JP3491529B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3491529B2 JP3491529B2 JP17884198A JP17884198A JP3491529B2 JP 3491529 B2 JP3491529 B2 JP 3491529B2 JP 17884198 A JP17884198 A JP 17884198A JP 17884198 A JP17884198 A JP 17884198A JP 3491529 B2 JP3491529 B2 JP 3491529B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- manganese
- active material
- amount
- positive electrode
- 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
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
【０００１】[0001]
【発明の属する技術分野】本発明は非水電解液二次電池
の放置特性及び充放電サイクル特性の改善に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of the leaving characteristics and charge / discharge cycle characteristics of non-aqueous electrolyte secondary batteries.
【０００２】[0002]
【従来の技術】携帯用電話機、コードレス電話、ビデオ
カメラなどの映像機器、パソコンなどの事務用機器、家
電機器、電気自動車などの主電源あるいはバックアップ
用電源として、長時間使用できるリチウムイオン二次電
池が強く要求されている。なお、これらのリチウムイオ
ン二次電池に使用されている正極活物質としては、リチ
ウムコバルト複合酸化物、リチウムニッケル複合酸化
物、リチウムマンガン複合酸化物などが用いられてお
り、その中でも資源的に豊富で安価なマンガンを主原料
としたリチウムマンガン複合酸化物が注目をされてい
る。2. Description of the Related Art A lithium-ion secondary battery that can be used for a long time as a main power source or backup power source for portable telephones, cordless telephones, video equipment such as video cameras, office equipment such as personal computers, home appliances, electric vehicles, etc. Is strongly demanded. As the positive electrode active material used in these lithium ion secondary batteries, lithium cobalt composite oxide, lithium nickel composite oxide, lithium manganese composite oxide, etc. are used, and among them, it is rich in resources. Attention has been paid to lithium manganese composite oxides, which are inexpensive and mainly made of manganese.
【０００３】このリチウムマンガン複合酸化物は、リチ
ウムが出入りしやすいスピネル構造をとっている。そし
て、リチウムマンガン複合酸化物を正極活物質に用いた
場合には、初期のサイクル特性や放置特性はある程度満
足できるものの、充放電サイクルの進行や放置期間の長
期化に伴い、正極活物質中のマンガンがイオンとなって
電解液中に溶出し、溶出したマンガンイオンが負極の活
物質表面で析出して放電容量が劣化することが明らかに
なっている。This lithium-manganese composite oxide has a spinel structure in which lithium easily enters and leaves. When the lithium manganese composite oxide is used as the positive electrode active material, although the initial cycle characteristics and the leaving characteristics are satisfied to some extent, the progress of the charge / discharge cycle and the extension of the leaving period lead to It has been clarified that manganese becomes ions and is eluted into the electrolytic solution, and the eluted manganese ions are deposited on the surface of the active material of the negative electrode to deteriorate the discharge capacity.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、充放
電サイクルによる容量劣化が少なく、放置後の放電特性
が良好な非水電解液二次電池を提供することを目的する
ものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-aqueous electrolyte secondary battery which has little capacity deterioration due to charge / discharge cycles and has good discharge characteristics after being left standing.
【０００５】[0005]
【発明が解決しようとする手段】上記した課題を解決す
るために、第一の発明ではリチウムを吸蔵・放出可能な
スピネル構造を有するリチウムマンガン複合酸化物を主
たる正極活物質とし、炭素材を主たる負極活物質に使用
する非水電解液二次電池において、正極中にマンガンを
捕捉する捕捉剤を含むことを特徴とし、第二の発明では
前記マンガンを捕捉する捕捉剤が燐酸リチウム、タング
ステン酸リチウム、珪酸リチウム、アルミナイト、ホウ
酸リチウム、モリブデン酸リチウム、陽イオン交換樹脂
の群から選ばれる少なくとも一種類以上を含むことを特
徴とし、第三の発明では前記マンガンを捕捉する捕捉剤
の添加量が、正極活物質重量に対して０．１〜１０％で
あることを特徴としている。In order to solve the above problems, in the first invention, a lithium manganese composite oxide having a spinel structure capable of inserting and extracting lithium is used as a main positive electrode active material, and a carbon material is used as a main component. In the non-aqueous electrolyte secondary battery used for the negative electrode active material, the positive electrode contains a scavenger that traps manganese. In the second invention, the scavenger that traps manganese is lithium phosphate or lithium tungstate. , Lithium silicate, aluminite, lithium borate, lithium molybdate, characterized in that it contains at least one or more selected from the group of cation exchange resin, in the third invention the amount of the trapping agent for trapping manganese is added Is 0.1 to 10% with respect to the weight of the positive electrode active material.
【０００６】[0006]
【発明の実施の形態】本発明に用いた捕捉剤は、充放電
中あるいは放置中に正極活物質からマンガンイオンが電
解液中に溶出する前に早期に捕捉することにより、充放
電サイクル特性、放置特性に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ものである。本発明の正極
活物質としては、スピネル構造を有したリチウムマンガ
ン複合酸化物を用いた。なお、負極活物質としてはリチ
ウム金属、リチウムーアルミニウムなどのリチウム合
金、または、リチウムイオンを吸蔵・放出可能な炭素材
が用いられる。また、非水溶媒としては、エチレンカー
ボネイト、プロピレンカーボネイト、ブチレンカーボネ
イト、ジメチルカーボネイト、γ―ブチロラクトン、ア
セトニトリル、スルホラン、１，２−ヂメトキシエタ
ン、１，３−ジメトキシプロパン、ジメチルエーテル、
テトラヒドロプラン、２−メチルテトラヒドロプラン、
炭酸ジメチル、炭酸ジエチル、及びエチルメチルカーボ
ネイトなどから選ばれた単独もしくは二種類以上の混合
溶媒が使用できると挙げることができる。前記電解質と
しては、たとえば、過塩素酸リチウム（ＬｉＣｌＯ
４）、六フッ化燐酸リチウム（ＬｉＰＦ６）、ホウフッ
化リチウム（ＬｉＢＦ４）、六フッ化ヒ素リチウム（Ｌ
ｉＡｓＦ６）、トリフルオロメタンスルホン酸リチウム
（ＬｉＣＦ３ ＳＯ３）などのリチウム塩を挙げること
ができる。BEST MODE FOR CARRYING OUT THE INVENTION The scavenger used in the present invention has a charge / discharge cycle characteristic which is obtained by capturing manganese ions from a positive electrode active material early before elution into an electrolytic solution during charge / discharge or during standing. It is an object of the present invention to provide a non-aqueous electrolyte secondary battery having excellent storage characteristics. A lithium manganese composite oxide having a spinel structure was used as the positive electrode active material of the present invention. As the negative electrode active material, lithium metal, a lithium alloy such as lithium-aluminum, or a carbon material capable of inserting and extracting lithium ions is used. As the non-aqueous solvent, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, γ-butyrolactone, acetonitrile, sulfolane, 1,2-dimethoxyethane, 1,3-dimethoxypropane, dimethyl ether,
Tetrahydroplan, 2-methyltetrahydroplan,
It can be mentioned that a single solvent or a mixed solvent of two or more kinds selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and the like can be used. Examples of the electrolyte include lithium perchlorate (LiClO 2).
4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium arsenic hexafluoride (L
Examples thereof include lithium salts such as iAsF6) and lithium trifluoromethanesulfonate (LiCF3SO3).
【０００７】１．正極
正極活物質としては、平均粒径１０μmのリチウムマン
ガン複合酸化物、導電助剤としては平均粒径３μmの炭
素粉末、結着剤としてポリフッ化ビニリデン（以下、Ｐ
ＶｄＦと略す）とを８５：９：６の重量％で混合する。
本発明では、後述するようし、この混合物にマンガンイ
オンを捕捉可能な物質を添加した。そこに、Ｎ−メチル
−２−ピロリドンを投入混合して、スラリー状の溶液を
作製する。厚み２０μmのアルミニウム箔の両面にこの
スラリーを塗布し、溶剤を乾燥した後、ローラプレス機
にて圧延し、５４ｍｍ幅で長さが４５０ｍｍに切断して
短細状の正極を作製した。1. Positive electrode As a positive electrode active material, a lithium manganese composite oxide having an average particle size of 10 μm, as a conductive additive, carbon powder having an average particle size of 3 μm, and as a binder, polyvinylidene fluoride (hereinafter, P
(Abbreviated as VdF) at a weight ratio of 85: 9: 6.
In the present invention, as described later, a substance capable of capturing manganese ions was added to this mixture. N-methyl-2-pyrrolidone is charged and mixed therein to prepare a slurry-like solution. This slurry was applied to both sides of an aluminum foil having a thickness of 20 μm, the solvent was dried, and the product was rolled by a roller press machine and cut into a short thin positive electrode by cutting it into a width of 54 mm and a length of 450 mm.
【０００８】２．負極
負極活物質としては平均粒径２０μmの炭素材料とポリ
フッ化ビニリデン（ＰＶｄＦ）の結着剤を９２：８の重
量％で混合し、Ｎ−メチル−２−ピロリドンを投入混合
して、スラリー状の溶液を作製する。厚み１０μmの銅
箔の両面にこのスラリーを塗布し、溶剤を乾燥した後、
ローラプレス機にて圧延して、負極合剤電極を作製し、
その後５６ｍｍ幅で、長さが４９０ｍｍに切断して短冊
状の負極を作製した。2. Negative electrode As a negative electrode active material, a carbon material having an average particle size of 20 μm and a binder of polyvinylidene fluoride (PVdF) are mixed in a weight ratio of 92: 8, and N-methyl-2-pyrrolidone is added and mixed to form a slurry. To prepare a solution. After applying this slurry to both sides of a copper foil with a thickness of 10 μm and drying the solvent,
Roll with a roller press to produce a negative electrode mixture electrode,
Then, a strip-shaped negative electrode was produced by cutting it into a width of 56 mm and a length of 490 mm.
【０００９】３．電池
上記した方法で作製した正極と負極とを厚さ４０μm、
幅５８ｍｍのポリエチレン微多孔膜からなるセパレータ
を介して捲回し、スパイラル状の捲回群を作製する。こ
の捲回群を電池缶に挿入し、予め負極集電体の銅箔に溶
接しておいたニッケルタブ端子を電池缶底に溶接する。
次にエチレンカーボネートとジメチルカーボネートを体
積比で１：２に混合した溶液にＬｉＰＦ６を１ｍｏｌ／
ｌの濃度で溶解した電解液を５ｍｌ注入した。次に、予
め正極集電体のアルミニウム箔に溶接したアルミニウム
製のタブ端子を蓋に溶接して、蓋を絶縁性のガスケット
を介して電池缶の上部に配置させ、この部分をかしめて
密閉し、直径１８ｍｍ、高さ６５ｍｍの円筒型電池を作
製した。3. Battery A positive electrode and a negative electrode produced by the above-mentioned method have a thickness of 40 μm,
Winding is performed through a separator made of a polyethylene microporous film having a width of 58 mm to produce a spiral winding group. This winding group is inserted into a battery can, and a nickel tab terminal previously welded to the copper foil of the negative electrode current collector is welded to the bottom of the battery can.
Next, 1 mol / mL of LiPF6 was added to a solution in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 2.
5 ml of an electrolytic solution dissolved at a concentration of 1 was injected. Next, an aluminum tab terminal previously welded to the aluminum foil of the positive electrode current collector is welded to the lid, and the lid is placed on the top of the battery can through the insulating gasket, and this portion is caulked and sealed. A cylindrical battery having a diameter of 18 mm and a height of 65 mm was produced.
【００１０】４．初期充放電試験
作製した電池を２５℃にて２４時間放置後、初期の充放
電試験をした。すなわち、充放電条件として、充電電圧
４．２Ｖ（ただし、制限電流９００ｍＡ）で４時間充電
した後、放電電流３００ｍＡで放電終止電圧２．７Ｖの
条件下で１０サイクル行った。4. Initial Charge / Discharge Test After leaving the manufactured battery at 25 ° C. for 24 hours, an initial charge / discharge test was performed. That is, as charging / discharging conditions, after charging for 4 hours at a charging voltage of 4.2 V (however, a limiting current of 900 mA), 10 cycles were performed under a condition of a discharging current of 300 mA and a discharge end voltage of 2.7 V.
【００１１】５．サイクル試験
初期充放電試験をした電池の一部は、５０℃にて充電電
流９００ｍＡで充電終止電圧４．２Ｖ、放電電流３００
ｍＡにて放電終止電圧２．７Ｖの条件下で充放電サイク
ル試験を行った。１００サイクル充放電後の電池を分解
し、電解液中へのマンガンイオン量及び負極合剤中のマ
ンガン量を測定した。5. Cycle test Some of the batteries that have been subjected to the initial charge / discharge test have a charge current of 900 mA at 50 ° C, a charge end voltage of 4.2 V, and a discharge current of 300.
A charge / discharge cycle test was performed under the condition of a discharge end voltage of 2.7 V at mA. The battery after 100 cycles of charge and discharge was disassembled and the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture were measured.
【００１２】６．放置試験
初期充放電試験をした電池の一部は、充電状態で５０
℃、１４日間放置し、その後電池を分解し、電解液中へ
のマンガンイオン量、負極合剤中のマンガン量を測定し
た。6. Leaving test Some of the batteries that have been subjected to the initial charge / discharge test are 50% charged.
After leaving it at 14 ° C. for 14 days, the battery was disassembled, and the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture were measured.
【００１３】[0013]
【実施例】本発明を実施例及び比較例により、詳細に説
明する。但し、本発明はこれらに限定されるものではな
い。EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these.
【００１４】（実施例１、２）前記した、正極用スラリ
ー中にマンガンイオンを捕捉可能な物質として燐酸リチ
ウムを正極活物質に対して１％添加た。その他の負極、
電池の製造条件等は前記したものである。Examples 1 and 2 1% of lithium phosphate as a substance capable of capturing manganese ions was added to the positive electrode active material in the positive electrode slurry. Other negative electrodes,
The battery manufacturing conditions and the like are as described above.
【００１５】（比較例１、２）比較例として、燐酸リチ
ウムを添加していない正極に用いた。その他の負極、電
池の製造条件等は前記したものである。(Comparative Examples 1 and 2) As comparative examples, a positive electrode to which lithium phosphate was not added was used. Other negative electrodes, battery manufacturing conditions and the like are as described above.
【００１６】前記した、５０℃にて充放電サイクル試験
を行い、容量維持率（初期放電容量に対する１００サイ
クル充放電後の放電容量）、電解液中のマンガンイオン
量及び負極合剤中のマンガン量を測定した結果を表１に
示す。表１より本発明を用いると容量維持率が高く、電
解液中のマンガンイオン量や負極合剤中のマンガン量を
抑えることができる。The above-mentioned charge / discharge cycle test was carried out at 50 ° C., and the capacity retention ratio (discharge capacity after 100 cycles of charge / discharge with respect to the initial discharge capacity), the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture. Table 1 shows the result of measurement. From Table 1, when the present invention is used, the capacity retention rate is high, and the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture can be suppressed.
【００１７】[0017]
【表１】 [Table 1]
【００１８】前記した、充電状態で５０℃、１４日間放
置した後に電池を分解し、電解液中のマンガンイオン
量、負極合剤中のマンガン量を測定した結果を表２に示
す。表２より本発明を用いると放置後における電解液中
のマンガンイオン量や負極合剤中のマンガン量を抑える
ことができる。Table 2 shows the results of measuring the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture after disassembling the battery after leaving it in the charged state at 50 ° C. for 14 days. From Table 2, when the present invention is used, the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture after standing can be suppressed.
【００１９】[0019]
【表２】 [Table 2]
【００２０】（実施例３〜７）マンガンイオンの補捉剤
として燐酸リチウムを用い、正極活物質量に対して０．
０１、０．１、５、１０、２０％添加した電池を作製し
て試験した。(Examples 3 to 7) Lithium phosphate was used as a scavenger of manganese ions, and the amount of the positive electrode active material was set to 0.
Batteries with additions of 01, 0.1, 5, 10, 20% were prepared and tested.
【００２１】比較例１を１００とした場合の初期放電容
量及び５０℃にて１００サイクルの充放電試験を行い、
電解液中のマンガンイオン量及び負極合剤中のマンガン
量を測定した結果を表３に示す。捕捉剤として用いた燐
酸リチウムの添加量は、活物質重量に対して０．１から
２０％で効果が認められるが、添加量が多くなると電池
の容量が減少するため、好ましくは０．１〜１０％添加
することが望ましい。A charge / discharge test was conducted for 100 cycles at an initial discharge capacity and 50 ° C. when Comparative Example 1 was set to 100,
Table 3 shows the measurement results of the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture. The amount of lithium phosphate used as a scavenger is 0.1 to 20% based on the weight of the active material, and the effect is recognized. It is desirable to add 10%.
【００２２】[0022]
【表３】 [Table 3]
【００２３】（実施例８）補捉剤として、タングステン
酸リチウムの添加量を正極活物質量に対して１％添加し
た。それ以外は実施例１と同様の円筒型電池を作製し
た。(Example 8) As a scavenger, 1% of lithium tungstate was added to the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２４】 （実施例９）
捕捉剤として、タングステン酸リチウムの添加量を正極
活物質量に対して０．１％添加した。それ以外は実施例
１と同様の円筒型電池を作製した。Example 9 As a scavenger, the amount of lithium tungstate added was 0.1% with respect to the amount of the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２５】（実施例１０）補捉剤として、珪酸リチウ
ムの添加量を正極活物質量に対して１％添加した。それ
以外は実施例１と同様の円筒型電池を作製した。Example 10 As a trapping agent, the amount of lithium silicate added was 1% with respect to the amount of the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２６】（実施例１１）補捉剤として、アルミナイ
トの添加量を正極活物質量に対して１％添加した。それ
以外は実施例１と同様の円筒型電池を作製した。(Example 11) As a scavenger, 1% of an aluminite was added to the amount of the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２７】（実施例１２）補捉剤として、ホウ酸リチ
ウムの添加量を正極活物質量に対して１％添加した。そ
れ以外は実施例１と同様の円筒型電池を作製した。(Example 12) As a scavenger, 1% of lithium borate was added to the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２８】（実施例１３）補捉剤として、モリブデン
酸リチウムの添加量を正極活物質量に対して添加１％に
した。それ以外は実施例１と同様の円筒型電池を作製し
た。Example 13 As a trapping agent, the amount of lithium molybdate added was 1% with respect to the amount of the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００２９】（実施例１４）補捉剤として、陽イオン交
換樹脂（Ｒ−ＣＨ２ＳＯ３Ｈ型）としての添加量を正極
活物質量に対して１％添加した。それ以外は実施例１と
同様の円筒型電池を作製した。(Example 14) As a scavenger, 1% of a cation exchange resin (R-CH2SO3H type) was added to the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００３０】（実施例１５）補捉剤として、陽イオン交
換樹脂（Ｒ−ＳＯ３Ｈ型）の添加量を正極活物質量に対
して１％添加した。それ以外は実施例１と同様の円筒型
電池を作製した。(Example 15) As a trapping agent, 1% of a cation exchange resin (R-SO3H type) was added to the positive electrode active material. A cylindrical battery was manufactured in the same manner as in Example 1 except for the above.
【００３１】以上、（実施例８〜１５）について初期充
放電試験をした後、５０℃にて１００サイクルの充放電
試験を行い、電解液中のマンガンイオン量及び負極合剤
中のマンガン量を測定した結果を表４に示す。（実施例
８〜１５）においても、電解液中のマンガンイオン量及
び負極合剤中のマンガン量ともに比較例１より少ないこ
とが確認された。After carrying out the initial charge / discharge test on (Examples 8 to 15) as described above, a charge / discharge test was conducted at 50 ° C. for 100 cycles to determine the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture. Table 4 shows the measurement results. Also in (Examples 8 to 15), it was confirmed that both the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode mixture were smaller than those in Comparative Example 1.
【００３２】[0032]
【表４】 [Table 4]
【００３３】[0033]
【発明の効果】上述したように本発明を用いると、電解
液中のマンガンイオン量及び負極中のマンガン量を少な
くでき、充放電サイクル及び放置特性に優れた非水電解
液二次電池を提供することができる。また、本実施例で
は円筒型電池を例に記載しているが、角型、コイン型
等、種々の形状の電池に適用できる。As described above, by using the present invention, the amount of manganese ions in the electrolytic solution and the amount of manganese in the negative electrode can be reduced, and a non-aqueous electrolytic solution secondary battery excellent in charge / discharge cycle and leaving characteristics is provided. can do. Further, although a cylindrical battery is described as an example in the present embodiment, it can be applied to batteries having various shapes such as a prismatic type and a coin type.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 東本 晃二 東京都中央区日本橋本町２丁目８番７号 新神戸電機株式会社内 (56)参考文献 特開 平８−213016（ＪＰ，Ａ) 特開 平９−259863（ＪＰ，Ａ) 特開 平９−265984（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/00 - 4/62 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Koji Higashimoto 2-8-7 Nihonbashihonmachi, Chuo-ku, Tokyo Inside Shin-Kobe Electric Machinery Co., Ltd. (56) Reference JP-A-8-213016 (JP, A) JP Hei 9-259863 (JP, A) JP 9-265984 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/00-4/62
Claims (3)
を有するリチウムマンガン複合酸化物を主たる正極活物
質とし、炭素材を主たる負極活物質に使用する非水電解
液二次電池において、正極中にマンガンを捕捉する捕捉
剤を含むことを特徴とする非水電解液二次電池。1. A non-aqueous electrolyte secondary battery in which a lithium manganese composite oxide having a spinel structure capable of inserting and extracting lithium is used as a main positive electrode active material, and a carbon material is used as a main negative electrode active material. A non-aqueous electrolyte secondary battery comprising a scavenger that traps manganese.
ウム、タングステン酸リチウム、珪酸リチウム、アルミ
ナイト、ホウ酸リチウム、モリブデン酸リチウム、陽イ
オン交換樹脂の群から選ばれる少なくとも一種類以上を
含むことを特徴とする請求項１記載の非水電解液二次電
池。2. The capture agent for capturing manganese contains at least one selected from the group consisting of lithium phosphate, lithium tungstate, lithium silicate, aluminite, lithium borate, lithium molybdate, and cation exchange resin. The non-aqueous electrolyte secondary battery according to claim 1.
が、正極活物質重量に対して０．１から１０％であるこ
とを特徴とする請求項１記載の非水電解液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the amount of the trapping agent that traps manganese is 0.1 to 10% based on the weight of the positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884198A JP3491529B2 (en) | 1998-06-25 | 1998-06-25 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884198A JP3491529B2 (en) | 1998-06-25 | 1998-06-25 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000011996A JP2000011996A (en) | 2000-01-14 |
| JP3491529B2 true JP3491529B2 (en) | 2004-01-26 |
Family
ID=16055611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17884198A Expired - Fee Related JP3491529B2 (en) | 1998-06-25 | 1998-06-25 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3491529B2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004342595A (en) * | 2003-04-25 | 2004-12-02 | Nec Tokin Corp | Electrode for electrochemical cell, and electrochemical cell using it |
| JP2005071617A (en) * | 2003-08-21 | 2005-03-17 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery and its manufacturing method |
| KR100705262B1 (en) | 2004-12-07 | 2007-04-09 | 주식회사 엘지화학 | Nonaqueous electrolyte comprising oxyanion and lithium secondary battery using the same |
| JP5079461B2 (en) | 2007-11-14 | 2012-11-21 | ソニー株式会社 | Positive electrode for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery |
| US20110292568A1 (en) * | 2008-11-28 | 2011-12-01 | Sumitomo Chemical Company, Limited | Electrode film, electrode, method for manufacturing the electrode, and electrical storage device |
| JP2011150873A (en) * | 2010-01-21 | 2011-08-04 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP5583419B2 (en) * | 2010-02-03 | 2014-09-03 | 日立マクセル株式会社 | Lithium ion secondary battery |
| JP5549321B2 (en) * | 2010-03-31 | 2014-07-16 | 日亜化学工業株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| JP2012089402A (en) * | 2010-10-21 | 2012-05-10 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
| JP5623241B2 (en) * | 2010-10-29 | 2014-11-12 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP5858295B2 (en) * | 2013-08-29 | 2016-02-10 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| US10454107B2 (en) | 2014-03-20 | 2019-10-22 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| JP6295324B2 (en) * | 2014-06-18 | 2018-03-14 | 株式会社日立製作所 | Lithium ion battery and manufacturing method thereof |
| KR101655241B1 (en) | 2015-02-24 | 2016-09-08 | 주식회사 포스코이에스엠 | Manufacturing method of lithium manganese complex oxide coated with lithium polysilicate, lithium manganese complex oxide for lithium rechargeable batteries made by the same, and lithium rechargeable batteries comprising the same |
| KR102614833B1 (en) * | 2015-06-04 | 2023-12-15 | 도아고세이가부시키가이샤 | Ion scavenger for lithium ion secondary cell, liquid electrolyte, separator, and lithium ion secondary cell |
| JP6390917B2 (en) * | 2015-11-05 | 2018-09-19 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| JP6848199B2 (en) * | 2016-04-06 | 2021-03-24 | 住友金属鉱山株式会社 | A method for producing a positive electrode material for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery using the positive electrode material, and a positive electrode material for a non-aqueous electrolyte secondary battery. |
| KR102435872B1 (en) * | 2016-06-15 | 2022-08-23 | 이리카 테크놀로지스 리미티드 | Lithium borosilicate glass as electrolyte and electrode protective layer |
| JP2022013953A (en) * | 2018-10-26 | 2022-01-19 | 株式会社豊田自動織機 | Electrode and solid-type lithium ion secondary battery |
| US11094998B2 (en) * | 2019-06-19 | 2021-08-17 | GM Global Technology Operations LLC | Ceramic-coated separators for lithium-containing electrochemical cells and methods of making the same |
| CN115072703B (en) * | 2022-08-02 | 2024-01-30 | 洛阳月星新能源科技有限公司 | Composite anode material and preparation method and application thereof |
-
1998
- 1998-06-25 JP JP17884198A patent/JP3491529B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000011996A (en) | 2000-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3491529B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2001325988A (en) | Charging method of non-aqueous electrolyte secondary battery | |
| JP4489207B2 (en) | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery | |
| JPH11121012A (en) | Nonaqueous electrolytic battery | |
| JP3287376B2 (en) | Lithium secondary battery and method of manufacturing the same | |
| JP2000021442A (en) | Nonaqueous electrolyte secondary battery | |
| JP3580209B2 (en) | Lithium ion secondary battery | |
| JPH09147910A (en) | Lithium secondary battery | |
| JP4219187B2 (en) | Non-aqueous lithium secondary battery | |
| JP4780361B2 (en) | Lithium secondary battery | |
| JP2887632B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2000012079A (en) | Nonaqueous electrolyte secondary battery | |
| JP3016447B2 (en) | Non-aqueous electrolyte battery | |
| JP2003168427A (en) | Nonaqueous electrolyte battery | |
| JP2003229179A (en) | Nonaqueous electrolyte secondary battery | |
| JP2002025626A (en) | Aging method for lithium secondary battery | |
| JP2000012026A (en) | Nonaqueous electrolyte secondary battery | |
| JP2003168478A (en) | Lithium ion non-aqueous electrolyte secondary battery | |
| JPH09171825A (en) | Secondary battery having nonaqueous solvent | |
| EP4078711B1 (en) | Electrolyte for li secondary batteries | |
| JP2001196073A (en) | Nonaqueous electrolyte battery | |
| JP2000021441A (en) | Nonaqueous electrolyte secondary battery | |
| JP3663694B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH06275269A (en) | Nonaqueous electrolyte secondary battery and its manufacture | |
| JP3331608B2 (en) | Non-aqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071114 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091114 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091114 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101114 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101114 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111114 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111114 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121114 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121114 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131114 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |