JPH0212768A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH0212768A JPH0212768A JP63163461A JP16346188A JPH0212768A JP H0212768 A JPH0212768 A JP H0212768A JP 63163461 A JP63163461 A JP 63163461A JP 16346188 A JP16346188 A JP 16346188A JP H0212768 A JPH0212768 A JP H0212768A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- oxide
- active material
- positive electrode
- charge
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims abstract description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- 239000001989 lithium alloy Substances 0.000 claims abstract description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 22
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000000737 periodic effect Effects 0.000 abstract description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 abstract description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 abstract 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 abstract 1
- QMDYMCDOBQRJFO-UHFFFAOYSA-M [Li+].[F-].F.F.F.F.F.[AsH3] Chemical compound [Li+].[F-].F.F.F.F.F.[AsH3] QMDYMCDOBQRJFO-UHFFFAOYSA-M 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JJVGROTXXZVGGN-UHFFFAOYSA-H [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[F-].[F-] Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[F-].[F-] JJVGROTXXZVGGN-UHFFFAOYSA-H 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide 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
- H01M4/48—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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はリチウムまたはリチウム合金を負極活物質とす
るリチウム二次電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a lithium secondary battery using lithium or a lithium alloy as a negative electrode active material.
従来の技術
非水電解液系二次電池の正極活物質としては、すでに種
々の硫化物、酸化物などが提案されている（たとえば、
Ｊ、 ｏｆ Ｐｏｗｅｒ ５ｏｕｒｃｅｓ、第９巻、３
０７〜３２０頁（１９８３） ）。また、電池特性の向
上のために五酸化バナジウムを正極活物質とすることは
、Ｅｌｅｃｔｒｏｃｈｅｍ、 Ｓｏｃ、 Ｍｅｅｔｉｎ
ｇ （Ｔｏｒｏｎｔｏ、 Ｍａｙ １１−１６゜１９７
５ ｒＩ＆１２７ ）で提案されている。その後、二次
電池用正極活物質としても、種々の検討、提案がなされ
ており、たとえば、非晶質化（特開昭６１−２００６６
７号公報）、複合酸化物（特開昭６１−２８１４６２号
公報）、ナトリウムブロンズ（特開昭６２−１９５８５
４号公報）などがある。Conventional technology Various sulfides, oxides, etc. have already been proposed as positive electrode active materials for non-aqueous electrolyte secondary batteries (for example,
J, of Power 5 sources, Volume 9, 3.
07-320 (1983)). Furthermore, the use of vanadium pentoxide as a positive electrode active material to improve battery characteristics has been proposed by Electrochem, Soc, and Meetin.
g (Toronto, May 11-16゜197
5rI&127). Since then, various studies and proposals have been made for positive electrode active materials for secondary batteries, including amorphousization (Japanese Patent Laid-Open No. 61-20066
7), composite oxide (Japanese Patent Application Laid-Open No. 61-281462), sodium bronze (Japanese Patent Application Laid-open No. 62-19585)
Publication No. 4).
発明が解決しようとする課題
上記従来の五酸化バナジウムを正極活物質として使用し
た二次電池においては、電池特性上必ずしも十分ではな
かった。特に、バナジウム系酸化物を正極活物質とした
電池においては、充放電サイクルの進行に伴なう反応の
非可逆化、すなわち容量の劣化が大きいという課題を有
していた。これは、充放電によるバナジウム酸化物の構
造破壊、あるいは電解液の酸化分解によるものとされて
いる。Problems to be Solved by the Invention The conventional secondary batteries using vanadium pentoxide as a positive electrode active material have not always had sufficient battery characteristics. In particular, batteries using a vanadium-based oxide as a positive electrode active material have a problem in that the reaction becomes irreversible as the charge/discharge cycle progresses, that is, the capacity deteriorates significantly. This is thought to be due to structural destruction of vanadium oxide due to charging and discharging, or oxidative decomposition of the electrolyte.
本発明は上記従来の課題を解決するもので、サイクル特
性の優れた、小型軽量でエネルギー密度の大きなリチウ
ム二次電池を提供することを目的とする。The present invention solves the above-mentioned conventional problems, and aims to provide a lithium secondary battery with excellent cycle characteristics, small size, light weight, and high energy density.
課題を解決するための手段
この課題を解決するために本発明のリチウム二次電池は
、正極活物質として、五酸化バナジウムに周期表第ｖｎ
＋族の酸化物、たとえば三二酸化鉄（Ｆｅ２０り、四三
酸化コバルト（Ｃ０３０４）、酸化−’−７ケル（Ｎｉ
ｏ）のいずれかを５〜１０モル％添加混合し、加熱処理
した複合酸化物を用いることを特徴とし、負極はリチウ
ムまたはリチウム合金であり、また電解液は炭酸エチレ
ン（ＥＣ）、炭酸プロピレン（ｐｃ）、１．２、ジメト
キシエタン（ＤＭＥ ）、２メチルテトラヒドロフラン
（ＭｅＴＨＦ）などの非プロトン性有機溶媒に、過塩素
酸リチウム（ＬｉＣｔＯ，）、６フフ化砒酸リチウム（
Ｌｉ Ａｓ Ｆ６）、リチウムトリフルオロメタンスル
フォネイト（ＬｉＣＦ、５Ｏ３）などのリチウム塩を溶
解させたものである。Means for Solving the Problem In order to solve this problem, the lithium secondary battery of the present invention uses vanadium pentoxide as a positive electrode active material,
+ group oxides, such as iron sesquioxide (Fe20), tricobalt tetroxide (C0304), -'-7 Kel oxide (Ni
It is characterized by using a composite oxide which is mixed with 5 to 10 mol% of any of o) and heat-treated, the negative electrode is lithium or a lithium alloy, and the electrolyte is ethylene carbonate (EC), propylene carbonate ( pc), 1.2, lithium perchlorate (LiCtO,), lithium hexafluoride arsenate (
Lithium salts such as LiAs F6) and lithium trifluoromethanesulfonate (LiCF, 5O3) are dissolved therein.
作用
上記構成によると、正極活物質を、五酸化バナジウムに
少量の第ｖｍ族酸化物、たとえば三二酸化鉄（Ｆｅ２Ｏ
３）、四三酸化コバルト（Ｃｏ、Ｕ４）、酸化ニッケル
（ＮｉＯ）のいずれかを添加した複合酸化物とすること
により、充放電サイクル時の五酸化バナジウム結晶格子
内へのリチウムイオン（Ｌｉ◆）の挿入、脱離に起因す
る五酸化バナジウムの結晶構造破壊が緩和され、充放電
サイクル特性が改善される。Function According to the above configuration, the positive electrode active material is formed by adding a small amount of Vm group oxide to vanadium pentoxide, such as iron sesquioxide (Fe2O
3) By making a composite oxide containing either tricobalt tetroxide (Co, U4) or nickel oxide (NiO), lithium ions (Li◆ ) destruction of the crystal structure of vanadium pentoxide due to insertion and desorption is alleviated, and charge/discharge cycle characteristics are improved.
実施例
以下、本発明の一実施例について、図面を参照しながら
説明する。EXAMPLE Hereinafter, an example of the present invention will be described with reference to the drawings.
第１図は本発明に係るリチウム二次電池、特にその正極
活物質を評価するために用いた直径２０ｗ１、総高１．
６ｎｏ＋の電池の半断面図である。１はリチウム負極、
２はステンレス製負極集電体、３はステンレス製封口板
、４はポリプロピレン製ガスケット、５は微細孔をもつ
ポリプロピレン製セパレータ、６は正極活物質７０重量
％、カーボンブラック２５重量％、フッ素樹脂系結着剤
５重量％から成る正極合剤、７はチタン製正極集電体、
８はステンレス製ケースである。電解液は炭酸プロピレ
ン（ＰＣ）と１．２、ジメトキシエタン（Ｌ）ＭＥ ）
の体積比１：１の混合溶媒に６７フ化砒酸リチウム（Ｌ
ｉＡｓＦａ）をｘｍｏｌ／ｌｆ８解させたものを使用し
ている。FIG. 1 shows a lithium secondary battery according to the present invention, with a diameter of 20 w1 and a total height of 1.
FIG. 6 is a half cross-sectional view of a 6no+ battery. 1 is a lithium negative electrode,
2 is a stainless steel negative electrode current collector, 3 is a stainless steel sealing plate, 4 is a polypropylene gasket, 5 is a polypropylene separator with micropores, 6 is a positive electrode active material 70% by weight, carbon black 25% by weight, fluororesin system Positive electrode mixture consisting of 5% by weight of binder, 7 is a titanium positive electrode current collector,
8 is a stainless steel case. The electrolyte is propylene carbonate (PC) and 1.2, dimethoxyethane (L) ME)
67 Lithium arsenate fluoride (L
The xmol/lf8 solution of iAsFa) is used.
正極活物質は、メタバナジン酸アンモニウム（ＮＨ４Ｖ
Ｏ３）の熱分解により得られた五酸化バナジウム（Ｖ！
０、）に、所定量の三二酸化鉄（Ｆｅ２Ｏ２）を添加混
合し、ボールミルなどで充分に混合した後、７００°Ｃ
で８〜２４時間焼成を行なった。この複合酸化物の粉末
Ｘ線回折の結果からＦｅＶＯ４ｓ Ｆｅｏ、ｏｒ Ｖｌ
、１１３０４などの回折ピークは認められなかった。な
お、三二酸化鉄の代わりに四三酸化コバルト（Ｃｏ、（
Ｊ４）、酸化ニッケル（Ｎｉ□）を添加した場合にも同
様の結果であった。The positive electrode active material is ammonium metavanadate (NH4V
Vanadium pentoxide (V!) obtained by thermal decomposition of O3)
Add and mix a predetermined amount of iron sesquioxide (Fe2O2) to 0, ), mix thoroughly with a ball mill, etc., and heat to 700°C.
Firing was performed for 8 to 24 hours. From the powder X-ray diffraction results of this composite oxide, FeVO4s Feo, or Vl
, 11304, and other diffraction peaks were not observed. Note that tricobalt tetroxide (Co, (
J4), similar results were obtained when nickel oxide (Ni□) was added.
第２図に、この電池を、１ｍＡ定亀流でｚｏＶ〜３．８
Ｖの電圧範囲の充放電サイクルを行なった際の、充放電
サイクルによる放電容量の変動を示している。ＡとＢは
本発明の一実施例である■２０．とＦｅ。Figure 2 shows this battery at 1 mA constant current of zoV ~ 3.8.
It shows the variation in discharge capacity due to charge/discharge cycles when charge/discharge cycles are performed in the voltage range of V. A and B are examples of the present invention.■20. and Fe.
Ｏｓの複合酸化物を正極活物質とした電池の特性である
。ＡはＦｅ３Ｏ．５モル％、ＢはＦｅ３Ｏ３を１０モル
％混合したものである。Ｃは比較例のＦｅ、Ｏ，を１５
モル％混合したものであり、Ｄは従来例の五酸化バナジ
ウム（Ｖｔ Ｏｓ ）である。These are the characteristics of a battery using a composite oxide of Os as a positive electrode active material. A is Fe3O. 5 mol%, and B is a mixture of 10 mol% Fe3O3. C is Fe, O, of the comparative example 15
D is a conventional example of vanadium pentoxide (VtOs).
Ａの５モル％Ｆｅ２Ｏ，を混合した場合には、放電特性
は従来例りのｖ２０．とほぼ同一であるが、８０ザイク
ル後の放電容量は初期容量の約８６％と低減比率が小さ
くなる。Ｂの１０モル％Ｆｅ！Ｏ，を混合した場合も、
放電容量はやや小さくなるが、同様の挙動を示し、８０
サイクル後の放電容量は初期の８０％以上得られる。一
方、Ｄの従来例の場合逍は、放電初期容量は大きいが、
サイクル劣化が大きいため、８０サイクル後の放電容量
は初期の約５５％に低下している。また、Ｃの比較例の
１５モル％Ｆｅ２Ｏ。When 5 mol% Fe2O of A was mixed, the discharge characteristics were the same as conventional v20. However, the discharge capacity after 80 cycles is about 86% of the initial capacity, which is a small reduction ratio. 10 mol% Fe of B! Even when O, is mixed,
Although the discharge capacity is slightly smaller, it shows the same behavior and is 80
The discharge capacity after cycling is 80% or more of the initial capacity. On the other hand, in the case of conventional example D, although the initial discharge capacity is large,
Due to the large cycle deterioration, the discharge capacity after 80 cycles was reduced to about 55% of the initial value. In addition, 15 mol% Fe2O of comparative example C.
を混合した場合には、初期放電容量が小さくなり、サイ
クル特性の改善も見られず、８０サイクル後の容量は初
期の約５５％となっている。When these were mixed, the initial discharge capacity was small and no improvement in cycle characteristics was observed, with the capacity after 80 cycles being approximately 55% of the initial capacity.
また、四三酸化コバルト（Ｃｏ３０４） 、酸化ニッケ
ル（ＮｉＯ）を添加した場合も、図示していないが、ほ
ぼ同様の結果が得られた。Although not shown, almost similar results were obtained when tricobalt tetroxide (Co304) and nickel oxide (NiO) were added.
以上の結果より、五酸化バナジウム（Ｖ６Ｏ１３）に周
期表第Ｖｌ族の酸化物（Ｆｅ、 ０． 、 Ｃｏ３０．
、 ＮｉＯなど）を少ｆ、［５〜１０モル％）添加し
た複合酸化物を正極活物質とすることにより、放電容量
が大きく、充放電サイクル特性を著しく改良することが
分った。From the above results, vanadium pentoxide (V6O13) is combined with oxides of group Vl of the periodic table (Fe, 0., Co30.
It has been found that by using a composite oxide to which a small amount (5 to 10 mol %) of NiO, NiO, etc. is added as the positive electrode active material, the discharge capacity is large and the charge/discharge cycle characteristics are significantly improved.
また、Ｘ線回折の結果から、これらの複合酸化物は明確
な結晶構造となっていないものと考えられる。充放電サ
イクル特性の改善は、第■族の酸化物が五酸化バナジウ
ム（■ｚ Ｏｓ ）の結晶格子内に不規則に挿入される
ことにより、■３Ｏ．結晶格子の歪みなどが発生し、充
電時のリチウムイオン（Ｌｉつの結晶格子内への挿入お
よび脱離がより容易に起り得るようになったためと考え
られる。Moreover, from the results of X-ray diffraction, it is considered that these composite oxides do not have a clear crystal structure. The improvement in the charge/discharge cycle characteristics is due to the irregular insertion of group Ⅰ oxides into the crystal lattice of vanadium pentoxide (■zOs). This is thought to be because distortion of the crystal lattice occurs, and lithium ions (Li) can more easily be inserted into and removed from the crystal lattice during charging.
発明の効果
以上のように本発明の構成によれば、１招活物質として
周期表第■族の酸化物を５〜１０モル％混合したバナジ
ウム複合酸化物を用いることにより、エネルギー密度が
大きくかつ充放電サイクル特性に優れたリチウム二次電
池を提供することができる。Effects of the Invention As described above, according to the structure of the present invention, by using a vanadium composite oxide mixed with 5 to 10 mol% of an oxide of Group I of the periodic table as the first active material, energy density is large and A lithium secondary battery with excellent charge/discharge cycle characteristics can be provided.
第１図は本発明の一実施例におけるリチウム二次電池の
半断面図、第２図は各リチウム二次電池の放電容量と充
放電サイクルとの関係を示すグラフ図である。
１・・・リチウム負極、５・・・セパレータ、６・・・
正極合剤。FIG. 1 is a half-sectional view of a lithium secondary battery according to an embodiment of the present invention, and FIG. 2 is a graph showing the relationship between discharge capacity and charge/discharge cycle of each lithium secondary battery. 1... Lithium negative electrode, 5... Separator, 6...
Positive electrode mixture.
Claims (1)
、非水電解液とを備え、五酸化バナジウムに周期表第V
III族の酸化物を５〜１０ｍｏｌ％添加した複合酸化物
を正極活物質としたリチウム二次電池。 ２、第VIII族酸化物が、三二酸化鉄（Ｆｅ＿２Ｏ＿３）
、四三酸化コバルト（Ｃｏ＿３Ｏ＿４）、酸化ニッケル
（ＮｉＯ）、のうちから選ばれたものである請求項１に
記載のリチウム二次電池。[Claims] 1. Comprising a negative electrode using lithium or a lithium alloy as an active material and a non-aqueous electrolyte, vanadium pentoxide is
A lithium secondary battery using a composite oxide containing 5 to 10 mol% of a group III oxide as a positive electrode active material. 2. Group VIII oxide is iron sesquioxide (Fe_2O_3)
2. The lithium secondary battery according to claim 1, wherein the lithium secondary battery is selected from the group consisting of tricobalt tetroxide (Co_3O_4), and nickel oxide (NiO).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63163461A JPH0212768A (en) | 1988-06-29 | 1988-06-29 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63163461A JPH0212768A (en) | 1988-06-29 | 1988-06-29 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0212768A true JPH0212768A (en) | 1990-01-17 |
Family
ID=15774319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63163461A Pending JPH0212768A (en) | 1988-06-29 | 1988-06-29 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0212768A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196278A (en) * | 1991-03-07 | 1993-03-23 | Fuji Photo Film Co., Ltd. | Lithium secondary battery with a cathode comprising lithium, cobalt and vanadium |
| US6432585B1 (en) | 1997-01-28 | 2002-08-13 | Canon Kabushiki Kaisha | Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery |
| US6730434B1 (en) | 1998-09-18 | 2004-05-04 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US6835332B2 (en) | 2000-03-13 | 2004-12-28 | Canon Kabushiki Kaisha | Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery |
| US6949312B1 (en) | 1998-09-18 | 2005-09-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
-
1988
- 1988-06-29 JP JP63163461A patent/JPH0212768A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196278A (en) * | 1991-03-07 | 1993-03-23 | Fuji Photo Film Co., Ltd. | Lithium secondary battery with a cathode comprising lithium, cobalt and vanadium |
| US6432585B1 (en) | 1997-01-28 | 2002-08-13 | Canon Kabushiki Kaisha | Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery |
| US6730434B1 (en) | 1998-09-18 | 2004-05-04 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US6949312B1 (en) | 1998-09-18 | 2005-09-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US7183018B2 (en) | 1998-09-18 | 2007-02-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US7534528B2 (en) | 1998-09-18 | 2009-05-19 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| EP2219253A2 (en) | 1998-09-18 | 2010-08-18 | Canon Kabushiki Kaisha | Electrode material |
| US6835332B2 (en) | 2000-03-13 | 2004-12-28 | Canon Kabushiki Kaisha | Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery |
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