JPS6319761A - Manufacture of positive active material for nonaqueous electrolyte battery - Google Patents
Manufacture of positive active material for nonaqueous electrolyte batteryInfo
- Publication number
- JPS6319761A JPS6319761A JP61163234A JP16323486A JPS6319761A JP S6319761 A JPS6319761 A JP S6319761A JP 61163234 A JP61163234 A JP 61163234A JP 16323486 A JP16323486 A JP 16323486A JP S6319761 A JPS6319761 A JP S6319761A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- nickel
- positive electrode
- electrode active
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はリチウムを負極とする非水電解液電池用正極活
物質の製造方法に関するものであり、従来とは異なる正
極活物質を得ることにより、新しい非水電解液電池の提
供を可能にしたものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for producing a positive electrode active material for non-aqueous electrolyte batteries using lithium as a negative electrode. This made it possible to provide non-aqueous electrolyte batteries.
従来の技術
近年、電子ｎ器の発展に伴って、小形軽量で長期間保存
性のよい電池の要求が高まっており、その要求に適する
電池としてリチウム、ナトリウムあるいはマグネシウム
を負極とする非水電解液電池が注目されている。この電
池の正極活物質としては種々のものが提案されているが
、実用段階にあるのは（ＣＦ）ｎ 、ＡｇＱｒ Ｏａ
、Ｍｎ ０２および５ＯＣＩ ２のみであり、いずれも
−次電池用の正極活物質である。したがって、新しい正
極活物質、特に二次電池用正極活物質の出現が期待され
ている。Background of the Invention In recent years, with the development of electronic devices, there has been an increasing demand for batteries that are small, lightweight, and have a long shelf life.Non-aqueous electrolytes with lithium, sodium, or magnesium as the negative electrode are suitable batteries to meet these demands. Batteries are attracting attention. Various positive electrode active materials have been proposed for this battery, but the ones that are in the practical stage are (CF)n, AgQr Oa
, Mn 02 and 5OCI 2 , all of which are positive electrode active materials for secondary batteries. Therefore, the emergence of new positive electrode active materials, particularly positive electrode active materials for secondary batteries, is expected.
発明が解決しようとする問題点
アルカリ電池用正極活物質としては二酸化マンガンおよ
び水酸化ニッケルがあり、前者は一次電池用、後者は二
次電池用の正極活物質として広く用いられている。また
前者の二酸化マンガンの場合は非水電解液電池の正極活
物質としても使用されているが、後者の水酸化ニッケル
の場合は、非水電解液中では電気化学的に不活性である
ため、非水電解液電池の一次電池はもとより二次電池の
正極活物質としても用いられていなかった。Problems to be Solved by the Invention Manganese dioxide and nickel hydroxide are available as positive electrode active materials for alkaline batteries, and the former is widely used as a positive electrode active material for primary batteries and the latter for secondary batteries. The former, manganese dioxide, is also used as a positive electrode active material in non-aqueous electrolyte batteries, while the latter, nickel hydroxide, is electrochemically inactive in non-aqueous electrolytes. It has not been used as a positive electrode active material in secondary batteries, let alone in primary batteries of non-aqueous electrolyte batteries.
本発明の目的は、従来、非水電解液中では不活性であっ
た水酸化ニッケルを改質して、非水電解液を用いた電池
の正極活物質として用いることにある。An object of the present invention is to modify nickel hydroxide, which has conventionally been inactive in non-aqueous electrolytes, and to use the modified nickel hydroxide as a positive electrode active material for batteries using non-aqueous electrolytes.
問題点を解決するための手段
本発明は、非水電解液電池用正極活物質としては従来、
不活性であるとされている水酸化ニッケルを水酸化リチ
ウム水溶液やリチウムを含むアルカリ水溶液中でアノー
ド酸化することによって活性化し、非水電解液電池の正
極活物質にすることを特徴とするものである。その場合
、コバルトを添加した水酸化ニッケルを用いると、その
効果をさらに高めることができる。Means for Solving the Problems The present invention solves the problems conventionally used as positive electrode active materials for non-aqueous electrolyte batteries.
It is characterized by activating nickel hydroxide, which is considered inert, by anodizing it in an aqueous lithium hydroxide solution or an alkaline aqueous solution containing lithium, and using it as a positive electrode active material for non-aqueous electrolyte batteries. be. In that case, the effect can be further enhanced by using nickel hydroxide to which cobalt is added.
実施例 以下、本発明を実施例を用いて説明づる。Example The present invention will be explained below using examples.
実施例１
５〜５０μの水酸化ニッケル粉末をニッケルメツシュの
容器に入れた後、４．５Ｍの水酸化リチウム水溶液中で
、対極にニッケル板を用い、水酸化ニッケル１ｇ当り０
．３への電流で２時間アノード酸化をした。その後、湯
洗し、そして２００℃で２時間乾燥して本発明による正
極活物質を（ｑた。Example 1 After putting nickel hydroxide powder of 5 to 50μ in a nickel mesh container, in a 4.5M lithium hydroxide aqueous solution, using a nickel plate as a counter electrode, 0 per 1 g of nickel hydroxide.
．． Anodic oxidation was performed for 2 hours at a current of 3. Thereafter, the positive electrode active material according to the present invention was washed with hot water and dried at 200° C. for 2 hours.
実施例２
５〜５０μの水酸化ニッケル粉末１００重量部とグラフ
ァイト１０重量部とを混合し、これをニッケルメツシュ
の容器に入れた後１．４．５Ｍの水酸化リチウム水溶液
中で、対極としてニッケル板を用い、水酸化ニッケル１
ｇ当り０．３Δの電流で２時間アノード酸化をした。そ
の後、湯洗し、そして２００℃で２時−間乾燥して本発
明による正極活物質を１ｑた。Example 2 100 parts by weight of 5-50μ nickel hydroxide powder and 10 parts by weight of graphite were mixed, placed in a nickel mesh container, and then mixed as a counter electrode in a 1.4.5M lithium hydroxide aqueous solution. Using a nickel plate, 1 nickel hydroxide
Anodic oxidation was performed for 2 hours at a current of 0.3Δ/g. Thereafter, it was washed with hot water and dried at 200° C. for 2 hours to obtain 1 q of positive electrode active material according to the present invention.
実施例３
水酸化コバルトを１０ｗｔ％含む５〜５０μの水酸化ニ
ッケル粉末１００１聞部とグラファイト１ｏ重邑部を混
合し、これをニッケルメツシュの容器に入れた後、４．
５Ｍの水酸化リチウム水溶液中で、対極にニッケル板を
用い、水酸化ニッケル１ｇ当り０．３Ａの電流で２時１
間アノード酸化をした。その後、湯洗し、そして２００
℃で２時間乾燥して本発明による正極活物質を得た。Example 3 After mixing 5 to 50 micron nickel hydroxide powder containing 10 wt% of cobalt hydroxide with 100 μm of graphite and placing it in a nickel mesh container, 4.
In a 5M lithium hydroxide aqueous solution, a nickel plate was used as a counter electrode, and a current of 0.3 A per 1 g of nickel hydroxide was applied for 2 hours to 1 hour.
Anodized oxidation was performed during the period. After that, wash with hot water, and
After drying at ℃ for 2 hours, a positive electrode active material according to the present invention was obtained.
実施例４
水酸化コバルトを１０ｗｔ％を含む５〜５０μの水酸化
ニッケル粉末１００重量部とグラファイト１ｏ重邑部を
混合し、これをニッケルメツシュの容器に入れた後、４
．５Ｍの水酸化リチウム水溶液と４．５Ｍの水酸化ナト
リウム水溶液の１：１の混合水溶液中で、対極にニッケ
ル板を用い、水酸化ニッケル１ｇ当り０．３Ａの電流で
２時間アノード酸化をした。その後、湯洗し、そして２
００℃で２時間乾燥して本発明による正極活物質を１ｑ
た。Example 4 100 parts by weight of 5-50μ nickel hydroxide powder containing 10 wt% of cobalt hydroxide and 10% of graphite were mixed, and this was placed in a nickel mesh container.
．． In a 1:1 mixed aqueous solution of 5M lithium hydroxide aqueous solution and 4.5M sodium hydroxide aqueous solution, anodic oxidation was performed for 2 hours at a current of 0.3 A per 1 g of nickel hydroxide using a nickel plate as a counter electrode. After that, wash with hot water, and
1q of the positive electrode active material according to the present invention was dried at 00°C for 2 hours.
Ta.
なお、実施例３で水酸化コバルトを含む水酸化ニッケル
粉末を用いたが、この粉末は通常、次の２つの方法で製
作することができる。第１の方法は、コバルトを含む硫
酸ニッケル水溶液、塩化ニッケル水溶液あるいは硝酸ニ
ッケル水溶液をアルカリ水溶液、例えば水酸化ナトリウ
ム水溶液、水酸化カリウム水溶液等で処理して水酸化物
の共沈物を生じさせ、ついで湯洗、乾燥して製作すると
いう方法である。第２の方法は、コバルトを含む硝酸ニ
ッケル溶液を１５０〜２５０℃の温度で加熱処理した後
、さらに水酸化ナトリウム水溶液等のアカリ水溶液に浸
漬してから、湯洗、乾燥するという方法である。Although nickel hydroxide powder containing cobalt hydroxide was used in Example 3, this powder can usually be produced by the following two methods. The first method is to treat a cobalt-containing nickel sulfate aqueous solution, nickel chloride aqueous solution, or nickel nitrate aqueous solution with an alkaline aqueous solution, such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, etc. to produce a coprecipitate of hydroxide; The method is to wash it in hot water and dry it. The second method is to heat-treat a nickel nitrate solution containing cobalt at a temperature of 150 to 250°C, and then immerse it in an alkali aqueous solution such as a sodium hydroxide aqueous solution, followed by washing with hot water and drying.
次に前記のようにして得られた本発明による正極活物質
と負極にリチウムを用いた非水電解液電池について述べ
る。Next, a non-aqueous electrolyte battery using the positive electrode active material according to the present invention obtained as described above and lithium for the negative electrode will be described.
実施例１で得た活物質ｏ、４ｇと導電材として１５ｖｔ
％のグラフフィト、結着剤として５ｗｔ％のポリテトラ
フルオロエチレン粉末をよく混合した後、４００Ｋｑ／
−の圧力で円板状（１１ｍｍφ）に成形して正極板を作
り、負楊板は金属リチウムを圧延した１、２５ｍｍのシ
ートから円板状（７，５ｎ＋ｍφ）を打法いて製作した
。このリチウム負極をステンレス製の負極缶に溶接した
ステンレス網の集電体に圧着し、正極板も同様に正極缶
に圧着させた。電解液には過塩素酸リチウム（Ｌｉ Ｃ
１０４）を１ ｍｏｌＺ見溶解させたプロピレンカー
ボネートを用い、これをポリプロピレン不織布のせパレ
ータに含浸させて使用した。これらのエレメントをポリ
プロピレン類の絶縁バッキングを介してかしめ、外形１
１．６ｍｍ、高さ４．２ｍｍの本発明によるボタン形非
水電解液電池をＶ１作した。この電池を八とする。また
実施例２，３および４で１ワた本発明による正極活物質
を用いて、前記と同様な方法でリチウムを負極とする非
水電解液電池を製作した。この場合は、電池Ａの場合と
異なり、活物質粉末にはすでに導電材としてのグラファ
イトが含まれているため、新たにグラファイトを添加し
なかった。実施例２、実施例３および実施例４の活物質
を用いた電池をそれぞれＢ、ＣおよびＤとする。4g of the active material o obtained in Example 1 and 15vt as a conductive material
% of graphite and 5 wt% of polytetrafluoroethylene powder as a binder were thoroughly mixed, and then 400Kq/
A positive electrode plate was made by molding it into a disk shape (11 mmφ) under a pressure of -, and a negative toothpick plate was produced by punching a disk shape (7.5 n+mφ) from a 1.25 mm sheet of rolled metallic lithium. This lithium negative electrode was crimped to a stainless steel mesh current collector welded to a stainless steel negative electrode can, and the positive electrode plate was similarly crimped to the positive electrode can. The electrolyte contains lithium perchlorate (Li C
104) was dissolved in 1 molZ of propylene carbonate, and a polypropylene nonwoven fabric pallet was impregnated with the propylene carbonate. These elements are caulked through an insulating backing made of polypropylene, and the outer diameter is 1.
A button-shaped non-aqueous electrolyte battery according to the present invention having a size of 1.6 mm and a height of 4.2 mm was manufactured as V1. Let's call this battery 8. In Examples 2, 3, and 4, non-aqueous electrolyte batteries with lithium as a negative electrode were manufactured in the same manner as described above using one watt of the positive electrode active material according to the present invention. In this case, unlike the case of Battery A, since the active material powder already contained graphite as a conductive material, no new graphite was added. Batteries using the active materials of Example 2, Example 3, and Example 4 are designated as B, C, and D, respectively.
これらの電池を２０℃の温度下で１ １１１Ａの電流で
、端子電圧が４．５Ｖになるまで充電した後、２０にΩ
の定抵抗を介して２．５Ｖまで放電した時の放電特性を
図に示す。After charging these batteries at a temperature of 20°C with a current of 1111A until the terminal voltage reached 4.5V, the voltage was reduced to 20Ω.
The figure shows the discharge characteristics when discharging to 2.5V through a constant resistance.
図より、本発明による正極活ｖＩＪ質を用いた電池は充
放電が可能であり、その族７１７４圧は３．４〜３．７
Ｖである。その中で、正極活物質にコバルトを含んだ電
池Ｃの放電持続時間が最も長く良好であるが、活物質製
造時に水酸化リチウムと水酸化ナトリウムの混合水溶液
を用いてアノード酸化した電池りの放電持続時間が短か
った。またそれぞれの′ｔ′Ｇ池を同様な条件で充放電
を３回行なったところ、いずれの電池の場合も、３回目
の放電持続時間は第１サイクルロの約８０％となったが
、充放電を繰り返すことができた。From the figure, the battery using the positive electrode active VIJ material according to the present invention can be charged and discharged, and the group 7174 voltage is 3.4 to 3.7.
It is V. Among them, Battery C, which contains cobalt in the positive electrode active material, has the longest discharge duration and is good; The duration was short. Furthermore, when each 't'G battery was charged and discharged three times under the same conditions, the duration of the third discharge was approximately 80% of the first cycle, but the was able to repeat.
比較のためにアルカリニ次電池用に使用されている水酸
化ニッケルを用いて同様なボタン形非水電解液電池を製
作して、同様な充放電を行なったが、充放電は不可能で
あった。For comparison, we fabricated a similar button-shaped non-aqueous electrolyte battery using nickel hydroxide, which is used for alkaline secondary batteries, and performed similar charging and discharging, but charging and discharging was not possible. .
このように本発明による正極活物質は充放電が可能であ
る。その理由を調べるために、実施例１〜４で製作した
本発明による正極活物質についてＸｒＡ回析分析分析な
ったところ、いずれの場合にも１−ｉＮｉ０２の回折ビ
ークが検出された。したがって、本究明による正極活物
質の活性度は１−ｉＮ１０２によるものと推定され、充
電を行なうとこのリチウムが電解液中に移動し、放電時
には逆にリチウムが活物質中に入ってゆくことにより、
活性度が生ずるものと考えられる。In this way, the positive electrode active material according to the present invention can be charged and discharged. In order to investigate the reason, XrA diffraction analysis was performed on the positive electrode active materials according to the present invention prepared in Examples 1 to 4, and a diffraction peak of 1-iNi02 was detected in all cases. Therefore, the activity of the positive electrode active material according to this research is estimated to be due to 1-iN102, and when charging, this lithium moves into the electrolyte, and when discharging, lithium goes into the active material. ,
This is thought to be caused by the degree of activity.
発明の効果
以上述べたように本発明によれば、従来、アルカリニ次
電池の活物質として用いられてきた水酸化ニッケルを改
質して、従来とは異なる新しい非水電解液電池用正極活
物質を得ることができる。Effects of the Invention As described above, according to the present invention, nickel hydroxide, which has conventionally been used as an active material in alkaline secondary batteries, is modified to produce a new positive electrode active material for non-aqueous electrolyte batteries, which is different from conventional ones. can be obtained.
図は本発明により得られた正極活物質を用いた非水電解
液電池の放電特性である。
θ １１！７θ ２６０
３ρθ ４θり教化宵銹狩閲 ／ｈThe figure shows the discharge characteristics of a non-aqueous electrolyte battery using the positive electrode active material obtained according to the present invention. θ 11!7θ 260
3ρθ 4θ Re-enlightenment evening sermon review /h
Claims (2)
リチウムを含むアルカリ水溶液中でアノード酸化するこ
とを特徴とする非水電解液電池用正極活物質の製造方法
。(1) A method for producing a positive electrode active material for a non-aqueous electrolyte battery, which comprises anodizing nickel hydroxide in an aqueous lithium hydroxide solution or an alkaline aqueous solution containing lithium.
徴とする特許請求の範囲第（１）項記載の非水電解液電
池用正極活物質の製造方法。(2) A method for producing a positive electrode active material for a non-aqueous electrolyte battery according to claim (1), characterized in that nickel hydroxide containing cobalt is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61163234A JPH0687419B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing positive electrode active material for non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61163234A JPH0687419B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing positive electrode active material for non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6319761A true JPS6319761A (en) | 1988-01-27 |
| JPH0687419B2 JPH0687419B2 (en) | 1994-11-02 |
Family
ID=15769881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61163234A Expired - Fee Related JPH0687419B2 (en) | 1986-07-10 | 1986-07-10 | Method for producing positive electrode active material for non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0687419B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180574A (en) * | 1990-07-23 | 1993-01-19 | Moli Energy (1990) Limited | Hydrides of lithiated nickel dioxide and secondary cells prepared therefrom |
| US5264201A (en) * | 1990-07-23 | 1993-11-23 | Her Majesty The Queen In Right Of The Province Of British Columbia | Lithiated nickel dioxide and secondary cells prepared therefrom |
| US5783334A (en) * | 1996-04-01 | 1998-07-21 | Japan Storage Battery Co., Ltd. | Method for producing lithium nickelate positive electrode and lithium battery using the same |
| EP0809310A3 (en) * | 1996-05-24 | 1999-12-15 | Japan Storage Battery Company Limited | Lithium battery and method producing positive electrode active material therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1030217A (en) * | 1996-07-18 | 1998-02-03 | Tepitsukusu:Kk | Display partition body and display body |
-
1986
- 1986-07-10 JP JP61163234A patent/JPH0687419B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180574A (en) * | 1990-07-23 | 1993-01-19 | Moli Energy (1990) Limited | Hydrides of lithiated nickel dioxide and secondary cells prepared therefrom |
| US5264201A (en) * | 1990-07-23 | 1993-11-23 | Her Majesty The Queen In Right Of The Province Of British Columbia | Lithiated nickel dioxide and secondary cells prepared therefrom |
| EP0702421A1 (en) | 1990-07-23 | 1996-03-20 | Moli Energy (1990) Limited | Lithiated nickel dioxide and secondary cells prepared therefrom |
| US5783334A (en) * | 1996-04-01 | 1998-07-21 | Japan Storage Battery Co., Ltd. | Method for producing lithium nickelate positive electrode and lithium battery using the same |
| EP0809310A3 (en) * | 1996-05-24 | 1999-12-15 | Japan Storage Battery Company Limited | Lithium battery and method producing positive electrode active material therefor |
| US6335119B1 (en) | 1996-05-24 | 2002-01-01 | Japan Storage Battery Co., Ltd. | Lithium battery and method of producing positive electrode active material therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0687419B2 (en) | 1994-11-02 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |