ラック、１１張黒鉛、金属粉末等が挙げられ、これらを
必要に応じて炭素質材料に対して５０重量％未満、好ま
しくは３０重量％未満、さらに好ましくは０１１〜１０
重量％添加する。また、結着剤としては、ポリオレフィ
ン系樹脂、ポリテトラフルオロエチレン等のフッ素系樹
脂等が挙げられ、これらを炭素質材料に対して２０重量
％未満、好ましくは１〜１０重量％添加する。The above-mentioned carbonaceous material is used alone or after being kneaded with a conductive material, a binder, etc., and then pressure-molded to form a negative electrode body. Examples of the conductive material used at this time include acetylene black, carbon black, 11-layered graphite, metal powder, etc. If necessary, these may be added in an amount of less than 50% by weight, preferably less than 30% by weight, based on the carbonaceous material. More preferably 011-10
Add % by weight. Examples of the binder include polyolefin resins and fluororesins such as polytetrafluoroethylene, and these are added in an amount of less than 20% by weight, preferably 1 to 10% by weight, based on the carbonaceous material.
次に活物質について述べる０本発明の二次電池における
活物質は、リチウム又はリチウムを主体とするアルカリ
金属であり、この活物質は、電池の充放電に対応して正
極体と負極体との間を往復移動する。活物質はあらかじ
め前述の正極体及び／又は負極体に担持させる。担持の
方法としては、例えば所定濃度のＬｉイオン又はアルカ
リ金属イオンを含有する電解液中に負極体を浸漬し、か
つ対極にＬｉを７ノードとして用い、負極体をカソード
にして電気分解させる方法を適用することができる。ま
た、同様の方法で正極体にリチウム又はリチウムを主体
とするアルカリ金属を担持させることができる。活物質
の担持は、このような電気化学的方法以外に化学的方法
、物理的方法によっても行うことができる。また、負極
体にＬｉ金属シートをはり合わせて電池セルを構成し、
充放電反応によりＬｉ金属を負極体に担持させることも
できる。Next, we will discuss the active material. The active material in the secondary battery of the present invention is lithium or an alkali metal mainly composed of lithium. move back and forth between The active material is supported on the above-mentioned positive electrode body and/or negative electrode body in advance. As a method of supporting, for example, the negative electrode body is immersed in an electrolytic solution containing Li ions or alkali metal ions at a predetermined concentration, Li is used as a counter electrode as a 7 node, and the negative electrode body is used as a cathode to cause electrolysis. Can be applied. Further, in a similar manner, lithium or an alkali metal mainly composed of lithium can be supported on the positive electrode body. In addition to such an electrochemical method, the active material can be supported by a chemical method or a physical method. In addition, a battery cell is constructed by gluing a Li metal sheet to the negative electrode body,
Li metal can also be supported on the negative electrode body through a charge/discharge reaction.
本発明の二次電池は、上述した活物質を担持させた負極
体及び正極体を従来と同様の方法で他の要素と共に組込
んで製作することができる。すなわち、正極体と負極体
をセパレータを介して対峙させ、セパレータには通常、
Ｌ＋金属塩又はアルカリ金属塩を溶解させた非水電解液
を保持させる。このとき用いられる非水電解液は前記し
た従来の二次電池に使用されるものを用いる。あるいは
、Ｌｉイオン又はアルカリ金属イオンの導電体である固
体電解質を正極体及び負極体の間に介在させることもで
きる。The secondary battery of the present invention can be manufactured by incorporating the negative electrode body and the positive electrode body carrying the above-described active material together with other elements in a conventional manner. That is, the positive electrode body and the negative electrode body are faced to each other with a separator interposed between them, and the separator usually contains
A nonaqueous electrolyte in which an L+ metal salt or an alkali metal salt is dissolved is held. The nonaqueous electrolyte used at this time is the one used in the conventional secondary battery described above. Alternatively, a solid electrolyte that is a conductor of Li ions or alkali metal ions can be interposed between the positive electrode body and the negative electrode body.
かくして、本発明の二次電池においては、次のような反
応が進行する。すなわち、
充電時：
正極体では、Ｖ２０５ （Ｌｉ）→
！
Ｖ２０５ ＋ｘＬｉ” ＋ｘｅ
負極体では、Ｃ＋ｘＬｉ” ＋Ｘｅ＋ｃｌ Ｌｉ。Thus, in the secondary battery of the present invention, the following reaction proceeds. That is, during charging: In the positive electrode body, V205 (Li) → ! V205 +xLi" +xe In the negative electrode body, C+xLi" +Xe+cl Li.
放電時：
正極体では、Ｖ２０Ｂ ＋ｘＬｉ” ＋ｘｅ−＋Ｖ２Ｏ
５（Ｌｉ）！
負極体では、Ｃ＠ Ｌｉ ＋Ｃ＋ｘＬ’ｉ” ＋ｘｅ！
の反応である。During discharge: In the positive electrode body, V20B +xLi” +xe-+V2O
5 (Li)! In the negative electrode body, the reaction is C@Li +C+xL'i" +xe!.
すなわち、本発明の二次電池において１例えば負極体で
は充電時にＬｉイオンのドープ現象が起り、また放電時
には負極体に担持されているＬｉイオンの脱ドープ現象
が生起して、可逆的な電気化学的酸化還元反応が充放電
に伴って進行するため、負極体がＬｉ箔であった場合に
その表面で生起したデンドライト形状の電析物の形成は
なくなるのである。That is, in the secondary battery of the present invention, for example, a doping phenomenon of Li ions occurs in the negative electrode body during charging, and a dedoping phenomenon of Li ions supported on the negative electrode body occurs during discharging, resulting in reversible electrochemical Since the target oxidation-reduction reaction progresses with charging and discharging, the formation of dendrite-shaped deposits that occur on the surface of the negative electrode body when it is a Li foil disappears.
なお、本発明において１元素分析、Ｘ線広角回折、なら
びに電子スピン共鳴スペクトルの各測定は下記方法によ
り実施した。In the present invention, single-element analysis, X-ray wide-angle diffraction, and electron spin resonance spectroscopy were carried out by the following methods.
「元素分析」
サンプルを１２０℃で約１５時間減圧乾燥し、その後ド
ライボックス内のホットプレート上で１００℃において
１時間乾燥した。ついで、アルゴン雰囲気中でアルミニ
ウムカップにサンプリングし、燃焼により発生するＣ０
２ガスの重量から炭素含有量を、また、発生するＨ２Ｏ
の重量から水素含有量を求める。なお、後述する本発明
の実施例では、パーキンエルマー２４０Ｃ型元素分析計
を使用して測定した。"Elemental Analysis" Samples were dried under reduced pressure at 120° C. for about 15 hours, then dried at 100° C. for 1 hour on a hot plate in a dry box. Then, the CO generated by combustion was sampled in an aluminum cup in an argon atmosphere.
2 The carbon content from the weight of the gas, and the generated H2O
Determine the hydrogen content from the weight of. In the Examples of the present invention described later, measurements were made using a PerkinElmer 240C elemental analyzer.
ｒＸ線広角回折」
（１） （００２）面の面間隔（ｄ００２ ）および
（１１０）面の面間隔（ｄｌｌＧ）
炭素質材料が粉末の場合はそのまま、微小片状の場合に
はメノウ乳鉢で粉末化し、試料に対して約１５重量％の
Ｘ線標準用高純度シリコン粉末を内部標準物質として加
え混合し、試料セルにつめ、グラファイトモノクロメー
タ−で単色化したＣｕＫａ線を線源とし、反射式デイフ
ラクトメーター法によって広角Ｘ線回折曲線を測定する
０曲線の補正には、いわゆるローレンツ、偏光因子、吸
収因子、原子散乱因子等に関する補正は行なわず次の簡
便法を用いる。即ち（００２）、および（１１０）回折
に相当する曲線のベースラインを引き、ベースラインか
らの実質強度をプロットし直して（００２）面、および
（１１０）面の補正曲線を得る。この曲線のピーク高さ
の３分の２の高さに引いた角度軸に平行な線が回折曲線
と交わる線分の中点を求め、中点の角度を内部標準で補
正し、これを回折角の２倍とし、ＣｕＫａ線の波長入と
から次式のブラッグ式によってｄ ００２およびｄｌｌ
ｏを求める。rX-ray wide-angle diffraction" (1) Interplanar spacing between (002) planes (d002) and interplanar spacing between (110) planes (dllG) If the carbonaceous material is in the form of a powder, it can be left as is; if it is in the form of minute pieces, it can be powdered in an agate mortar. 15% by weight of high-purity silicon powder for X-ray standards was added to the sample as an internal standard substance, mixed, packed into a sample cell, and using a graphite monochromator as a monochromatic CuKa beam as a radiation source. To correct the 0 curve when measuring a wide-angle X-ray diffraction curve using the diffractometer method, the following simple method is used without making corrections regarding so-called Lorentz, polarization factors, absorption factors, atomic scattering factors, etc. That is, baselines of curves corresponding to (002) and (110) diffraction are drawn, and the real intensities from the baseline are plotted again to obtain correction curves for the (002) and (110) planes. Find the midpoint of the line segment where a line parallel to the angular axis drawn at two-thirds of the peak height of this curve intersects with the diffraction curve, correct the angle at the midpoint using an internal standard, and calculate this. d 002 and dll by the following Bragg equation from the wavelength input of the CuKa line.
Find o.
λ ：１．５４１８Ａ
θ、θ′：ｄｏｏ２．ｄｌｌｏに相当する回折角（２）
Ｃ軸およびａ軸方向の結晶子の大きさ：Ｌｃ ； Ｌａ
前項で得た補正回折曲線において、ピーク高さの半分の
位置におけるいわゆる半価中βを用いてＣ軸およびａ軸
方向の結晶子の大きさを次式より求める。λ: 1.5418A θ, θ': doo2. Diffraction angle corresponding to dllo (2)
Crystallite size in the C-axis and a-axis directions: Lc; La In the corrected diffraction curve obtained in the previous section, the crystallite size in the C-axis and a-axis directions is Find the size using the following formula.
β＋ｃｏｓθ
β・ｃｏｗθ′
形状因子Ｋについては種々議論もあるが、Ｋ＝０．０９
を用いた。入、θおよびθ′については前項と同じ意味
である。β+cosθ β・cowθ′ There are various discussions about the shape factor K, but K=0.09
was used. Input, θ, and θ' have the same meanings as in the previous section.
「電子スピン共鳴の線幅：ΔＨＰＰＪ
電子スピン共鳴の一部微分吸収スベクトルはＪＥＯＬ
ＪＥＳ−ＦＥ ＩＸ ＥＳＲｘペクトロメーター
を用い、Ｘバンドで測定する。粉末状の試料はそのまま
、微小片状試料はメノウ乳鉢で粉末化して、外径２■の
毛細管に入れ、さらに毛細管を外径５■のＥＳＲ管に入
れる。高周波磁場の変調中は６．３ガウスとする０以上
すべて、空気雰囲気下、２３℃で行う、−次微分吸収ス
ペクトルのピーク間の線幅（ΔＨｐｐ）は、Ｍｎ”／Ｍ
ｇＯ標準試料を用いて決定する。“Linewidth of electron spin resonance: ΔHPPJ Partial differential absorption vector of electron spin resonance is JEOL
Measure in the X band using a JES-FE IX ESRx spectrometer. Powdered samples are left as they are, and fine flake samples are pulverized in an agate mortar and placed in a capillary tube with an outer diameter of 2 mm, and the capillary tube is then placed in an ESR tube with an outer diameter of 5 mm. The peak-to-peak linewidth (ΔHpp) of the −th order differential absorption spectrum is Mn”/M when the modulation of the high-frequency magnetic field is 6.3 Gauss.
Determine using gO standard sample.
（実施例） 以下、実施例をあげて本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
（１）正極体の製造
Ｍ ｎ Ｏ２粉末８０ｇ、導電材としてのカーボンブラ
ック１０ｇおよび結着剤としての粉末状のポリテトラフ
ルオロエチレン５ｇとを混練し、得られた混線物をロー
ル成形して厚み０．４ｍ■のシートとした。(1) Manufacture of positive electrode body 80 g of MnO2 powder, 10 g of carbon black as a conductive material, and 5 g of powdered polytetrafluoroethylene as a binder were kneaded, and the resulting mixed wire was roll-formed to give a thickness. It was made into a sheet of 0.4 m.
このシートの片面を集電体である線径０．１濡脂、６０
メツシユのステンレス鋼ネットに圧着して正極とした。One side of this sheet was coated with a wire diameter of 0.1 as a current collector, and
It was crimped onto a mesh stainless steel net to serve as a positive electrode.
（２）負極体の製造
オルトクレゾール１０８ｇ、パラホルムアルデヒド３２
ｇおよびエチルセロンルブ２４０ｇを硫１ｆｉｌｏｇと
ともに反応器に仕込み、攪拌しながら１１５℃で４時間
反応させた０反応終了後ＮａＨＣＯ３１７ｇと水３０ｇ
とを加えて中和した。ついで、高速で攪拌しながら水２
文中に反応液を投入して沈澱してくる生成物をか別乾燥
して１１５ｇの線状高分子量ノボラック樹脂を得た。(2) Manufacture of negative electrode body 108 g of orthocresol, 32 g of paraformaldehyde
g and 240 g of ethylseron lube were charged into a reactor along with 1 filog of sulfur and reacted at 115°C for 4 hours with stirring. After the reaction was completed, 17 g of NaHCO and 30 g of water were added.
It was neutralized by adding Next, add 2 ounces of water while stirring at high speed.
The reaction solution was added to the solution, and the precipitated product was separated and dried to obtain 115 g of a linear high molecular weight novolak resin.
上記のノボラック樹脂２２５ｇとへキサミン２５ｇを５
００＋１＆／のメノウ製容器に入れ、直径３０ｍ１のメ
ノウ製ポール５個と直径２０ｍｍのメノウ製ボール１０
個を入れてボールミルにセットし、２０分間粉砕、混合
した。5 g of the above novolak resin and 25 g of hexamine
Place in an agate container of 00+1&/, 5 agate poles with a diameter of 30 m1 and 10 agate balls with a diameter of 20 mm.
The mixture was placed in a ball mill, and ground and mixed for 20 minutes.
かくして得られたノボラック樹脂とへキサミンとの混合
パウダーを、Ｎ２ガス中、２５０℃で３時間加熱処理を
行った。さらに、このものを電気加熱炉にセットし、Ｎ
２ガス流下に２５０℃／時の速度で５００℃まで昇温し
、さらに２００℃／時の速度で９００℃まで昇温し、そ
のままの温度に１．５時間保持して、その後自然放冷し
た。The thus obtained mixed powder of novolac resin and hexamine was heat-treated at 250° C. for 3 hours in N2 gas. Furthermore, set this thing in an electric heating furnace, and
The temperature was raised to 500°C at a rate of 250°C/hour under two gas flows, and further raised to 900°C at a rate of 200°C/hour, maintained at that temperature for 1.5 hours, and then allowed to cool naturally. .
次に、焼成後の材料を別な電気炉にセットし、真空下に
２５℃／分の速度で２１００℃まで昇温し、そのままの
温度でさらに１．５時間加熱し、炭素化を実施した。Next, the fired material was placed in a separate electric furnace, heated under vacuum at a rate of 25°C/min to 2100°C, and heated at that temperature for an additional 1.5 hours to carry out carbonization. .
かくして得られた炭素化物を２５０１ｋｌのメノウ製容
器に入れ、直径３０濡嘗のメノウ製ボール１個、直径り
５ｍ層のメノウ製ボール３個、及び直径２０ｍ層のメノ
ウ製ボール１３側を入れてボールミルにセットし、Ｖ／
Ｖｏ≧５（Ｖ、Ｖｏは前記と同義）となるまで粉砕し、
目的とする炭素質材料を得た。The carbonized product thus obtained was placed in a 2501 kl agate container, and 1 agate ball with a diameter of 30 ml, 3 agate balls with a diameter of 5 m layer, and 13 side of the agate ball with a diameter of 20 m layer were placed. Set it in a ball mill, and
Pulverize until Vo≧5 (V and Vo are the same as above),
The desired carbonaceous material was obtained.
この炭素質材料は、元素分析、Ｘ線広角回折等の分析の
結果、以下の特性を有していた。As a result of analysis such as elemental analysis and X-ray wide-angle diffraction, this carbonaceous material had the following characteristics.
水素／炭素（原子比）＝０．０３
ｄｏｇ２ ＝３．６ＯＡ、Ｌｃ＝１３．６人ａ６（２ｄ
Ｏｏ２）＝２ 、４２Ａ 、 Ｌａ＝２１ 、５人また
、濡洩アイオニクス社智オートソーブｌを用いてこの炭
素質材料について、窒素ガスを吸着させ液体窒素温度（
７７Ｋ）における脱離等混線を求め、これよりＢ、Ｊ、
Ｈ法にて積算細孔容積及びその分布を求めた。結果を以
下に示す。Hydrogen/carbon (atomic ratio) = 0.03 dog2 = 3.6OA, Lc = 13.6 people a6 (2d
Oo2) = 2, 42A, La = 21, 5 people.Nitrogen gas was adsorbed on this carbonaceous material using Yuyuri Ionics Autosorb L, and the temperature of liquid nitrogen (
77K), and from this, B, J,
The integrated pore volume and its distribution were determined using the H method. The results are shown below.
細孔半径１０〜２５０人である細孔の積算細孔容積は０
．０２１０４ｗＪ／ｇ細孔半径１０〜２５０人未満の細
孔の積算細孔容積細孔半径１０〜２５０人の細孔の積算
細孔容積この炭素質材料に、体積平均粒径２０−のポリ
エチレン粉末を７重量％混合した混合物を加圧成形して
、厚み０．５ｍｍのペレットとした。The cumulative pore volume of pores with a pore radius of 10 to 250 is 0.
．． 02104 wJ/g Cumulative pore volume of pores with a pore radius of 10 to less than 250 pores Cumulative pore volume of pores with a pore radius of 10 to 250 pores Add polyethylene powder with a volume average particle size of 20 to this carbonaceous material. The mixture containing 7% by weight was pressure molded to form pellets with a thickness of 0.5 mm.
（３）電池の組立
ステンレス鋼製の正極缶に、上記した正極体を集電体を
下にして着設し、その上にポリプロピレン不織布を載置
したのち、そこにＬｉＣ文ｏ４を濃度１モル／文でプロ
ピレンカーボネートに溶解せしめた非水電解液を含浸せ
しめた。ついでその上に上記負極体を載置して発電要素
を構成した。(3) Assembly of the battery Place the above-mentioned positive electrode body in a stainless steel positive electrode can with the current collector facing down, place a polypropylene nonwoven fabric on top of it, and then add LiC O4 at a concentration of 1 molar. / impregnated with a non-aqueous electrolyte dissolved in propylene carbonate. Then, the negative electrode body was placed thereon to form a power generation element.
なお、正極体は、電池に組込むに先立ち、濃度１モル／
文のＬｉイオン電解液中に浸漬し、正極体をカソードと
し、リチウムを７ノードとする電解処理に付した。電解
条件は、浴温２０℃、電流密度１ｍＡ／ｃｍ２．電解時
間１０時間とした。このような処理により、正極体には
容量６．０１ＡｈのＬｉが担持されたことになる。Note that the positive electrode body should be prepared at a concentration of 1 mol/min before being incorporated into the battery.
The sample was immersed in a Li-ion electrolyte of 100% and subjected to electrolytic treatment using the positive electrode body as the cathode and lithium as the 7 nodes. The electrolytic conditions were a bath temperature of 20°C and a current density of 1mA/cm2. The electrolysis time was 10 hours. Through such treatment, Li with a capacity of 6.01 Ah was supported on the positive electrode body.
かくして、第１図に示したようなボタン形二次電池を製
作した。In this way, a button-shaped secondary battery as shown in FIG. 1 was manufactured.
（４）電池の特性
このようにして製作した電池について、３〜２ｖの間で
定電圧充電−２０にΩ定抵抗放電を反復し、５サイクル
及び１００サイクルにおける電池の充電容量及び放電容
量を測定した。その結果を表１に示した。(4) Characteristics of the battery The battery manufactured in this way was repeatedly charged at a constant voltage of 3 to 2 V and discharged at a constant resistance of -20 Ω, and the charging capacity and discharging capacity of the battery were measured at 5 cycles and 100 cycles. did. The results are shown in Table 1.
比較例１ （１）正極体の製造 実施例１と同様にして正極体を製造した。Comparative example 1 (1) Manufacture of positive electrode body A positive electrode body was manufactured in the same manner as in Example 1.
（２）負極体の製造
メゾフェースピッチｌｏｇを３００℃、１．５ｔｏｎ／
ａｍ２に加熱・加圧してシート状に成形した。(2) Negative electrode manufacturing mesoface pitch log at 300℃, 1.5ton/
It was heated and pressurized to am2 and formed into a sheet shape.
次いでこのシートをＮ２ガス中で１０００℃／時の速度
で３０００℃まで昇温し、さらにこの温度で１時間加熱
後自然放冷した。この焼成物をボールミルで粉砕し、平
均粒径５００μの炭素質材料を得た。Next, this sheet was heated to 3000° C. at a rate of 1000° C./hour in N2 gas, further heated at this temperature for 1 hour, and then allowed to cool naturally. This fired product was ground in a ball mill to obtain a carbonaceous material with an average particle size of 500 μm.
この炭素質材料は、分析の結果以下の特性を有していた
。As a result of analysis, this carbonaceous material had the following properties.
水素／炭素（ｉＫ子比）＝０．０１
ｄ（１０２＝３．３８Ａ、Ｌｃ＝１５６Ａ１０〜２５０
人の細孔半径を有する細孔の積算細孔容積 １．５Ｘ
１０−３ａＪ／ｇ未満この炭素質材料粉末とポリエチレ
ン粉末７型景％とを混合し、全体を加圧成形して厚み０
．５■のペレットにした。Hydrogen/carbon (iK ratio) = 0.01 d (102 = 3.38A, Lc = 156A10~250
Cumulative pore volume of pores with human pore radius 1.5X
Less than 10-3aJ/g This carbonaceous material powder and 7% polyethylene powder were mixed and the whole was pressure-molded to a thickness of 0.
．． It was made into 5-inch pellets.
（３）電池の組立 実施例１と同様にして電池を組み立てた。(3) Battery assembly A battery was assembled in the same manner as in Example 1.
（４）電池の特性
実施例１と同様にして同一の条件で、電池特性を測定し
、結果を表１に併記した。(4) Battery characteristics Battery characteristics were measured in the same manner as in Example 1 under the same conditions, and the results are also listed in Table 1.
比較例２
Ｌｉ金属箔を負極体として用いた以外は実施例１と同様
にして、電池を組み立て、同一条件で電池特性を測定し
、その結果を表１に併記した。Comparative Example 2 A battery was assembled in the same manner as in Example 1 except that Li metal foil was used as the negative electrode body, and battery characteristics were measured under the same conditions. The results are also listed in Table 1.
［発明の効果］
本発明の二次電池は、充放電サイクル寿命が長く、信頼
性の高い電池であるので、繰返し充放電を行うことがで
き、種々の電子機器への使用が可能である。[Effects of the Invention] The secondary battery of the present invention has a long charge/discharge cycle life and is a highly reliable battery, so it can be repeatedly charged and discharged and can be used in various electronic devices.
第１図はボタン形構造の非水電解液二次電池の縦断面図
であり、第２図は積算細孔容積分布の図である。
ｌ・・・正極体 ２・・・セパレータ３・・・負極体
４・・・正極缶
５・・・負極毎 ６・・・絶縁バッキング７・・・集
電体
第１図FIG. 1 is a longitudinal cross-sectional view of a non-aqueous electrolyte secondary battery with a button-shaped structure, and FIG. 2 is a diagram of the integrated pore volume distribution. l...Positive electrode body 2...Separator 3...Negative electrode body 4...Positive electrode can 5...Each negative electrode 6...Insulating backing 7...Current collector Figure 1
Claims (1)
パレータに保持された電解質と、該セパレータに載置さ
れた負極体と、該正極体及び／又は該負極体に包含され
充放電反応に対応して該正、負極体間を移動する活物質
とから成る発電要素が内蔵された二次電池において、 （ａ）正極体が、遷移金属カルコゲン化合物からなり、 （ｂ）負極体が、水素／炭素の原子比０．１０未満、Ｘ
線広角回折法による（００２）面の面間隔（ｄ＿０＿０
＿２）３．３７Å以上３．７５Å以下、Ｃ軸方向の結晶
子の大きさ（Ｌｃ）５Å以上１５０Å以下、細孔半径が
１０〜２５０Åである細孔の積算細孔容積が１．０×１
０＾−＾３ｍｌ／ｇ以上ならびに該積算細孔容積の分布
が、 ０．５≧細孔半径１０Å以上２０Å未満の細孔の積算細
孔容積／細孔半径１０〜２５０Åの細孔の積算細孔容積
≧０．１０．７≧細孔半径２０Å以上１００Å未満の細
孔の積算細孔容積／細孔半径１０〜２５０Åの細孔の積
算細孔容積≧０．１及び ０．５≧細孔半径１００〜２５０Åの細孔の積算細孔容
積／細孔半径１０〜２５０Åの細孔の積算細孔容積≧０
．１である炭素質材料からなり、 （ｃ）活物質が、リチウム又はリチウムを主体とするア
ルカリ金属である ことを特徴とする二次電池。[Claims] A positive electrode body, a separator placed on the positive electrode body, an electrolyte held in the separator, a negative electrode body placed on the separator, and the positive electrode body and/or the negative electrode body. (a) The positive electrode body is made of a transition metal chalcogen compound; (a) the positive electrode body is made of a transition metal chalcogen compound; b) The negative electrode body has a hydrogen/carbon atomic ratio of less than 0.10,
Interplanar spacing (d_0_0) of (002) plane by line wide-angle diffraction method
_2) Cumulative pore volume of pores with 3.37 Å or more and 3.75 Å or less, crystallite size (Lc) in the C-axis direction of 5 Å or more and 150 Å or less, and pore radius of 10 to 250 Å is 1.0×1
0^-^3ml/g or more and the distribution of the cumulative pore volume is 0.5≧Cumulative pore volume of pores with a pore radius of 10 Å or more and less than 20 Å/Cumulative pore volume of pores with a pore radius of 10 to 250 Å Pore volume≧0.10.7≧Cumulative pore volume of pores with a pore radius of 20 Å or more and less than 100 Å/Cumulative pore volume of pores with a pore radius of 10 to 250 Å≧0.1 and 0.5≧pores Cumulative pore volume of pores with a radius of 100 to 250 Å / Cumulative pore volume of pores with a pore radius of 10 to 250 Å ≧ 0
．． 1, and (c) the active material is lithium or an alkali metal mainly composed of lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62318692A JPH01161677A (en) | 1987-12-18 | 1987-12-18 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62318692A JPH01161677A (en) | 1987-12-18 | 1987-12-18 | Secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01161677A true JPH01161677A (en) | 1989-06-26 |
Family
ID=18101949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62318692A Pending JPH01161677A (en) | 1987-12-18 | 1987-12-18 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01161677A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0767505A1 (en) * | 1995-10-03 | 1997-04-09 | Kureha Kagaku Kogyo Kabushiki Kaisha | Carbonaceous electrode material for secondary battery and process for production thereof |
| EP0810679A1 (en) * | 1996-05-29 | 1997-12-03 | Ucar Carbon Technology Corporation | Compacted carbon, selected from graphite and coke, having a high R-ray density, for electrochemical cells |
| EP0896377A1 (en) * | 1997-08-05 | 1999-02-10 | Mitsubishi Chemical Corporation | Carbonaceous negative electrode material for nonaqueous secondary battery, process for producing the same, and nonaqueous secondary battery |
| EP1115130A1 (en) * | 1998-08-25 | 2001-07-11 | Kanebo Ltd. | Electrode material and method for producing the same |
| EP1876663A1 (en) * | 2005-04-26 | 2008-01-09 | Fuji Jukogyo Kabushiki Kaisha | Negative electrode active material for charging device |
| JP2010021032A (en) * | 2008-07-11 | 2010-01-28 | Hitachi Chem Co Ltd | Anode material for lithium secondary battery and lithium secondary battery |
-
1987
- 1987-12-18 JP JP62318692A patent/JPH01161677A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0767505A1 (en) * | 1995-10-03 | 1997-04-09 | Kureha Kagaku Kogyo Kabushiki Kaisha | Carbonaceous electrode material for secondary battery and process for production thereof |
| EP0810679A1 (en) * | 1996-05-29 | 1997-12-03 | Ucar Carbon Technology Corporation | Compacted carbon, selected from graphite and coke, having a high R-ray density, for electrochemical cells |
| EP0896377A1 (en) * | 1997-08-05 | 1999-02-10 | Mitsubishi Chemical Corporation | Carbonaceous negative electrode material for nonaqueous secondary battery, process for producing the same, and nonaqueous secondary battery |
| EP1115130A1 (en) * | 1998-08-25 | 2001-07-11 | Kanebo Ltd. | Electrode material and method for producing the same |
| EP1115130A4 (en) * | 1998-08-25 | 2007-05-02 | Fuji Heavy Ind Ltd | Electrode material and method for producing the same |
| EP1876663A1 (en) * | 2005-04-26 | 2008-01-09 | Fuji Jukogyo Kabushiki Kaisha | Negative electrode active material for charging device |
| EP1876663A4 (en) * | 2005-04-26 | 2010-09-29 | Fuji Heavy Ind Ltd | Negative electrode active material for charging device |
| US8142930B2 (en) | 2005-04-26 | 2012-03-27 | Fuji Jukogyo Kabushiki Kaisha | Negative electrode active material for charging device |
| JP2010021032A (en) * | 2008-07-11 | 2010-01-28 | Hitachi Chem Co Ltd | Anode material for lithium secondary battery and lithium secondary battery |
| JP4670908B2 (en) * | 2008-07-11 | 2011-04-13 | 日立化成工業株式会社 | Negative electrode material for lithium secondary battery and lithium secondary battery |
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