JPH07192719A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH07192719A JPH07192719A JP5347811A JP34781193A JPH07192719A JP H07192719 A JPH07192719 A JP H07192719A JP 5347811 A JP5347811 A JP 5347811A JP 34781193 A JP34781193 A JP 34781193A JP H07192719 A JPH07192719 A JP H07192719A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- secondary battery
- electrolyte secondary
- active material
- transition metal
- 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
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Classifications
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- 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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、充放電領域において２
Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）以上の電位を示す遷移金属酸
化物又は遷移金属複合酸化物を正極活物質とする正極
と、金属リチウム又はリチウムイオンを吸蔵・放出する
ことが可能な物質を負極材料とする負極と、非水電解質
とを備える非水電解質二次電池に係わり、詳しくは当該
非水電解質二次電池のサイクル特性を改善することを目
的とした、正極活物質の改良に関する。BACKGROUND OF THE INVENTION The present invention relates to a charging / discharging region.
A positive electrode using a transition metal oxide or a transition metal composite oxide having a potential of V (vs. Li / Li + ) or more as a positive electrode active material, and a material capable of inserting and extracting lithium metal or lithium ions as a negative electrode The present invention relates to a non-aqueous electrolyte secondary battery including a negative electrode as a material and a non-aqueous electrolyte, and more particularly, to an improvement of a positive electrode active material for the purpose of improving cycle characteristics of the non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
非水電解質二次電池が、エネルギー密度が高く、しかも
水の分解電圧を考慮する必要が無いため高電圧化が可能
であるなどの利点があることから、次世代の二次電池と
して、注目されている。2. Description of the Related Art In recent years,
The non-aqueous electrolyte secondary battery has attracted attention as a next-generation secondary battery because it has advantages such as high energy density and higher voltage because there is no need to consider the decomposition voltage of water. ing.
【０００３】高電圧型の非水電解質二次電池の正極活物
質としては、充放電領域において２Ｖ（ｖｓ．Ｌｉ／Ｌ
ｉ+ ）以上の電位を示すＬｉＮｉＯ2 、ＬｉＣｏＯ2 等
の遷移金属複合酸化物が提案されているが、充放電サイ
クルの進行に伴う容量低下が著しいという問題があっ
た。As a positive electrode active material for a high voltage type non-aqueous electrolyte secondary battery, 2 V (vs. Li / L) in a charge / discharge region is used.
Although a transition metal composite oxide such as LiNiO 2 or LiCoO 2 having a potential of i + ) or more has been proposed, there is a problem that the capacity is significantly reduced with the progress of charge and discharge cycles.
【０００４】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、正極活物質
として特定の遷移金属複合酸化物を用いることにより、
サイクル特性に優れた高電圧型の非水電解質二次電池を
提供するにある。The present invention has been made to solve this problem, and its purpose is to use a specific transition metal composite oxide as a positive electrode active material.
It is to provide a high-voltage type non-aqueous electrolyte secondary battery having excellent cycle characteristics.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水電解質二次電池（以下、「本発明電
池」と称する。）は、組成式Ｌｉx Ｎｉ1-y Ｍ yＯ
z （但し、０＜ｘ＜１．３、０．０２≦ｙ≦０．９８、
１．８＜ｚ＜２．２、ＭはＣｏ又はＣｏを主体とする２
種以上の遷移元素である。）で表される遷移金属複合酸
化物を正極活物質とする正極と、金属リチウム又はリチ
ウムイオンを吸蔵及び放出することが可能な物質を負極
材料とする負極と、非水電解質とを備える非水電解質二
次電池において、前記遷移金属複合酸化物が、六方晶と
して計算した場合の、格子定数ａが２．８１８〜２．８
７８であり、且つ、格子定数ｃが１４．０４７〜１４．
１８４であるＬｉＣｏＯ2 型結晶相（Ａ）と、六方晶と
して計算した場合の、格子定数ａが２．８１８〜２．８
７８であり、且つ、格子定数ｃが１４．０４７〜１４．
１８４であるＬｉＮｉＯ2 型結晶相（Ｂ）との複合構造
をなすものである。A non-aqueous electrolyte secondary battery according to the present invention (hereinafter, referred to as "the battery of the present invention") for achieving the above object is a composition formula Li x Ni 1- y My. O
z (however, 0 <x <1.3, 0.02 ≦ y ≦ 0.98,
1.8 <z <2.2, M is Co or Co is the main component 2
More than one kind of transition element. ) A non-aqueous electrolyte comprising a positive electrode having a transition metal composite oxide represented by the formula (4) as a positive electrode active material, a negative electrode having a material capable of inserting and extracting metal lithium or lithium ions as a negative electrode material, and a non-aqueous electrolyte. In the electrolyte secondary battery, the transition metal complex oxide has a lattice constant a of 2.818 to 2.8 when calculated as a hexagonal crystal.
78, and the lattice constant c is 14.047-14.
A LiCoO 2 type crystal phase (A) of 184 and a lattice constant a of 2.818 to 2.8 when calculated as a hexagonal crystal.
78, and the lattice constant c is 14.047-14.
184, which is a composite structure with the LiNiO 2 type crystal phase (B).
【０００６】本発明が、特定の遷移金属複合酸化物を正
極活物質とする正極を備えた非水電解質二次電池を対象
とするのは、充放電領域において２Ｖ（vs. Ｌｉ／Ｌｉ
+ ）以上の電位を有するこの種の正極活物質を用いた場
合に、特に充放電サイクル時の結晶構造の崩壊に因る特
性劣化が著しいからである。The present invention is directed to a non-aqueous electrolyte secondary battery provided with a positive electrode using a specific transition metal composite oxide as a positive electrode active material, and is intended to have a voltage of 2 V (vs. Li / Li) in a charge / discharge region.
This is because, when this type of positive electrode active material having a potential of + ) or more is used, the characteristic deterioration due to the collapse of the crystal structure during charge / discharge cycles is remarkable.
【０００７】本発明における負極材料としては、金属リ
チウム又はリチウムイオンを吸蔵及び放出することが可
能な物質が用いられる。リチウムイオンを吸蔵及び放出
することが可能な物質としては、コークス、黒鉛、有機
物焼成体等の炭素材料が例示される。As the negative electrode material in the present invention, a substance capable of inserting and extracting metallic lithium or lithium ions is used. Examples of the substance capable of inserting and extracting lithium ions include carbon materials such as coke, graphite, and a fired organic material.
【０００８】[0008]
【作用】本発明電池においては、複合構造をなす特定の
遷移金属複合酸化物が正極活物質として用いられている
ので、充放電サイクル時のリチウムイオンの吸蔵及び放
出に伴う正極活物質の結晶構造の崩壊が起こりにくい。
このため容量低下が抑制される。In the battery of the present invention, since the specific transition metal composite oxide having a composite structure is used as the positive electrode active material, the crystal structure of the positive electrode active material accompanying the occlusion and release of lithium ions during the charge / discharge cycle. Is unlikely to collapse.
Therefore, the capacity decrease is suppressed.
【０００９】[0009]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the examples described below, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１０】（実施例） 〔正極の作製〕ＬｉＯＨと平均粒径がともに２０μｍ以
上であるＮｉ（ＯＨ）2 及びＣｏ（ＯＨ）2 とを乳鉢に
て所定の割合で混合した後、乾燥空気雰囲気下にて、７
５０°Ｃで２０時間熱処理し、次いで石川式らいかい乳
鉢中で平均粒径約５μｍの粉末に粉砕し、組成式ＬｉＮ
ｉ1-y Ｃｏy Ｏ2 （ｙ＝０．０２、０．２、０．５、
０．８、０．９８）で表される正極活物質としての５種
類の遷移金属複合酸化物粉末を得た。これらの遷移金属
複合酸化物の第１相（ＬｉＣｏＯ2 型の六方晶構造に近
似した結晶構造を有する。）及び第２相（ＬｉＮｉＯ2
型の六方晶構造に近似した結晶構造を有する。）の格子
定数ａ及びｃを次の表１にまとめて示す。(Preparation of Positive Electrode) LiOH and Ni (OH) 2 and Co (OH) 2 having an average particle size of 20 μm or more were mixed in a mortar at a predetermined ratio and then in a dry air atmosphere. Below, 7
Heat treatment at 50 ° C for 20 hours, then pulverize into powder with an average particle size of about 5 μm in an Ishikawa-type Raikai mortar, composition formula LiN
i 1-y Co y O 2 (y = 0.02, 0.2, 0.5,
Five kinds of transition metal composite oxide powders as a positive electrode active material represented by 0.8 and 0.98) were obtained. The first phase (having a crystal structure similar to the LiCoO 2 type hexagonal crystal structure) and the second phase (LiNiO 2 ) of these transition metal composite oxides
It has a crystal structure similar to the hexagonal crystal structure of the mold. The lattice constants a and c of) are collectively shown in Table 1 below.
【００１１】[0011]
【表１】 [Table 1]
【００１２】このようにして得た遷移金属複合酸化物粉
末と、導電剤としてのアセチレンブラックと、結着剤と
してのフッ素樹脂粉末とを、重量比９０：６：４の比率
で混合して正極合剤を調製し、この正極合剤を成形圧２
トン／ｃｍ2 で直径２０ｍｍの円板状に加圧成形したの
ち２５０°Ｃで熱処理して正極を作製した。The transition metal composite oxide powder thus obtained, acetylene black as a conductive agent, and fluororesin powder as a binder are mixed in a weight ratio of 90: 6: 4 to obtain a positive electrode. A mixture is prepared, and this positive electrode mixture is molded at a molding pressure of 2
A positive electrode was prepared by press-molding into a disk shape having a diameter of 20 mm at ton / cm 2 and then heat-treating at 250 ° C.
【００１３】〔負極の作製〕リチウム圧延板を直径２０
ｍｍの円板状に打ち抜いて負極を作製した。[Preparation of Negative Electrode] A rolled lithium plate having a diameter of 20
A negative electrode was manufactured by punching out into a disc shape of mm.
【００１４】〔電解液の調製〕プロピレンカーボネート
と１，２−ジメトキシエタンとの等体積混合溶媒に、過
塩素酸リチウムを１モル／リットル溶かして電解液（非
水電解液）を調製した。[Preparation of Electrolytic Solution] 1 mol / liter of lithium perchlorate was dissolved in an equal volume mixed solvent of propylene carbonate and 1,2-dimethoxyethane to prepare an electrolytic solution (non-aqueous electrolytic solution).
【００１５】〔電池の作製〕以上の正負両極及び非水電
解液を用いて扁平型の本発明電池ＢＡ１〜ＢＡ５を組み
立てた（電池寸法：直径２４．０ｍｍ、厚さ３．０ｍ
ｍ）。なお、セパレータとしては、ポリプロピレン製の
微多孔膜（ヘキストセラニーズ社製、商品名「セルガー
ド」）を使用し、これに先の電解液を含浸させた。[Fabrication of Battery] Flat type batteries BA1 to BA5 of the present invention were assembled using the positive and negative electrodes and the non-aqueous electrolyte described above (battery size: diameter 24.0 mm, thickness 3.0 m).
m). As the separator, a polypropylene microporous film (manufactured by Hoechst Celanese Co., Ltd., trade name “Celgard”) was used and impregnated with the electrolytic solution.
【００１６】図１は、組み立てた本発明電池ＢＡ１を模
式的に示す断面図であり、同図に示す本発明電池ＢＡ１
は、正極１、負極２、これら両電極１、２を互いに離間
するセパレータ３、正極缶４、負極缶５、正極集電体
６、負極集電体７及びポリプロピレン製の絶縁パッキン
グ８などからなる。FIG. 1 is a sectional view schematically showing the assembled battery BA1 of the present invention. The battery BA1 of the present invention shown in FIG.
Is composed of a positive electrode 1, a negative electrode 2, a separator 3 for separating the electrodes 1, 2 from each other, a positive electrode can 4, a negative electrode can 5, a positive electrode current collector 6, a negative electrode current collector 7 and an insulating packing 8 made of polypropylene. .
【００１７】正極１及び負極２は、非水電解液を含浸し
たセパレータ３を介して対向して正負両極缶４，５が形
成する電池ケース内に収納されており、正極１は正極集
電体６を介して正極缶４に、また負極２は負極集電体７
を介して負極缶５に接続され、電池内部に生じた化学エ
ネルギーを正極缶４及び負極缶５の両端子から電気エネ
ルギーとして外部へ取り出し得るようになっている。The positive electrode 1 and the negative electrode 2 are housed in a battery case formed by positive and negative bipolar cans 4 and 5 facing each other with a separator 3 impregnated with a non-aqueous electrolytic solution interposed therebetween. The positive electrode 1 is a positive electrode current collector. 6 to the positive electrode can 4 and the negative electrode 2 to the negative electrode current collector 7
It is connected to the negative electrode can 5 via the so that the chemical energy generated inside the battery can be taken out as electric energy from both terminals of the positive electrode can 4 and the negative electrode can 5.
【００１８】（比較例）平均粒径がともに２０μｍ以上
のＮｉ（ＯＨ）2 及びＣｏ（ＯＨ）2 に代えて、平均粒
径がともに２μｍ以下のＮｉ（ＯＨ）2 及びＣｏ（Ｏ
Ｈ）2 を用いたこと以外は実施例と同様にして、比較電
池ＢＣ１〜ＢＣ７を組み立てた。Comparative Example Instead of Ni (OH) 2 and Co (OH) 2 having an average particle size of 20 μm or more, Ni (OH) 2 and Co (O) having an average particle size of 2 μm or less are used.
Comparative batteries BC1 to BC7 were assembled in the same manner as in the example except that H) 2 was used.
【００１９】また、ＬｉＣｏＯ2 とＬｉＮｉＯ2 とを、
Ｃｏ及びＮｉの総モルに対するＣｏのモル比が、順に
０．０２、０．２、０．５、０．８又は０．９８となる
ように混合して得た混合物を正極活物質として用いたこ
と以外は実施例と同様にして、比較電池ＢＣ８〜ＢＣ１
２を組み立てた。Further, LiCoO 2 and LiNiO 2 are
A mixture obtained by mixing so that the molar ratio of Co with respect to the total moles of Co and Ni was 0.02, 0.2, 0.5, 0.8 or 0.98 was used as the positive electrode active material. Comparative batteries BC8 to BC1 were made in the same manner as the example except for the above.
Assembled 2.
【００２０】上記比較例で用いた正極活物質の第１相及
び第２相の格子定数ａ及びｃを先の表１にまとめて示
す。The lattice constants a and c of the first phase and the second phase of the positive electrode active material used in the above comparative example are summarized in Table 1 above.
【００２１】なお、図２は本発明電池ＢＡ３に用いた正
極活物質のＸ線回折パターンであり図３は比較電池ＢＣ
３に用いた正極活物質のＸ線回折パターンである。図２
中、○符号を付した回折ピークが格子定数ａ及びｃが比
較的大きいＬｉＮｉＯ2 型結晶相（Ｂ）の回折ピークで
あり、また△符号を付した回折ピークが格子定数ａ及び
ｃが比較的小さいＬｉＣｏＯ2 型結晶相（Ａ）の回折ピ
ークである。図２のＸ線回折パターンをＪＣＰＤＳカー
ドＮｏｓ．１６−４２７（ＬｉＣｏＯ2 ）及び９−６３
（ＬｉＮｉＯ2 ）と照合して、本発明電池ＢＡ３に用い
た正極活物質は、ＬｉＣｏＯ2 型結晶相（Ａ）とＬｉＮ
ｉＯ2 型結晶相（Ｂ）とが均一に固溶化した二相構造か
らなるものであるのに対して、比較電池ＢＣ３に用いた
正極活物質は、単一相からなるものであることを確認し
た。2 is an X-ray diffraction pattern of the positive electrode active material used in the battery BA3 of the present invention, and FIG. 3 is a comparative battery BC.
3 is an X-ray diffraction pattern of the positive electrode active material used in 3. Figure 2
Among them, the diffraction peaks marked with ◯ are those of the LiNiO 2 type crystal phase (B) having relatively large lattice constants a and c, and the diffraction peaks marked with Δ are relatively large in lattice constants a and c. It is a diffraction peak of a small LiCoO 2 type crystal phase (A). The X-ray diffraction pattern of FIG. 16-427 (LiCoO 2 ) and 9-63
In comparison with (LiNiO 2 ), the positive electrode active material used in the battery BA3 of the present invention was LiCoO 2 type crystal phase (A) and LiN.
It was confirmed that the positive electrode active material used in Comparative Battery BC3 was composed of a single phase, while the iO 2 type crystal phase (B) was composed of a two-phase structure in which it was uniformly solid-soluted. did.
【００２２】〔各電池の充放電サイクル特性〕本発明電
池ＢＡ１〜ＢＡ５及び比較電池ＢＣ１〜ＢＣ１２につい
て、充電電流密度１ｍＡ／ｃｍ2 で４．３Ｖまで充電し
た後、放電電流密度３ｍＡ／ｃｍ2 で２．５Ｖまで放電
する工程を１サイクルとする充放電サイクル試験を行
い、１００サイクル目の放電容量の１サイクル目の放電
容量に対する容量劣化率を求めた。結果を先の表１に示
す。[Charge / Discharge Cycle Characteristics of Each Battery] The batteries BA1 to BA5 of the present invention and the comparative batteries BC1 to BC12 were charged at a charging current density of 1 mA / cm 2 to 4.3 V and then at a discharging current density of 3 mA / cm 2 . A charging / discharging cycle test in which the step of discharging to 2.5 V was defined as one cycle was performed, and the capacity deterioration rate of the discharge capacity at the 100th cycle with respect to the discharge capacity at the first cycle was determined. The results are shown in Table 1 above.
【００２３】表１より、本発明電池は、正極活物質の結
晶構造が単一相からなる比較電池ＢＣ１〜ＢＣ７に比
し、１００サイクル目における容量劣化率が格段に小さ
いことから、サイクル特性に極めて優れていることが分
かる。また、比較電池ＢＣ８〜ＢＣ１２の１００サイク
ル目における容量劣化率が極めて良くないことから、Ｌ
ｉＣｏＯ2 とＬｉＮｉＯ2 とを単に混合使用したので
は、リチウムイオンの吸蔵及び放出に伴う結晶構造の崩
壊が起こりにくい電気化学的に安定な正極活物質は得ら
れないことが分かる。From Table 1, the battery of the present invention has a significantly smaller capacity deterioration rate at the 100th cycle than the comparative batteries BC1 to BC7 in which the crystal structure of the positive electrode active material is a single phase. It turns out that it is extremely excellent. In addition, since the capacity deterioration rates of the comparative batteries BC8 to BC12 at the 100th cycle were not very good, L
It can be seen that if iCoO 2 and LiNiO 2 are simply mixed and used, an electrochemically stable positive electrode active material in which the crystal structure is less likely to collapse due to the absorption and desorption of lithium ions cannot be obtained.
【００２４】叙上の実施例では本発明を扁平型電池に適
用する場合を例に挙げて説明したが、電池の形状に特に
制限はなく、本発明は円筒型、角型等、種々の形状の非
水電解質二次電池に適用し得るものである。In the above embodiments, the case where the present invention is applied to a flat type battery has been described as an example, but the shape of the battery is not particularly limited, and the present invention is applicable to various shapes such as a cylindrical shape and a square shape. It is applicable to the non-aqueous electrolyte secondary battery of.
【００２５】また、電解液として非水電解液を用いた
が、固体電解質を用いることももとより可能である。Although the nonaqueous electrolytic solution is used as the electrolytic solution, it is naturally possible to use a solid electrolyte.
【００２６】[0026]
【発明の効果】ＬｉＣｏＯ2 型結晶相（Ａ）とＬｉＮｉ
Ｏ2 型結晶相（Ｂ）との複合構造からなる電気化学的に
安定した結晶構造を有する特定の遷移金属複合酸化物が
正極活物質として用いられているので、充放電サイクル
時のリチウムイオンの吸蔵及び放出に伴う正極活物質の
結晶構造の崩壊が起こりにくく、それゆえサイクル特性
に優れる。EFFECT OF THE INVENTION LiCoO 2 type crystal phase (A) and LiNi
Since a specific transition metal composite oxide having an electrochemically stable crystal structure composed of a composite structure with the O 2 type crystal phase (B) is used as a positive electrode active material, it is possible to reduce the amount of lithium ion during charge / discharge cycles. The collapse of the crystal structure of the positive electrode active material due to occlusion and release is unlikely to occur, and therefore the cycle characteristics are excellent.
【図１】実施例で作製した本発明電池（扁平型電池）の
断面図である。FIG. 1 is a cross-sectional view of a battery of the present invention (flat battery) manufactured in an example.
【図２】本発明電池の作製に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 the positive electrode active material used for producing the battery of the present invention.
【図３】比較電池の作製に用いた正極活物質のＸ線回折
パターンである。FIG. 3 is an X-ray diffraction pattern of a positive electrode active material used for manufacturing a comparative battery.
ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ BA1 Inventive battery 1 Positive electrode 2 Negative electrode 3 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小路 良浩 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Koji 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (72) Koji Nishio 2-5 Keihanhondori, Moriguchi City, Osaka Prefecture No. 5 Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (1)
＜ｘ＜１．３、０．０２≦ｙ≦０．９８、１．８＜ｚ＜
２．２、ＭはＣｏ又はＣｏを主体とする２種以上の遷移
元素である。）で表される遷移金属複合酸化物を正極活
物質とする正極と、金属リチウム又はリチウムイオンを
吸蔵及び放出することが可能な物質を負極材料とする負
極と、非水電解質とを備える非水電解質二次電池におい
て、前記遷移金属複合酸化物が、六方晶として計算した
場合の、格子定数ａが２．８１８〜２．８７８であり、
且つ、格子定数ｃが１４．０４７〜１４．１８４である
ＬｉＣｏＯ2 型結晶相（Ａ）と、六方晶として計算した
場合の、格子定数ａが２．８１８〜２．８７８であり、
且つ、格子定数ｃが１４．０４７〜１４．１８４である
ＬｉＮｉＯ2 型結晶相（Ｂ）との複合構造をなすもので
あることを特徴とする非水電解質二次電池。1. A composition formula Li x Ni 1-y M y O z (however, 0
<X <1.3, 0.02 ≦ y ≦ 0.98, 1.8 <z <
2.2 and M are Co or two or more kinds of transition elements mainly composed of Co. ) A non-aqueous electrolyte comprising a positive electrode having a transition metal composite oxide represented by the formula (4) as a positive electrode active material, a negative electrode having a material capable of inserting and extracting metal lithium or lithium ions as a negative electrode material, and a non-aqueous electrolyte. In the electrolyte secondary battery, the transition metal complex oxide has a lattice constant a of 2.818 to 2.878 when calculated as a hexagonal crystal,
Further, the LiCoO 2 type crystal phase (A) having a lattice constant c of 14.047 to 14.184 and the lattice constant a of 2.818 to 2.878 when calculated as a hexagonal crystal,
A non-aqueous electrolyte secondary battery having a composite structure with a LiNiO 2 type crystal phase (B) having a lattice constant c of 14.047 to 14.184.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34781193A JP3167518B2 (en) | 1993-12-24 | 1993-12-24 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34781193A JP3167518B2 (en) | 1993-12-24 | 1993-12-24 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07192719A true JPH07192719A (en) | 1995-07-28 |
| JP3167518B2 JP3167518B2 (en) | 2001-05-21 |
Family
ID=18392751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34781193A Expired - Lifetime JP3167518B2 (en) | 1993-12-24 | 1993-12-24 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3167518B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0973217A2 (en) * | 1998-07-13 | 2000-01-19 | Ngk Insulators, Ltd. | Lithium transition metal compound for lithium secondary battery |
| WO2019171623A1 (en) * | 2018-03-07 | 2019-09-12 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary batteries, and lithium ion secondary battery |
-
1993
- 1993-12-24 JP JP34781193A patent/JP3167518B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0973217A2 (en) * | 1998-07-13 | 2000-01-19 | Ngk Insulators, Ltd. | Lithium transition metal compound for lithium secondary battery |
| EP0973217A3 (en) * | 1998-07-13 | 2000-06-28 | Ngk Insulators, Ltd. | Lithium transition metal compound for lithium secondary battery |
| US6368750B1 (en) | 1998-07-13 | 2002-04-09 | Ngk Insulators, Ltd. | Lithium secondary battery |
| WO2019171623A1 (en) * | 2018-03-07 | 2019-09-12 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary batteries, and lithium ion secondary battery |
| JP2019160801A (en) * | 2018-03-07 | 2019-09-19 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
| JP6601593B1 (en) * | 2018-03-07 | 2019-11-06 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| US11646412B2 (en) | 2018-03-07 | 2023-05-09 | Hitachi Metals, Ltd. | Cathode active material used for lithium ion secondary battery and lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3167518B2 (en) | 2001-05-21 |
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