JPS63285871A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPS63285871A JPS63285871A JP62120216A JP12021687A JPS63285871A JP S63285871 A JPS63285871 A JP S63285871A JP 62120216 A JP62120216 A JP 62120216A JP 12021687 A JP12021687 A JP 12021687A JP S63285871 A JPS63285871 A JP S63285871A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- lithium
- battery
- electrode active
- 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 description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 abstract description 4
- 239000001989 lithium alloy Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 description 15
- -1 halide anions Chemical class 0.000 description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- FKQOMXQAEKRXDM-UHFFFAOYSA-N [Li].[As] Chemical compound [Li].[As] FKQOMXQAEKRXDM-UHFFFAOYSA-N 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
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000006123 lithium glass Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、高エネルギー密度で充放電寿命が長く、安定
性、信頼性に優れた充放電可能な非水電解質二次電池に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chargeable/dischargeable non-aqueous electrolyte secondary battery that has high energy density, long charge/discharge life, and excellent stability and reliability.
ｔｌＥガ技泗及び発明が解決しようとす７！訓題点従来
から、リチウムを負極活物質として用いる高エネルギー
密度電池に関しては多くの提案がなされており、フッ化
黒鉛や二酸化マンガンを正極活物質として用いたリチウ
ム電池が既に市販されている。しかし、これらの電池は
一次電池であり、充電できない欠点があった。tlE techniques and inventions are trying to solve 7! Training points Many proposals have been made for high-energy density batteries that use lithium as the negative electrode active material, and lithium batteries that use fluorinated graphite or manganese dioxide as the positive electrode active material are already on the market. However, these batteries are primary batteries and have the disadvantage that they cannot be recharged.
リチウムを負極活物質として用いる二次電池については
、正極活物質としてチタン、モリブデン。For secondary batteries that use lithium as the negative electrode active material, titanium and molybdenum are used as the positive electrode active material.
ニオビウム、バナジウム、ジルコニウムのカルコゲナイ
ド（硫化物、セレン化物、テルル化物）を用いた電池が
提案されているが、電池特性及び経済性が必ずしも十分
でないために、実用化されているものは少ない。最近、
硫化モリブデンを用いた二次電池が実用化されたが、こ
れも放電電位が低く、過充電に弱いなどの欠点を持って
いる。放電電位の高い正極活物質としては酸化クロム、
五酸化バナジウムなどが知られているが、酸化クロムは
充放電のサイクル特性が悪く、五酸化バナジウムは導電
性が低く、十分なカソード特性を得るには至っていない
。Batteries using chalcogenides (sulfides, selenides, tellurides) of niobium, vanadium, and zirconium have been proposed, but few have been put into practical use because the battery characteristics and economic efficiency are not necessarily sufficient. recently,
Secondary batteries using molybdenum sulfide have been put into practical use, but they also have drawbacks such as low discharge potential and vulnerability to overcharging. Chromium oxide is a positive electrode active material with a high discharge potential.
Vanadium pentoxide and the like are known, but chromium oxide has poor charge-discharge cycle characteristics, vanadium pentoxide has low conductivity, and has not yet achieved sufficient cathode properties.
このため、高エネルギー密度で充放電寿命が長く、安定
性、信頼性に優れたリチウム二次電池の開発が望まれる
。Therefore, it is desired to develop a lithium secondary battery that has high energy density, long charging/discharging life, and excellent stability and reliability.
本発明は上記事情に鑑みなされたもので、導電性が良好
でしかも容量の大きい正極活物質を用いることにより、
導電付与剤の添加量を少なくして高エネルギー密度を達
成し得ると共に、高電位でサイクル特性に優れた非水電
解質リチウム二次電池を提供することを目的とする。The present invention was made in view of the above circumstances, and by using a positive electrode active material with good conductivity and large capacity,
It is an object of the present invention to provide a non-aqueous electrolyte lithium secondary battery that can achieve high energy density by reducing the amount of a conductivity-imparting agent added, and has excellent cycle characteristics at a high potential.
間 点を解決するための手段 び作
本発明は上記目的を達成するため、下記式（１）％式％
）
（但し、式中Ｘ≦１．ｚ＜ｙ≦ｌ、ｍ＋ｎ≦１）から選
ばれる物質を正極活物質とし、リチウム又はリチウムを
吸蔵及び放出可能なリチウム合金を負極活物質とし、か
つリチウムイオンが前記正極活物質と電気化学反応をす
るために移動を行ない得る非水物質を電解質としたもの
である６″ 即ち、本発明者らは、非水電解質リチウム
二次電池の正極活物質として優れた特性を有する物質に
ついて鋭意検討を行なった結果、理想的な五酸化バナジ
ウムは３ｄ及び４ｓ軌道の５個の電子（五個）が酸素と
結合しており、導電性を持たないが、そのバナジウムの
一部をよりイオン半径の大きいモリブデン及び／又はタ
ングステンで置換すると共に、更にリチウムを部分的に
導入することにより得た前記（１）〜（５）式の化合物
が優れた正極活物質としての特性を示し、これらの化合
物は四価のバナジウムが生成され、ホッピング電導性が
付与されて導電性が改良され、また構造に歪みが与えら
れてリチウムとのトポケミカルな反応が容易になるとい
う性質を示し、これら（１）〜（５）式の化合物を非水
電解質リチウム二次電池の正極活物質°として用いた場
合、充放電特性が顕著に改良されることを知見し１本発
明をなすに至ったものである６
以下、本発明につき更に詳しく説明する。In order to achieve the above object, the present invention solves the problem by using the following formula (1) % formula %
) (However, in the formula, a material selected from The electrolyte is a non-aqueous substance that can migrate in order to undergo an electrochemical reaction with the positive electrode active material. That is, the present inventors have found that the electrolyte is an excellent positive electrode active material for non-aqueous electrolyte lithium secondary batteries. As a result of intensive research on materials with such characteristics, we found that ideal vanadium pentoxide has five electrons (five) in the 3d and 4s orbits bonded to oxygen, and has no conductivity. Compounds of the formulas (1) to (5) above obtained by replacing a part of the compound with molybdenum and/or tungsten having a larger ionic radius and further introducing lithium partially are found to be excellent positive electrode active materials. These compounds exhibit the properties that tetravalent vanadium is generated, imparting hopping conductivity to improve conductivity, and structural distortion to facilitate topochemical reactions with lithium. We have found that when the compounds of formulas (1) to (5) are used as positive electrode active materials of non-aqueous electrolyte lithium secondary batteries, the charge-discharge characteristics are significantly improved. The present invention will be explained in more detail below.
本発明に係る二次電池は、上述したように下記式（１）
〜（５）
％式％）
（但し、式中Ｘ≦１ ｙ ｚ ＜ ｙ≦１．ｍ＋ｎ≦１
）から選ばれる材料を正極活物質とするものである。As mentioned above, the secondary battery according to the present invention has the following formula (1):
~(5) % formula %) (However, in the formula, X≦1 y z < y≦1.m+n≦1
) is used as the positive electrode active material.
ここで、Ｘｖ’ｊ及びｍ＋ｎはそれぞれ１以下であれば
よいが、より好ましくはｘ、ｙ及びｍ＋ｎはそれぞれ０
．１以上０．７以下である。Here, Xv'j and m+n each need to be 1 or less, but more preferably x, y and m+n are each 0.
．． It is 1 or more and 0.7 or less.
この正極材料を用いて正極を作成する場合、正極材料の
粒径は必ずしも制限されないが、平均粒径が３μ以下の
ものを用いるとより高性能の正極を作ることができる。When creating a positive electrode using this positive electrode material, the particle size of the positive electrode material is not necessarily limited, but a positive electrode with higher performance can be created by using one with an average particle size of 3 μm or less.
この場合、これらの粉末に対し、アセチレンブラック等
の導電剤やフッ素樹脂粉末等の結着剤などを添加混合し
、有機溶剤で混練りし、ロールで圧延し、乾燥する等の
方法により正極を作成することができる。なお、導電剤
の混合量は（１）〜（５）式の正極材料１００重量部に
対し３〜２５重量部、特に５〜１５重量部とすることが
でき、本発明にあってはその正極材料の導電性が良好で
あるため、導電剤使用量を少なくすることができる。ま
た結着剤の配合量は上記正極材料１００重量部に対し２
〜２５重量部とすることが好ましい。ここで、正極を作
成するに際し、（１）〜（５）式の正極材料はその１種
を単独で使用してもよく、２種以上を混合して使用する
ようにしてもよい。In this case, the positive electrode is prepared by adding and mixing a conductive agent such as acetylene black or a binder such as fluororesin powder to these powders, kneading with an organic solvent, rolling with a roll, and drying. can be created. The amount of the conductive agent mixed can be 3 to 25 parts by weight, particularly 5 to 15 parts by weight, based on 100 parts by weight of the positive electrode material of formulas (1) to (5). Since the material has good conductivity, the amount of conductive agent used can be reduced. The amount of binder added is 2 parts by weight per 100 parts by weight of the above positive electrode material.
It is preferable to set it as 25 parts by weight. Here, when creating a positive electrode, one type of the positive electrode materials of formulas (1) to (5) may be used alone, or two or more types may be used in combination.
ナオ、（１）、 （２） 、 （５）式ノ正極材料は、
ｖ２０５に対しＭ ｏ Ｏ□及び／又はＷＯ２を加える
と共に。Nao, the positive electrode material of formulas (1), (2), and (5) is
Along with adding M o O□ and/or WO2 to v205.
Ｌ１□○やＬｉ２Ｃｏ３を添加混合し、窒素、アルゴン
等の不活性ガス中において温度５００〜７００℃で３〜
４８時間加熱反応させるなどの方法で製造することがで
きる。Add and mix L1□○ and Li2Co3 and heat in an inert gas such as nitrogen or argon at a temperature of 500 to 700℃ for 3 to 30 minutes.
It can be produced by a method such as heating reaction for 48 hours.
また、（３）、（４）式の正極材料はＶ２Ｏ，に対しＭ
２Ｏ３とＶＯ２又はＷＯ，とＶＯ２を加えると共に、Ｌ
ｉ２ＯやＬｉ、ＧＯ，を添加混合し、窒素、アルゴン等
の不活性ガス中において温度５００〜７００℃で３〜４
８時間加熱反応させるなどの方法で製造することができ
る。In addition, the positive electrode material in equations (3) and (4) is M
While adding 2O3 and VO2 or WO, and VO2, L
Add and mix i2O, Li, and GO, and heat in an inert gas such as nitrogen or argon at a temperature of 500 to 700°C for 3 to 4 hours.
It can be produced by a method such as heating reaction for 8 hours.
本発明の二次電池負極活物質としては、リチウム又はリ
チウムを吸蔵、放出可能なリチウム合金が用いられる。As the secondary battery negative electrode active material of the present invention, lithium or a lithium alloy capable of inserting and releasing lithium is used.
この場合、リチウム合金としては、リチウムを含むＩｌ
ａ、 ＩＩｂ、■ａ、ＩＶａ、 Ｖａ族の金属又はその
２種以上の合金が使用可能であるが、特にリチウムを含
むＡＱ、 Ｉ ｎ、 Ｓｎ、 Ｐｂ、 Ｂｉ、Ｃ：ｄ、
Ｚｎ又はこれらの２種以上の合金が好適である。In this case, the lithium alloy is Il containing lithium.
a, IIb, ■a, IVa, Va group metals or alloys of two or more thereof can be used, especially AQ containing lithium, In, Sn, Pb, Bi, C:d,
Zn or an alloy of two or more of these is preferred.
更に、本発明の二次電池に使用する電解質としては、前
記正極活物質及び負極活物質に対して化学的に安定であ
り、かつリチウムイオンが前記正極活物賛成いは前記負
極活物質と電気化学反応をするための移動を行ない得る
非水物質であればいずれのものでも使用することができ
、特にカチオンとアニオンとの組合せよりなる化合物で
あって、カチオンとしてはＬｉ＋、またアニオンの例と
してはＰＦ６”、 ＡｓＦＧ−，５ｂＦ６−、５ｂＣ４
−の如きＶａ族元素のハロゲン化物アニオン、Ｂ Ｆ、
−、ＡｎＣＱ４−の如きｍａ族元素のハロゲン化物アニ
オン、ド（Ｉａ−ＬＢｒ−ｙ ＣΩ−の如きハロゲンア
ニオン、ＣＱＯ４−の如き過塩素酸アニオン、ＨＦ、−
、ＣＦ、Ｓｏ、−，５ＣＮ−等のアニオンを有する化合
物等を挙げることができるが、必ずしもこれらのアニオ
ンに限定されるものではない。このようなアニオン、カ
チオンをもつ電解質の具体例としては、ＬｉＰＦＧ、
ＬｉＡｓＦＧ、 Ｌｉ５ｂＦ、、 ＬｉＢＦ４゜ＬＬＣ
ＱＯ，、ＬｉＩ、 ＬｉＢｒ、 ＬｉＣＱ、 ＬｉＡＱ
ＣＩ２４． ＬｉＨＦ７゜Ｌｉ５ＣＮ＋Ｌｉ５０３ＣＦ
、等が挙げられる。これらのうちでは特にＬｉＰＦ、、
ＬｉＡｓＦ、、 ＬｉＢＦ、、 ＬｉＣＱＯ，。Furthermore, the electrolyte used in the secondary battery of the present invention must be chemically stable with respect to the positive electrode active material and the negative electrode active material, and lithium ions can be electrically connected to the positive electrode active material or the negative electrode active material. Any non-aqueous substance that can undergo movement for a chemical reaction can be used, especially compounds consisting of a combination of a cation and an anion, with Li+ as the cation and Li+ as an example of the anion. is PF6”, AsFG-, 5bF6-, 5bC4
- halide anions of group Va elements such as B F,
-, halide anions of ma group elements such as AnCQ4-, halogen anions such as Do(Ia-LBr-y CΩ-, perchlorate anions such as CQO4-, HF, -
Examples include compounds having anions such as , CF, So, -, 5CN-, but are not necessarily limited to these anions. Specific examples of electrolytes having such anions and cations include LiPFG,
LiAsFG, Li5bF, LiBF4゜LLC
QO,, LiI, LiBr, LiCQ, LiAQ
CI24. LiHF7゜Li5CN+Li503CF
, etc. Among these, especially LiPF,
LiAsF,, LiBF,, LiCQO,.
Ｌｉ５ｂＦ、、 Ｌｉ５Ｏ，ＣＦ３が好適である。Li5bF, Li5O, CF3 are preferred.
なお、上記電解質は通常溶媒により溶解された状態で使
用され５この場合溶媒は特に限定されないが、比較的極
性の大きい溶媒が好適に用いられる。具体的には、プロ
ピレンカーボネート、エチレンカーボネート、テトラヒ
ドロフラン、２−メチルテトラヒドロフラン、ジオキソ
ラン、ジオキサン、ジメトキシエタン、ジエチレングリ
コールジメチルエーテル等のグライム類、γ−ブチロラ
クトン等のラクトン類、トリエチルフォスフェート等の
リン酸エステル類、ホウ酸トリエチル等のホウ酸エステ
ル類、スルホラン、ジメチルスルホキシド等の硫黄化合
物、アセトニトリル等のニトリル類、ジメチルホルムア
ミド、ジメチルアセトアミド等のアミド類、硫酸ジメチ
ル、ニトロメタン、ニトロベンゼン、ジクロロエタンな
どの１種又は２種以上の混合物を挙げることができる。Note that the electrolyte is usually used in a state dissolved in a solvent.5 In this case, the solvent is not particularly limited, but a relatively highly polar solvent is preferably used. Specifically, glymes such as propylene carbonate, ethylene carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, lactones such as γ-butyrolactone, phosphoric acid esters such as triethyl phosphate, One or two types of boric acid esters such as triethyl borate, sulfur compounds such as sulfolane and dimethyl sulfoxide, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, dimethyl sulfate, nitromethane, nitrobenzene, and dichloroethane. Mixtures of the above may be mentioned.
これらのうちでは、特にエチレンカーボネート、プロピ
レンカーボネート、ブチレンカーボネート。Among these, especially ethylene carbonate, propylene carbonate, butylene carbonate.
テトラヒドロフラン、２−メチルテトラヒドロフラン、
ジメトキシエタン、ジオキソラン及びγ−ブチロラクト
ンから選ばれた１種又は２種以上の混合溶媒が好適であ
る。Tetrahydrofuran, 2-methyltetrahydrofuran,
One or more mixed solvents selected from dimethoxyethane, dioxolane, and γ-butyrolactone are suitable.
更に本発明の二次電池を構成する電解質としては、上記
電解質を例えばポリエチレンオキサイド、ポリプロピレ
ンオキサイド、ポリエチレンオキサイドのイソシアネー
ト架橋体、エチレンオキサイドオリゴマーを側鎖に持つ
ホスファゼンポリマー等の重合体に含浸させた有機固体
電解質、Ｌｉ、Ｎ。Furthermore, the electrolyte constituting the secondary battery of the present invention may be an organic material impregnated with a polymer such as polyethylene oxide, polypropylene oxide, an isocyanate crosslinked product of polyethylene oxide, or a phosphazene polymer having an ethylene oxide oligomer in its side chain. Solid electrolyte, Li, N.
ＬｉＢＣＱ４等の無機イオン導電体、Ｌｉ、ＳｉＯ４゜
Ｌｉ、ＢＯ３等のリチウムガラスなどの無機固体電解質
を用いることもできる。Inorganic solid electrolytes such as inorganic ionic conductors such as LiBCQ4, lithium glasses such as Li, SiO4°Li, and BO3 can also be used.
本発明の二次電池は１通常正負極間に電解液を介在させ
ることにより構成されるが、この場合正負両極間に両極
の接触による電流の短絡を防ぐためセパレーターを介装
することができる。セパレーターとしては多孔質で電解
液を通したり含んだりすることのできる材料、例えばポ
リテトラフルオロエチレン、ポリプロピレンやポリエチ
レンなどの合成樹脂製の不織布、織布及び網等を使用す
ることができる。The secondary battery of the present invention is usually constructed by interposing an electrolyte between the positive and negative electrodes, but in this case, a separator may be interposed between the positive and negative electrodes to prevent short-circuiting of current due to contact between the two electrodes. As the separator, it is possible to use porous materials that allow the electrolyte to pass through or be contained therein, such as nonwoven fabrics, woven fabrics, and nets made of synthetic resins such as polytetrafluoroethylene, polypropylene, and polyethylene.
発明の効果
本発明に係る二次電池は、導電性が良好でかつ容量の大
きい（１）〜（５）式の化合物を正極活物質として使用
したことにより、高エネルギー密度である上、高電位で
サイクル特性に優れ、安定性、信頼性に優れたものであ
る。Effects of the Invention The secondary battery according to the present invention has high energy density and high potential by using compounds of formulas (1) to (5) with good conductivity and large capacity as positive electrode active materials. It has excellent cycle characteristics, stability, and reliability.
以下、本発明の正極活物質の製造例及び実施例と比較例
を示すが、本発明は下記の例に制限されるものではない
。Hereinafter, production examples, examples, and comparative examples of the positive electrode active material of the present invention will be shown, but the present invention is not limited to the following examples.
（２−ｘ）モルのＶ２Ｏ５に２ｘモルのＭＯ２（Ｍ＝Ｍ
ｏ又はＷ）とＸモルのＬｉ２Ｏ又はＬｉ２Ｃｏ３を加え
、よく混合した後、不活性ガス中で６５０℃。(2-x) moles of V2O5 to 2x moles of MO2 (M=M
o or W) and X moles of Li2O or Li2Co3, mixed well, and then heated at 650°C in an inert gas.
４８時間加熱反応させてβ−ＬｉＸＭＸＶ２−ｙｃＯ５
を得た。After a heating reaction for 48 hours, β-LiXMXV2-ycO5
I got it.
また、（２−ｍ−ｎ）モルのＶ２Ｏ５に２ｍモルのＭ
ｏ Ｏ，と２ｎモルのＷＯ，と（ｍ＋ｎ）モルのＬｉ２
Ｏ又はＬｉ２Ｃ○３を加え、よく混合した後、不活性ガ
ス中で６５０℃、４８時間加熱反応させてβ−Ｌ ｉｍ
＋。Ｍ ｏＩ、ｌＷ ｎＶ ２−＋ｍ−ｎ○５を得た。Also, in (2-m-n) moles of V2O5, 2 mmoles of M
o O, and 2n moles of WO, and (m+n) moles of Li2
After adding O or Li2C○3 and mixing well, a heating reaction was carried out at 650°C for 48 hours in an inert gas to form β-L im
+. MoI, lW nV 2-+m-n○5 was obtained.
更に、（２−ｙ）モルのＶ２Ｏ，に２ｚモルのＭＯ。Additionally, (2-y) moles of V2O, and 2z moles of MO.
（Ｍ＝＝Ｍｏ又はＷ）と２（ｙ−ｚ）モルのＶＯ，及び
ｙモルのＬｉ２Ｏ又はＬｉ、ＣＯ，を加え、よく混合し
た後、不活性ガス中で６５０℃、４８時間加熱反応させ
てβ−Ｌ ｉｙ Ｍ ｚ Ｖ ２−Ｚ Ｏｓを得た。(M==Mo or W), 2 (y-z) moles of VO, and y moles of Li2O or Li, CO, were added, mixed well, and then reacted by heating at 650°C for 48 hours in an inert gas. β-LiyMzV2-ZOs was obtained.
〔実施例１〕
正極活物質としてβ−Ｌｉ、、２．Ｍｏ。、２．Ｖ、、
、５０゜粉末を使用し、その１００重量部に導電剤とし
てアセチレンブラック１５重量部及び結着剤としてフッ
素樹脂粉末１５重量部を加え、十分混合した後、有機溶
剤で混練りし、ロールで約３５０ｐに圧延し、１５０℃
で真空乾燥し、所定の径に打抜いたものを正極とした。[Example 1] β-Li as the positive electrode active material, 2. Mo. , 2. V...
, 50° powder, 15 parts by weight of acetylene black as a conductive agent and 15 parts by weight of fluororesin powder as a binder were added to 100 parts by weight of the powder, mixed thoroughly, kneaded with an organic solvent, and rolled with a roll to approx. Rolled to 350p, 150℃
The positive electrode was dried in vacuum and punched out to a predetermined diameter.
負極は所定寸法に打抜いたアルミニウム板にリチウムを
圧着し、電解液中でアルミニウムーリチウム（Ａｌ１−
ＬＬ）合金化したものを用い、またプロピレンカーボネ
ートとエチレンカーボネートとの混合溶媒（容量比１：
１）にリチウム・六フッ化リン（Ｌ Ｉ Ｐ Ｆ ４
）を１モル／Ｑで溶解したものを電解液として使用し、
第１図に示す電池を組み立てた。The negative electrode is made by pressing lithium onto an aluminum plate punched to a predetermined size, and forming aluminum-lithium (Al1-
LL) alloyed one, and a mixed solvent of propylene carbonate and ethylene carbonate (volume ratio 1:
1) with lithium/phosphorus hexafluoride (L I P F 4
) dissolved at 1 mol/Q is used as an electrolyte,
The battery shown in FIG. 1 was assembled.
ここで、第１図において、１は正極、２はステンレスス
チール製の正極集電体で、正極１と集電体２とは一体化
されており、集電体２は正極缶３の内底面にスポット溶
接されている。また、４は負極、５は負極集電体で、負
極４は負極缶６の内底面に固着した集電体にスポット溶
接されている。Here, in FIG. 1, 1 is a positive electrode, 2 is a positive electrode current collector made of stainless steel, and the positive electrode 1 and current collector 2 are integrated, and the current collector 2 is the inner bottom surface of the positive electrode can 3. spot welded on. Further, 4 is a negative electrode, 5 is a negative electrode current collector, and the negative electrode 4 is spot-welded to the current collector fixed to the inner bottom surface of the negative electrode can 6.
更に、７はポリプロピレン不織布よりなるセパレーター
であり、これに前記電解液が含浸されている。なお、８
は絶縁バッキングである。また、電池寸法は直径２０．
０＋ｎｍ、厚さ１．６ｍｍである。Furthermore, 7 is a separator made of polypropylene nonwoven fabric, which is impregnated with the electrolytic solution. In addition, 8
is an insulating backing. Also, the battery dimensions are 20mm in diameter.
The thickness is 0+nm and the thickness is 1.6mm.
この電池を充放電電流１ｍＡにおいて放電終止電圧２．
ＯＶ、充電終止電圧３．５ｖで充放電を繰り返し、５サ
イクル目の放電曲線とその時の容量を調べた。第２図に
放電曲線を、第１表にその時の容量の結果を示す。This battery was charged at a discharge end voltage of 2.0 mA at a charging/discharging current of 1 mA.
Charging and discharging were repeated at OV and a charge end voltage of 3.5 V, and the discharge curve at the 5th cycle and the capacity at that time were examined. Figure 2 shows the discharge curve, and Table 1 shows the capacity results.
〔実施例２〕
ｔ［活物’ｆｆとり、てβ−ＬＬ０，３Ｗ、、、Ｖ１．
７０５を使用した以外は実施例１と同様な方法で正極及
び負極を作成し、電解液としてリチウム・六フッ化ヒ素
（ＬｉＡｓＦ、）１モル／Ｑをエチレンカーボネートと
２−メチルテトラヒドロフランとの混合溶媒（容量比１
：１）に溶解したものを用いて第１図に示す電池を実施
例１と同様にして組み立てた。[Example 2] t [Live material'ff taken, β-LL0,3W, , V1.
A positive electrode and a negative electrode were prepared in the same manner as in Example 1 except that 705 was used, and 1 mol/Q of lithium arsenic hexafluoride (LiAsF) was used as an electrolyte in a mixed solvent of ethylene carbonate and 2-methyltetrahydrofuran. (Capacity ratio 1
:1) was used to assemble the battery shown in FIG. 1 in the same manner as in Example 1.
次にこの電池を用いて実施例１と同様の充放電試験を行
なった。５サイクル目の放電曲線を第３図に、その時の
容量を第１表に示す。Next, a charge/discharge test similar to that in Example 1 was conducted using this battery. The discharge curve at the 5th cycle is shown in FIG. 3, and the capacity at that time is shown in Table 1.
〔実施例３〕
正極活物質としてβ−Ｌｉ０１Ｍｏ、、ｚＷｆｉ、２Ｖ
、、ＣＯ９を用いた以外は実施例１と同様にして第１図
に示す電池を作成した。[Example 3] β-Li01Mo, zWfi, 2V as positive electrode active material
The battery shown in FIG. 1 was produced in the same manner as in Example 1 except that ,,CO9 was used.
この電池につき実施例１と同様の充放電試験を行なった
。５サイクル目の放電曲線を第４図に、その時の容量を
第１表に示す。A charge/discharge test similar to that in Example 1 was conducted on this battery. The discharge curve at the 5th cycle is shown in FIG. 4, and the capacity at that time is shown in Table 1.
〔実施例４〕
正極活物質としてβ−Ｌｉｅ、ｉＭｏ６．１Ｖ□、、’
Ｏｓを用いた以外は実施例１と同様にして第１図に示す
電池を作成した。[Example 4] β-Lie, iMo6.1V□,,' as positive electrode active material
The battery shown in FIG. 1 was produced in the same manner as in Example 1 except that Os was used.
この電池につき実施例１と同様の充放電試験を行なった
。５サイクル目の放電曲線を第５図に。A charge/discharge test similar to that in Example 1 was conducted on this battery. Figure 5 shows the discharge curve of the 5th cycle.
その時の容量を第１表に示す。The capacity at that time is shown in Table 1.
〔実施例５〕
正極活物質としてβ−Ｌｉｅ、、Ｗ、、、Ｖ１．．Ｏ，
を用いた以外は実施例１と同様にして第１図に示す電池
を作成した。[Example 5] β-Lie, W, V1. ．． O,
The battery shown in FIG. 1 was produced in the same manner as in Example 1 except that the battery was used.
この電池につき実施例１と同様の充放電試験を行なった
。５サイクル目の放電曲線を第６図に。A charge/discharge test similar to that in Example 1 was conducted on this battery. Figure 6 shows the discharge curve of the 5th cycle.
その時の容量を第１表に示す。The capacity at that time is shown in Table 1.
正極活物質としてＶ、 Ｏ，を用いた以外は実施例２と
同様にして第１図に示す電池を作成した。A battery shown in FIG. 1 was prepared in the same manner as in Example 2 except that V, O, and the like were used as the positive electrode active materials.
この電池につき充電終止電圧を３．３ｖにした以外は実
施例１と同様の方法で充放電試験を行なった。５サイク
ル目の放電曲線を第７図に、その時の容量を第１表に示
す。なお、充電終止電圧を３．３ｖにしたのは、これよ
り電位を高くすると充電曲線が急に立ち上るためである
。A charge/discharge test was conducted on this battery in the same manner as in Example 1, except that the end-of-charge voltage was set to 3.3V. The discharge curve at the 5th cycle is shown in FIG. 7, and the capacity at that time is shown in Table 1. Note that the charging end voltage was set to 3.3 V because the charging curve would rise abruptly if the potential was made higher than this.
第 １ 表
なお、実施例１〜３及び比較例に示した正極活物質１０
０重量部に対して、アセナシンブラシ９５重斌部及び結
着剤としてフッ素樹脂粉末を１５重量部加え、実施例１
と同様な方法で正極シートを作成すると共に、これら正
極シートを四端子法で直流抵抗を測定した結果は第２表
に示す通りである。Table 1 In addition, the positive electrode active materials 10 shown in Examples 1 to 3 and Comparative Examples
Example 1: To 0 parts by weight, 95 parts by weight of an acenacin brush and 15 parts by weight of fluororesin powder as a binder were added.
Positive electrode sheets were prepared in the same manner as above, and the DC resistance of these positive electrode sheets was measured using the four-terminal method. The results are shown in Table 2.
第 ２ 表
以上の結果より、Ｖ、 Ｏ，はＬｉ−ＡＱを負極に用い
た電池において、２ｖ以上の電位で使う場合に容量が小
さく、導電性も低いのに対して、実施例に示したβ−タ
イプの複合酸化物は放電電位が高く、２ｖ以上での容量
も大きく、また導電性も良好であることが知見される。From the results shown in Table 2, it can be seen that in a battery using Li-AQ as the negative electrode, the capacity is small and the conductivity is low when used at a potential of 2 V or higher, whereas the It has been found that the β-type composite oxide has a high discharge potential, a large capacity at 2 V or more, and good conductivity.
従って、本発明によれば、高電位で高い放電容量を有す
る優れた非水電解液二次電池を得ることができるもので
あり。Therefore, according to the present invention, it is possible to obtain an excellent non-aqueous electrolyte secondary battery having a high potential and high discharge capacity.
その工業的価値は極めて大である。Its industrial value is extremely large.
第１図は充放電試験に使用した電池の断面図、第２図乃
至第７図はそれぞれ正極活物質としてＬｉ、、２６Ｍｏ
。、２５Ｖ、、７．Ｏ６，Ｌｉ０．、Ｗｏ、３Ｖ１．７
０ｓ。
Ｌ １０．４ ＭＯｏ、 ２ Ｗｏ、 ２ Ｖｌ、 ＠
０５ ） Ｌ ｉｇ、 ３ ＭＯｏ、Ｌ Ｖｌｏｇ
０５ ｐＬｉｏ、、Ｗｏ、ｔＶｘ、ｓ○５及び■２０５
を用いた電池の放電曲線を示す。Fig. 1 is a cross-sectional view of the battery used in the charge/discharge test, and Figs. 2 to 7 show Li, 26Mo as positive electrode active materials, respectively.
. , 25V, 7. O6, Li0. ,Wo,3V1.7
0s. L 10.4 MOo, 2 Wo, 2 Vl, @
05) L ig, 3 MOo, L Vlog
05 pLio, , Wo, tVx, s○5 and ■205
The discharge curve of the battery is shown.
Claims (1)
＿ｘＷ＿ｘＶ＿２＿−＿ｘＯ＿５……（２）Ｌｉ＿ｙＭ
ｏ＿ｚＶ＿２＿−＿ｚＯ＿５……（３）Ｌｉ＿ｙＷ＿ｚ
Ｖ＿２＿−＿ｚＯ＿５……（４）Ｌｉ＿ｍ＿＋＿ｎＭｏ
＿ｍＷ＿ｎＶ＿２＿−＿ｍ＿−＿ｎＯ＿５……（５）（
但し、式中ｘ≦１、ｚ＜ｙ≦１、ｍ＋ｎ≦１）から選ば
れる物質を正極活物質とし、リチウム又はリチウムを吸
蔵及び放出可能なリチウム合金を負極活物質とし、かつ
リチウムイオンが前記正極活物質と電気化学反応をする
ために移動を行ない得る非水物質を電解質としたことを
特徴とする非水電解質二次電池。[Claims] 1. The following formulas (1) to (5) Li_xMo_xV_2_-_xO_5...(1) Li
_xW_xV_2_-_xO_5...(2) Li_yM
o_zV_2_-_zO_5...(3) Li_yW_z
V_2_−_zO_5……(4) Li_m_+__nMo
_mW_nV_2_-_m_-_nO_5...(5)(
However, in the formula, a material selected from A non-aqueous electrolyte secondary battery characterized in that the electrolyte is a non-aqueous substance that can move to cause an electrochemical reaction with a positive electrode active material.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62120216A JPS63285871A (en) | 1987-05-19 | 1987-05-19 | Nonaqueous electrolyte secondary battery |
| US07/185,995 US4803137A (en) | 1987-05-19 | 1988-04-25 | Non-aqueous electrolyte secondary cell |
| DE3816778A DE3816778A1 (en) | 1987-05-19 | 1988-05-17 | SECOND ELEMENT WITH NON-AQUE ELECTROLYTE |
| FR8806670A FR2615657A1 (en) | 1987-05-19 | 1988-05-18 | NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62120216A JPS63285871A (en) | 1987-05-19 | 1987-05-19 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63285871A true JPS63285871A (en) | 1988-11-22 |
Family
ID=14780765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62120216A Pending JPS63285871A (en) | 1987-05-19 | 1987-05-19 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63285871A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992020112A1 (en) * | 1991-04-26 | 1992-11-12 | Sony Corporation | Nonaqueous electrolyte secondary battery |
-
1987
- 1987-05-19 JP JP62120216A patent/JPS63285871A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992020112A1 (en) * | 1991-04-26 | 1992-11-12 | Sony Corporation | Nonaqueous electrolyte secondary battery |
| US5427875A (en) * | 1991-04-26 | 1995-06-27 | Sony Corporation | Non-aqueous electrolyte secondary cell |
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