JP3110738B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3110738B2 JP3110738B2 JP01204171A JP20417189A JP3110738B2 JP 3110738 B2 JP3110738 B2 JP 3110738B2 JP 01204171 A JP01204171 A JP 01204171A JP 20417189 A JP20417189 A JP 20417189A JP 3110738 B2 JP3110738 B2 JP 3110738B2
- Authority
- JP
- Japan
- Prior art keywords
- cycle
- discharge capacity
- product
- capacity
- manganese dioxide
- 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.)
- Expired - Fee Related
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 122
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 48
- 229910052744 lithium Inorganic materials 0.000 claims description 48
- 239000007774 positive electrode material Substances 0.000 claims description 44
- 239000011572 manganese Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 39
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 30
- 230000008859 change Effects 0.000 description 20
- 239000011777 magnesium Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 239000011669 selenium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- AKFFNTKRAYWFRN-UHFFFAOYSA-N ethyl 5-(trifluoromethyl)-1h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C=1C=C(C(F)(F)F)NN=1 AKFFNTKRAYWFRN-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ この考案は、非水電解液二次電池に関し、詳しくは、
リチウムまたはリチウム合金を活物質とする負極と、二
酸化マンガンを主な活物質とする正極を用いて構成され
る、非水電解液二次電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a non-aqueous electrolyte secondary battery.
The present invention relates to a non-aqueous electrolyte secondary battery including a negative electrode using lithium or a lithium alloy as an active material and a positive electrode mainly using manganese dioxide as a main active material.
＜従来の技術＞ この種の非水電解液二次電池では、通常、上記のよう
にリチウムあるいはリチウム合金（例えばリチウム−ア
ルミニウム合金、リチウム−マグネシウム合金）などを
活物質とする負極が用いられており、この負極を、セパ
レータを介して正極と組合せ、また非水系の電解液を用
いる構成が採られている。<Prior Art> In a non-aqueous electrolyte secondary battery of this type, an anode including lithium or a lithium alloy (eg, lithium-aluminum alloy, lithium-magnesium alloy) as an active material is usually used as described above. The negative electrode is combined with the positive electrode through a separator, and a non-aqueous electrolytic solution is used.
正極に用いる正極活物質としては二酸化マンガンが広
く知られており、また例えば特開昭63−24554号公報，
特開昭63−114065号公報，特開昭63−126165号公報など
に記載されているように、カルシウムイオンをドーピン
グした二酸化マンガン，あるいはリチウムとの複合酸化
物であるLiMn2O4を主体とするもの，二酸化マンガンに
硫酸チタニウムを混合した後加熱して得たものなどを用
いることでサイクル性の改善を図るようにした技術が知
られている。Manganese dioxide is widely known as a positive electrode active material used for a positive electrode. For example, JP-A-63-24554 discloses
As described in JP-A-63-114065 and JP-A-63-126165, manganese dioxide doped with calcium ions or LiMn 2 O 4 which is a composite oxide with lithium is mainly used. There is known a technique for improving cycleability by using a material obtained by mixing titanium sulfate with manganese dioxide and heating the mixture.
また、負極活物質に用いられるリチウムが水との反応
性に富むことから、適当な熱処理を施して正極活物質か
らの水分を除去することが広く行われている。Further, since lithium used for the negative electrode active material has high reactivity with water, it is widely performed to remove moisture from the positive electrode active material by performing an appropriate heat treatment.
＜発明が解決しようとする課題＞ ところで、この非水電解液二次電池で上記の二酸化マ
ンガンなどを正極活物質として用いた場合、サイクル条
件にもよるが、実用上使用可能な電池寿命は30サイクル
程度と少ない。<Problems to be Solved by the Invention> By the way, when the above-mentioned manganese dioxide or the like is used as a positive electrode active material in this nonaqueous electrolyte secondary battery, the practically usable battery life depends on the cycle conditions, although it depends on the cycle conditions. Only about a cycle.
このようにサイクル性が悪い理由としては、充放電に
伴うリチウムイオンの出入りの際に二酸化マンガンの結
晶が膨脹・収縮を繰返すのでその結晶構造が変化し、こ
の結果充放電サイクルにより結晶が緩んだり崩壊したり
することや、充電の際にリチウムイオンが安定な形で結
晶中に取込まれてしまい、このため次の充電の際に正極
からのリチウムイオンの放出が旨くおこなわれなくなる
ことなどが考えられている。The reason for the poor cycleability is that the manganese dioxide crystal repeatedly expands and contracts when lithium ions enter and exit during charging and discharging, thus changing its crystal structure. It may collapse, or lithium ions may be taken into the crystal in a stable form during charging, which prevents lithium ions from being released from the positive electrode during the next charging. It is considered.
また、例えば正極活物質を上記のようにLiMn2O4を主
体とする構成とした場合、サイクル特性は比較的良好で
あるものの、二酸化マンガンを用いた場合に比べて絶対
容量が小さくなり、このため電池の放電容量自体がかな
り低下してしまうこともある。Further, for example, when the positive electrode active material is mainly composed of LiMn 2 O 4 as described above, although the cycle characteristics are relatively good, the absolute capacity is smaller than when manganese dioxide is used. Therefore, the discharge capacity of the battery itself may be considerably reduced.
この発明は、二酸化マンガンを主な正極活物質として
用いる場合において、容量が大きく且つサイクル特性の
優れた非水電解液二次電池を提供することを目的とす
る。An object of the present invention is to provide a nonaqueous electrolyte secondary battery having a large capacity and excellent cycle characteristics when manganese dioxide is used as a main positive electrode active material.
＜課題を解決するための手段＞ この発明の非水電解液二次電池は、リチウムやリチウ
ム合金を負極活物質とし、また二酸化マンガン中にLa,A
l,Ce,Se,Er,Mgから選ばれた１種の元素がドーピングさ
れた正極活物質を用いる非水電解液二次電池において、
前記正極活物質は、La,Al,Ce,Se,ErについてはMn原子に
対する各元素の添加量が５〜25モル％に相当する化合物
を250〜450℃で熱処理してドーピングしたものであり、
MgについてはMn原子に対するMg元素の添加量が10〜15モ
ル％に相当する化合物を250〜400℃で熱処理してドーピ
ングしたものであることを要旨とする。<Means for Solving the Problems> The nonaqueous electrolyte secondary battery of the present invention uses lithium or a lithium alloy as a negative electrode active material, and contains La, A in manganese dioxide.
In a non-aqueous electrolyte secondary battery using a positive electrode active material doped with one element selected from l, Ce, Se, Er, Mg,
For the positive electrode active material, La, Al, Ce, Se, and Er are doped with a compound corresponding to an addition amount of 5 to 25 mol% of each element with respect to Mn atoms by heat treatment at 250 to 450 ° C.,
The gist of the invention is that Mg is obtained by doping a compound corresponding to an amount of the Mg element of 10 to 15 mol% with respect to the Mn atom by heat treatment at 250 to 400 ° C.
この熱処理の温度が250℃より低い場合には性能向上
の度合が小さい。これは、熱処理温度が250℃より低い
と以下に説明するような複合酸化物が形成されたりある
いはドーピングが行われるための反応が十分には行われ
ず、また二酸化マンガンからの水分除去が不十分になる
ことが原因と考えられる。一方、熱処理温度が450℃よ
り高いと、二酸化マンガンの活性度が低下して電池の性
能低下を招く虞がある。When the temperature of this heat treatment is lower than 250 ° C., the degree of performance improvement is small. This is because if the heat treatment temperature is lower than 250 ° C., a complex oxide as described below is formed or a reaction for doping is not sufficiently performed, and moisture is not sufficiently removed from manganese dioxide. Is considered to be the cause. On the other hand, if the heat treatment temperature is higher than 450 ° C., the activity of manganese dioxide may decrease, leading to a decrease in battery performance.
上記熱処理としては、この他、高温高湿下でのオート
クレーブ処理や水溶液中でのマイクロ波加熱処理などを
適宜用いることもできる。In addition, as the heat treatment, an autoclave treatment under a high temperature and a high humidity, a microwave heating treatment in an aqueous solution, or the like can be appropriately used.
そして、上記のような熱処理によって、上記元素が二
酸化マンガン中にマンガンとの複酸化物（例えばLaMnO3
やMg6MnO8）として含有されたり、あるいは上記元素が
二酸化マンガン中にドーピングされた状態になると考え
られる。Then, by the heat treatment as described above, the element is mixed with manganese dioxide in manganese dioxide (for example, LaMnO 3
Or Mg 6 MnO 8 ), or the above-mentioned elements are considered to be doped in manganese dioxide.
即ち、上記熱処理により得られた正極活物質をＸ線回
析すると、原料である二酸化マンガンや上記化合物など
のピークはあるが、新しいピークが明確にでてこない。
しかしながら、この得られた正極活物質を用いた電池の
特性（放電特性やサイクル特性）は、二酸化マンガンの
ものとは異なるしまた上記複酸化物のものでもなく、従
って、上記元素が二酸化マンガンに何等かの作用をして
いることは確かである。That is, when the positive electrode active material obtained by the above heat treatment is subjected to X-ray diffraction, there are peaks of manganese dioxide as the raw material and the above compounds, but no new peak clearly appears.
However, the characteristics (discharge characteristics and cycle characteristics) of the battery using the obtained positive electrode active material are different from those of manganese dioxide and are not those of the above-mentioned double oxide. Certainly it does something.
本発明者の考察によれば、これは、正極活物質内に微
量でも上記のような複合酸化物が結晶の状態で形成され
ていること、及び／または、二酸化マンガン中に上記元
素がはいりこんで二酸化マンガン結晶の一部でMnが上記
元素に置換されていたり、二酸化マンガン中に上記元素
とMnと酸素とが部分的に結合した領域があること、つま
り上記元素が二酸化マンガン中にドーピングされている
状態となっていることなどによるものと思われる。According to the present inventor's consideration, this is because the above-mentioned complex oxide is formed in a crystalline state even in a minute amount in the positive electrode active material, and / or the element is contained in manganese dioxide. In the manganese dioxide crystal, Mn is substituted with the above element, or there is a region in the manganese dioxide where the above element, Mn and oxygen are partially bonded, that is, the above element is doped in the manganese dioxide. It seems to be due to the fact that it is in a state of being.
尚、二酸化マンガンとしては、電解二酸化マンガン，
化学二酸化マンガンなどを用いることができる。In addition, as manganese dioxide, electrolytic manganese dioxide,
Chemical manganese dioxide or the like can be used.
＜作用＞ 上記元素がトンネル構造を形成しているとされる二酸
化マンガンの結晶構造に作用して以下の，のような
影響を与える結果、電池の性能向上が図れるものと推測
される。<Action> It is presumed that the above elements act on the crystal structure of manganese dioxide, which is considered to form a tunnel structure, and have the following effects, thereby improving the performance of the battery.
リチウムイオンの拡散経路が広がって充放電における
リチウムイオンのスムーズな移動が可能になるため、電
池の放電容量及びサイクル性が良好になる。Since the diffusion path of the lithium ions is widened and the lithium ions can smoothly move during charge and discharge, the discharge capacity and cycleability of the battery are improved.
二酸化マンガンの結晶構造が強固となり、充放電に伴
う二酸化マンガンの膨脹，収縮に対する抵抗力が高まっ
て崩れ難くなり、電池のサイクル性が向上する。The crystal structure of manganese dioxide becomes strong, the resistance to swelling and shrinkage of manganese dioxide due to charge and discharge increases, and the manganese dioxide becomes less susceptible to collapse, thereby improving the cycleability of the battery.
＜実施例＞ 以下に実施例を説明する。<Example> An example will be described below.
実施例１ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化ランタンLa2O3をLa/Mnのモ
ル比0.15（Mn1モルに対し、La0.15モル）で混合し、ま
たこの混合物を温度300〜450℃で10時間焼成を行ない正
極活物質を得た。Example 1 Comparison of cyclability with comparative product Electrolytic manganese dioxide and lanthanum oxide La 2 O 3 were mixed at a La / Mn molar ratio of 0.15 (0.15 mol of La to 1 mol of Mn), and the mixture was heated at a temperature of 300. Baking was performed at -450 ° C for 10 hours to obtain a positive electrode active material.
この正極活物質８重量部に黒鉛１重量部,PTFE粉末１
重量部を混合したものを円盤状に加圧成形し、直径15m
m,厚さ0.6mmの正極合剤を作製した。1 part by weight of graphite and 1 part by weight of PTFE powder
A mixture of parts by weight is press-formed into a disc shape, and the diameter is 15m.
A positive electrode mixture having a thickness of 0.6 mm and a thickness of 0.6 mm was prepared.
そして第１図のように、上記で得た正極合剤１の上面
に、多孔質ポリプロピレンフィルムからなるセパレータ
２を介して、リチウム−アルミニウム合金を活物質とす
る負極３を重ね合せ、またプロピレンカーボネイトとジ
メトキシエタンとを容量比1:1で混合した有機溶媒中にL
iClO4を1mol/溶解したものを電解液として用い、更に
以上の発電要素を、電池缶４と端子板５をそれらの周縁
部に介在させた絶縁ガスケット６を挟持させてなる電池
ケース内に収納して、直径20mm,厚さ1.6mmのコイン形リ
チウム二次電池（本発明品１）を作製した。Then, as shown in FIG. 1, a negative electrode 3 containing a lithium-aluminum alloy as an active material is overlapped on a top surface of the positive electrode mixture 1 obtained above via a separator 2 made of a porous polypropylene film. And dimethoxyethane in an organic solvent mixed at a volume ratio of 1: 1
1 mol / dissolved iClO 4 is used as an electrolytic solution, and the above power generating elements are further housed in a battery case in which an insulating gasket 6 having a battery can 4 and a terminal plate 5 interposed therebetween is sandwiched. As a result, a coin-type lithium secondary battery having a diameter of 20 mm and a thickness of 1.6 mm (Product 1 of the present invention) was produced.
一方、電解二酸化マンガンに水酸化リチウムLiOHを二
酸化マンガン１モルに対して0.5モル混合したものを400
℃で熱処理し、こうして得たものを正極活物質とした以
外は本発明品１と同様にして、直径20mm,厚さ1.6mmのコ
イン形リチウム二次電池（比較品）を作製した。On the other hand, a mixture of electrolytic manganese dioxide and lithium hydroxide, LiOH, mixed with 0.5 mol per 1 mol of manganese dioxide is 400
A coin-shaped lithium secondary battery having a diameter of 20 mm and a thickness of 1.6 mm (comparative product) was produced in the same manner as in the product 1 of the present invention, except that the composition was heat-treated at ℃ and the obtained product was used as a positive electrode active material.
これらの電池を、2mAの電流で電池電圧2.2Vまで放電
し、また1mAの電流で電池電圧3.5Vまで充電するという
条件で充放電サイクルを繰返した。These batteries were repeatedly charged and discharged under the condition that the batteries were discharged to a battery voltage of 2.2 V at a current of 2 mA and charged to a battery voltage of 3.5 V at a current of 1 mA.
本発明品１の初度の放電容量を１とした時の各サイク
ルにおける各電池の放電容量を、容量比（そのサイクル
の放電容量／本発明品１の初度の放電容量）として第２
図（Ａ）に示した。The discharge capacity of each battery in each cycle when the initial discharge capacity of the product 1 of the present invention is set to 1 is defined as a capacity ratio (discharge capacity of the cycle / initial discharge capacity of the product 1 of the present invention).
This is shown in FIG.
ランタンの添加量の検討 二酸化マンガンと酸化ランタンとの混合モル比を適宜
調整してマンガンに対するランタンの添加量（La/Mn）
を０〜0.25の範囲で種々変え、またこれらを温度400℃
で10時間熱処理したものを正極活物質とした他は本発明
品１と同じコイン形リチウム二次電池を種々作製した。Investigation of the amount of lanthanum added The amount of lanthanum added to manganese (La / Mn) by appropriately adjusting the mixing molar ratio of manganese dioxide and lanthanum oxide
Are varied in the range of 0 to 0.25, and these are brought to a temperature of 400 ° C.
Various coin-shaped lithium secondary batteries were manufactured in the same manner as the product 1 of the present invention except that the material heat-treated for 10 hours was used as the positive electrode active material.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）、並びに、正極活物
質に電解二酸化マンガンを単独で用いた以外は同一構成
のコイン形リチウム一次電池の放電容量を１とした時
の、これら電池の第100サイクルにおける容量比（各電
池の第100サイクル目の放電容量／コイン形リチウム一
次電池の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio when a charge / discharge cycle was performed under the same conditions as described above (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle), and electrolytic manganese dioxide alone as the positive electrode active material When the discharge capacity of the coin-type lithium primary batteries of the same configuration was set to 1 except that they were used in (1), the capacity ratio of these batteries in the 100th cycle (discharge capacity in the 100th cycle of each battery / coin-type lithium primary battery) Discharge capacity).
これらの結果は第２図（Ｂ）の通りで、ランタンの添
加量を0.05〜0.25の範囲とすればサイクルでの容量低下
が少なく且つ容量の高い電池とすることができる。尚、
図において実線は容量変化比を、また点線は容量比をそ
れぞれ示す。These results are as shown in FIG. 2 (B). When the amount of lanthanum is in the range of 0.05 to 0.25, a battery having a small capacity decrease in the cycle and a high capacity can be obtained. still,
In the figure, the solid line shows the capacitance change ratio, and the dotted line shows the capacitance ratio.
熱処理温度の検討 マンガンに対するランタンの添加量（La/Mn）が0.15
となるように二酸化マンガンと酸化ランタンとの混合モ
ル比を調整し、また熱処理温度を200〜500℃の範囲で種
々変えて得たものを正極活物質とした他は本発明品１と
同様なコイン形リチウム二次電池を種々作製した。Examination of heat treatment temperature The amount of lanthanum added to manganese (La / Mn) is 0.15
The same as the product 1 of the present invention except that a mixture obtained by adjusting the mixing molar ratio of manganese dioxide and lanthanum oxide so that the heat treatment temperature was variously changed in the range of 200 to 500 ° C. was used as the positive electrode active material. Various coin-shaped lithium secondary batteries were manufactured.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第２図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃程度とすればサイクルでの容量低下を少
なく抑えることができる。The results are as shown in FIG. 2 (c). From this result, when the heat treatment temperature is set to about 250 to 450 ° C., the capacity decrease in the cycle can be suppressed to a small extent.
他の実施例 電解二酸化マンガン１モルに対し水酸化ランタンLa
（OH）３を0.5モル混合した物を温度400℃で72時間熱処
理を行なって得たものを正極活物質とした他は本発明品
１と同様なコイン形リチウム二次電池を作製し、またこ
の電池を上記と同様な条件で充放電させ、第20サイクル
目の放電容量を調べた所、本発明品１の第20サイクル目
の放電容量を100とした場合、放電容量は103であった。Another Example Lanthanum hydroxide La per mole of electrolytic manganese dioxide
A coin-shaped lithium secondary battery similar to the product 1 of the present invention was produced except that a mixture obtained by subjecting a mixture of 0.5 mol of (OH) 3 to heat treatment at a temperature of 400 ° C. for 72 hours was used as a positive electrode active material. The battery was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 1 of the present invention was 100, the discharge capacity was 103. .
電解二酸化マンガン１モルに対し炭酸ランタンLa2（C
O3）３・8H2Oを0.1モル混合した物を温度400℃で72時間
熱処理を行なって得たものを正極活物質とした他は本発
明品１と同様なコイン形リチウム二次電池を作製し、ま
たこの電池を上記と同様な条件で充放電させ、第20サイ
クル目の放電容量を調べた所、本発明品１の第20サイク
ル目の放電容量を100とした場合、放電容量は110であっ
た。Lanthanum carbonate La 2 (C
The O 3) 3 · 8H 2 O at a temperature 400 ° C. The material was 0.1 mol mixing those obtained by performing 72 hours heat treatment except that the positive electrode active material present invention product 1 and similar coin type lithium secondary battery The battery was manufactured and charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 1 of the present invention was 100, the discharge capacity was It was 110.
実施例２ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化アルミニウムAl2O3をAl/Mn
のモル比0.15（Mn1モルに対し、Al0.15モル）で混合
し、またこの混合物を温度300〜450℃で10時間焼成を行
なって得た正極活物質を用いた他は本発明品１と同様に
して、コイン形リチウム二次電池（本発明品２）を作製
した。Example 2 Comparison of cyclability with comparative product Electrolytic manganese dioxide and aluminum oxide Al 2 O 3 were converted to Al / Mn
And a mixture of 0.15 mol of Al and 0.15 mol of Al per mole of Mn. The mixture was baked at a temperature of 300 to 450 ° C. for 10 hours. Similarly, a coin-type lithium secondary battery (Product 2 of the present invention) was produced.
この本発明品２と前記比較品とを上記と同じ条件で充
放電させた。本発明品２の初度の放電容量を１とした時
の各サイクルにおけるこれらの電池の放電容量を、容量
比（そのサイクルの放電容量／本発明品２の初度の放電
容量）として第３図（Ａ）に示した。The product 2 of the present invention and the comparative product were charged and discharged under the same conditions as described above. FIG. 3 shows the discharge capacity of these batteries in each cycle when the initial discharge capacity of the product 2 of the present invention is 1 as a capacity ratio (discharge capacity of the cycle / initial discharge capacity of the product 2 of the present invention). A).
アルミニウムの添加量の検討 二酸化マンガンと酸化アルミニウムとの混合モル比を
適宜調整してマンガンに対するアルミニウムの添加量
（Al/Mn）を０〜0.25の範囲で種々変え、またこれらを
温度400℃で10時間熱処理したものを正極活物質とした
以外は本発明品２と同様なコイン形リチウム二次電池を
それぞれ作製した。Examination of the amount of aluminum added The amount of aluminum added to manganese (Al / Mn) was varied in the range of 0 to 0.25 by appropriately adjusting the mixing molar ratio of manganese dioxide and aluminum oxide. Coin-shaped lithium secondary batteries similar to the product 2 of the present invention were prepared, except that the heat-treated one was used as the positive electrode active material.
これらの電池を上記と同じ条件で充放電させた時の容
量変化比（第100サイクル目の放電容量／第10サイクル
目の放電容量）、並びに前記コイン形リチウム一次電池
の放電容量を１とした時のこれらの電池の第100サイク
ルにおける容量比（各電池の第100サイクル目の放電容
量／コイン形リチウム一次電池の放電容量）をそれぞれ
調べた。The capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when these batteries were charged and discharged under the same conditions as above, and the discharge capacity of the coin-type lithium primary battery were set to 1. At this time, the capacity ratio of these batteries in the 100th cycle (discharge capacity of the 100th cycle of each battery / discharge capacity of the coin-type lithium primary battery) was examined.
これらの結果は第３図（Ｂ）の通りで、ランタンの添
加量を0.05〜0.25の範囲とすればサイクルでの容量低下
が少なく且つ容量の高い電池とすることができる。図に
おいて実線は容量変化比を、また点線は容量比をそれぞ
れ示す。These results are as shown in FIG. 3 (B). When the amount of lanthanum is in the range of 0.05 to 0.25, a battery having a small capacity decrease in the cycle and a high capacity can be obtained. In the figure, the solid line shows the capacitance change ratio, and the dotted line shows the capacitance ratio.
熱処理温度の検討 マンガンに対するアルミニウムの添加量（Al/Mn）が
0.15となるように二酸化マンガンと酸化アルミニウムと
の混合モル比を調整し、また熱処理温度を200〜500℃の
範囲で種々変えたものを正極活物質とした以外は本発明
品２と同様なコイン形リチウム二次電池をそれぞれ作製
した。Examination of heat treatment temperature The amount of aluminum added to manganese (Al / Mn)
A coin similar to the product 2 of the present invention except that the mixture molar ratio of manganese dioxide and aluminum oxide was adjusted to be 0.15, and that the heat treatment temperature was variously changed in the range of 200 to 500 ° C. as the positive electrode active material. A lithium secondary battery was manufactured.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第３図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃程度とすればサイクルでの容量低下を少
なく抑えることができる。The results are as shown in FIG. 3 (c). From this result, when the heat treatment temperature is set at about 250 to 450 ° C., it is possible to suppress a decrease in capacity in the cycle.
他の実施例 電解二酸化マンガン１モルに対して水酸化アルミニウ
ムAl（OH）３を0.15モル混合した物を温度400℃で48時
間熱処理を行なって得たものを正極活物質とした他は本
発明品２と同様なコイン形リチウム二次電池を作製し、
またこの電池を上記と同様な条件で充放電させ、第20サ
イクル目の放電容量を調べた所、本発明品２の第20サイ
クル目の放電容量を100とした場合、放電容量は105であ
った。Other Examples The present invention is the same as the present invention except that a mixture obtained by heat-treating a mixture of 0.15 mol of aluminum hydroxide Al (OH) 3 with respect to 1 mol of electrolytic manganese dioxide at a temperature of 400 ° C. for 48 hours is used as a positive electrode active material. A coin-shaped lithium secondary battery similar to the product 2 is manufactured,
This battery was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 2 of the present invention was 100, the discharge capacity was 105. Was.
実施例３ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化セリウムCeO2をCe/Mnのモ
ル比0.1（Mn1モルに対し、Ce0.1モル）で混合し、また
この混合物を温度300〜450℃で10時間焼成を行なって得
た正極活物質を用いた他は上記本発明品１と同様にし
て、コイン形リチウム二次電池（本発明品３）を作製し
た。Example 3 Comparison of cyclability with comparative product Electrolytic manganese dioxide and cerium oxide CeO 2 were mixed at a Ce / Mn molar ratio of 0.1 (0.1 mole of Mn to 1 mole of Mn), and the mixture was heated to a temperature of 300 to 450. A coin-type lithium secondary battery (Product 3 of the present invention) was produced in the same manner as Product 1 of the present invention except that the positive electrode active material obtained by baking at 10 ° C. for 10 hours was used.
この本発明品３と前記比較品とを上記と同じ条件で充
放電させた。本発明品３の初度の放電容量を１とした時
の各サイクルにおける各電池の放電容量を、容量比（そ
のサイクルの放電容量／本発明品３の初度の放電容量）
として第４図（Ａ）に示した。The product 3 of the present invention and the comparative product were charged and discharged under the same conditions as described above. The discharge capacity of each battery in each cycle when the initial discharge capacity of the product 3 of the present invention is set to 1 is a capacity ratio (discharge capacity of that cycle / initial discharge capacity of the product 3 of the present invention).
FIG. 4 (A).
セリウムの添加量の検討 二酸化マンガンと酸化セリウムとの混合モル比を適宜
調整してマンガンに対するセリウムの添加量（Ce/Mn）
を０〜0.25の範囲で種々変え、またこれらを温度400℃
で10時間熱処理したものを正極活物質とした以外は本発
明品３と同様なコイン形リチウム二次電池をそれぞれ作
製した。Examination of the amount of cerium added The amount of cerium added to manganese (Ce / Mn) by appropriately adjusting the mixing molar ratio of manganese dioxide and cerium oxide
Are varied in the range of 0 to 0.25, and these are brought to a temperature of 400 ° C.
A coin-shaped lithium secondary battery was produced in the same manner as the product 3 of the present invention, except that the material heat-treated for 10 hours was used as the positive electrode active material.
これらの電池を上記と同じ条件で充放電させた時の容
量変化比（第100サイクル目の放電容量／第10サイクル
目の放電容量）、並びに上記コイン形リチウム一次電池
の放電容量を１とした時のこれら電池の第100サイクル
における容量比（各電池の第100サイクル目の放電容量
／コイン形リチウム一次電池の放電容量）をそれぞれ調
べた。The capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when these batteries were charged and discharged under the same conditions as described above, and the discharge capacity of the coin-type lithium primary battery were set to 1. At this time, the capacity ratio of the batteries in the 100th cycle (discharge capacity of the 100th cycle of each battery / discharge capacity of the coin-type lithium primary battery) was examined.
これらの結果は第４図（Ｂ）の通りで、セリウムの添
加量を0.05〜0.25の範囲とすればサイクルでの容量低下
が少なく且つ容量の高い電池とすることができる。尚、
図において実線は容量変化比を、また点線は容量比をそ
れぞれ示す。These results are as shown in FIG. 4 (B). When the amount of cerium added is in the range of 0.05 to 0.25, a battery having a small capacity decrease in the cycle and a high capacity can be obtained. still,
In the figure, the solid line shows the capacitance change ratio, and the dotted line shows the capacitance ratio.
熱処理温度の検討 マンガンに対するセリウムの添加量（Ce/Mn）が0.1と
なるように二酸化マンガンと酸化セリウムとの混合モル
比を調整し、また熱処理温度を200〜500℃の範囲でいろ
いろ変えたものを正極活物質とした他は本発明品３と同
様なコイン形リチウム二次電池を種々作製した。Examination of heat treatment temperature The mixture molar ratio of manganese dioxide and cerium oxide was adjusted so that the amount of cerium added to manganese (Ce / Mn) became 0.1, and the heat treatment temperature was varied in the range of 200 to 500 ° C. Various coin-shaped lithium secondary batteries similar to the product 3 of the present invention except that was used as a positive electrode active material were produced.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第４図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃程度とすればサイクルでの容量低下を少
なく抑えることができる。The results are as shown in FIG. 4 (c). From this result, when the heat treatment temperature is set at about 250 to 450 ° C., it is possible to suppress a decrease in capacity in the cycle.
他の実施例 電解二酸化マンガン１モルに対して炭酸セリウムCe
（CO3）３・5H2Oを0.1モル混合した物を温度400℃で72
時間熱処理を行なって得たものを正極活物質とした他は
本発明品３と同様なコイン形リチウム二次電池を作製
し、またこの電池を上記と同様な条件で充放電させ、第
20サイクル目の放電容量を調べた所、本発明品３の第20
サイクル目の放電容量を100とした場合、放電容量は97
であった。Other Examples Cerium carbonate Ce per mole of electrolytic manganese dioxide
(CO 3) 3 · 5H 2 O at a temperature 400 ° C. The material was 0.1 mol mixed 72
A coin-shaped lithium secondary battery similar to the product 3 of the present invention was produced except that the material obtained by performing the heat treatment for a time was used as the positive electrode active material, and the battery was charged and discharged under the same conditions as described above.
When the discharge capacity at the 20th cycle was examined, the 20th cycle
When the discharge capacity at the cycle is 100, the discharge capacity is 97
Met.
電解二酸化マンガン１モルに対して水酸化セリウムCe
（OH）３を0.1モル混合した物を温度400℃で72時間熱処
理を行なって得たものを正極活物質とした他は本発明品
３と同様なコイン形リチウム二次電池を作製し、またこ
の電池を上記と同様な条件で充放電させ、第20サイクル
目の放電容量を調べた所、本発明品２の第20サイクル目
の放電容量を100とした場合、放電容量は107であった。Cerium hydroxide Ce per mole of electrolytic manganese dioxide
A coin-shaped lithium secondary battery similar to the product 3 of the present invention was prepared except that a mixture obtained by subjecting 0.1 mol of (OH) 3 to a heat treatment at a temperature of 400 ° C. for 72 hours was used as a positive electrode active material. The battery was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 2 of the present invention was 100, the discharge capacity was 107. .
実施例４ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化セレンSeO2をSe/Mnのモル
比0.15（Mn1モルに対し、Se0.15モル）で混合し、また
この混合物を温度300〜450℃で10時間焼成を行なって得
た正極活物質を用いた他は上記本発明品１と同様にし
て、コイン形リチウム二次電池（本発明品４）を作製し
た。Example 4 Comparison of cyclability with comparative product Electrolytic manganese dioxide and selenium oxide SeO 2 were mixed at a molar ratio of Se / Mn of 0.15 (0.15 mol of Se to 1 mol of Mn), and the mixture was heated at a temperature of 300 to 450. A coin-type lithium secondary battery (Product 4 of the present invention) was produced in the same manner as Product 1 of the present invention except that the positive electrode active material obtained by baking at 10 ° C. for 10 hours was used.
この本発明品４と前記比較品とを上記と同じ条件で充
放電させた。本発明品４の初度の放電容量を１とした時
のサイクルにおける各電池の放電容量を、容量比（その
サイクルの放電容量／本発明品４の初度の放電容量）と
して第５図（Ａ）に示した。The product 4 of the present invention and the comparative product were charged and discharged under the same conditions as described above. FIG. 5A shows the discharge capacity of each battery in the cycle when the initial discharge capacity of the product 4 of the present invention is 1 as a capacity ratio (discharge capacity of the cycle / initial discharge capacity of the product 4 of the present invention). It was shown to.
セレンの添加量の検討 二酸化マンガンと酸化セレンとの混合モル比を適宜調
整してマンガンに対するセレンの添加量（Se/Mn）を０
〜0.25の範囲で種々変え、またこれらを温度400℃で10
時間熱処理したものを正極活物質とした他は本発明品４
と同様なコイン形リチウム二次電池を種々作製した。Examination of the amount of selenium added The molar ratio of manganese dioxide and selenium oxide is adjusted as appropriate to reduce the amount of selenium added to manganese (Se / Mn) to zero.
~ 0.25, and these are changed at 400 ° C for 10
Inventive product 4 except that the heat-treated one was used as the positive electrode active material.
Various coin-type lithium secondary batteries similar to the above were produced.
これらの電池を上記と同じ条件で充放電させた時の容
量変化比（第100サイクル目の放電容量／第10サイクル
目の放電容量）、並びに上記コイン形リチウム一次電池
の放電容量を１とした時のこれら電池の第100サイクル
における容量比（各電池の第100サイクル目の放電容量
／コイン形リチウム一次電池の放電容量）をそれぞれ調
べた。The capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when these batteries were charged and discharged under the same conditions as described above, and the discharge capacity of the coin-type lithium primary battery were set to 1. At this time, the capacity ratio of the batteries in the 100th cycle (discharge capacity of the 100th cycle of each battery / discharge capacity of the coin-type lithium primary battery) was examined.
これらの結果は第５図（Ｂ）の通りで、セレンの添加
量を0.05〜0.25の範囲とすればサイクルでの容量低下が
少なく且つ容量の高い電池とすることができる。尚、図
において実線は容量変化比を、また点線は容量比をそれ
ぞれ示す。These results are as shown in FIG. 5 (B). When the amount of selenium added is in the range of 0.05 to 0.25, a battery having a small capacity reduction in the cycle and a high capacity can be obtained. In the drawing, the solid line indicates the capacitance change ratio, and the dotted line indicates the capacitance ratio.
熱処理温度の検討 マンガンに対するセレンの添加量（Se/Mn）が0.15と
なるように二酸化マンガンと酸化セレンとの混合モル比
を調整し、また熱処理温度を200〜500℃の範囲で種々変
えたものを正極活物質とした他は本発明品４と同様なコ
イン形リチウム二次電池をそれぞれ作製した。尚、熱処
理温度が350℃以上の条件では二酸化マンガン中のセレ
ンの含有率は５重量％以下であった。Examination of heat treatment temperature The mixture molar ratio of manganese dioxide and selenium oxide was adjusted so that the amount of selenium added to manganese (Se / Mn) was 0.15, and the heat treatment temperature was varied in the range of 200 to 500 ° C. The same coin-shaped lithium secondary battery as that of the product 4 of the present invention except that was used as a positive electrode active material was produced. When the heat treatment temperature was 350 ° C. or higher, the selenium content in manganese dioxide was 5% by weight or less.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第５図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃とすればサイクルでの容量低下を少なく
抑えることができる。The results are as shown in FIG. 5 (c). From this result, when the heat treatment temperature is set at 250 to 450 ° C., it is possible to suppress a decrease in capacity in the cycle.
他の実施例 電解二酸化マンガン30gとH2SeO410gを水20mlに溶解し
た溶液を混合し、また温度60℃で水分除去を行った後、
温度400℃で10時間熱処理を行なって得たものを正極活
物質とした他は本発明品４と同様なコイン形リチウム二
次電池を作製し、またこの電池を上記と同様な条件で充
放電させ、第20サイクル目の放電容量を調べた所、本発
明品４の第20サイクル目の放電容量を100とした場合、
放電容量は118であった。Other Examples 30 g of electrolytic manganese dioxide and a solution of 10 g of H 2 SeO 4 dissolved in 20 ml of water were mixed, and after removing water at a temperature of 60 ° C.,
A coin-shaped lithium secondary battery similar to the product 4 of the present invention was produced except that the material obtained by performing the heat treatment at a temperature of 400 ° C. for 10 hours was used as a positive electrode active material, and the battery was charged and discharged under the same conditions as above. When the discharge capacity at the 20th cycle was determined and the discharge capacity at the 20th cycle of the product 4 of the present invention was set to 100,
The discharge capacity was 118.
実施例５ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化エルビウムEr2O3をEr/Mnの
モル比0.15（Mn1モルに対し、Er0.15モル）で混合し、
またこの混合物を温度300〜450℃で10時間焼成を行なっ
て得た正極活物質を用いた他は上記本発明品１と同様に
して、コイン形リチウム二次電池（本発明品５）を作製
した。Example 5 Comparison of cyclability with comparative product Electrolytic manganese dioxide and erbium oxide Er 2 O 3 were mixed at a molar ratio of Er / Mn of 0.15 (Er of 0.15 mol with respect to 1 mol of Mn).
Further, a coin-type lithium secondary battery (Product 5 of the present invention) was prepared in the same manner as Product 1 of the present invention except that the positive electrode active material obtained by baking this mixture at a temperature of 300 to 450 ° C. for 10 hours was used. did.
この本発明品５と前記比較品とを上記と同じ条件で充
放電させた。本発明品５の初度の放電容量を１とした時
の各サイクルにおける各電池の放電容量を、容量比（そ
のサイクルの放電容量／本発明品５の初度の放電容量）
として第６図（Ａ）に示した。The product 5 of the present invention and the comparative product were charged and discharged under the same conditions as described above. The discharge capacity of each battery in each cycle when the initial discharge capacity of the product 5 of the present invention is set to 1 is a capacity ratio (discharge capacity of the cycle / initial discharge capacity of the product 5 of the present invention).
FIG. 6 (A).
エルビウムの添加量の検討 二酸化マンガンと酸化エルビウムとの混合モル比を適
宜調整してマンガンに対するエルビウムの添加量（Er/M
n）を０〜0.25の範囲で種々変え、またこれらを温度400
℃で10時間熱処理したものを正極活物質とした以外は本
発明品５と同様なコイン形リチウム二次電池をそれぞれ
作製した。Examination of the amount of erbium added The amount of erbium to manganese (Er / M) was adjusted by appropriately adjusting the mixing molar ratio of manganese dioxide and erbium oxide.
n) is varied in the range of 0 to 0.25, and these are changed to a temperature of 400
A coin-shaped lithium secondary battery was produced in the same manner as the product 5 of the present invention, except that the heat treatment at 10 ° C. for 10 hours was used as the positive electrode active material.
これらの電池を上記と同じ条件で充放電させた時の容
量変化比（第100サイクル目の放電容量／第10サイクル
目の放電容量）、並びに上記コイン形リチウム一次電池
の放電容量を１とした時のこれら電池の第100サイクル
における容量比（各電池の第100サイクル目の放電容量
／コイン形リチウム一次電池の放電容量）をそれぞれ調
べた。The capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when these batteries were charged and discharged under the same conditions as described above, and the discharge capacity of the coin-type lithium primary battery were set to 1. At this time, the capacity ratio of the batteries in the 100th cycle (discharge capacity of the 100th cycle of each battery / discharge capacity of the coin-type lithium primary battery) was examined.
これらの結果は第６図（Ｂ）の通りで、エルビウムの
添加量を0.05〜0.25の範囲とすればサイクルでの容量低
下が少なく且つ容量の高い電池とすることができる。
尚、図において実線は容量変化比を、また点線は容量比
をそれぞれ示す。These results are as shown in FIG. 6 (B). When the amount of erbium added is in the range of 0.05 to 0.25, a battery having a small capacity decrease in the cycle and a high capacity can be obtained.
In the drawing, the solid line indicates the capacitance change ratio, and the dotted line indicates the capacitance ratio.
熱処理温度の検討 マンガンに対するエルビウムの添加量（Er/Mn）が0.2
となるように二酸化マンガンと酸化エルビウムとの混合
モル比を調整し、また熱処理温度を200〜500℃の範囲で
種々変えたものを正極活物質とした以外は本発明品５と
同様なコイン形リチウム二次電池をそれぞれ作製した。Examination of heat treatment temperature The amount of erbium added to manganese (Er / Mn) is 0.2
The same coin shape as that of the product 5 of the present invention except that the mixture molar ratio between manganese dioxide and erbium oxide was adjusted so that the heat treatment temperature was variously changed in the range of 200 to 500 ° C. as the positive electrode active material. Lithium secondary batteries were produced.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第６図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃程度とすればサイクルでの容量低下を少
なく抑えることができる。The results are as shown in FIG. 6 (c). From this result, when the heat treatment temperature is set to about 250 to 450 ° C., it is possible to suppress a decrease in capacity in the cycle.
他の実施例 電解二酸化マンガン30gと硝酸エルビウムEr（NO3）３
・5H2O31gを水100mlに溶解した溶液を50mlづつ２回に分
けて混合し、また温度70℃で乾燥して水分除去を行った
後、温度400℃で72時間熱処理を行なって得たものを正
極活物質とした他は本発明品５と同様なコイン形リチウ
ム二次電池を作製し、またこの電池を上記と同様な条件
で充放電させ、第20サイクル目の放電容量を調べた所、
本発明品５の第20サイクル目の放電容量を100とした場
合、放電容量は115であった。Other Example 30 g of electrolytic manganese dioxide and erbium nitrate Er (NO 3 ) 3
A solution obtained by mixing 5H 2 O31g in water 100ml in two 50ml portions, drying at 70 ° C to remove water, and then heat-treating at 400 ° C for 72 hours. A coin-shaped lithium secondary battery similar to that of the product 5 of the present invention was produced except that was used as the positive electrode active material. The battery was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. ,
When the discharge capacity at the 20th cycle of the product 5 of the present invention was set to 100, the discharge capacity was 115.
電解二酸化マンガン30gと炭酸エルビウムEr2（CO3）3
16gを混合し、また温度400℃で72時間熱処理を行なって
得たものを正極活物質とした他は本発明品５と同様なコ
イン形リチウム二次電池を作製し、またこの電池を上記
と同様な条件で充放電させ、第20サイクル目の放電容量
を調べた所、本発明品５の第20サイクル目の放電容量を
100とした場合、放電容量は103であった。30 g of electrolytic manganese dioxide and erbium carbonate Er 2 (CO 3 ) 3
A coin-shaped lithium secondary battery similar to the product 5 of the present invention was prepared except that the mixture obtained by mixing 16 g and heat-treating at a temperature of 400 ° C. for 72 hours was used as a positive electrode active material. Charge and discharge were performed under the same conditions, and the discharge capacity at the 20th cycle was examined.
When it was set to 100, the discharge capacity was 103.
実施例６ 比較品とのサイクル性の比較 電解二酸化マンガンと酸化マグネシウムMgOをMg/Mnの
モル比0.15（Mn1モルに対し、Mg0.15モル）で混合し、
またこの混合物を温度300〜450℃で10時間焼成を行なっ
て得た正極活物質を用いた他は上記本発明品１と同様に
して、コイン形リチウム二次電池（本発明品６）を作製
した。Example 6 Comparison of cycle property with comparative product Electrolytic manganese dioxide and magnesium oxide MgO were mixed at a molar ratio of Mg / Mn of 0.15 (1 mol of Mn to 0.15 mol of Mg),
A coin-type lithium secondary battery (Product 6 of the present invention) was prepared in the same manner as Product 1 of the present invention, except that the mixture was fired at a temperature of 300 to 450 ° C. for 10 hours to obtain a positive electrode active material. did.
この本発明品６と前記比較品とを上記と同じ条件で充
放電させた。本発明品６の初度の放電容量を１とした時
の各サイクルにおける各電池の放電容量を、容量比（そ
のサイクルの放電容量／本発明品６の初度の放電容量）
として第７図（Ａ）に示した。The product 6 of the present invention and the comparative product were charged and discharged under the same conditions as described above. The discharge capacity of each battery in each cycle when the initial discharge capacity of the product 6 of the present invention is set to 1 is a capacity ratio (discharge capacity of the cycle / initial discharge capacity of the product 6 of the present invention).
FIG. 7 (A).
マグネシウムの添加量の検討 二酸化マンガンと酸化マグネシウムとの混合モル比を
適宜調整してマンガンに対するマグネシウムの添加量
（Mg/Mn）を０〜0.25の範囲で種々変え、またこれらの
温度400℃で10時間熱処理したものを正極活物質とした
以外は本発明品６と同様なコイン形リチウム二次電池を
それぞれ作製した。Examination of the addition amount of magnesium The addition amount of magnesium to manganese (Mg / Mn) was variously changed in the range of 0 to 0.25 by appropriately adjusting the mixing molar ratio of manganese dioxide and magnesium oxide. Coin-shaped lithium secondary batteries similar to the product 6 of the present invention were produced, except that the heat-treated one was used as the positive electrode active material.
これらの電池を上記と同じ条件で充放電させた時の容
量変化比（第100サイクル目の放電容量／第10サイクル
目の放電容量）、並びに上記コイン形リチウム一次電池
の放電容量を１とした時のこれら電池の第100サイクル
における容量比（各電池の第100サイクル目の放電容量
／コイン形リチウム一次電池の放電容量）をそれぞれ調
べた。The capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when these batteries were charged and discharged under the same conditions as described above, and the discharge capacity of the coin-type lithium primary battery were set to 1. At this time, the capacity ratio of the batteries in the 100th cycle (discharge capacity of the 100th cycle of each battery / discharge capacity of the coin-type lithium primary battery) was examined.
これらの結果は第７図（Ｂ）の通りで、エルビウムの
添加量を0.05〜0.25の範囲とすればサイクルでの容量低
下が少なく且つ容量の高い電池とすることができる。図
において実線は容量変化比を、また点線は容量比をそれ
ぞれ示す。These results are as shown in FIG. 7 (B). When the amount of erbium added is in the range of 0.05 to 0.25, a battery having a small capacity decrease in the cycle and a high capacity can be obtained. In the figure, the solid line shows the capacitance change ratio, and the dotted line shows the capacitance ratio.
熱処理温度の検討 マンガンに対するマグネシウムの添加量（Mg/Mn）が
0.15となるように二酸化マンガンと酸化マグネシウムと
の混合モル比を調整し、また熱処理温度を200〜500℃の
範囲で種々変えたものを正極活物質とした以外は本発明
品６と同様なコイン形リチウム二次電池をそれぞれ作製
した。Examination of heat treatment temperature The addition amount of magnesium to manganese (Mg / Mn)
A coin similar to that of the product 6 of the present invention except that the mixture molar ratio of manganese dioxide and magnesium oxide was adjusted to be 0.15, and that the heat treatment temperature was variously changed in the range of 200 to 500 ° C. as the positive electrode active material. A lithium secondary battery was manufactured.
これらの電池について、上記と同じ条件で充放電サイ
クルを行った時の容量変化比（第100サイクル目の放電
容量／第10サイクル目の放電容量）をそれぞれ調べた。For these batteries, the capacity change ratio (discharge capacity at the 100th cycle / discharge capacity at the 10th cycle) when a charge / discharge cycle was performed under the same conditions as above was examined.
結果は第７図（ｃ）の通りで、この結果より熱処理温
度を250〜450℃とすればサイクルにおける容量低下を少
なく抑えることができる。The results are as shown in FIG. 7 (c). From this result, when the heat treatment temperature is set to 250 to 450 ° C., the capacity decrease in the cycle can be suppressed to a small extent.
他の実施例 電解二酸化マンガン１モルに対し水酸化マグネシウム
Mg（OH）２を0.25モル混合した物を温度400℃で72時間
熱処理を行なって得たものを正極活物質とした他は本発
明品６と同様なコイン形リチウム二次電池を作製し、ま
たこの電池を上記と同様な条件で充放電させ、第20サイ
クル目の放電容量を調べた所、本発明品６の第20サイク
ル目の放電容量を100とした場合、放電容量は101であっ
た。Other Examples Magnesium hydroxide per mole of electrolytic manganese dioxide
A coin-shaped lithium secondary battery similar to the product 6 of the present invention was prepared except that a mixture obtained by heat-treating a mixture of 0.25 mol of Mg (OH) 2 at a temperature of 400 ° C. for 72 hours was used as a positive electrode active material. This battery was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 6 of the present invention was 100, the discharge capacity was 101. Was.
電解二酸化マンガン１モルに対し炭酸マグネシウムMg
CO3を0.25モル混合した物を温度400℃で72時間熱処理を
行なって得たものを正極活物質とした他は本発明品６と
同様なコイン形リチウム二次電池を作製し、またこの電
池を上記と同様な条件で充放電させ、第20サイクル目の
放電容量を調べた所、本発明品６の第20サイクル目の放
電容量を100とした場合、放電容量は98であった。Magnesium carbonate Mg per mole of electrolytic manganese dioxide
A coin-shaped lithium secondary battery similar to the product 6 of the present invention was prepared except that a mixture obtained by heat-treating a mixture of 0.25 mol of CO 3 at a temperature of 400 ° C. for 72 hours was used as a positive electrode active material. Was charged and discharged under the same conditions as above, and the discharge capacity at the 20th cycle was examined. Assuming that the discharge capacity at the 20th cycle of the product 6 of the present invention was 100, the discharge capacity was 98.
電解二酸化マンガン30gと硝酸マグネシウムMg（NO3）
３・6H2O22gを水60mlに溶解した溶液を２回に分けて浸
漬→温度70℃で乾燥して水分除去を行った後、温度400
℃で48時間熱処理を行なって得たものを正極活物質とし
た他は本発明品６と同様なコイン形リチウム二次電池を
作製し、またこの電池を上記と同様な条件で充放電さ
せ、第20サイクル目の放電容量を調べた所、本発明品６
の第20サイクル目の放電容量を100とした場合、放電容
量は105であった。Electrolytic manganese dioxide 30g magnesium nitrate Mg (NO 3)
The 3 · 6H 2 O22g dried at soaking → temperature 70 ° C. in portions solution twice dissolved in water 60ml After moisture removal, temperature 400
A coin-shaped lithium secondary battery similar to the product 6 of the present invention was prepared except that the material obtained by performing the heat treatment at 48 ° C. for 48 hours was used as the positive electrode active material, and the battery was charged and discharged under the same conditions as above. When the discharge capacity at the 20th cycle was examined, the product 6 of the present invention was found.
Assuming that the discharge capacity in the 20th cycle was 100, the discharge capacity was 105.
以上はLa,Al,Ce,Se,Er,Mgなどの元素を単体で用いた
例であるが、これらの元素を２種以上組合わせて用いる
こともでき、同様な効果が得られる。Although the above is an example in which elements such as La, Al, Ce, Se, Er, and Mg are used alone, two or more of these elements can be used in combination, and similar effects can be obtained.
＜発明の効果＞ 以上のようにこの発明によれば、二酸化マンガンを主
な正極活物質とするものであって、サイクル特性が良好
で且つ容量が大きな非水電解液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 present invention, it is possible to provide a non-aqueous electrolyte secondary battery that has manganese dioxide as a main positive electrode active material and has good cycle characteristics and a large capacity. Can be.
第１図は実施例の電池の断面図、第２図（Ａ），第３図
（Ａ），第４図（Ａ），第５図（Ａ），第６図（Ａ），
第７図（Ａ）は実施例の電池と比較電池のサイクル特性
を示したグラフ、第２図（Ｂ），第３図（Ｂ），第４図
（Ｂ），第５図（Ｂ），第６図（Ｂ），第７図（Ｂ）は
正極における各元素の添加量と容量変化比並びに容量比
の関係を示したグラフ、第２図（Ｃ），第３図（Ｃ），
第４図（Ｃ），第５図（Ｃ），第６図（Ｃ），第７図
（Ｃ）は正極活物質の処理温度と容量変化比の関係を示
したグラフである。 １……正極合剤、３……負極、４……電池缶、５……端
子板。FIG. 1 is a cross-sectional view of the battery of the embodiment, FIG. 2 (A), FIG. 3 (A), FIG. 4 (A), FIG. 5 (A), FIG.
FIG. 7 (A) is a graph showing the cycle characteristics of the battery of the example and the comparative battery, and FIGS. 2 (B), 3 (B), 4 (B), 5 (B), and 5 (C). FIGS. 6 (B) and 7 (B) are graphs showing the relationship between the amount of addition of each element and the capacity change ratio and the capacity ratio in the positive electrode, FIGS. 2 (C), 3 (C), and 3 (C).
FIGS. 4 (C), 5 (C), 6 (C), and 7 (C) are graphs showing the relationship between the processing temperature of the positive electrode active material and the capacity change ratio. 1 ... Positive electrode mixture, 3 ... Negative electrode, 4 ... Battery can, 5 ... Terminal plate.
フロントページの続き (72)発明者 中西 正典 東京都港区新橋５丁目36番11号 富士電 気化学株式会社内 (72)発明者 名倉 秀哲 東京都港区新橋５丁目36番11号 富士電 気化学株式会社内 (56)参考文献 特開 昭57−50768（ＪＰ，Ａ) 特開 昭56−103864（ＪＰ，Ａ) 特開 平２−283621（ＪＰ，Ａ) 特表 昭60−501730（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/36 - 4/62 Continued on the front page. (72) Inventor Masanori Nakanishi 5-36-11 Shimbashi, Minato-ku, Tokyo Inside Fuji Electric Chemical Co., Ltd. (72) Inventor Hidenori Nakura 5-36-11 Shimbashi, Minato-ku, Tokyo Fuji Electric In Chemical Co., Ltd. (56) References JP-A-57-50768 (JP, A) JP-A-56-103864 (JP, A) JP-A-2-283621 (JP, A) JP-A-60-501730 (JP, A) , A) (58) Field surveyed (Int.Cl. 7 , DB name) H01M 4/36-4/62
Claims (1)
し、また二酸化マンガン中にLa,Al,Ce,Se,Er,Mgから選
ばれた１種の元素がドーピングされた正極活物質を用い
る非水電解液二次電池において、 前記正極活物質は、La,Al,Ce,Se,ErについてはMn原子に
対する各元素の添加量が５〜25モル％に相当する化合物
を250〜450℃で熱処理してドーピングしたものであり、
MgについてはMn原子に対するMg元素の添加量が10〜15モ
ル％に相当する化合物を250〜400℃で熱処理してドーピ
ングしたものであることを特徴とする非水電解液二次電
池。1. A non-aqueous solution using lithium or a lithium alloy as a negative electrode active material and a positive electrode active material in which manganese dioxide is doped with one element selected from La, Al, Ce, Se, Er and Mg. In the electrolyte secondary battery, the positive electrode active material is a heat treatment at 250 to 450 ° C. of a compound corresponding to an addition amount of each element to Mn atoms of 5 to 25 mol% for La, Al, Ce, Se, and Er. Doping,
A non-aqueous electrolyte secondary battery characterized in that Mg is obtained by doping a compound corresponding to 10 to 15 mol% of Mg element to Mn atom by heat treatment at 250 to 400 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01204171A JP3110738B2 (en) | 1989-08-07 | 1989-08-07 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01204171A JP3110738B2 (en) | 1989-08-07 | 1989-08-07 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0367463A JPH0367463A (en) | 1991-03-22 |
| JP3110738B2 true JP3110738B2 (en) | 2000-11-20 |
Family
ID=16486012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01204171A Expired - Fee Related JP3110738B2 (en) | 1989-08-07 | 1989-08-07 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3110738B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004119167A (en) * | 2002-09-26 | 2004-04-15 | Mitsui Mining & Smelting Co Ltd | Method for producing positive electrode active material for battery and electrolytic manganese dioxide, and battery |
| WO2010004973A1 (en) * | 2008-07-09 | 2010-01-14 | 三洋電機株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery, method for production of positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| JP4989683B2 (en) * | 2008-07-09 | 2012-08-01 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material, non-aqueous electrolyte secondary battery positive electrode active material manufacturing method, non-aqueous electrolyte secondary battery positive electrode, and non-aqueous electrolyte secondary battery |
| JP4989682B2 (en) * | 2008-12-03 | 2012-08-01 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material, non-aqueous electrolyte secondary battery positive electrode active material manufacturing method, non-aqueous electrolyte secondary battery positive electrode, and non-aqueous electrolyte secondary battery |
| JP4989670B2 (en) * | 2008-09-30 | 2012-08-01 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material, non-aqueous electrolyte secondary battery positive electrode active material manufacturing method, non-aqueous electrolyte secondary battery positive electrode, and non-aqueous electrolyte secondary battery |
| CN116314742A (en) * | 2023-01-04 | 2023-06-23 | 北京理工大学 | A kind of ion-doped modified manganese oxide cathode material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56103864A (en) * | 1980-01-21 | 1981-08-19 | Matsushita Electric Ind Co Ltd | Battery |
| JPS5750768A (en) * | 1980-09-12 | 1982-03-25 | Fuji Elelctrochem Co Ltd | Battery |
| JPH0649577B2 (en) * | 1989-04-25 | 1994-06-29 | 工業技術院長 | Novel manganese compound and method for producing the same |
-
1989
- 1989-08-07 JP JP01204171A patent/JP3110738B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0367463A (en) | 1991-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1998040923A1 (en) | Nonaqueous electrolyte battery and charging method therefor | |
| JP2006344509A (en) | Lithium secondary battery | |
| JP3649996B2 (en) | Cathode active material for non-aqueous electrolyte secondary battery | |
| JP4232277B2 (en) | Non-aqueous electrolyte battery | |
| JP3110738B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3050885B2 (en) | Non-aqueous solvent secondary battery and method of manufacturing the same | |
| JP3289256B2 (en) | Method for producing positive electrode active material for lithium battery | |
| JP3578503B2 (en) | Positive active material for lithium secondary battery and secondary battery using the same | |
| JPH1064592A (en) | Lithium secondary battery | |
| JP3268924B2 (en) | Non-aqueous electrolyte battery | |
| JP4106651B2 (en) | Positive electrode material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same | |
| JPH10321228A (en) | Positive active material for lithium battery, method for producing the same, and lithium battery using the same | |
| JP3188108B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3331824B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH10144291A (en) | Non-aqueous electrolyte battery and manufacture of its positive electrode | |
| JP2528183B2 (en) | Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same | |
| JPH0495362A (en) | Nonaqueous electrolytic battery | |
| JP3613025B2 (en) | Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same | |
| JPH02253560A (en) | Battery | |
| JP2975727B2 (en) | Non-aqueous electrolyte battery | |
| JPH0393163A (en) | Nonaqueous system secondary battery | |
| JP3092823B2 (en) | Lithium battery | |
| JP2798991B2 (en) | Manufacturing method of non-aqueous electrolyte secondary battery | |
| JPH10199530A (en) | Nonaqueous electrolyte battery | |
| JP4165717B2 (en) | Lithium secondary battery and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |