JPH04253162A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH04253162A JPH04253162A JP3029537A JP2953791A JPH04253162A JP H04253162 A JPH04253162 A JP H04253162A JP 3029537 A JP3029537 A JP 3029537A JP 2953791 A JP2953791 A JP 2953791A JP H04253162 A JPH04253162 A JP H04253162A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- positive electrode
- battery
- licoo2
- lithium
- 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.)
- Granted
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
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 14
- 239000011149 active material Substances 0.000 claims abstract description 14
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 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
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020040 NbS Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はリチウム二次電池に関す
るもので、さらに詳しくはその正極に関するものである
。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to a positive electrode thereof.
【０００２】0002
【従来の技術】リチウムを負極活物質として用いるリチ
ウム電池は、高電圧、高エネルギー密度及び高信頼性を
有する特長から広く一般に用いられるようになってきた
が、これらは１次電池である。最近では、２次電池の研
究も盛んに行われ、一部では実用化もされている。しか
し、これらの電池の特性は未だに十分ではない。その原
因の一つとして正極活物質の特性が悪いことがあげられ
る。2. Description of the Related Art Lithium batteries using lithium as a negative electrode active material have come to be widely used because of their characteristics of high voltage, high energy density, and high reliability, but these are primary batteries. Recently, research on secondary batteries has been actively conducted, and some have even been put into practical use. However, the characteristics of these batteries are still not sufficient. One of the reasons for this is that the characteristics of the positive electrode active material are poor.
【０００３】従来研究されてきた代表的な正極活物質と
してはＭｏＳ２ ，Ｖ２ Ｏ５ ，ＭｎＯ２ ，ＮｂＳ
ｅ３ ，ＴｉＳ２ などがある。これらの中で、特にＭ
ｎＯ２ は安価であるということから注目され、改質さ
れたマンガン酸化物が種々提案されている。例えば特願
昭６３−２５８９４０号や特願平１−１５９１号に開示
されているが、これらのマンガン酸化物はいずれも作動
電圧が３Ｖ程度であり、容量はさほど大きくない。Typical positive electrode active materials that have been studied in the past include MoS2, V2O5, MnO2, and NbS.
e3, TiS2, etc. Among these, especially M
nO2 has attracted attention because it is inexpensive, and various modified manganese oxides have been proposed. For example, as disclosed in Japanese Patent Application No. 63-258940 and Japanese Patent Application No. 1-1591, the operating voltage of these manganese oxides is about 3 V, and the capacity is not so large.
【０００４】極最近では、容量はマンガン酸化物と同程
度であるが、作動電圧が４Ｖ程度と高いＬｉＣｏＯ２
が高電圧、高エネルギー密度を得られる活物質として注
目され研究されている。[0004] Very recently, LiCoO2 has a capacity similar to that of manganese oxide, but has a high operating voltage of about 4V.
is attracting attention and research as an active material that can provide high voltage and high energy density.
【０００５】そこで、ＬｉＣｏＯ２ を用いて深い深度
の充放電サイクル試験を行ったところ、サイクルの進行
に伴って容量が劣化することが判った。これはリチウム
の挿入・脱離に伴う結晶構造の変化が大きいために、活
物質自身の可逆性が低下することと、電極が膨張収縮を
繰り返すうちに活物質と導電剤の接触が不十分になるこ
とが原因であると考えられることから、結晶構造の変化
の小さいＬｉＣｏＯ２ を作製する必要があるという問
題点があった。[0005] When a deep charge/discharge cycle test was conducted using LiCoO2, it was found that the capacity deteriorated as the cycle progressed. This is because the reversibility of the active material itself decreases due to large changes in the crystal structure due to insertion and desorption of lithium, and as the electrode repeatedly expands and contracts, the contact between the active material and the conductive agent becomes insufficient. This is thought to be the cause of the change in crystal structure, and therefore there was a problem in that it was necessary to produce LiCoO2 with a small change in crystal structure.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記問題点を
解消するために、深い深度での充放電サイクルにおいて
も可逆性に優れ、結晶構造変化の少ないＬｉＣｏＯ２
を得ることを目的とする。[Problems to be Solved by the Invention] In order to solve the above-mentioned problems, the present invention provides LiCoO2, which has excellent reversibility even in charge-discharge cycles at deep depths and has little change in crystal structure.
The purpose is to obtain.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＬｉＣｏＯ２
のＣｏの一部をＰｂ，Ｂｉ，Ｂの中から選ばれた少な
くとも１種の元素で置換したものを活物質とした正極を
具備するリチウム二次電池である。[Means for Solving the Problems] The present invention provides LiCoO2
This is a lithium secondary battery comprising a positive electrode whose active material is a part of Co of which is replaced with at least one element selected from Pb, Bi, and B.
【０００８】[0008]
【作 用】ＬｉＣｏＯ２ に一部をＰｂ，Ｂｉ，Ｂの
中から選ばれた少なくとも１種の元素で置換することに
より、リチウムの挿入脱離に伴う結晶構造の変化が抑え
られるために、サイクル特性が向上する。このメカニズ
ムは明らかではないが考えられるものとして、置換元素
が非遷移金属であることから、電池内の酸化還元反応に
寄与せず、はじめから取り込んでいるリチウムを放出し
ないためにその部分のリチウムが柱の役目をし、他のリ
チウムが取り除かれた部分の酸素同士の反発力による結
晶構造の変化を抑えているのではないかということが挙
げられる。また、一方では置換元素が酸素と強く結合し
ているために、酸素同士の反発力が弱められ、結晶構造
の変化が抑えられているのではないかとも考えられる。[Function] By substituting a portion of LiCoO2 with at least one element selected from Pb, Bi, and B, changes in the crystal structure due to intercalation and desorption of lithium are suppressed, which improves cycle characteristics. will improve. The mechanism for this is not clear, but it is possible that since the replacement element is a non-transition metal, it does not contribute to the redox reaction in the battery and does not release the lithium that was taken in from the beginning. One possibility is that it acts as a pillar, suppressing changes in the crystal structure due to the repulsive force between oxygen atoms in areas where other lithium has been removed. On the other hand, it is also possible that the strong bond between the substituent elements and oxygen weakens the repulsive force between the oxygen atoms, suppressing changes in the crystal structure.
【０００９】[0009]
【実施例】以下本発明の詳細について実施例に基づき説
明する。EXAMPLES The details of the present invention will be explained below based on examples.
【００１０】（実施例１）まず、正極活物質の調製にあ
たっては、市販特級試薬の炭酸リチウム３７ｇと炭酸コ
バルト１０７ｇと二酸化鉛２４ｇとをボールミルで粉砕
しながら十分混合し、混合物をアルミナ坩堝に入れ空気
中６５０℃で５時間仮焼成したのち、９５０℃で２０時
間焼成した。焼成後室温までゆっくり冷却し、粉砕した
ものを正極活物質とした。得られた生成物のＸ線回折パ
ターンを図１に示す。図１より、ＬｉＣｏＯ２ のＣｏ
に一部がＰｂで置換されたものが単一相で得られている
ことが判る。さらにこの生成物について化学定量分析を
行ったところ、その組成はＬｉＣｏ０．９０Ｐｂ０．１
０Ｏ２ であることが判った。(Example 1) First, in preparing a positive electrode active material, 37 g of lithium carbonate, 107 g of cobalt carbonate, and 24 g of lead dioxide, which are commercially available special grade reagents, were sufficiently mixed while being ground in a ball mill, and the mixture was placed in an alumina crucible. After pre-baking in air at 650°C for 5 hours, it was fired at 950°C for 20 hours. After firing, it was slowly cooled to room temperature, and the resulting powder was used as a positive electrode active material. The X-ray diffraction pattern of the obtained product is shown in FIG. From Figure 1, Co of LiCoO2
It can be seen that a single phase was obtained in which a portion of Pb was substituted with Pb. Further chemical quantitative analysis of this product revealed that its composition was LiCo0.90Pb0.1
It was found to be 0O2.
【００１１】このようにして得られた活物質とアセチレ
ンブラック及びポリテトラフルオロエチレン粉末とを重
量比８５：１０：５で混合し、トルエンを加えて十分混
練した。これをローラープレスにより厚み０．８ｍｍの
シート状に成形した。次にこれを１６ｍｍに円形に打ち
抜き減圧下２００℃で１５時間熱処理し、リチウム含有
マンガン酸化物を活物質とした正極を得た。負極は厚み
０．３ｍｍのリチウム箔を直径１５ｍｍの円形に打ち抜
き、集電体を介して負極缶に圧着して用いた。非水電解
液にはγ−ブチロラクトンに１ｍｏｌ ／ｌ のＬｉＢ
Ｆ４を溶解したものを用い、セパレータにはポリプロピ
レン製微孔薄膜を用いた。上記正極、負極、電解液及び
セパレータを用いて直径２０ｍｍ厚さ１．６ｍｍのボタ
ン型のリチウム電池を作製した。この電池をＡ１とする
。The active material thus obtained, acetylene black and polytetrafluoroethylene powder were mixed in a weight ratio of 85:10:5, toluene was added, and the mixture was thoroughly kneaded. This was molded into a sheet with a thickness of 0.8 mm using a roller press. Next, this was punched into a circular shape of 16 mm and heat treated at 200° C. under reduced pressure for 15 hours to obtain a positive electrode using lithium-containing manganese oxide as an active material. The negative electrode was used by punching out a lithium foil with a thickness of 0.3 mm into a circular shape with a diameter of 15 mm, and press-fitting it to the negative electrode can via a current collector. The non-aqueous electrolyte contains 1 mol/l of LiB in γ-butyrolactone.
A solution of F4 was used, and a microporous thin film made of polypropylene was used as a separator. A button-shaped lithium battery with a diameter of 20 mm and a thickness of 1.6 mm was produced using the above positive electrode, negative electrode, electrolyte, and separator. This battery is designated as A1.
【００１２】（実施例２）二酸化鉛の代わりに酸化ビス
マス２３ｇを用いたことを除いては、実施例１と同様の
工程で正極活物質を得た。さらにこの活物質を用いて実
施例１と同様の工程で電池を作製した。この電池をＡ２
とする。(Example 2) A positive electrode active material was obtained in the same process as in Example 1, except that 23 g of bismuth oxide was used instead of lead dioxide. Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is A2
shall be.
【００１３】（実施例３）二酸化鉛の代わりに酸化ホウ
素３．５ｇを用いたことを除いては、実施例１と同様の
工程で正極活物質を得た。さらにこの活物質を用いて実
施例１と同様の工程で電池を作製した。この電池をＡ３
とする。(Example 3) A positive electrode active material was obtained in the same manner as in Example 1, except that 3.5 g of boron oxide was used instead of lead dioxide. Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is A3
shall be.
【００１４】（実施例４）二酸化鉛２４ｇの代わりに二
酸化鉛１２ｇと酸化ビスマス１２ｇの混合物を用いたこ
とを除いては、実施例１と同様の工程で正極活物質を得
た。さらにこの活物質を用いて、実施例１と同様の工程
で電池を作製した。この電池をＡ４とする。(Example 4) A positive electrode active material was obtained in the same manner as in Example 1, except that a mixture of 12 g of lead dioxide and 12 g of bismuth oxide was used instead of 24 g of lead dioxide. Furthermore, a battery was produced using this active material in the same steps as in Example 1. This battery is called A4.
【００１５】[0015]
【比較例】市販特級試薬の炭酸リチウム３７ｇと炭酸コ
バルト１１９ｇとをボールミルで粉砕しながら十分混合
し、混合物をアルミナ坩堝に入れ空気中６５０℃で５時
間仮焼成したのち、９５０℃で２０時間焼成した。焼成
後室温までゆっくり冷却し、粉砕したものを正極活物質
とした。得られた生成物のＸ線回折パターンを図２に示
す。図２により、得られた生成物がＬｉＣｏＯ２ であ
ることが判った。さらに生成物について化学定量分析を
行ったところ、その組成はＬｉＣｏＯ２ であることが
判った。このようにして得られた活物質を用いて、実施
例１と同様の工程で電池を作製した。この電池をＢとす
る。[Comparative example] 37 g of lithium carbonate, a commercially available special grade reagent, and 119 g of cobalt carbonate were thoroughly mixed while pulverizing with a ball mill, the mixture was placed in an alumina crucible, and the mixture was pre-calcined in air at 650°C for 5 hours, and then calcined at 950°C for 20 hours. did. After firing, it was slowly cooled to room temperature, and the resulting powder was used as a positive electrode active material. The X-ray diffraction pattern of the obtained product is shown in FIG. From FIG. 2, it was found that the obtained product was LiCoO2. Further chemical quantitative analysis of the product revealed that its composition was LiCoO2. Using the active material thus obtained, a battery was produced in the same steps as in Example 1. This battery is called B.
【００１６】このようにして作製した電池Ａ１，Ａ２，
Ａ３，Ａ４，Ｂを用いて、充放電サイクル試験を行った
。試験条件は、充電電流３ｍＡ、充電終止電圧４．５Ｖ
、放電電流３ｍＡ、放電終止電圧３．０Ｖとした。この
結果を図３に示した。[0016] Batteries A1, A2, and
A charge/discharge cycle test was conducted using A3, A4, and B. Test conditions are charging current 3mA, charging end voltage 4.5V.
, a discharge current of 3 mA, and a discharge end voltage of 3.0V. The results are shown in FIG.
【００１７】図３より、本発明電池Ａ１〜Ａ４はいずれ
も比較電池Ｂよりもサイクル特性が向上していることが
判る。これはＬｉＣｏＯ２ のＣｏの一部をＰｂ，Ｂｉ
，Ｂの中から選ばれた少なくとも１種の元素で置換した
ことによって、結晶構造の変化が抑えられ、その結果活
物質と導電剤の接触が良好に保たれたことに起因してい
るものと考えられる。From FIG. 3, it can be seen that all of the batteries A1 to A4 of the present invention have better cycle characteristics than comparative battery B. This means that some of the Co in LiCoO2 is converted into Pb, Bi
This is due to the fact that the substitution with at least one element selected from . Conceivable.
【００１８】[0018]
【発明の効果】上述した如く、ＬｉＣｏＯ２ の一部を
Ｐｂ，Ｂｉ，Ｂの中から選ばれた少なくとも１種の元素
で置換して得られるものを活物質とした正極は、置換し
ていないＬｉＣｏＯ２ を活物質とした正極に比べて充
放電サイクルにともなう容量劣化が小さい。その結果、
本発明による正極と負極及び電解質とを具備したリチウ
ム二次電池は、従来のリチウム二次電池のサイクル特性
を大幅に改善することができる。Effects of the Invention As described above, a positive electrode whose active material is obtained by substituting a portion of LiCoO2 with at least one element selected from Pb, Bi, and B can be obtained by replacing a portion of LiCoO2 with at least one element selected from Pb, Bi, and B. Capacity deterioration due to charging and discharging cycles is smaller than that of positive electrodes with active materials. the result,
A lithium secondary battery including a positive electrode, a negative electrode, and an electrolyte according to the present invention can significantly improve cycle characteristics of conventional lithium secondary batteries.
【００１９】なお、本発明は実施例に記載された負極、
電解質、セパレータ及び電池形状などに限定されるもの
ではなく、負極に有機焼成体を用いるものや電解液、セ
パレータの代わりに固体電解質を用いたものなどにも適
用可能である。[0019] The present invention also applies to the negative electrodes described in the Examples,
The present invention is not limited to electrolytes, separators, battery shapes, etc., and is also applicable to those using an organic fired body for the negative electrode, electrolytes, and solid electrolytes instead of separators.
【図１】実施例１で用いた正極活物質のＸ線回折パター
ンである。FIG. 1 is an X-ray diffraction pattern of the positive electrode active material used in Example 1.
【図２】比較例で用いた正極活物質のＸ線回折パターン
である。FIG. 2 is an X-ray diffraction pattern of a positive electrode active material used in a comparative example.
【図３】サイクル数と容量保持率との関係図である。FIG. 3 is a diagram showing the relationship between the number of cycles and capacity retention rate.
Claims (1)
Ｂｉ、Ｂの中から選ばれた少なくとも１種の元素で置換
したものを活物質とした正極を具備することを特徴とす
るリチウム二次電池。[Claim 1] Part of Co in LiCoO2 is replaced by Pb,
A lithium secondary battery comprising a positive electrode whose active material is substituted with at least one element selected from Bi and B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029537A JP2586747B2 (en) | 1991-01-29 | 1991-01-29 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029537A JP2586747B2 (en) | 1991-01-29 | 1991-01-29 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04253162A true JPH04253162A (en) | 1992-09-08 |
| JP2586747B2 JP2586747B2 (en) | 1997-03-05 |
Family
ID=12278863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3029537A Expired - Lifetime JP2586747B2 (en) | 1991-01-29 | 1991-01-29 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2586747B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0672622A1 (en) * | 1994-03-07 | 1995-09-20 | TDK Corporation | Layer structure oxide |
| JP2000113884A (en) * | 1998-10-01 | 2000-04-21 | Ngk Insulators Ltd | Lithium secondary battery |
| EP1154503A1 (en) | 2000-05-11 | 2001-11-14 | Sony Corporation | Positive electrode active material, non-aqueous electrolyte secondary cell and method for preparation thereof |
| US6395426B1 (en) | 1998-10-30 | 2002-05-28 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte cell having a positive electrode with Ti-attached LiCoO2 |
| US6579475B2 (en) | 1999-12-10 | 2003-06-17 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| US6794085B2 (en) | 1997-05-15 | 2004-09-21 | Fmc Corporation | Metal oxide containing multiple dopants and method of preparing same |
| EP1492180A1 (en) * | 2002-03-28 | 2004-12-29 | Mitsubishi Chemical Corporation | Positive electrode material for lithium secondary cell and secondary cell using the same, and method for producing positive electrode material for lithium secondary cell |
| WO2008078695A1 (en) | 2006-12-26 | 2008-07-03 | Mitsubishi Chemical Corporation | Lithium transition metal compound powder, process for production thereof, spray-dried product useful as firing precursor, and positive electrode for lithium secondary battery and lithium secondary battery made by using the same |
| US7998619B2 (en) | 2002-03-28 | 2011-08-16 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
-
1991
- 1991-01-29 JP JP3029537A patent/JP2586747B2/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5503930A (en) * | 1994-03-07 | 1996-04-02 | Tdk Corporation | Layer structure oxide |
| EP0672622A1 (en) * | 1994-03-07 | 1995-09-20 | TDK Corporation | Layer structure oxide |
| US6794085B2 (en) | 1997-05-15 | 2004-09-21 | Fmc Corporation | Metal oxide containing multiple dopants and method of preparing same |
| JP2000113884A (en) * | 1998-10-01 | 2000-04-21 | Ngk Insulators Ltd | Lithium secondary battery |
| US6395426B1 (en) | 1998-10-30 | 2002-05-28 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte cell having a positive electrode with Ti-attached LiCoO2 |
| US6932922B2 (en) | 1999-12-10 | 2005-08-23 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| US6579475B2 (en) | 1999-12-10 | 2003-06-17 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| EP1154503A1 (en) | 2000-05-11 | 2001-11-14 | Sony Corporation | Positive electrode active material, non-aqueous electrolyte secondary cell and method for preparation thereof |
| EP1492180A1 (en) * | 2002-03-28 | 2004-12-29 | Mitsubishi Chemical Corporation | Positive electrode material for lithium secondary cell and secondary cell using the same, and method for producing positive electrode material for lithium secondary cell |
| EP1492180A4 (en) * | 2002-03-28 | 2010-06-23 | Mitsubishi Chem Corp | Positive electrode material for lithium secondary cell and secondary cell using the same, and method for producing positive electrode material for lithium secondary cell |
| US7998619B2 (en) | 2002-03-28 | 2011-08-16 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
| US8383270B2 (en) | 2002-03-28 | 2013-02-26 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
| WO2008078695A1 (en) | 2006-12-26 | 2008-07-03 | Mitsubishi Chemical Corporation | Lithium transition metal compound powder, process for production thereof, spray-dried product useful as firing precursor, and positive electrode for lithium secondary battery and lithium secondary battery made by using the same |
| EP2337125A1 (en) | 2006-12-26 | 2011-06-22 | Mitsubishi Chemical Corporation | Lithium transition metal based compound powder and method for manufacturing the same |
| EP2341570A1 (en) | 2006-12-26 | 2011-07-06 | Mitsubishi Chemical Corporation | Lithium transition metal based compound powder and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2586747B2 (en) | 1997-03-05 |
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