JP3197763B2 - Non-aqueous battery - Google Patents
Non-aqueous batteryInfo
- Publication number
- JP3197763B2 JP3197763B2 JP25762394A JP25762394A JP3197763B2 JP 3197763 B2 JP3197763 B2 JP 3197763B2 JP 25762394 A JP25762394 A JP 25762394A JP 25762394 A JP25762394 A JP 25762394A JP 3197763 B2 JP3197763 B2 JP 3197763B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- mol
- powder
- carbonate
- 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
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水系電池に係わり、
詳しくは非水系電池の高温における保存特性を改善する
ことを目的とした、正極の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous battery,
More specifically, the present invention relates to improvement of a positive electrode for the purpose of improving storage characteristics of a nonaqueous battery at a high temperature.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
金属リチウム又はリチウムイオンを吸蔵、放出し得る合
金若しくは炭素材料などを負極材料とし、リチウム−遷
移金属複合酸化物を正極材料とする非水系電池が、高エ
ネルギー密度を有する電池として注目されつつある。2. Description of the Related Art In recent years,
A non-aqueous battery using an alloy or a carbon material capable of occluding and releasing lithium metal or lithium ion as a negative electrode material and a lithium-transition metal composite oxide as a positive electrode material has been attracting attention as a battery having a high energy density.
【０００３】上記リチウム−遷移金属複合酸化物として
は、ＬｉＭｎＯ2 、ＬｉＦｅＯ2 及びＬｉX Ｎｉ1-Y Ｃ
ｏY ＯZ （但し、０＜Ｘ＜１．３、０≦Ｙ≦１、１．８
＜Ｚ＜２．２）などがよく知られているが、なかでも、
ＬｉX Ｎｉ1-Y ＣｏY ＯZ は、容量が大きく、最も注目
されている正極活物質の一つである。The lithium-transition metal composite oxides include LiMnO 2 , LiFeO 2 and Li x Ni 1 -YC
o Y O Z (where 0 <X <1.3, 0 ≦ Y ≦ 1, 1.8
<Z <2.2) and the like are well known.
Li X Ni 1-Y Co Y O Z is large capacity, is one of the positive electrode active material has received the most attention.
【０００４】しかしながら、ＬｉX Ｎｉ1-Y ＣｏY ＯZ
を正極活物質として用いた非水系電池を長期間高温で保
存したり、特に二次電池の場合において、充電後の状態
（正極活物質からリチウムイオンが放出された状態）で
長期間高温で保存したりすると、電池の内部抵抗が上昇
する。このように内部抵抗が上昇するのは、次の理由に
よると考えられる。[0004] However, Li X Ni 1-Y Co Y O Z
A non-aqueous battery using as a positive electrode active material can be stored at high temperature for a long time, especially in the case of a secondary battery, in a charged state (with lithium ions released from the positive electrode active material) for a long time at high temperature Doing so increases the internal resistance of the battery. The increase in the internal resistance is considered to be as follows.
【０００５】すなわち、充電時には上記正極活物質から
リチウムが放出されて、充電後は活物質中のニッケル又
はコバルトの酸化数が３を超え、また放電時にも活物質
中のニッケル又はコバルトの酸化数が３を超えている。
更に、一次電池においても放電時には活物質中のニッケ
ル又はコバルトの酸化数が３を超えている。このように
ニッケル又はコバルトの酸化数が３を超えると、これら
の正極活物質の触媒作用により電解液が分解してガスが
発生し、この発生したガスにより、正極の極板形状に変
形が起こり、正極活物質層と芯体（集電体）などとの密
着性が低下して内部抵抗が上昇するのである。That is, lithium is released from the positive electrode active material during charging, the oxidation number of nickel or cobalt in the active material exceeds 3 after charging, and the oxidation number of nickel or cobalt in the active material also during discharging. Exceeds three.
Furthermore, even in the primary battery, the oxidation number of nickel or cobalt in the active material exceeds 3 at the time of discharging. When the oxidation number of nickel or cobalt exceeds 3, the electrolytic solution is decomposed by the catalytic action of these positive electrode active materials and gas is generated, and the generated gas causes deformation of the positive electrode plate shape. In addition, the adhesion between the positive electrode active material layer and the core (current collector) or the like decreases, and the internal resistance increases.
【０００６】このように、この種の正極活物質を使用し
た非水系電池には、高温下で長期間放置される自動車電
話などの電源としては不向きであるという問題があった
ため、その改善が要望されていた。As described above, the non-aqueous battery using such a positive electrode active material has a problem that it is unsuitable as a power source for a mobile phone or the like which is left at a high temperature for a long time. It had been.
【０００７】本発明は、かかる要望に応えるべくなされ
たものであって、その目的とするところは、高温保存特
性に優れたＬｉX Ｎｉ1-Y ＣｏY ＯZ を正極活物質とす
る非水系電池を提供するにある。The present invention has been made to meet such a demand, and an object of the present invention is to provide a non-aqueous system using Li X Ni 1 -Y Co YO Z excellent in high-temperature storage characteristics as a positive electrode active material. To provide batteries.
【０００８】[0008]
【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、リチウムを負極活物質とする負極と、式：Ｌ
ｉX Ｎｉ1-Y ＭY ＯZ（但し、０＜Ｘ＜１．３、０≦Ｙ
≦１、１．８＜Ｚ＜２．２であり、且つ、Ｍはコバルト
又はコバルトを含む２種以上の遷移金属である。）で表
されるリチウム−遷移金属複合酸化物を正極活物質とす
る正極とを備える非水系電池において、前記正極活物質
に対して、ナトリウム、マグネシウム、アルミニウム、
カリウム、カルシウム、スカンジウム、チタン、バナジ
ウム、クロム、マンガン、鉄、コバルト、ニッケル、銅
及び亜鉛よりなる群から選ばれた金属の塩、及び／又
は、マグネシウム、アルミニウム、カルシウム、スカン
ジウム、チタン、バナジウム、クロム、マンガン、鉄、
コバルト、ニッケル、銅及び亜鉛よりなる群から選ばれ
た金属の水酸化物の１種又は２種以上が、総量で０．１
〜２０モル％添加されてなる。In order to achieve the above object, a non-aqueous battery according to the present invention (hereinafter referred to as "battery of the present invention") comprises: a negative electrode having lithium as a negative electrode active material;
i X Ni 1-Y M Y O Z (where 0 <X <1.3, 0 ≦ Y
≦ 1, 1.8 <Z <2.2, and M is cobalt or two or more transition metals containing cobalt. A) a positive electrode comprising a lithium-transition metal composite oxide as a positive electrode active material, wherein sodium, magnesium, aluminum,
A salt of a metal selected from the group consisting of potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc ; and / or
Is magnesium, aluminum, calcium, scan
Indium, titanium, vanadium, chromium, manganese, iron,
Selected from the group consisting of cobalt, nickel, copper and zinc
One or more of the metal hydroxides is 0.1% in total.
２０20 mol% is added.
【０００９】本発明における金属塩としては、塩化ナト
リウム、塩化カリウム、塩化マグネシウム、塩化銅等の
ハロゲン化物、シュウ酸ナトリウム、シュウ酸カリウム
等のシュウ酸塩、酢酸ナトリウム、酢酸カリウム等の酢
酸塩、炭酸ナトリウム、炭酸カリウム、炭酸アルミニウ
ム等の炭酸塩、硝酸銅等の硝酸塩、硫酸銅等の硫酸塩が
代表的なものとして例示されるが、なかでもシュウ酸
塩、酢酸塩、炭酸塩などの炭素を含有する塩が好まし
く、それらのなかでも炭酸塩が特に好ましく、炭酸塩の
なかでも炭酸コバルト及び炭酸ニッケルが最も好まし
い。The metal salt in the present invention includes halides such as sodium chloride, potassium chloride, magnesium chloride and copper chloride; oxalates such as sodium oxalate and potassium oxalate; acetates such as sodium acetate and potassium acetate; Representative examples include carbonates such as sodium carbonate, potassium carbonate, and aluminum carbonate, nitrates such as copper nitrate, and sulfates such as copper sulfate. Among them, carbon such as oxalate, acetate, and carbonate are exemplified. Are preferred, and among them, carbonates are particularly preferred, and among the carbonates, cobalt carbonate and nickel carbonate are most preferred.
【００１０】金属塩及び／又は金属水酸化物の添加量
が、正極活物質に対して総量で０．１〜２０モル％（正
極活物質１００モル部に対して０．１〜２０モル部）に
規制されるのは、０．１モル％未満では添加効果（触媒
毒として働き電解液の分解を抑制する効果）が充分に発
現されず、一方２０モル％を超えると、これらの金属塩
及び金属水酸化物の導電性が低いことに起因して電池の
内部抵抗が上昇するとともに、充放電時の正極における
リチウムの拡散が悪くなるため充放電効率が低下するか
らである。The total amount of the metal salt and / or metal hydroxide added is 0.1 to 20 mol% with respect to the positive electrode active material (0.1 to 20 mol parts per 100 mol parts of the positive electrode active material). If the content is less than 0.1 mol%, the effect of addition (the effect of acting as a catalyst poison and suppressing the decomposition of the electrolytic solution) is not sufficiently exhibited, while if it exceeds 20 mol%, these metal salts and This is because the internal resistance of the battery increases due to the low conductivity of the metal hydroxide, and the diffusion of lithium in the positive electrode during charging and discharging deteriorates, thereby lowering the charging and discharging efficiency.
【００１１】金属塩又は金属水酸化物は、それぞれ必要
に応じて２種以上添加しても良い。この場合において
も、それらの総量を、正極活物質に対して０．１〜２０
モル％に規制する必要がある。Two or more metal salts or metal hydroxides may be added as necessary. Also in this case, the total amount thereof is 0.1 to 20 with respect to the positive electrode active material.
It is necessary to regulate to mol%.
【００１２】本発明におけるリチウムを負極活物質とす
る負極としては、金属リチウム、及び、リチウムイオン
を吸蔵、放出し得る合金又は炭素材料を電極材料として
用いたものが例示される。Examples of the negative electrode using lithium as the negative electrode active material in the present invention include those using metal lithium and an alloy or carbon material capable of occluding and releasing lithium ions as an electrode material.
【００１３】本発明は、ＬｉX Ｎｉ1-Y ＣｏY ＯZ を正
極活物質として用いた場合に問題となっていた電解液の
分解を、金属塩及び／又は金属水酸化物を正極活物質に
添加することにより抑制し、もって非水系電池の高温下
での保存特性を改善することに成功したものである。そ
れゆえ、電解液など、電池を構成する他の部材について
は従来非水系電池用として提案され、或いは実用されて
いる種々の材料を特に制限なく用いることが可能であ
る。The present invention, Li X Ni 1-Y Co Y O Z decomposition of the electrolytic solution, which has been a problem when using as a positive electrode active material, the positive electrode active material a metal salt and / or metal hydroxide To improve the storage characteristics of non-aqueous batteries at high temperatures. Therefore, as for other members constituting the battery, such as an electrolytic solution, it is possible to use various materials which have been conventionally proposed or practically used for non-aqueous batteries without any particular limitation.
【００１４】非水電解液としては、エチレンカーボネー
ト、ビニレンカーボネート、プロピ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 、ＬｉＣｌＯ4、
ＬｉＣＦ3 ＳＯ3 などの溶質を０．７〜１．５Ｍ（モル
／リットル）の割合で溶かした溶液が例示される。Examples of the non-aqueous electrolyte include organic solvents such as ethylene carbonate, vinylene carbonate and propylene carbonate, and dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2
- diethoxyethane, in a mixed solvent of low boiling point solvent such as ethoxymethoxy ethane, LiPF 6, LiClO 4,
A solution in which a solute such as LiCF 3 SO 3 is dissolved at a ratio of 0.7 to 1.5 M (mol / liter) is exemplified.
【００１５】[0015]
【作用】本発明においては、金属塩及び／又は金属水酸
化物が、電解液の分解反応において触媒毒として働くの
で、長期間保存しても（特に、二次電池にあって充電後
の状態で長期間保存しても）、ガスが発生しにくい。こ
のため、正極の極板形状に変形が起こりにくくなり、電
池の内部抵抗の上昇が抑制される。In the present invention, since the metal salt and / or metal hydroxide acts as a catalyst poison in the decomposition reaction of the electrolytic solution, the metal salt and / or the metal hydroxide can be stored for a long period of time (especially in a secondary battery after charging. Gas is hardly generated. For this reason, deformation of the electrode plate of the positive electrode is less likely to occur, and an increase in the internal resistance of the battery is suppressed.
【００１６】[0016]
【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 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００１７】（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 nonaqueous battery (battery of the present invention) was manufactured.
【００１８】〔正極〕ＬｉＯＨと、Ｎｉ（ＯＨ）2 と、
Ｃｏ（ＯＨ）2 とをモル比２：１：１で乳鉢にて混合し
た後、この混合物を乾燥空気雰囲気下にて、７５０°Ｃ
で２０時間熱処理し、ＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 で示さ
れる正極活物質を得た。次いで、石川式らいかい乳鉢中
で粉砕して、平均粒径が５μｍの正極活物質粉末を得た
後、この正極活物質粉末に対して塩化カリウム粉末を
０．１モル％添加混合した。[Positive electrode] LiOH, Ni (OH) 2 ,
After mixing with Co (OH) 2 at a molar ratio of 2: 1: 1 in a mortar, the mixture was dried at 750 ° C. in a dry air atmosphere.
For 20 hours to obtain a positive electrode active material represented by LiNi 0.5 Co 0.5 O 2 . Next, the mixture was pulverized in an Ishikawa rai mortar to obtain a positive electrode active material powder having an average particle size of 5 μm, and then 0.1 mol% of potassium chloride powder was added to the positive electrode active material powder and mixed.
【００１９】次いで、上記塩化カリウム粉末を添加混合
した正極活物質粉末と、導電剤としてのアセチレンブラ
ックと、結着剤としてのポリフッ化ビニリデンとを、重
量比９０：６：４で混合して正極合剤を調製し、この正
極合剤を２トン／ｃｍ2 の圧力で直径２０ｍｍの円板状
に加圧成型した後、２５０°Ｃで２時間熱処理して正極
を作製した。Then, the positive electrode active material powder to which the potassium chloride powder was added and mixed, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were mixed at a weight ratio of 90: 6: 4 to form a positive electrode. A mixture was prepared, and this positive electrode mixture was press-molded into a disc having a diameter of 20 mm at a pressure of 2 ton / cm 2 , and then heat-treated at 250 ° C. for 2 hours to produce a positive electrode.
【００２０】〔負極〕所定の厚みを有する金属リチウム
の圧延板を直径２０ｍｍの円板状に打ち抜いて負極を作
製した。[Negative Electrode] A rolled sheet of metallic lithium having a predetermined thickness was punched into a disc having a diameter of 20 mm to produce a negative electrode.
【００２１】〔非水電解液〕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１Ｍ（モル／リットル）の割合で溶かし
て非水電解液を調製した。[Non-Aqueous Electrolyte] A non-aqueous electrolyte was prepared by dissolving lithium perchlorate at a ratio of 1 M (mol / L) in an equal volume mixed solvent of propylene carbonate and 1,2-dimethoxyethane.
【００２２】〔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を作製した（電
池寸法：直径２４．０ｍｍ、厚さ３．０ｍｍ）。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、これに先の非水電解液を含浸させた。[Preparation of Battery] A flat type battery BA1 of the present invention was prepared using the above positive and negative electrodes and a non-aqueous electrolyte (battery dimensions: diameter: 24.0 mm, thickness: 3.0 mm). In addition,
As the separator, a microporous polypropylene film (manufactured by Hoechst Celanese Co., Ltd., trade name "Celgard") was used, and this was impregnated with the above nonaqueous electrolyte.
【００２３】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 cross-sectional view schematically showing a battery BA1 of the present invention produced, and the battery BA1 of the present invention shown in FIG.
Is composed of a positive electrode 1, a negative electrode 2, a separator 3 separating the 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, an insulating packing 8 made of polypropylene, and the like. .
【００２４】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 with positive and negative bipolar cans 4 and 5 facing each other via a separator 3 impregnated with a non-aqueous electrolyte. 6, the negative electrode 2 is connected to the positive electrode can 4
Is connected to the negative electrode can 5 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.
【００２５】（実施例２〜５）正極活物質粉末に対する
塩化カリウム粉末の添加量を、それぞれ５モル％、１０
モル％、１５モル％、２０モル％としたこと以外は上記
実施例１と同様にして、正極を作製した。次いで、これ
らの正極を用いたこと以外は実施例１と同様にして、順
に本発明電池ＢＡ２（塩化カリウム粉末の添加量：５モ
ル％）、ＢＡ３（塩化カリウム粉末の添加量：１０モル
％）、ＢＡ４（塩化カリウム粉末の添加量：１５モル
％）、ＢＡ５（塩化カリウム粉末の添加量：２０モル
％）を作製した。Examples 2 to 5 The amounts of potassium chloride powder added to the positive electrode active material powder were 5 mol%, 10
A positive electrode was produced in the same manner as in Example 1 except that the mol%, 15 mol%, and 20 mol% were used. Then, in the same manner as in Example 1, except that these positive electrodes were used, the battery BA2 of the present invention (addition amount of potassium chloride powder: 5 mol%) and BA3 (addition amount of potassium chloride powder: 10 mol%) were sequentially obtained. And BA4 (addition amount of potassium chloride powder: 15 mol%) and BA5 (addition amount of potassium chloride powder: 20 mol%) were prepared.
【００２６】（実施例６〜１０）塩化カリウム粉末に代
えてシュウ酸カリウム粉末を用いたこと以外は実施例１
〜５と同様にして、正極を作製した。次いで、これらの
正極を用いたこと以外は実施例１と同様にして、順に本
発明電池ＢＡ６（シュウ酸カリウム粉末の添加量：０．
１モル％）、ＢＡ７（シュウ酸カリウム粉末の添加量：
５モル％）、ＢＡ８（シュウ酸カリウム粉末の添加量：
１０モル％）、ＢＡ９（シュウ酸カリウム粉末の添加
量：１５モル％）、ＢＡ１０（シュウ酸カリウム粉末の
添加量：２０モル％）を作製した。Examples 6 to 10 Example 1 except that potassium oxalate powder was used instead of potassium chloride powder.
In the same manner as in Examples 5 to 5, a positive electrode was produced. Then, in the same manner as in Example 1, except that these positive electrodes were used, the battery BA6 of the present invention (addition amount of the potassium oxalate powder: 0.1.
1 mol%), BA7 (addition amount of potassium oxalate powder:
5 mol%), BA8 (addition amount of potassium oxalate powder:
10 mol%), BA9 (addition amount of potassium oxalate powder: 15 mol%), and BA10 (addition amount of potassium oxalate powder: 20 mol%) were prepared.
【００２７】（実施例１１〜１５）塩化カリウム粉末に
代えて酢酸カリウム粉末を用いたこと以外は実施例１〜
５と同様にして、正極を作製した。次いで、これらの正
極を用いたこと以外は実施例１と同様にして、順に本発
明電池ＢＡ１１（酢酸カリウム粉末の添加量：０．１モ
ル％）、ＢＡ１２（酢酸カリウム粉末の添加量：５モル
％）、ＢＡ１３（酢酸カリウム粉末の添加量：１０モル
％）、ＢＡ１４（酢酸カリウム粉末の添加量：１５モル
％）、ＢＡ１５（酢酸カリウム粉末の添加量：２０モル
％）を作製した。Examples 11 to 15 Except that potassium acetate powder was used instead of potassium chloride powder,
In the same manner as in 5, a positive electrode was produced. Next, in the same manner as in Example 1 except that these positive electrodes were used, the battery BA11 of the present invention (addition amount of potassium acetate powder: 0.1 mol%) and BA12 (addition amount of potassium acetate powder: 5 mol) were sequentially used. %), BA13 (addition amount of potassium acetate powder: 10 mol%), BA14 (addition amount of potassium acetate powder: 15 mol%), and BA15 (addition amount of potassium acetate powder: 20 mol%).
【００２８】（実施例１６〜２０）塩化カリウム粉末に
代えて炭酸カリウム粉末を用いたこと以外は実施例１〜
５と同様にして、正極を作製した。次いで、これらの正
極を用いたこと以外は実施例１と同様にして、順に本発
明電池ＢＡ１６（炭酸カリウム粉末の添加量：０．１モ
ル％）、ＢＡ１７（炭酸カリウム粉末の添加量：５モル
％）、ＢＡ１８（炭酸カリウム粉末の添加量：１０モル
％）、ＢＡ１９（炭酸カリウム粉末の添加量：１５モル
％）、ＢＡ２０（炭酸カリウム粉末の添加量：２０モル
％）を作製した。Examples 16-20 Examples 1-20 except that potassium carbonate powder was used instead of potassium chloride powder.
In the same manner as in 5, a positive electrode was produced. Then, in the same manner as in Example 1 except that these positive electrodes were used, the battery BA16 of the present invention (addition amount of potassium carbonate powder: 0.1 mol%) and BA17 (addition amount of potassium carbonate powder: 5 mol) %), BA18 (addition amount of potassium carbonate powder: 10 mol%), BA19 (addition amount of potassium carbonate powder: 15 mol%), and BA20 (addition amount of potassium carbonate powder: 20 mol%).
【００２９】（比較例１）正極活物質粉末に塩化カリウ
ム粉末を添加混合しなかったこと以外は実施例１と同様
にして、正極を作製した。次いで、この正極を用いたこ
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 1 A positive electrode was manufactured in the same manner as in Example 1 except that potassium chloride powder was not added to and mixed with the positive electrode active material powder. Next, a comparative battery BC1 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００３０】（比較例２）正極活物質粉末に対する塩化
カリウム粉末の添加量を２５モル％としたこと以外は実
施例１と同様にして、正極を作製した。次いで、この正
極を用いたこと以外は実施例１と同様にして、比較電池
ＢＣ２を作製した。Comparative Example 2 A positive electrode was prepared in the same manner as in Example 1 except that the amount of the potassium chloride powder was 25 mol% relative to the positive electrode active material powder. Next, a comparative battery BC2 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００３１】（比較例３）正極活物質粉末に対するシュ
ウ酸カリウム粉末の添加量を２５モル％としたこと以外
は実施例６と同様にして、正極を作製した。次いで、こ
の正極を用いたこと以外は実施例１と同様にして、比較
電池ＢＣ３を作製した。Comparative Example 3 A positive electrode was prepared in the same manner as in Example 6, except that the amount of the potassium oxalate powder added to the positive electrode active material powder was 25 mol%. Next, a comparative battery BC3 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００３２】（比較例４）正極活物質粉末に対する酢酸
カリウム粉末の添加量を２５モル％としたこと以外は実
施例１１と同様にして、正極を作製した。次いで、この
正極を用いたこと以外は実施例１と同様にして、比較電
池ＢＣ４を作製した。Comparative Example 4 A positive electrode was produced in the same manner as in Example 11 except that the amount of the potassium acetate powder added to the positive electrode active material powder was 25 mol%. Next, a comparative battery BC4 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００３３】（比較例５）正極活物質粉末に対する炭酸
カリウム粉末の添加量を２５モル％としたこと以外は実
施例１６と同様にして、正極を作製した。次いで、この
正極を用いたこと以外は実施例１と同様にして、比較電
池ＢＣ５を作製した。Comparative Example 5 A positive electrode was produced in the same manner as in Example 16 except that the amount of the potassium carbonate powder added to the positive electrode active material powder was 25 mol%. Next, a comparative battery BC5 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００３４】（比較例６〜１１）塩化カリウム粉末に代
えて炭酸リチウム粉末を用いたこと以外は実施例１〜５
及び比較例２と同様にして、正極を作製した。次いで、
これらの正極を用いたこと以外は実施例１と同様にし
て、順に比較電池ＢＣ６（炭酸リチウム粉末の添加量：
０．１モル％）、ＢＣ７（炭酸リチウム粉末の添加量：
５モル％）、ＢＣ８（炭酸リチウム粉末の添加量：１０
モル％）、ＢＣ９（炭酸リチウム粉末の添加量：１５モ
ル％）、ＢＣ１０（炭酸リチウム粉末の添加量：２０モ
ル％）、ＢＣ１１（炭酸リチウム粉末の添加量：２５モ
ル％）を作製した。Comparative Examples 6 to 11 Examples 1 to 5 were repeated except that lithium carbonate powder was used instead of potassium chloride powder.
In the same manner as in Comparative Example 2, a positive electrode was produced. Then
Except that these positive electrodes were used, a comparative battery BC6 (addition amount of lithium carbonate powder:
0.1 mol%), BC7 (addition amount of lithium carbonate powder:
5 mol%), BC8 (addition amount of lithium carbonate powder: 10)
Mol%), BC9 (addition amount of lithium carbonate powder: 15 mol%), BC10 (addition amount of lithium carbonate powder: 20 mol%), and BC11 (addition amount of lithium carbonate powder: 25 mol%).
【００３５】本発明電池ＢＡ１〜ＢＡ１５及び比較電池
ＢＣ１〜ＢＣ４の各正極の作製において正極活物質粉末
に添加した金属塩粉末の種類及び添加量を、次の表１に
まとめて示し、本発明電池ＢＡ１６〜ＢＡ２０及び比較
電池ＢＣ５〜ＢＣ１１の各正極の作製において正極活物
質粉末に添加した金属塩粉末の種類及び添加量（モル
％）を、次の表２にまとめて示す。The types and amounts of the metal salt powders added to the positive electrode active material powder in the preparation of the respective positive electrodes of the batteries BA1 to BA15 of the present invention and the comparative batteries BC1 to BC4 are shown in Table 1 below. Table 2 below summarizes the types and amounts (mol%) of the metal salt powder added to the positive electrode active material powder in the production of each of the positive electrodes of BA16 to BA20 and comparative batteries BC5 to BC11.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】〔保存特性〕本発明電池ＢＡ１〜ＢＡ２０
及び比較電池ＢＣ１〜ＢＣ１１を充電した後、８０°Ｃ
で３０日間保存し、各電池の保存特性を調べた。結果を
図２に示す。保存特性は電池の内部抵抗の上昇率（％）
で評価した。電池の内部抵抗を１ｋＨｚで測定し、内部
抵抗の上昇率を下式により算出した。[Storage characteristics] Batteries BA1 to BA20 of the present invention
And 80 ° C after charging the comparative batteries BC1 to BC11.
For 30 days, and the storage characteristics of each battery were examined. The results are shown in FIG. The storage characteristics are the rate of increase (%) of the internal resistance
Was evaluated. The internal resistance of the battery was measured at 1 kHz, and the rate of increase of the internal resistance was calculated by the following equation.
【００３９】電池の内部抵抗の上昇率（％）＝（保存後
の内部抵抗−保存前の内部抵抗）×１００／保存前の内
部抵抗Increase rate (%) of internal resistance of battery = (internal resistance after storage−internal resistance before storage) × 100 / internal resistance before storage
【００４０】図２は、各電池の保存特性を、縦軸に電池
の内部抵抗の上昇率（％）を、また横軸に金属塩の添加
量（モル％）をとって示したグラフであり、同図に示す
ように本発明電池ＢＡ１〜ＢＡ２０では電池の内部抵抗
の上昇率が５０％以下と低いのに対して、比較電池ＢＣ
１〜ＢＣ１１では電池の内部抵抗の上昇率が１００％以
上と高い。このことから、高温で保存したときの電池の
内部抵抗の上昇が、カリウム塩を正極活物質に対して
０．１〜２０モル％添加することにより抑制されること
が分かる。特に、シュウ酸カリウム、酢酸カリウム又は
炭酸カリウムを添加した本発明電池ＢＡ６〜ＢＡ２０で
は電池の内部抵抗の上昇率が４０％以下と低く、そのな
かでも炭酸カリウムを添加した本発明電池ＢＡ１６〜Ｂ
Ａ２０では電池の内部抵抗の上昇率が数％と極めて低
い。したがって、シュウ酸塩、酢酸塩、炭酸塩などの炭
素を含む塩が好ましく、なかでも炭酸塩が特に好ましい
ことが分かる。また、図２より、炭酸リチウム（リチウ
ム塩）を正極活物質に添加した場合（比較電池ＢＣ６〜
ＢＣ１１）、電池の内部抵抗の上昇を抑制できないどこ
ろか、むしろ無添加（比較電池ＢＣ１）のときよりも電
池の内部抵抗の上昇が大きくなり、却って保存特性が悪
くなることが分かる。FIG. 2 is a graph showing the storage characteristics of each battery, the vertical axis represents the rate of increase in the internal resistance of the battery (%), and the horizontal axis represents the amount of metal salt added (mol%). As shown in the figure, in the batteries BA1 to BA20 of the present invention, the increase rate of the internal resistance of the batteries was as low as 50% or less, while the comparative battery BC
1 to BC11, the increase rate of the internal resistance of the battery is as high as 100% or more. This indicates that an increase in the internal resistance of the battery when stored at a high temperature is suppressed by adding 0.1 to 20 mol% of the potassium salt to the positive electrode active material. In particular, in the batteries BA6 to BA20 of the present invention to which potassium oxalate, potassium acetate or potassium carbonate was added, the rate of increase in the internal resistance of the batteries was as low as 40% or less, and among the batteries BA16 to B of the present invention to which potassium carbonate was added.
In A20, the rate of increase in the internal resistance of the battery is extremely low at several percent. Therefore, it is understood that salts containing carbon such as oxalates, acetates, and carbonates are preferable, and carbonates are particularly preferable. FIG. 2 shows that lithium carbonate (lithium salt) was added to the positive electrode active material (comparative batteries BC6 to BC6).
BC11), the increase in the internal resistance of the battery cannot be suppressed, but rather, the increase in the internal resistance of the battery becomes larger than in the case of no addition (comparative battery BC1), and the storage characteristics deteriorate rather.
【００４１】（実施例２１〜２５）塩化カリウム粉末に
代えて塩化ナトリウム粉末を用いたこと以外は実施例１
〜５と同様にして、正極を作製した。次いで、これらの
正極を用いたこと以外は実施例１と同様にして、順に本
発明電池ＢＡ２１（塩化ナトリウム粉末の添加量：０．
１モル％）、ＢＡ２２（塩化ナトリウム粉末の添加量：
５モル％）、ＢＡ２３（塩化ナトリウム粉末の添加量：
１０モル％）、ＢＡ２４（塩化ナトリウム粉末の添加
量：１５モル％）、ＢＡ２５（塩化ナトリウム粉末の添
加量：２０モル％）を作製した。Examples 21 to 25 Example 1 was repeated except that sodium chloride powder was used instead of potassium chloride powder.
In the same manner as in Examples 5 to 5, a positive electrode was produced. Next, in the same manner as in Example 1 except that these positive electrodes were used, the battery BA21 of the present invention (addition amount of sodium chloride powder: 0.1%) was sequentially used.
1 mol%), BA22 (addition amount of sodium chloride powder:
5 mol%), BA23 (addition amount of sodium chloride powder:
10 mol%), BA24 (addition amount of sodium chloride powder: 15 mol%), and BA25 (addition amount of sodium chloride powder: 20 mol%) were prepared.
【００４２】（実施例２６〜３０）塩化カリウム粉末に
代えて塩化マグネシウム粉末を用いたこと以外は実施例
１〜５と同様にして、正極を作製した。次いで、これら
の正極を用いたこと以外は実施例１と同様にして、順に
本発明電池ＢＡ２６（塩化マグネシウム粉末の添加量：
０．１モル％）、ＢＡ２７（塩化マグネシウム粉末の添
加量：５モル％）、ＢＡ２８（塩化マグネシウム粉末の
添加量：１０モル％）、ＢＡ２９（塩化マグネシウム粉
末の添加量：１５モル％）、ＢＡ３０（塩化マグネシウ
ム粉末の添加量：２０モル％）を作製した。Examples 26 to 30 Positive electrodes were produced in the same manner as in Examples 1 to 5, except that magnesium chloride powder was used instead of potassium chloride powder. Next, in the same manner as in Example 1 except that these positive electrodes were used, the battery BA26 of the present invention (addition amount of magnesium chloride powder:
0.1 mol%), BA27 (addition amount of magnesium chloride powder: 5 mol%), BA28 (addition amount of magnesium chloride powder: 10 mol%), BA29 (addition amount of magnesium chloride powder: 15 mol%), BA30 (Amount of magnesium chloride powder added: 20 mol%).
【００４３】（実施例３１〜３５）塩化カリウム粉末に
代えて塩化銅粉末を用いたこと以外は実施例１〜５と同
様にして、正極を作製した。次いで、これらの正極を用
いたこと以外は実施例１と同様にして、順に本発明電池
ＢＡ３１（塩化銅粉末の添加量：０．１モル％）、ＢＡ
３２（塩化銅粉末の添加量：５モル％）、ＢＡ３３（塩
化銅粉末の添加量：１０モル％）、ＢＡ３４（塩化銅粉
末の添加量：１５モル％）、ＢＡ３５（塩化銅粉末の添
加量：２０モル％）を作製した。(Examples 31 to 35) Positive electrodes were prepared in the same manner as in Examples 1 to 5, except that copper chloride powder was used instead of potassium chloride powder. Then, in the same manner as in Example 1 except that these positive electrodes were used, the battery BA31 of the present invention (addition amount of copper chloride powder: 0.1 mol%), BA
32 (addition amount of copper chloride powder: 5 mol%), BA33 (addition amount of copper chloride powder: 10 mol%), BA34 (addition amount of copper chloride powder: 15 mol%), BA35 (addition amount of copper chloride powder) : 20 mol%).
【００４４】（比較例１２）正極活物質粉末に対する塩
化ナトリウム粉末の添加量を２５モル％としたこと以外
は実施例２１と同様にして、正極を作製した。次いで、
この正極を用いたこと以外は実施例１と同様にして、比
較電池ＢＣ１２を作製した。Comparative Example 12 A positive electrode was produced in the same manner as in Example 21 except that the amount of the sodium chloride powder relative to the positive electrode active material powder was 25 mol%. Then
A comparative battery BC12 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００４５】（比較例１３）正極活物質粉末に対する塩
化マグネシウム粉末の添加量を２５モル％としたこと以
外は実施例２６と同様にして、正極を作製した。次い
で、この正極を用いたこと以外は実施例１と同様にし
て、比較電池ＢＣ１３を作製した。Comparative Example 13 A positive electrode was produced in the same manner as in Example 26 except that the amount of the magnesium chloride powder added to the positive electrode active material powder was 25 mol%. Next, a comparative battery BC13 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００４６】（比較例１４）正極活物質粉末に対する塩
化銅粉末の添加量を２５モル％としたこと以外は実施例
３１と同様にして、正極を作製した。次いで、この正極
を用いたこと以外は実施例１と同様にして、比較電池Ｂ
Ｃ１４を作製した。Comparative Example 14 A positive electrode was prepared in the same manner as in Example 31 except that the amount of the copper chloride powder added to the positive electrode active material powder was 25 mol%. Next, a comparative battery B was prepared in the same manner as in Example 1 except that this positive electrode was used.
C14 was produced.
【００４７】本発明電池ＢＡ２１〜ＢＡ３５及び比較電
池ＢＣ１２〜ＢＣ１４の各正極の作製において正極活物
質粉末に添加した金属塩粉末の種類及び添加量（モル
％）を、次の表３にまとめて示す。The types and amounts (mol%) of the metal salt powder added to the positive electrode active material powder in the production of each positive electrode of the batteries BA21 to BA35 of the present invention and the comparative batteries BC12 to BC14 are shown in Table 3 below. .
【００４８】[0048]
【表３】 [Table 3]
【００４９】〔保存特性〕先と同様にして、本発明電池
ＢＡ２１〜ＢＡ３５及び比較電池ＢＣ１２〜ＢＣ１４の
保存特性（８０°Ｃで３０日間保存）を調べた。結果を
図３に示す。なお、図３中には、比較の便宜のために、
比較電池ＢＣ１の結果（図２より転記）も示してある。[Storage Characteristics] In the same manner as above, the storage characteristics of the batteries BA21 to BA35 of the present invention and the comparative batteries BC12 to BC14 (storage at 80 ° C. for 30 days) were examined. The results are shown in FIG. In FIG. 3, for convenience of comparison,
The result (transferred from FIG. 2) of the comparative battery BC1 is also shown.
【００５０】図３は、各電池の保存特性を、縦軸に電池
の内部抵抗の上昇率（％）を、また横軸に金属塩の添加
量（モル％）をとって示したグラフであり、同図に示す
ように本発明電池ＢＡ２１〜ＢＡ３５では電池の内部抵
抗の上昇率が５０％以下と低いのに対して、比較電池Ｂ
Ｃ１２〜ＢＣ１４では電池の内部抵抗の上昇率が１００
％以上と高い。このことから、高温で保存したときの電
池の内部抵抗の上昇が、塩化ナトリウム等の金属塩を正
極活物質粉末に対して０．１〜２０モル％添加すること
により顕著に抑制されることが分かる。FIG. 3 is a graph showing the storage characteristics of each battery, the vertical axis representing the increase rate (%) of the internal resistance of the battery, and the horizontal axis representing the addition amount (mol%) of the metal salt. As shown in the figure, in the batteries BA21 to BA35 of the present invention, the rate of increase in the internal resistance of the batteries was as low as 50% or less, whereas the batteries of Comparative Battery B
In C12 to BC14, the rate of increase of the internal resistance of the battery is 100
% And higher. This indicates that the increase in the internal resistance of the battery when stored at a high temperature is significantly suppressed by adding 0.1 to 20 mol% of a metal salt such as sodium chloride to the positive electrode active material powder. I understand.
【００５１】（実施例３６〜４７） 塩化カリウム粉末に代えて、アルミニウム、カルシウ
ム、スカンジウム、チタン、バナジウム、クロム、マン
ガン、鉄、コバルト、ニッケル、銅及び亜鉛の各水酸化
物粉末を用い、且つ各水酸化物粉末の添加量を５モル％
としたこと以外は実施例１と同様にして、正極を作製し
た。次いで、これらの正極を用いたこと以外は実施例１
と同様にして、順に本発明電池ＢＡ３６（水酸化アルミ
ニウム添加）、ＢＡ３８（水酸化カルシウム添加）、Ｂ
Ａ３９（水酸化スカンジウム添加）、ＢＡ４０（水酸化
チタン添加）、ＢＡ４１（水酸化バナジウム添加）、Ｂ
Ａ４２（水酸化クロム添加）、ＢＡ４３（水酸化マンガ
ン添加）、ＢＡ４４（水酸化鉄添加）、ＢＡ４５（水酸
化コバルト添加）、ＢＡ４６（水酸化ニッケル添加）、
ＢＡ４７（水酸化銅添加）、ＢＡ４８（水酸化亜鉛添
加）を作製した。[0051] Instead of (Example 36-47) potassium chloride powder, aluminum, mosquito Rushiu <br/> arm, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, each hydroxide of copper and zinc Powder and the amount of each hydroxide powder added was 5 mol%
A positive electrode was produced in the same manner as in Example 1 except that Next, Example 1 was performed except that these positive electrodes were used.
In the same manner as in the above, battery BA36 (with aluminum hydroxide added) , BA 38 (with calcium hydroxide added), B
A39 (addition of scandium hydroxide), BA40 (addition of titanium hydroxide), BA41 (addition of vanadium hydroxide), B
A42 (chromium hydroxide added), BA43 (manganese hydroxide added), BA44 (iron hydroxide added), BA45 (cobalt hydroxide added), BA46 (nickel hydroxide added),
BA47 (adding copper hydroxide) and BA48 (adding zinc hydroxide) were produced.
【００５２】〔保存特性〕 先と同様にして、本発明電池ＢＡ３６、ＢＡ３８〜ＢＡ
４８の保存特性（８０°Ｃで３０日間保存）を調べた。
結果を図４に示す。[Storage Characteristics] In the same manner as above, the batteries of the present invention BA36 , BA38-BA
Forty-eight storage characteristics (preserved at 80 ° C. for 30 days) were examined.
FIG. 4 shows the results.
【００５３】図４は、各電池の保存特性を、縦軸に電池
の内部抵抗の上昇率（％）を、また横軸に水酸化物中の
金属元素をとって示したグラフであり、同図に示すよう
に、本発明電池ＢＡ３６、ＢＡ３８〜ＢＡ４８の内部抵
抗の上昇率は１０％程度と低い。このことから、高温で
保存したときの電池の内部抵抗の上昇が、水酸化アルミ
ニウム等の金属水酸化物を正極活物質粉末に添加するこ
とにより顕著に抑制されることが分かる。FIG. 4 is a graph showing the storage characteristics of each battery, the vertical axis represents the increase rate (%) of the internal resistance of the battery, and the horizontal axis represents the metal element in the hydroxide. as shown, the rate of increase in the internal resistance of the present battery BA36, B A38~BA48 about 10 percent lower. Therefore, the increase in internal resistance of the battery when stored at high temperature, aluminum hydroxide
It is seen to be remarkably inhibited by adding a metal hydroxide iodonium such as the positive electrode active material powder.
【００５４】（実施例４８〜５２） 塩化カリウム粉末に代えて、炭酸コバルト粉末を用いた
こと以外は実施例１〜５と同様にして、正極を作製し
た。次いで、これらの正極を用いたこと以外は実施例１
と同様にして、順に本発明電池ＢＡ４９（炭酸コバルト
の添加量：０．１モル％）、ＢＡ５０（炭酸コバルトの
添加量：５モル％）、ＢＡ５１（炭酸コバルトの添加
量：１０モル％）、ＢＡ５２（炭酸コバルトの添加量：
１５モル％）、ＢＡ５３（炭酸コバルトの添加量：２０
モル％）を作製した。(Examples 48 to 52 ) Positive electrodes were produced in the same manner as in Examples 1 to 5 except that cobalt carbonate powder was used instead of potassium chloride powder. Next, Example 1 was performed except that these positive electrodes were used.
In the same manner as described above, the battery BA49 (addition amount of cobalt carbonate: 0.1 mol%), BA50 (addition amount of cobalt carbonate: 5 mol%), BA51 (addition amount of cobalt carbonate: 10 mol%), BA52 (addition amount of cobalt carbonate:
15 mol%), BA53 (addition amount of cobalt carbonate: 20)
Mol%).
【００５５】（実施例５３〜５７） 塩化カリウム粉末に代えて、炭酸ニッケル粉末を用いた
こと以外は実施例１〜５と同様にして、正極を作製し
た。次いで、これらの正極を用いたこと以外は実施例１
と同様にして、順に本発明電池ＢＡ５４（炭酸ニッケル
の添加量：０．１モル％）、ＢＡ５５（炭酸ニッケルの
添加量：５モル％）、ＢＡ５６（炭酸ニッケルの添加
量：１０モル％）、ＢＡ５７（炭酸ニッケルの添加量：
１５モル％）、ＢＡ５８（炭酸ニッケルの添加量：２０
モル％）を作製した。Examples 53 to 57 Positive electrodes were produced in the same manner as in Examples 1 to 5, except that nickel carbonate powder was used instead of potassium chloride powder. Next, Example 1 was performed except that these positive electrodes were used.
In the same manner as in the above, battery BA54 of the present invention (addition amount of nickel carbonate: 0.1 mol%), BA55 (addition amount of nickel carbonate: 5 mol%), BA56 (addition amount of nickel carbonate: 10 mol%), BA57 (addition amount of nickel carbonate:
15 mol%), BA58 (addition amount of nickel carbonate: 20)
Mol%).
【００５６】（実施例５８〜６２） 塩化カリウム粉末に代えて、炭酸ナトリウム粉末を用い
たこと以外は実施例１〜５と同様にして、正極を作製し
た。次いで、これらの正極を用いたこと以外は実施例１
と同様にして、順に本発明電池ＢＡ５９（炭酸ナトリウ
ムの添加量：０．１モル％）、ＢＡ６０（炭酸ナトリウ
ムの添加量：５モル％）、ＢＡ６１（炭酸ナトリウムの
添加量：１０モル％）、ＢＡ６２（炭酸ナトリウムの添
加量：１５モル％）、ＢＡ６３（炭酸ナトリウムの添加
量：２０モル％）を作製した。Examples 58 to 62 Positive electrodes were produced in the same manner as in Examples 1 to 5, except that sodium carbonate powder was used instead of potassium chloride powder. Next, Example 1 was performed except that these positive electrodes were used.
In the same manner as described above, the battery BA59 of the present invention (addition amount of sodium carbonate: 0.1 mol%), BA60 (addition amount of sodium carbonate: 5 mol%), BA61 (addition amount of sodium carbonate: 10 mol%), BA62 (addition amount of sodium carbonate: 15 mol%) and BA63 (addition amount of sodium carbonate: 20 mol%) were produced.
【００５７】（比較例１５） 正極活物質粉末に対する炭酸コバルト粉末の添加量を２
５モル％としたこと以外は実施例４８と同様にして、正
極を作製した。次いで、この正極を用いたこと以外は実
施例１と同様にして、比較電池ＢＣ１５を作製した。Comparative Example 15 The amount of the cobalt carbonate powder added to the positive electrode active material powder was 2
A positive electrode was produced in the same manner as in Example 48 except that the content was 5 mol%. Next, a comparative battery BC15 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００５８】（比較例１６） 正極活物質粉末に対する炭酸ニッケル粉末の添加量を２
５モル％としたこと以外は実施例５３と同様にして、正
極を作製した。次いで、この正極を用いたこと以外は実
施例１と同様にして、比較電池ＢＣ１６を作製した。Comparative Example 16 The addition amount of the nickel carbonate powder to the positive electrode active material powder was 2
A positive electrode was produced in the same manner as in Example 53 except that the content was 5 mol%. Next, a comparative battery BC16 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００５９】（比較例１７） 正極活物質粉末に対する炭酸ナトリウム粉末の添加量を
２５モル％としたこと以外は実施例５８と同様にして、
正極を作製した。次いで、この正極を用いたこと以外は
実施例１と同様にして、比較電池ＢＣ１７を作製した。Comparative Example 17 The procedure of Example 58 was repeated, except that the amount of the sodium carbonate powder to the positive electrode active material powder was 25 mol%.
A positive electrode was produced. Next, a comparative battery BC17 was produced in the same manner as in Example 1 except that this positive electrode was used.
【００６０】本発明電池ＢＡ４９〜ＢＡ６３及び比較電
池ＢＣ１５〜ＢＣ１７の各正極の作製において正極活物
質粉末に添加した金属塩粉末の種類及び添加量（モル
％）を、次の表４にまとめて示す。The types and amounts (mol%) of the metal salt powder added to the positive electrode active material powder in the production of each positive electrode of the batteries BA49 to BA63 of the present invention and the comparative batteries BC15 to BC17 are summarized in Table 4 below. .
【００６１】[0061]
【表４】 [Table 4]
【００６２】〔保存特性〕先と同様にして、本発明電池
ＢＡ４９〜ＢＡ６３及び比較電池ＢＣ１５〜ＢＣ１７の
保存特性（８０°Ｃで３０日間保存）を調べた。結果を
図５に示す。なお、図５中には、比較の便宜のために、
比較電池ＢＣ１、ＢＣ５及び本発明電池ＢＡ１６〜ＢＡ
２０の結果（図２より転記）も示してある。[Storage Characteristics] In the same manner as above, the storage characteristics of the batteries BA49 to BA63 of the present invention and the comparative batteries BC15 to BC17 (storage at 80 ° C. for 30 days) were examined. The results are shown in FIG. In FIG. 5, for convenience of comparison,
Comparative batteries BC1, BC5 and batteries BA16 to BA of the present invention
20 (transferred from FIG. 2) is also shown.
【００６３】図５は、このときの各電池の保存特性を図
２及び図３と同じ座標系のグラフに示したものであり、
同図に示すように本発明電池ＢＡ１６〜ＢＡ２０及びＢ
Ａ４９〜ＢＡ６３では電池の内部抵抗の上昇率が数％と
極めて低いのに対して、比較電池ＢＣ１，ＢＣ５，ＢＣ
１５〜ＢＣ１７では電池の内部抵抗の上昇率が１００％
以上と高い。このことから、高温で保存したときの電池
の内部抵抗の上昇が、炭酸塩を正極活物質粉末に対して
０．１〜２０モル％添加することにより顕著に抑制され
ることが分かる。FIG. 5 is a graph showing the storage characteristics of each battery at this time in the same coordinate system graph as in FIGS.
As shown in FIG.
In A49-BA63, the rate of increase in the internal resistance of the battery was as extremely low as several percent, whereas the comparative batteries BC1, BC5, and BC
15 to BC17, the increase rate of the internal resistance of the battery is 100%
Above and high. This indicates that the increase in the internal resistance of the battery when stored at a high temperature is significantly suppressed by adding 0.1 to 20 mol% of the carbonate to the positive electrode active material powder.
【００６４】次に、本発明電池ＢＡ１６〜ＢＡ２０及び
ＢＡ４９〜ＢＡ６３及び比較電池ＢＣ１，ＢＣ５，ＢＣ
１５〜１７を充電した後、８０°Ｃで６０日間保存し、
各電池の保存特性を調べた。結果を図６に示す。Next, the batteries BA16 to BA20 and BA49 to BA63 of the present invention and the comparative batteries BC1, BC5 and BC
After charging 15-17, store at 80 ° C for 60 days,
The storage characteristics of each battery were examined. FIG. 6 shows the results.
【００６５】図６は、このときの各電池の保存特性を図
２及び図３と同じ座標系のグラフに示したものであり、
同図に示すように本発明電池ＢＡ１６〜ＢＡ２０及びＢ
Ａ４９〜ＢＡ６３では電池の内部抵抗の上昇率が５０％
以下と低いのに対して、比較電池ＢＣ１，ＢＣ５，ＢＣ
１５〜ＢＣ１７では電池の内部抵抗の上昇率が１００％
以上と高い。このことから、高温で長期間保存したとき
の電池の内部抵抗の上昇が、炭酸塩を正極活物質粉末に
対して０．１〜２０モル％添加することにより顕著に抑
制されることが分かる。特に炭酸コバルト又は炭酸ニッ
ケルを添加した本発明電池ＢＡ４９〜ＢＡ５８では電池
の内部抵抗の上昇率が１０％以下と極めて低い。炭酸塩
の中でも、炭酸コバルト又は炭酸ニッケルが特に好まし
いことが分かる。FIG. 6 shows the storage characteristics of each battery at this time in a graph in the same coordinate system as in FIGS. 2 and 3.
As shown in FIG.
For A49-BA63, the rate of increase of the internal resistance of the battery is 50%
Comparative batteries BC1, BC5, BC
15 to BC17, the increase rate of the internal resistance of the battery is 100%
Above and high. This indicates that the increase in the internal resistance of the battery when stored at a high temperature for a long period of time is significantly suppressed by adding 0.1 to 20 mol% of the carbonate to the positive electrode active material powder. In particular, in the batteries BA49 to BA58 of the present invention to which cobalt carbonate or nickel carbonate is added, the rate of increase in the internal resistance of the battery is extremely low at 10% or less. It can be seen that among carbonates, cobalt carbonate or nickel carbonate is particularly preferred.
【００６６】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、本発明は電池形
状に特に制限はなく、円筒型、角型など、他の種々の形
状の非水系一次電池又は非水系二次電池に適用し得るも
のである。In the above embodiment, the case where the present invention is applied to a flat type battery has been described as an example. However, the present invention is not particularly limited in the shape of the battery, and various other shapes such as a cylindrical type and a square type are available. The present invention can be applied to a non-aqueous primary battery or a non-aqueous secondary battery having the following shape.
【００６７】また、実施例では金属塩として、コバルト
塩、ニッケル塩、カリウム塩、ナトリウム塩、マグネシ
ウム塩及び銅塩を用いたが、アルミニウム塩、カルシウ
ム塩、スカンジウム塩、チタン塩、バナジウム塩、クロ
ム塩、マンガン塩、鉄塩及び亜鉛塩を用いても高温保存
特性に優れた非水系電池が得られ、また金属水酸化物と
して、水酸化マグネシウムを用いても高温保存特性に優
れた非水系電池が得られる。In the examples, cobalt salts, nickel salts, potassium salts, sodium salts, magnesium salts and copper salts were used as metal salts, but aluminum salts, calcium salts, scandium salts, titanium salts, vanadium salts, chromium salts salt, manganese salt, be used iron salt and zinc salt obtained non-aqueous battery having excellent high-temperature storage characteristics, and as the metal hydroxide, a non-aqueous battery is also excellent in high-temperature storage characteristics with water magnesium oxide Is obtained.
【００６８】さらに、実施例では正極活物質としてＬｉ
Ｎｉ0.5 Ｃｏ0.5 Ｏ2 を用いたが、本発明で規制する他
のリチウム−遷移金属複合酸化物を用いた場合において
も、上記実施例と同様の優れた効果が得られる。Further, in the examples, Li was used as the positive electrode active material.
Although Ni 0.5 Co 0.5 O 2 is used, the same excellent effects as in the above embodiment can be obtained also when another lithium-transition metal composite oxide regulated by the present invention is used.
【００６９】なお、本発明者らは電池系内のガスの発生
は主に非水電解液の分解によるものと考えたが、結着剤
の分解によるガスの発生も考えられる。本発明による保
存特性の向上が、後者のガスの発生をも抑制したことに
よるものであるとすれば、本発明は液体電解質電池に限
らず固体電解質電池にも適用可能と考えられる。Although the present inventors have considered that the generation of gas in the battery system is mainly due to the decomposition of the non-aqueous electrolyte, the generation of gas due to the decomposition of the binder may also be considered. If the improvement in storage characteristics according to the present invention is due to the suppression of the latter gas generation, the present invention is considered to be applicable not only to liquid electrolyte batteries but also to solid electrolyte batteries.
【００７０】[0070]
【発明の効果】正極活物質に特定の金属塩及び／又は金
属水酸化物が添加されているので、高温保存時に電解液
の分解が起こりにくい。このため、電池の内部抵抗の上
昇が小さく、保存特性に優れる。According to the present invention, since a specific metal salt and / or metal hydroxide is added to the positive electrode active material, decomposition of the electrolytic solution hardly occurs during high-temperature storage. Therefore, the increase in the internal resistance of the battery is small, and the battery has excellent storage characteristics.
【図１】扁平型の本発明電池の断面図である。FIG. 1 is a sectional view of a flat type battery of the present invention.
【図２】本発明電池及び比較電池の保存特性（８０°Ｃ
で３０日間保存）を示すグラフである。FIG. 2 shows the storage characteristics (80 ° C.) of a battery of the present invention and a comparative battery.
Is stored for 30 days.
【図３】本発明電池及び比較電池の保存特性（８０°Ｃ
で３０日間保存）を示すグラフである。FIG. 3 shows the storage characteristics (80 ° C.) of the battery of the present invention and a comparative battery.
Is stored for 30 days.
【図４】本発明電池の保存特性（８０°Ｃで３０日間保
存）を示すグラフである。FIG. 4 is a graph showing the storage characteristics (storage at 80 ° C. for 30 days) of the battery of the present invention.
【図５】本発明電池及び比較電池の保存特性（８０°Ｃ
で３０日間保存）を示すグラフである。FIG. 5 shows the storage characteristics (80 ° C.) of the battery of the present invention and a comparative battery.
Is stored for 30 days.
【図６】本発明電池及び比較電池の保存特性（８０°Ｃ
で６０日間保存）を示すグラフである。FIG. 6 shows the storage characteristics (80 ° C.) of the battery of the present invention and a comparative battery.
Is stored for 60 days).
ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ BA1 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 (72)発明者 前田 丈志 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 (56)参考文献 特開 平５−290890（ＪＰ，Ａ) 特開 平４−169076（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 - 4/04 H01M 4/36 - 4/62 H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Nishio, Inventor 2-5-5, Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-5-2, Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd. (72) Inventor Takeshi Maeda 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (56) References JP 5-290890 (JP, A) JP Hei 4-169076 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/02-4/04 H01M 4/36-4/62 H01M 10/40
Claims (4)
ＬｉX Ｎｉ1-Y ＭY ＯZ （但し、０＜Ｘ＜１．３、０≦
Ｙ≦１、１．８＜Ｚ＜２．２であり、且つ、Ｍはコバル
ト又はコバルトを含む２種以上の遷移金属である。）で
表されるリチウム−遷移金属複合酸化物を正極活物質と
する正極とを備える非水系電池において、前記正極活物
質に対して、ナトリウム、マグネシウム、アルミニウ
ム、カリウム、カルシウム、スカンジウム、チタン、バ
ナジウム、クロム、マンガン、鉄、コバルト、ニッケ
ル、銅及び亜鉛よりなる群から選ばれた金属の塩、及び
／又は、マグネシウム、アルミニウム、カルシウム、ス
カンジウム、チタン、バナジウム、クロム、マンガン、
鉄、コバルト、ニッケル、銅及び亜鉛よりなる群から選
ばれた金属の水酸化物の１種又は２種以上が、総量で
０．１〜２０モル％添加されていることを特徴とする非
水系電池。A negative electrode comprising lithium as a negative electrode active material;
Li X Ni 1-Y M Y O Z (where 0 <X <1.3, 0 ≦
Y ≦ 1, 1.8 <Z <2.2, and M is cobalt or two or more transition metals containing cobalt. A) a positive electrode comprising a lithium-transition metal composite oxide as a positive electrode active material, wherein sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, and vanadium are used with respect to the positive electrode active material. A salt of a metal selected from the group consisting of, chromium, manganese, iron, cobalt, nickel, copper and zinc ; and
/ Or magnesium, aluminum, calcium, sulfur
Candium, titanium, vanadium, chromium, manganese,
Select from the group consisting of iron, cobalt, nickel, copper and zinc
A non-aqueous battery, characterized in that one or more of the metal hydroxides are added in a total amount of 0.1 to 20 mol%.
項１記載の非水系電池。2. The non-aqueous battery according to claim 1, wherein the salt is a metal salt containing carbon.
請求項２記載の非水系電池。3. The non-aqueous battery according to claim 2, wherein the metal salt containing carbon is a carbonate.
ニッケルである請求項３記載の非水系電池。4. The non-aqueous battery according to claim 3, wherein the carbonate is cobalt carbonate and / or nickel carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25762394A JP3197763B2 (en) | 1993-11-18 | 1994-09-26 | Non-aqueous battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-314533 | 1993-11-18 | ||
| JP31453393 | 1993-11-18 | ||
| JP25762394A JP3197763B2 (en) | 1993-11-18 | 1994-09-26 | Non-aqueous battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07192721A JPH07192721A (en) | 1995-07-28 |
| JP3197763B2 true JP3197763B2 (en) | 2001-08-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25762394A Expired - Fee Related JP3197763B2 (en) | 1993-11-18 | 1994-09-26 | Non-aqueous battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197763B2 (en) |
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| JPH07192721A (en) | 1995-07-28 |
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