JPH06275275A - Nonaqueous battery - Google Patents
Nonaqueous batteryInfo
- Publication number
- JPH06275275A JPH06275275A JP5084134A JP8413493A JPH06275275A JP H06275275 A JPH06275275 A JP H06275275A JP 5084134 A JP5084134 A JP 5084134A JP 8413493 A JP8413493 A JP 8413493A JP H06275275 A JPH06275275 A JP H06275275A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- boron
- active material
- composite oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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】本発明は非水系電池に係わり、詳
しくは信頼性（安全性）の向上を目的とした正極活物質
の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous battery, and more particularly to improvement of a positive electrode active material for the purpose of improving reliability (safety).
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム電池等の非水系電池が、ニッケル・カドミウム
電池等の水系電池と異なり水の分解電圧を考慮する必要
がないため高電圧設計が可能であるなどの理由から、脚
光を浴びつつある。2. Description of the Related Art In recent years,
Unlike non-aqueous batteries such as nickel-cadmium batteries, it is not necessary to consider the decomposition voltage of water, and non-aqueous batteries such as lithium batteries are in the limelight because they can be designed at high voltage.
【０００３】而して、従来、非水系電池の正極活物質の
一つとして、リチウムに対して４Ｖ以上の高電位を示す
ＬｉＣｏＯ2 が提案されている。因みに、このＬｉＣｏ
Ｏ2は、一般にリチウム化合物とコバルト化合物との混
合物を焼成することにより得られる。Thus, conventionally, LiCoO 2 has been proposed as one of the positive electrode active materials for non-aqueous batteries, which exhibits a high potential of 4 V or more with respect to lithium. By the way, this LiCo
O 2 is generally obtained by firing a mixture of a lithium compound and a cobalt compound.
【０００４】ところで、ＬｉＣｏＯ2 には、放電容量が
ＬｉＮｉＯ2 に比し小さいとともに、高価なコバルト化
合物を原材料として使用するため製造コストが高くつく
という問題があるが、これらの問題は原材料として比較
的安価なニッケル化合物を過半量併用することにより解
消される。この場合の正極活物質は、ＬｉＣｏＯ2 中の
コバルト原子の過半数がニッケル原子で置換された構造
の金属複合酸化物となり、組成式ＬｉＮｉｐＣｏ1-ｐＯ
2 （１／２＜ｐ＜１）、より正確には組成式ＬｉｘＮｉ
ｐＣｏ1-ｐＯ2 （０＜ｘ＜１．３（但しｘは充放電に伴
い変動する値）；１／２＜ｐ≦１）で表される。By the way, LiCoO 2 has a problem that the discharge capacity is smaller than that of LiNiO 2 and the manufacturing cost is high because an expensive cobalt compound is used as a raw material. It can be solved by using an inexpensive nickel compound together in a majority amount. In this case, the positive electrode active material is a metal composite oxide having a structure in which a majority of cobalt atoms in LiCoO 2 are replaced with nickel atoms, and the composition formula LiNipCo 1- pO
2 (1/2 <p <1), more accurately the composition formula LixNi
pCo 1− pO 2 (0 <x <1.3 (where x is a value that varies with charging / discharging); 1/2 <p ≦ 1).
【０００５】しかしながら、この金属複合酸化物は、短
絡等により電池温度が少し上昇すると電解液と反応（発
熱反応）するため、電池温度が異常に上昇する虞れがあ
ることが分かった。However, it has been found that the metal composite oxide reacts with the electrolytic solution (exothermic reaction) when the battery temperature slightly rises due to a short circuit or the like, so that the battery temperature may rise abnormally.
【０００６】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
と電解液との反応開始温度が高いため、内部短絡などに
より電池温度がある程度上昇した場合でも正極活物質と
電解液とが反応しにくいため異常発熱しにくい、信頼性
（安全性）の高い非水系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 raise the reaction temperature of the positive electrode active material and the electrolytic solution at a high temperature, so that the battery temperature is increased to some extent due to an internal short circuit. An object of the present invention is to provide a highly reliable (safety) non-aqueous battery in which abnormal heat generation is unlikely to occur because the positive electrode active material and the electrolytic solution do not easily react even when the temperature rises.
【０００７】[0007]
【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系電池（以下、「本発明電池」と称
する。）は、負極にリチウムイオンを吸蔵放出可能な材
料又は金属リチウムが使用されてなる非水系電池におい
て、正極活物質として、組成式ＬｉｘＢｙＮｉｚＣｏｗ
Ｏａ（但し、０＜ｘ＜１．３、ｙ＞０、０≦ｗ＜ｚ、ｙ
＋ｚ＋ｗ＝１、１．８≦ａ≦２．２である。）で表され
るホウ素含有金属複合酸化物が使用されてなる。A non-aqueous battery according to the present invention for achieving the above object (hereinafter referred to as "the battery of the present invention") is a material or metallic lithium capable of inserting and extracting lithium ions in a negative electrode. In the non-aqueous battery, the composition formula LixByNizCow is used as the positive electrode active material.
Oa (however, 0 <x <1.3, y> 0, 0 ≦ w <z, y
+ Z + w = 1, 1.8 ≦ a ≦ 2.2. ) The boron-containing metal composite oxide represented by the formula (1) is used.
【０００８】本発明が改良せんとする電池（対象電池）
は、負極に金属リチウム、又は、リチウム合金、コーク
ス、黒鉛などのリチウムイオンを吸蔵放出可能な材料が
使用されてなる非水系電池である。そして、本発明で
は、この対象電池の正極活物質として、上記組成式で表
されるホウ素含有金属複合酸化物が使用される。このホ
ウ素含有金属複合酸化物は、先に述べた金属複合酸化物
ＬｉｘＮｉｐＣｏ1-ｐＯ 2 中のニッケル又はコバルトの
一部がホウ素で置換された構造を有するものであり、こ
のホウ素の導入により、理由は定かでないが、電解液と
の反応開始温度が高くなったものである。Battery to be improved by the present invention (target battery)
Is metallic lithium, lithium alloy, or coke on the negative electrode.
Materials that can store and release lithium ions such as graphite and graphite
It is a non-aqueous battery used. And in the present invention
Is the positive electrode active material of this target battery and is expressed by the above composition formula.
The boron-containing metal composite oxide is used. This ho
The metal complex oxide containing arsenic is the metal complex oxide described above.
LixNipCo1-pO 2Of nickel or cobalt
Part of which has a structure in which boron is substituted,
Although the reason is not clear due to the introduction of boron,
The reaction initiation temperature of is higher.
【０００９】好適なホウ素含有金属複合酸化物は、ホウ
素の含有量を示す上記組成式中のｙが０．０１〜０．３
のものである。ホウ素含有量が少なくてｙが０．０１よ
り小さいと、電解液との反応開始温度がさほど上昇せ
ず、またホウ素含有量が多くてｙが０．３より大きい
と、活物質として機能しないホウ素の占める比率が過大
となり、放電容量が低下するので、ともに好ましくな
い。A preferred boron-containing metal composite oxide is such that y in the above composition formula showing the content of boron is 0.01 to 0.3.
belongs to. When the boron content is low and y is less than 0.01, the reaction initiation temperature with the electrolytic solution does not rise so much, and when the boron content is high and y is more than 0.3, boron does not function as an active material. Is too large and the discharge capacity is reduced, which is not preferable.
【００１０】本発明におけるホウ素含有金属複合酸化物
は、例えばリチウムの水酸化物、酸化物、炭酸塩又は硝
酸塩と、ニッケルの水酸化物、酸化物、炭酸塩又は硝酸
塩と、コバルトの水酸化物、酸化物、炭酸塩又は硝酸塩
と、三酸化二ホウ素等のホウ素化合物とを所定の割合で
混合し、焼成することにより得られる。The boron-containing metal composite oxide in the present invention is, for example, lithium hydroxide, oxide, carbonate or nitrate, nickel hydroxide, oxide, carbonate or nitrate, and cobalt hydroxide. , An oxide, a carbonate or a nitrate, and a boron compound such as diboron trioxide are mixed at a predetermined ratio, and the mixture is fired.
【００１１】本発明電池は、上述した如く、負極にリチ
ウムイオンを吸蔵放出可能な材料又は金属リチウムが使
用されてなる非水系電池の正極活物質として、電解液と
の反応開始温度の高いホウ素含有金属複合酸化物を使用
した点に最大の特徴を有する。それゆえ、本発明電池を
構成する電解液等の他の部材については特に制限され
ず、非水系電池用として従来使用され、或いは提案され
ている種々の材料を制限無く使用することが可能であ
る。As described above, the battery of the present invention contains boron having a high reaction initiation temperature with an electrolytic solution as a positive electrode active material of a non-aqueous battery in which a material capable of inserting and extracting lithium ions or metallic lithium is used for the negative electrode. The greatest feature is that a metal composite oxide is used. Therefore, other members such as the electrolytic solution constituting the battery of the present invention are not particularly limited, and various materials conventionally used for non-aqueous batteries or proposed can be used without limitation. .
【００１２】たとえば、電解液としては、プロピレンカ
ーボネート、エチレンカーボネート、ビニレンカーボネ
ートなどの有機溶媒や、これらとジメチルカーボネー
ト、ジエチルカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、エトキシメトキシエタ
ンなどの低沸点溶媒との混合溶媒に、ＬｉＰＦ6 、Ｌｉ
ＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 などの電解液溶質を０．７
〜１．５Ｍ（モル／リットル）、就中１Ｍの割合で溶か
した溶液が例示される。For example, the electrolytic solution may be an organic solvent such as propylene carbonate, ethylene carbonate or vinylene carbonate, or dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane or ethoxymethoxyethane. In a mixed solvent with a low boiling point solvent such as LiPF 6 , Li
Electrolyte solutes such as ClO 4 and LiCF 3 SO 3 are added to 0.7
An example is a solution dissolved at a ratio of up to 1.5 M (mol / liter), especially 1 M.
【００１３】[0013]
【作用】本発明電池においては、電解液との反応開始温
度が高いホウ素含有金属複合酸化物が正極活物質として
使用されているので、内部短絡等により電池温度が或る
程度上昇しても当該正極活物質と電解液との反応（発熱
反応）が起こりにくい。In the battery of the present invention, since the boron-containing metal composite oxide having a high reaction initiation temperature with the electrolytic solution is used as the positive electrode active material, even if the battery temperature rises to some extent due to an internal short circuit, The reaction (exothermic reaction) between the positive electrode active material and the electrolytic solution is unlikely to occur.
【００１４】[0014]
【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。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 following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００１５】（実施例１）扁平型の非水系電池（本発明
電池）を作製した。Example 1 A flat non-aqueous battery (the battery of the present invention) was produced.
【００１６】〔正極の作製〕水酸化リチウム（ＬｉＯ
Ｈ）と三酸化二ホウ素（Ｂ2 Ｏ3 ）と水酸化ニッケル
（Ｎｉ（ＯＨ）2 ）と水酸化コバルト（Ｃｏ（Ｏ
Ｈ）2 ）とをＬｉ：Ｂ：Ｎｉ：Ｃｏの原子比１．０：
０．０１：０．５：０．４９の割合で乳鉢中で混合し、
８００°Ｃで２０時間焼成して組成式ＬｉＢ0.01Ｎｉ
0.5 Ｃｏ0.49Ｏ2 で表される正極活物質としてのホウ素
含有金属複合酸化物粉末を得た。[Preparation of Positive Electrode] Lithium hydroxide (LiO
H), diboron trioxide (B 2 O 3 ), nickel hydroxide (Ni (OH) 2 ) and cobalt hydroxide (Co (O
H) 2 ) and Li: B: Ni: Co atomic ratio 1.0:
Mix in a mortar at a ratio of 0.01: 0.5: 0.49,
Composition formula LiB 0.01 Ni after firing at 800 ° C for 20 hours
A boron-containing metal composite oxide powder as a positive electrode active material represented by 0.5 Co 0.49 O 2 was obtained.
【００１７】次いで、このホウ素含有金属複合酸化物粉
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、重量比率９０：６：４で混
合して正極合剤を得た。この正極合剤を成形圧２トン／
ｃｍ2 で加圧成形した後、２５０°Ｃで加熱処理して、
直径２０ｍｍの円板状の正極を作製した。なお、正極集
電体として、ステンレス鋼板（ＳＵＳ３０４）を使用し
た。Next, the boron-containing metal composite oxide powder, 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 mixture. It was Molding pressure of this positive electrode mixture is 2 tons /
After pressure molding at cm 2 , heat treatment at 250 ° C,
A disk-shaped positive electrode having a diameter of 20 mm was produced. A stainless steel plate (SUS304) was used as the positive electrode current collector.
【００１８】〔負極の作製〕リチウム圧延板を打ち抜い
て、金属リチウムからなる直径２０ｍｍの円板状の負極
を作製した。なお、負極集電体として、ステンレス鋼板
（ＳＵＳ３０４）を使用した。[Preparation of Negative Electrode] A rolled lithium plate was punched out to prepare a disc-shaped negative electrode made of metallic lithium and having a diameter of 20 mm. A stainless steel plate (SUS304) was used as the negative electrode current collector.
【００１９】〔電解液の調製〕プロピレンカーボネート
（ＰＣ）と１，２−ジメトキシエタン（ＤＭＥ）との等
体積混合溶媒に、ＬｉＣｌＯ4 （過塩素酸リチウム）を
１モル／リットルの割合で溶かして電解液を調製した。[Preparation of Electrolyte Solution] LiClO 4 (lithium perchlorate) was dissolved in an equal volume mixed solvent of propylene carbonate (PC) and 1,2-dimethoxyethane (DME) at a ratio of 1 mol / liter. An electrolytic solution was prepared.
【００２０】〔電池の作製〕以上の正負両極及び電解液
を用いて扁平型の本発明電池ＢＡ１（電池寸法：直径２
４ｍｍ、厚み：３．０ｍｍ）を作製した。セパレータと
しては、ポリプロピレン製の微多孔膜（ポリプラスチッ
クス社製、商品名「セルガード」）を使用し、これに先
に述べた電解液を含浸させた。[Production of Battery] Using the positive and negative electrodes and the electrolytic solution described above, the flat battery BA1 of the present invention (battery size: diameter 2
4 mm, thickness: 3.0 mm) was produced. As the separator, a polypropylene microporous film (manufactured by Polyplastics Co., trade name “Celguard”) was used and impregnated with the electrolytic solution described above.
【００２１】図１は作製した本発明電池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 manufactured battery BA1 of the present invention. The battery BA1 of the present invention shown in FIG.
It comprises a positive electrode 1, a negative electrode 2, a separator 3 separating these electrodes 1 and 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.
【００２２】正極１及び負極２は、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容されており、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、電池内部で生じた化学エネル
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 which face each other with a separator 3 impregnated with an electrolytic solution interposed therebetween, and the positive electrode 1 includes a positive electrode current collector 6. To the positive electrode can 4 and the negative electrode 2 to the negative electrode can 5 via the negative electrode current collector 7 so that the chemical energy generated inside the battery can be output as electrical energy from both terminals of the positive electrode can 4 and the negative electrode can 5 to the outside. You can take it out.
【００２３】（実施例２）水酸化リチウムと三酸化二ホ
ウ素と水酸化ニッケルと水酸化コバルトとのＬｉ：Ｂ：
Ｎｉ：Ｃｏの原子比を１．０：０．１：０．５：０．４
の割合に変えて作製した組成式ＬｉＢ0.1 Ｎｉ0.5 Ｃｏ
0.4 Ｏ2 で表されるホウ素含有金属複合酸化物粉末を正
極活物質として使用したこと以外は実施例１と同様にし
て、本発明電池ＢＡ２を作製した。Example 2 Li: B of lithium hydroxide, diboron trioxide, nickel hydroxide and cobalt hydroxide:
The atomic ratio of Ni: Co is 1.0: 0.1: 0.5: 0.4.
Of the composition formula LiB 0.1 Ni 0.5 Co
Battery BA2 of the present invention was produced in the same manner as in Example 1 except that the boron-containing metal composite oxide powder represented by 0.4 O 2 was used as the positive electrode active material.
【００２４】（実施例３）水酸化リチウムと三酸化二ホ
ウ素と水酸化ニッケルと水酸化コバルトとのＬｉ：Ｂ：
Ｎｉ：Ｃｏの原子比を１．０：０．２：０．５：０．３
の割合に変えて作製した組成式ＬｉＢ0.2 Ｎｉ0.5 Ｃｏ
0.3 Ｏ2 で表されるホウ素含有金属複合酸化物粉末を正
極活物質として使用したこと以外は実施例１と同様にし
て、本発明電池ＢＡ３を作製した。Example 3 Li: B of lithium hydroxide, diboron trioxide, nickel hydroxide and cobalt hydroxide:
The atomic ratio of Ni: Co is 1.0: 0.2: 0.5: 0.3.
Composition formula LiB 0.2 Ni 0.5 Co
Battery BA3 of the present invention was produced in the same manner as in Example 1 except that the boron-containing metal composite oxide powder represented by 0.3 O 2 was used as the positive electrode active material.
【００２５】（実施例４）水酸化リチウムと三酸化二ホ
ウ素と水酸化ニッケルと水酸化コバルトとのＬｉ：Ｂ：
Ｎｉ：Ｃｏの原子比を１．０：０．３：０．５：０．２
の割合に変えて作製した組成式ＬｉＢ0.3 Ｎｉ0.5 Ｃｏ
0.2 Ｏ2 で表されるホウ素含有金属複合酸化物粉末を正
極活物質として使用したこと以外は実施例１と同様にし
て、本発明電池ＢＡ４を作製した。Example 4 Li: B of lithium hydroxide, diboron trioxide, nickel hydroxide and cobalt hydroxide:
The atomic ratio of Ni: Co is 1.0: 0.3: 0.5: 0.2.
Composition formula LiB 0.3 Ni 0.5 Co
A battery BA4 of the present invention was produced in the same manner as in Example 1 except that the boron-containing metal composite oxide powder represented by 0.2 O 2 was used as the positive electrode active material.
【００２６】（実施例５）水酸化リチウムと三酸化二ホ
ウ素と水酸化ニッケルと水酸化コバルトとのＬｉ：Ｂ：
Ｎｉ：Ｃｏの原子比を１．０：０．３５：０．５：０．
１５の割合に変えて作製した組成式ＬｉＢ0.35Ｎｉ0.5
Ｃｏ0.15Ｏ2 で表されるホウ素含有金属複合酸化物粉末
を正極活物質として使用したこと以外は実施例１と同様
にして、本発明電池ＢＡ５を作製した。Example 5 Li: B of lithium hydroxide, diboron trioxide, nickel hydroxide and cobalt hydroxide:
The atomic ratio of Ni: Co is 1.0: 0.35: 0.5: 0.
The composition formula LiB 0.35 Ni 0.5 prepared by changing the ratio to 15
A battery BA5 of the present invention was produced in the same manner as in Example 1 except that the boron-containing metal composite oxide powder represented by Co 0.15 O 2 was used as the positive electrode active material.
【００２７】（比較例）水酸化リチウムと水酸化ニッケ
ルと水酸化コバルトとをモル比１．０：０．５：０．５
の割合で乳鉢中で混合し、８００°Ｃで２０時間焼成し
て組成式ＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 で表される正極活物
質としてのホウ素を含有しない金属複合酸化物粉末を得
た。この金属複合酸化物粉末を正極活物質として使用し
たこと以外は実施例１と同様にして、比較電池ＢＣ１を
作製した。(Comparative Example) Lithium hydroxide, nickel hydroxide and cobalt hydroxide were used in a molar ratio of 1.0: 0.5: 0.5.
Were mixed in a mortar at a ratio of 100 ° C. and baked at 800 ° C. for 20 hours to obtain a boron-free metal composite oxide powder as a positive electrode active material represented by a composition formula LiNi 0.5 Co 0.5 O 2 . A comparative battery BC1 was produced in the same manner as in Example 1 except that this metal composite oxide powder was used as the positive electrode active material.
【００２８】〔ホウ素含有量と反応開始温度との関係〕
上記実施例１〜５及び比較例で作製した各金属複合酸化
物粉末について、充電後の正極を電解液に浸漬し、徐々
に温度を上げていって、発熱反応が開始する温度を熱分
析により測定した。結果を図２に示す。[Relationship between Boron Content and Reaction Start Temperature]
For each of the metal composite oxide powders produced in Examples 1 to 5 and Comparative Example, the positive electrode after charging was immersed in an electrolytic solution, the temperature was gradually raised, and the temperature at which the exothermic reaction started was determined by thermal analysis. It was measured. The results are shown in Figure 2.
【００２９】図２は、ホウ素含有量と反応開始温度との
関係を、縦軸に反応開始温度（°Ｃ）を、横軸にホウ素
含有量（ｙ in 組成式ＬｉＢy Ｎｉ0.5 Ｃｏ(0.5-y) Ｏ
2 ）をとって示したグラフであり、同図よりホウ素含有
量が増加するにつれて反応開始温度が高くなること、及
び、反応開始温度を２１０°Ｃ以上にするためには、ｙ
が０．０１以上のホウ素含有金属複合酸化物を使用すれ
ばよいことが分かる。FIG. 2 shows the relationship between the boron content and the reaction start temperature, the vertical axis represents the reaction start temperature (° C), and the horizontal axis represents the boron content (y in composition formula LiB y Ni 0.5 Co ( 0.5- y) O
2 ) is a graph showing that the reaction initiation temperature becomes higher as the boron content increases and the reaction initiation temperature is set to 210 ° C. or higher as shown in FIG.
It is understood that a boron-containing metal composite oxide having a ratio of 0.01 or more should be used.
【００３０】〔ホウ素含有量と放電容量との関係〕室温
（２５°Ｃ）下、３ｍＡで充電終止電圧４．２Ｖまで充
電した後、３ｍＡで放電終止電圧２．７５Ｖまで放電し
て、ホウ素含有量と放電容量との関係を調べた。結果を
図３に示す。[Relationship between Boron Content and Discharge Capacity] At room temperature (25 ° C.), the battery was charged at 3 mA to a charge end voltage of 4.2 V, then discharged at 3 mA to a discharge end voltage of 2.75 V, and contained boron. The relationship between quantity and discharge capacity was investigated. The results are shown in Fig. 3.
【００３１】図３は、ホウ素含有量と放電容量との関係
を、縦軸に正極活物質単位重量当たりの放電容量（ｍＡ
ｈ／ｇ）を、横軸にホウ素含有量（ｙ in 組成式ＬｉＢ
y Ｎｉ0.5 Ｃｏ(0.5-y) Ｏ2 ）をとって示したグラフで
あり、同図よりホウ素含有量が増加するにつれて放電容
量が減少すること、及び、放電容量を１６５ｍＡｈ／ｇ
にするためにはｙが０．３以下のホウ素含有金属複合酸
化物を使用すればよいことが分かる。FIG. 3 shows the relationship between the boron content and the discharge capacity, the vertical axis being the discharge capacity per unit weight of the positive electrode active material (mA).
h / g), the horizontal axis represents the boron content (y in composition formula LiB
y Ni 0.5 Co (0.5-y) O 2 ), showing that the discharge capacity decreases as the boron content increases, and the discharge capacity is 165 mAh / g.
In order to achieve this, it is understood that a boron-containing metal composite oxide having y of 0.3 or less may be used.
【００３２】これら図２及び図３に示す結果から、反応
開始温度が２１０°Ｃ以上であって、且つ、放電容量が
１６５ｍＡｈ／ｇ以上のホウ素含有金属複合酸化物は、
組成式ＬｉＢy Ｎｉ0.5 Ｃｏ(0.5-y) Ｏ2 中のｙが０．
０１〜０．３の範囲内にあるものであることが分かる。From the results shown in FIGS. 2 and 3, the boron-containing metal composite oxide having a reaction initiation temperature of 210 ° C. or higher and a discharge capacity of 165 mAh / g or higher was
In the composition formula LiB y Ni 0.5 Co (0.5-y) O 2 , y is 0.
It can be seen that it is within the range of 01 to 0.3.
【００３３】叙上の実施例では、本発明を扁平型の非水
系電池に適用する場合を例に挙げて説明したが、電池の
形状は特に限定されず、円筒型、角型など種々の形状の
非水系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 the flat type non-aqueous battery has been described as an example, but the shape of the battery is not particularly limited, and various shapes such as a cylindrical shape and a square shape are used. It is applicable to the non-aqueous battery of.
【００３４】また、ホウ素含有金属複合酸化物の原料と
してリチウム、ニッケル、コバルトの各水酸化物を使用
する場合を一例として説明したが、先に示した他の材料
を使用してなるホウ素含有金属複合酸化物を使用した場
合においても上述した本発明電池ＢＡ１〜ＢＡ５と同様
の信頼性の高い非水系電池が得られる。The case where each of the hydroxides of lithium, nickel, and cobalt is used as the raw material of the boron-containing metal composite oxide has been described as an example. Even when the complex oxide is used, a highly reliable non-aqueous battery similar to the batteries BA1 to BA5 of the present invention described above can be obtained.
【００３５】[0035]
【発明の効果】本発明電池は、正極活物質として電解液
との反応開始温度の高い特定組成のホウ素含有金属複合
酸化物が使用されているので、内部短絡などが起こった
場合でも異常発熱しにくく信頼性（安全性）が高いな
ど、本発明は優れた特有の効果を奏する。The battery of the present invention uses a boron-containing metal composite oxide of a specific composition having a high reaction initiation temperature with an electrolytic solution as a positive electrode active material, so that abnormal heat generation occurs even when an internal short circuit occurs. The present invention has excellent unique effects such as difficulty and high reliability (safety).
【図１】扁平型の非水系電池（本発明電池）の断面図で
ある。FIG. 1 is a cross-sectional view of a flat non-aqueous battery (the battery of the present invention).
【図２】ホウ素含有量と反応開始温度との関係を示すグ
ラフである。FIG. 2 is a graph showing the relationship between the boron content and the reaction initiation temperature.
【図３】ホウ素含有量と放電容量との関係を示すグラフ
である。FIG. 3 is a graph showing the relationship between boron content and discharge capacity.
ＢＡ１ 非水系電池（本発明電池） １ 正極 ２ 負極 ３ セパレータ BA1 non-aqueous battery (battery of the present invention) 1 positive electrode 2 negative electrode 3 separator
フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目18番地 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18番地 三洋 電機株式会社内Front page continuation (72) Inventor Koji Nishio 2-18 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-18 Keihan Hondori, Moriguchi, Osaka Sanyo Electric Co., Ltd.
Claims (2)
料又は金属リチウムが使用されてなる非水系電池におい
て、正極活物質として、組成式ＬｉｘＢｙＮｉｚＣｏｗ
Ｏａ（但し、０＜ｘ＜１．３、ｙ＞０、０≦ｗ＜ｚ、ｙ
＋ｚ＋ｗ＝１、１．８≦ａ≦２．２である。）で表され
るホウ素含有金属複合酸化物が使用されていることを特
徴とする非水系電池。1. In a non-aqueous battery in which a material capable of inserting and extracting lithium ions or metallic lithium is used for a negative electrode, a composition formula LixByNizCow is used as a positive electrode active material.
Oa (however, 0 <x <1.3, y> 0, 0 ≦ w <z, y
+ Z + w = 1, 1.8 ≦ a ≦ 2.2. ) A non-aqueous battery comprising a boron-containing metal composite oxide represented by
る請求項１記載の非水系電池。2. The non-aqueous battery according to claim 1, wherein y in the composition formula is 0.01 to 0.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5084134A JPH06275275A (en) | 1993-03-17 | 1993-03-17 | Nonaqueous battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5084134A JPH06275275A (en) | 1993-03-17 | 1993-03-17 | Nonaqueous battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06275275A true JPH06275275A (en) | 1994-09-30 |
Family
ID=13822034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5084134A Pending JPH06275275A (en) | 1993-03-17 | 1993-03-17 | Nonaqueous battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06275275A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01125392A (en) * | 1979-09-10 | 1989-05-17 | Ciba Geigy Ag | Ammonium methyl methanephosphonate and its production |
| JPH08213052A (en) * | 1994-08-04 | 1996-08-20 | Seiko Instr Inc | Nonaqueous electrolyte secondary battery |
| US5989744A (en) * | 1996-07-31 | 1999-11-23 | Sony Corporation | Non-aqueous electrolyte secondary cell |
| EP1055389A2 (en) * | 1999-05-26 | 2000-11-29 | Miele & Cie. GmbH & Co. | Programmable dishwasher with device for drying the dishes |
| US6855461B2 (en) | 2001-06-15 | 2005-02-15 | Kureha Chemical Industry Co., Ltd. | Cathode material for lithium rechargeable batteries |
| US6921609B2 (en) | 2001-06-15 | 2005-07-26 | Kureha Chemical Industry Co., Ltd. | Gradient cathode material for lithium rechargeable batteries |
| EP0918041A4 (en) * | 1996-08-12 | 2006-05-17 | Toda Kogyo Corp | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
-
1993
- 1993-03-17 JP JP5084134A patent/JPH06275275A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01125392A (en) * | 1979-09-10 | 1989-05-17 | Ciba Geigy Ag | Ammonium methyl methanephosphonate and its production |
| JPH08213052A (en) * | 1994-08-04 | 1996-08-20 | Seiko Instr Inc | Nonaqueous electrolyte secondary battery |
| US5989744A (en) * | 1996-07-31 | 1999-11-23 | Sony Corporation | Non-aqueous electrolyte secondary cell |
| EP0918041A4 (en) * | 1996-08-12 | 2006-05-17 | Toda Kogyo Corp | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
| EP2058281A3 (en) * | 1996-08-12 | 2009-12-23 | Toda Kogyo Corporation | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
| EP1055389A2 (en) * | 1999-05-26 | 2000-11-29 | Miele & Cie. GmbH & Co. | Programmable dishwasher with device for drying the dishes |
| EP1055389A3 (en) * | 1999-05-26 | 2002-05-08 | Miele & Cie. GmbH & Co. | Programmable dishwasher with device for drying the dishes |
| US6855461B2 (en) | 2001-06-15 | 2005-02-15 | Kureha Chemical Industry Co., Ltd. | Cathode material for lithium rechargeable batteries |
| US6921609B2 (en) | 2001-06-15 | 2005-07-26 | Kureha Chemical Industry Co., Ltd. | Gradient cathode material for lithium rechargeable batteries |
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