JPH10289716A - Nickel-hydrogen storage battery - Google Patents
Nickel-hydrogen storage batteryInfo
- Publication number
- JPH10289716A JPH10289716A JP9095482A JP9548297A JPH10289716A JP H10289716 A JPH10289716 A JP H10289716A JP 9095482 A JP9095482 A JP 9095482A JP 9548297 A JP9548297 A JP 9548297A JP H10289716 A JPH10289716 A JP H10289716A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- hydroxide
- positive electrode
- hydrogen storage
- active material
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケル−水素蓄
電池に関するもので、正極活物質を改良して、その容量
密度を向上させるとともに、正極の特性を高めたもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nickel-hydrogen storage battery, in which a positive electrode active material is improved to increase its capacity density and to improve characteristics of a positive electrode.
【０００２】[0002]
【従来の技術】近年、アルカリ蓄電池は、携帯機器の普
及に伴いその高容量化が要望されている。特にニッケル
−水素蓄電池は、水酸化ニッケルを主体とした活物質か
らなる正極と、水素吸蔵合金を主体とした負極からなる
二次電池であり、高容量で高信頼性の二次電池として急
速に普及してきている。2. Description of the Related Art In recent years, with the spread of portable devices, there has been a demand for higher capacity alkaline storage batteries. In particular, nickel-hydrogen storage batteries are secondary batteries consisting of a positive electrode made of an active material mainly composed of nickel hydroxide and a negative electrode mainly composed of a hydrogen storage alloy, and are rapidly becoming high-capacity and highly reliable secondary batteries. It is becoming popular.
【０００３】アルカリ蓄電池用の正極としては、大別し
て焼結式と非焼結式とがある。焼結式正極は、ニッケル
粉末を焼結して得た多孔度８０％程度の多孔質ニッケル
焼結基板に、硝酸ニッケル水溶液等のニッケル塩溶液を
含浸し、次いで、アルカリ水溶液に浸漬するなどして多
孔質ニッケル焼結基板中に水酸化ニッケル活物質を生成
させて製造するものである。この電極は基板の多孔度を
これ以上大きくする事が困難であるため、充填される活
物質量を増加させる事ができず、高容量化には限界があ
る。The positive electrode for an alkaline storage battery is roughly classified into a sintered type and a non-sintered type. The sintered positive electrode is prepared by impregnating a nickel salt solution such as a nickel nitrate aqueous solution into a porous nickel sintered substrate having a porosity of about 80% obtained by sintering nickel powder, and then immersing the substrate in an alkaline aqueous solution. To produce a nickel hydroxide active material in a porous nickel sintered substrate. Since it is difficult to further increase the porosity of the substrate in this electrode, the amount of the filled active material cannot be increased, and there is a limit to increasing the capacity.
【０００４】非焼結式正極は、例えば、特開昭６０−４
０６６７号公報に開示された、ニッケル金属よりなる三
次元的に連続した多孔度９５％以上のスポンジ状多孔体
の孔部に、活物質である水酸化ニッケルを充填するもの
である。これは現在高容量のアルカリ蓄電池の正極とし
て広く用いられている。A non-sintered positive electrode is disclosed in, for example,
No. 0667 discloses a method in which three-dimensionally continuous sponge-like porous material made of nickel metal and having a porosity of 95% or more is filled with nickel hydroxide as an active material. It is currently widely used as the positive electrode of high capacity alkaline storage batteries.
【０００５】この非焼結式正極においては、高容量化の
点から、球状の水酸化ニッケルをスポンジ状ニッケル多
孔体の孔部に充填することが提案されている。これはス
ポンジ状ニッケル多孔体の孔部（ポア）サイズが、２０
０〜５００μｍ程度であり、このポアに粒径が数μｍ〜
数１０μｍの球状水酸化ニッケルを充填するものであ
る。この構成では、ニッケル多孔体の骨格近傍の水酸化
ニッケルは導電性が保たれているので、充放電反応がス
ムーズに進行するが、骨格から離れた水酸化ニッケルの
反応は十分に進まない。In this non-sintered type positive electrode, it has been proposed that spherical nickel hydroxide be filled into the pores of a sponge-like nickel porous material from the viewpoint of increasing the capacity. This is because the pore size of the sponge-like nickel porous body is 20
0 to 500 μm, and the pores have a particle size of several μm
It is filled with spherical nickel hydroxide of several tens of μm. In this configuration, the nickel hydroxide in the vicinity of the skeleton of the porous nickel body maintains conductivity, so that the charge / discharge reaction proceeds smoothly, but the reaction of nickel hydroxide separated from the skeleton does not sufficiently proceed.
【０００６】このため、非焼結式正極は、充填した水酸
化ニッケルの利用率を向上させるために、活物質である
水酸化ニッケル以外に導電剤を用いて、これで球状水酸
化ニッケルの粒子間を電気的に接続させて導電性ネット
ワークを形成している。この導電剤としては、水酸化コ
バルト、一酸化コバルトのようなコバルト化合物や、金
属コバルト、金属ニッケル等が用いられる。これによ
り、非焼結式正極では、活物質を高密度に充填しても導
電性を保つことが可能となり、高容量化が図れる。[0006] For this reason, the non-sintered positive electrode uses a conductive agent in addition to nickel hydroxide as an active material in order to improve the utilization of the filled nickel hydroxide. The conductive network is formed by making electrical connection between them. As the conductive agent, a cobalt compound such as cobalt hydroxide or cobalt monoxide, metallic cobalt, metallic nickel or the like is used. As a result, the non-sintered positive electrode can maintain conductivity even when the active material is filled at a high density, and can achieve high capacity.
【０００７】[0007]
【発明が解決しようとする課題】しかし、非焼結式正極
の活物質として用いられる球状水酸化ニッケルは、その
放電状態では活性水酸化ニッケル（β−Ｎｉ（Ｏ
Ｈ）2）とよばれるもので、ニッケルの平均価数は２．
１価である。この活物質は、充電状態ではβ型オキシ水
酸化ニッケル（β−ＮｉＯＯＨ）になり、ニッケルの平
均価数は３．１価近傍といわれている。However, the spherical nickel hydroxide used as the active material of the non-sintered positive electrode is in a discharged state in which activated nickel hydroxide (β-Ni (O
H) 2 ), and the average valence of nickel is 2.
It is monovalent. This active material becomes β-type nickel oxyhydroxide (β-NiOOH) in a charged state, and the average valence of nickel is said to be around 3.1.
【０００８】したがって、充放電では、ほぼ一電子反応
で利用率が１００％となる。（利用率は一電子反応を仮
定した理論単位重量当り容量２８９ｍＡｈ／ｇで実際に
計測される容量を割った値の百分率）その結果、この活
物質を用いると正極の容量密度は６５０ｍＡｈ／ｃｃ程
度になる。[0008] Therefore, in charge and discharge, the utilization rate becomes 100% by almost one-electron reaction. (The utilization is a percentage of a value obtained by dividing a capacity actually measured by a capacity per theoretical unit weight of 289 mAh / g assuming a one-electron reaction.) As a result, when this active material is used, the capacity density of the positive electrode is about 650 mAh / cc. become.
【０００９】また、ニッケル−水素蓄電池は、低温で連
続過充電を行なうと、正極のニッケル価数は、さらに高
次になり、３．６７価まで価数が上昇する事も確認され
ている。[0009] It has also been confirmed that when a nickel-hydrogen storage battery is continuously overcharged at a low temperature, the nickel valence of the positive electrode becomes higher and rises to 3.67 valence.
【００１０】しかし、ニッケルの平均価数が３．５価付
近を越えると水酸化ニッケルはγ型オキシ水酸化ニッケ
ル（γ−ＮｉＯＯＨ）になる。γ−ＮｉＯＯＨは、Ｃｕ
Ｋαを線源としたＸ線回折における回折角２θが１２度
付近（λ＝１．５４０５）に（００３）面の回折ピーク
をもつ物質で、ニッケル−ニッケル金属面の層間にカチ
オン、アニオンや水等が挿入されており、β−ＮｉＯＯ
Ｈ（密度４．６８ｇ／ｃｍ3）に比較して結晶が膨張し
易い。However, when the average valence of nickel exceeds about 3.5, the nickel hydroxide becomes γ-type nickel oxyhydroxide (γ-NiOOH). γ-NiOOH is Cu
A substance having a (003) plane diffraction peak at a diffraction angle 2θ of about 12 degrees (λ = 1.5405) in X-ray diffraction using Kα as a source. Cations, anions and water are present between the nickel-nickel metal plane layers. Are inserted, β-NiOO
The crystals are more likely to expand than H (density 4.68 g / cm 3 ).
【００１１】また、γ−ＮｉＯＯＨ（密度３．７９ｇ／
ｃｍ3）は、放電する際にα−３Ｎｉ（ＯＨ）2・２Ｈ2
Ｏ（密度２．８２ｇ／ｃｍ3）になる。この時の密度変
化は大きく、したがって活物質は膨張収縮を繰り返して
起こす。そのため球状水酸化ニッケルは、球状が崩れて
しまったり、充電状態のγ−ＮｉＯＯＨが放電しないで
蓄積されるため正極が膨潤して、電池内の電解液を吸っ
てしまう。Γ-NiOOH (density 3.79 g /
cm 3 ) is α-3Ni (OH) 2 .2H 2 when discharging.
O (density 2.82 g / cm 3 ). At this time, the density change is large, and thus the active material repeatedly expands and contracts. Therefore, the spherical nickel hydroxide loses its spherical shape, and the charged γ-NiOOH is accumulated without being discharged, so that the positive electrode swells and absorbs the electrolytic solution in the battery.
【００１２】その結果として、セパレータの保有してい
る電解液量が減少して液がれ状態になり、電池の内部抵
抗が上昇して放電が不可能になる。この現象は焼結式正
極を用いた場合でも古くから知られており、とくに密閉
型電池では正極の膨潤による電池特性の劣化が起こる。As a result, the amount of the electrolytic solution held by the separator is reduced and the electrolyte is leaked, and the internal resistance of the battery is increased, so that the battery cannot be discharged. This phenomenon has been known for a long time even when a sintered positive electrode is used. Particularly in a sealed battery, the battery characteristics deteriorate due to swelling of the positive electrode.
【００１３】本発明は、上記課題を解決するもので、正
極活物質を改良して、その容量密度を向上させるととも
に、正極の特性を高めたニッケル−水素蓄電池を提供す
ることを目的とする。An object of the present invention is to provide a nickel-hydrogen storage battery that improves the positive electrode active material, improves the capacity density thereof, and improves the characteristics of the positive electrode.
【００１４】[0014]
【課題を解決するための手段】上記目的を達成するため
に、本発明のニッケル−水素蓄電池は、水酸化ニッケル
を活物質の主体とした正極と、水素吸蔵合金を主体とし
た負極と、アルカリ電解液と、セパレータとからなり、
正極の主活物質である水酸化ニッケルは、遷移金属のう
ちの少なくとも１種類と、アルカリ土類金属のうちの少
なくとも１種類を固溶していて、充電状態のそれの結晶
構造はＣｕＫαを線源としたＸ線回折における回折角２
θが１６〜１９度付近に（００ｌ）面の回折ピークをも
つ六方晶系もしくは正方晶系で、規則配列がＮａＣｌ型
構造をもったものである。In order to achieve the above object, a nickel-hydrogen storage battery according to the present invention comprises a positive electrode mainly composed of nickel hydroxide as an active material, a negative electrode mainly composed of a hydrogen storage alloy, and an alkaline battery. Consisting of an electrolyte and a separator,
Nickel hydroxide, which is the main active material of the positive electrode, has at least one kind of transition metal and at least one kind of alkaline earth metal in a solid solution, and its crystal structure in a charged state is CuKα. Diffraction angle 2 in X-ray diffraction used as source
is a hexagonal system or a tetragonal system having a (00l) plane diffraction peak at about θ of 16 to 19 degrees, and a regular arrangement having a NaCl type structure.
【００１５】[0015]
【発明の実施の形態】請求項１に記載の発明は、正極活
物質が前記に示す結晶構造をもち、充電状態ではニッケ
ルの平均価数が３．５価という、β−ＮｉＯＯＨより高
次の価数になるので、反応電子数が増加して活物質の容
量密度が向上するとともに、正極の特性を向上させるこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION According to the first aspect of the present invention, the positive electrode active material has the crystal structure described above, and in a charged state, the average valence of nickel is 3.5, which is higher than β-NiOOH. Since the valence becomes valence, the number of reactive electrons increases, the capacity density of the active material improves, and the characteristics of the positive electrode can be improved.
【００１６】請求項２に記載の発明は、水酸化ニッケル
に固溶する金属は、遷移金属がＭｎ，Ａｌ，Ｃｒおよび
Ｃｏのうちの少なくとも１種類であること、アルカリ土
類金属がＭｇ，Ｃａ，ＳｒおよびＢａのうちの少なくと
も１種類であることを規定したものであり、充電状態の
それの結晶構造はＣｕＫαの線源としたＸ線回折におけ
る回折角２θが１６〜１９度付近に（００ｌ）面の回折
ピークをもつ六方晶系、もしくは正方晶系で、規則配列
がＮａＣｌ型構造であるのが好ましい。According to a second aspect of the present invention, the metal which forms a solid solution in nickel hydroxide is such that the transition metal is at least one of Mn, Al, Cr and Co, and the alkaline earth metal is Mg, Ca , Sr, and Ba, and the crystal structure of the charged state has a diffraction angle 2θ of about 16 to 19 degrees in X-ray diffraction using a CuKα radiation source (00l). ) It is preferable that a hexagonal system or a tetragonal system having a plane diffraction peak and a regular arrangement be a NaCl type structure.
【００１７】この規定した金属の好ましい固溶量は、水
酸化ニッケルの金属ニッケルに対して遷移金属が２〜１
０原子％、アルカリ土類金属が５〜１０原子％が適量で
ある。もし、この遷移金属の量が２原子％よりも少ない
か、またはアルカリ土類金属の量が５原子％より少ない
と、水酸化ニッケルに対する固溶量が十分でなく上記の
回折ピークが得られない。また、逆にその固溶量が１０
原子％よりも多いと、活物質である水酸化ニッケル自体
の量が相対的に減少して正極への活物質の充填量が少な
くなるので、正極の容量が低下する。The preferred solid solution amount of the specified metal is such that the transition metal is 2 to 1 with respect to the metal nickel of the nickel hydroxide.
The appropriate amount is 0 atomic% and the alkaline earth metal is 5 to 10 atomic%. If the amount of the transition metal is less than 2 atomic% or the amount of the alkaline earth metal is less than 5 atomic%, the solid solution amount to nickel hydroxide is not sufficient and the above-mentioned diffraction peak cannot be obtained. . Conversely, when the solid solution amount is 10
If the content is more than atomic%, the amount of nickel hydroxide itself, which is the active material, is relatively reduced, and the amount of the active material filled in the positive electrode is reduced, so that the capacity of the positive electrode is reduced.
【００１８】[0018]
【実施例】正極板としては、活物質である平均粒径１５
μｍの球状の水酸化ニッケル粉末にその金属ニッケルに
対してＭｎを８原子％，Ｃａを８原子％を固溶させたも
の１００重量部に、結着剤としてポリテトラフルオロエ
チレン０．５重量部と、導電剤として水酸化コバルト１
０重量部と、分散媒としての適量の水を加えてペースト
状とし、これをスポンジ状ニッケル多孔体の孔部に充填
した後乾燥し、ロールプレス機で圧延して作製した。こ
の正極板の寸法は、幅３５ｍｍ、長さ１２０ｍｍ、厚さ
０．７８ｍｍとした。この正極の理論容量（水酸化ニッ
ケルが１電子反応であると仮定して２８９ｍＡｈ／ｇと
して計算する）は１６００ｍＡｈであった。EXAMPLES As a positive electrode plate, an average particle size of 15 as an active material was used.
μm spherical nickel hydroxide powder in which 8 atomic% of Mn and 8 atomic% of Ca are dissolved in the metal nickel, 100 parts by weight, and 0.5 parts by weight of polytetrafluoroethylene as a binder And cobalt hydroxide 1 as a conductive agent
A paste was prepared by adding 0 parts by weight and an appropriate amount of water as a dispersion medium, filling the paste into the pores of the sponge-like nickel porous body, drying, and rolling with a roll press. The dimensions of the positive electrode plate were 35 mm in width, 120 mm in length, and 0.78 mm in thickness. The theoretical capacity of this positive electrode (calculated as 289 mAh / g assuming that nickel hydroxide is a one-electron reaction) was 1600 mAh.
【００１９】負極板としては、ＡＢ5型水素吸蔵合金粉
末１００重量部と、炭素粉末１重量部と、ポリテトラフ
ルオロエチレン１重量部と、適量の水を加えてペースト
状とし、これをパンチングメタルに塗布して乾燥した
後、圧延した。この負極板の寸法は、幅３５ｍｍ、長さ
１４５ｍｍ、厚み０．３９ｍｍとした。この負極の理論
容量(水素吸蔵合金の単位重量当りの電気量は２８０ｍ
Ａｈ／ｇとして計算する）は２９００ｍＡｈであった。[0019] the negative electrode plate, and the AB 5 type hydrogen absorbing alloy powder 100 parts by weight, and the carbon powder 1 part by weight, polytetrafluoroethylene 1 part by weight, a paste by adding an appropriate amount of water, which punched metal And then rolled. The dimensions of the negative electrode plate were 35 mm in width, 145 mm in length, and 0.39 mm in thickness. The theoretical capacity of this negative electrode (the amount of electricity per unit weight of the hydrogen storage alloy is 280 m
(Calculated as Ah / g) was 2900 mAh.
【００２０】上記で作製した正極板と、負極板と、この
両者間にポリプロピレン不織布製セパレータを配して全
体を渦巻状に巻回して極板群を構成し、これを電池ケー
スに挿入し、アルカリ電解液として水酸化ナトリウム１
０ｍｏｌ／ｌの水溶液を所定量注入した後、正極端子を
兼ねる封口板で密閉して４／５Ａサイズで、公称容量１
６００ｍＡｈのニッケル−水素蓄電池Ａを構成した。A positive electrode plate, a negative electrode plate, and a separator made of a nonwoven polypropylene fabric are disposed between the two, and the whole is spirally wound to form an electrode plate group, which is inserted into a battery case. Sodium hydroxide 1 as alkaline electrolyte
After injecting a predetermined amount of 0 mol / l aqueous solution, it is sealed with a sealing plate also serving as a positive electrode terminal, and is 4 / 5A in size, with a nominal capacity of 1
A 600 mAh nickel-hydrogen storage battery A was configured.
【００２１】また、上記で作製した正極板用活物質に代
えて、ＭｎとＣａを固溶させていない水酸化ニッケルを
用いた以外は、上記と同様な構成とした電池を比較例の
電池Ｂとした。A battery having the same structure as that of Comparative Example B except that nickel hydroxide in which Mn and Ca were not dissolved was used instead of the positive electrode plate active material prepared above. And
【００２２】この電池Ａ，Ｂそれぞれを１６０ｍＡで１
５時間充電し、１時間放置した後、３２０ｍＡで端子電
圧が１Ｖに至るまで放電する充放電サイクルを２回行な
った。Each of the batteries A and B was charged at 160 mA for 1
After charging for 5 hours and allowing to stand for 1 hour, two charge / discharge cycles were performed at 320 mA until the terminal voltage reached 1 V.
【００２３】さらに４５℃の温度雰囲気で３日間放置す
るエージングを行なった後、２０℃の温度雰囲気下で１
６０ｍＡの電流で１８時間充電し、１時間放置した後、
３２０ｍＡで端子電圧１Ｖに至るまで放電した。この時
の放電容量から求めた正極の活物質利用率（実際の放電
容量/正極理論容量を２８９ｍＡｈとした際の百分率）
は、電池Ａが１３３％であり、電池Ｂは１００％であっ
た。Further, after aging for 3 days in a temperature atmosphere of 45 ° C.,
After charging for 18 hours with a current of 60 mA and leaving for 1 hour,
Discharge was performed at 320 mA until the terminal voltage reached 1 V. The active material utilization rate of the positive electrode obtained from the discharge capacity at this time (percentage when the actual discharge capacity / the positive electrode theoretical capacity is 289 mAh)
The battery A was 133% and the battery B was 100%.
【００２４】確認のために、充電状態の電池Ａ，Ｂをそ
れぞれ分解して正極板を取り出し、活物質のＣｕＫαを
線源とした（波長λが１．５４０５）Ｘ線回折による分
析を行った。この分析により、回折角２θを求めた結
果、電池Ａの正極板は２θが１７度近くに（００ｌ）面
の回折ピークが確認できたが、電池Ｂの正極板は、電池
Ａのそれと同様な回折ピークを確認できなかった。For confirmation, the batteries A and B in the charged state were respectively disassembled, the positive electrode plate was taken out, and analyzed by X-ray diffraction using CuKα as an active material as a radiation source (wavelength λ was 1.5405). . The diffraction angle 2θ was determined by this analysis. As a result, a diffraction peak of the (00l) plane was confirmed in the positive electrode plate of Battery A at 2θ of about 17 °, but the positive electrode plate of Battery B was similar to that of Battery A. No diffraction peak could be confirmed.
【００２５】このことより、比較例の電池Ｂは、正極活
物質が充電状態では、β−ＮｉＯＯＨになり、そのニッ
ケルの平均価数は３．１価であるので、その正極活物質
の利用率は１００％になったものである。From the above, in the battery B of the comparative example, when the positive electrode active material is in a charged state, it becomes β-NiOOH, and the average valence of nickel is 3.1. Is 100%.
【００２６】実施例の電池Ａは、正極活物質が充電状態
では高次のニッケル酸化状態となり、平均価数も３．５
価と高まるので、比較例よりも反応電子数が増加し、水
酸化ニッケルそのものの容量密度が向上する。そのため
正極活物質の利用率は１３３％となり、比較例より３３
％向上した。In the battery A of the embodiment, when the positive electrode active material is in a charged state, it is in a higher nickel oxidation state and has an average valence of 3.5.
Since the number of reaction electrons increases, the number of reactive electrons increases as compared with the comparative example, and the capacity density of nickel hydroxide itself improves. Therefore, the utilization rate of the positive electrode active material was 133%, which was 33% higher than that of the comparative example.
% Improved.
【００２７】なお、本発明の実施例では、正極活物質で
ある水酸化ニッケルに、その金属ニッケルに対してＭｎ
を８原子％，Ｃａを８原子％固溶させたものを用いた
が、Ｍｎの固溶量は２〜１０原子％，Ｃａの固溶量は５
〜１０原子％の範囲であれば、実施例とほぼ同様な効果
が得られ、好ましい固溶量の範囲はＭｎが５〜１０原子
％，Ｃａが５〜１０原子％であった。In the embodiment of the present invention, nickel hydroxide as a positive electrode active material is provided with Mn with respect to the metal nickel.
Was used as a solid solution of 8 at% and Ca at 8 at%, but the solid solution amount of Mn was 2 to 10 atom% and the solid solution amount of Ca was 5%.
When the content is in the range of 10 to 10 atomic%, almost the same effect as in the example is obtained, and the preferable range of the solid solution amount is 5 to 10 atomic% for Mn and 5 to 10 atomic% for Ca.
【００２８】さらに、本発明の実施例では、正極活物質
である水酸化ニッケルへの固溶金属としては、遷移金属
がＭｎ、アルカリ土類金属がＣａとしたが、この外に遷
移金属はＡｌ，ＣｒおよびＣｏのうちのいずれか１種類
を、アルカリ土類金属はＭｇ，ＳｒおよびＢａのうちの
いずれか１種類を用いても実施例とほぼ同様な効果が得
られる。この際のそれぞれの金属の固溶量は、活物質で
ある水酸化ニッケルの金属ニッケルに対して、遷移金属
としてはＡｌならば２〜８原子％，Ｃｒならば２〜１０
原子％，Ｃｏならば７〜１０原子％、アルカリ土類金属
としてはＭｇならば５〜１０原子％，Ｓｒならば６〜１
０原子％，Ｂａならば６〜１０原子％が好ましい結果で
あった。Further, in the embodiment of the present invention, the transition metal was Mn and the alkaline earth metal was Ca as a solid solution metal in nickel hydroxide as the positive electrode active material. , Cr and Co, and the alkaline earth metal using any one of Mg, Sr and Ba can provide substantially the same effects as those of the embodiment. In this case, the solid solution amount of each metal is 2 to 8 atomic% for Al as a transition metal and 2 to 10 for Cr as a transition metal with respect to metallic nickel of nickel hydroxide as an active material.
Atomic%, 7-10 atomic% for Co, 5-10 atomic% for Mg as alkaline earth metal, and 6-1 for Sr.
0 at% and Ba to 6 to 10 at% were favorable results.
【００２９】さらにまた、正極活物質である水酸化ニッ
ケルへの固溶金属としては、前記のように遷移金属単独
とアルカリ土類金属単独の組み合わせばかりでなく、遷
移金属がＭｎ，Ａｌ，ＣｒおよびＣｏのうちのいずれか
を主体に組合わた併用状態と、アルカリ土類金属がＭ
ｇ，Ｃａ，ＳｒおよびＢａのいずれかを組み合わせた併
用状態でも実施例とほぼ同様な効果が得られる。その併
用時の固溶金属の総量は、活物質である水酸化ニッケル
の金属ニッケルに対して、遷移金属が２〜１０原子％、
アルカリ土類金属が５〜１０原子％の範囲とするのが好
ましい。Further, as a solid solution metal in nickel hydroxide as a positive electrode active material, not only a combination of a transition metal alone and an alkaline earth metal alone as described above, but also a transition metal of Mn, Al, Cr and Co in combination with any one of Co and M
In the combined state in which any one of g, Ca, Sr and Ba is combined, substantially the same effects as in the embodiment can be obtained. The total amount of the solid solution metal in the combined use is such that the transition metal is 2 to 10 atomic% with respect to the metal nickel of nickel hydroxide as the active material,
Preferably, the alkaline earth metal is in the range of 5 to 10 atomic%.
【００３０】なお、アルカリ電解液としては、前記では
水酸化ナトリウム１０ｍｏｌ／ｌの水溶液を用いたが、
この濃度に限定されるものではなく８〜１２ｍｏｌ／ｌ
の範囲であれば、実施例とほぼ同様な効果が得られる。As the alkaline electrolyte, an aqueous solution of sodium hydroxide 10 mol / l was used in the above,
It is not limited to this concentration but 8 to 12 mol / l
Within this range, substantially the same effects as in the embodiment can be obtained.
【００３１】また、上記のアルカリ電解液は水酸化ナト
リウムの単独水溶液としたが、これに限らず水酸化カリ
ウムの単独水溶液かあるいはこれらの混合水溶液、さら
にはこれらに水酸化リチウム、水酸化ルビジウムおよび
水酸化セシウムのうちの少なくとも１種類を加えた混合
水溶液を用いても、実施例とほぼ同様な効果が得られ
る。The above-mentioned alkaline electrolyte is a single aqueous solution of sodium hydroxide. However, the present invention is not limited to this. A single aqueous solution of potassium hydroxide or a mixed aqueous solution thereof, and further, lithium hydroxide, rubidium hydroxide and Even when a mixed aqueous solution to which at least one of cesium hydroxide is added is used, substantially the same effects as in the embodiment can be obtained.
【００３２】[0032]
【発明の効果】以上のように本発明の電池では正極の主
活物質である水酸化ニッケルは、遷移金属のうちの少な
くとも１種類と、アルカリ土類金属のうちの少なくとも
１種類を固溶していて、充電状態のそれはＣｕＫαを線
源としたＸ線回折における回折角２θの１６〜１９度付
近に（００ｌ）面の回折ピークをもつ六方晶系もしくは
正方晶系で、規則配列がＮａＣｌ型構造をもったもので
あるので、充電状態ではニッケルの平均価数が３．５価
と高次の価数になって、反応電子数が増加し活物質の容
量密度が向上して、正極の特性を高めることができる。As described above, in the battery of the present invention, nickel hydroxide, which is the main active material of the positive electrode, forms a solid solution of at least one of transition metals and at least one of alkaline earth metals. The charged state is a hexagonal or tetragonal system having a (00l) plane diffraction peak at a diffraction angle 2θ of 16 to 19 degrees around 16 to 19 degrees in X-ray diffraction using CuKα as a radiation source. In the charged state, the average valence of nickel becomes a higher valence of 3.5 valences, the number of reactive electrons increases, the capacity density of the active material increases, and the Characteristics can be enhanced.
フロントページの続き (72)発明者 湯浅 浩次 大阪府門真市大字門真1006番地 松下電器 産業株式会社内Continuation of front page (72) Inventor Koji Yuasa 1006 Kazuma Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.
Claims (6)
と、水素吸蔵合金を主体とした負極と、アルカリ電解液
と、セパレータとからなり、前記正極の主活物質である
水酸化ニッケルは、遷移金属のうちの少なくとも１種類
と、アルカリ土類金属のうちの少なくとも１種類を固溶
していて、充電状態のそれはＣｕＫαを線源としたＸ線
回折における回折角２θの１６〜１９度付近に（００
ｌ）面の回折ピークをもつ六方晶系もしくは正方晶系
で、規則配列がＮａＣｌ型構造をもったものであるニッ
ケル−水素蓄電池。1. A positive electrode mainly composed of nickel hydroxide as an active material, a negative electrode mainly composed of a hydrogen storage alloy, an alkaline electrolyte, and a separator. , At least one of transition metals and at least one of alkaline earth metals are in solid solution, and the charged state thereof is 16 to 19 degrees of diffraction angle 2θ in X-ray diffraction using CuKα as a radiation source. Near (00
1) A nickel-hydrogen storage battery having a hexagonal or tetragonal system having a plane diffraction peak and a regular arrangement having a NaCl type structure.
うちの少なくとも１種類であって、その固溶量は水酸化
ニッケルの金属ニッケルに対して２〜１０原子％であ
り、アルカリ土類金属はＭｇ，Ｃａ，ＳｒおよびＢａの
うちの少なくとも１種類であって、その固溶量は水酸化
ニッケルの金属ニッケルに対して５〜１０原子％である
請求項１記載のニッケル−水素蓄電池。2. The transition metal is at least one of Mn, Al, Cr and Co, and has a solid solution amount of 2 to 10 at% with respect to the metal nickel of nickel hydroxide. 2. The nickel-hydrogen storage battery according to claim 1, wherein the metal is at least one of Mg, Ca, Sr and Ba, and the amount of the solid solution is 5 to 10 atomic% based on the metal nickel of the nickel hydroxide.
と、水素吸蔵合金を主体とした負極と、アルカリ電解液
と、セパレータとからなり、前記正極の主活物質である
水酸化ニッケルは、その金属ニッケルに対してＭｎを５
〜１０原子％，Ｃａを５〜１０原子％固溶していて、充
電状態のそれはＣｕＫαを線源としたＸ線回折における
回折角２θの１６〜１９度付近に（００ｌ）面の回折ピ
ークをもつ六方晶系もしくは正方晶系で、規則配列がＮ
ａＣｌ型構造をもったものであるニッケル−水素蓄電
池。3. A positive electrode mainly composed of nickel hydroxide as an active material, a negative electrode mainly composed of a hydrogen storage alloy, an alkaline electrolyte, and a separator. And Mn of 5 for the metallic nickel
-10 at% and Ca at 5-10 at% solid solution, and in the charged state, the (00l) plane diffraction peak at around 16-19 degrees of diffraction angle 2θ in X-ray diffraction using CuKα as a source. Hexagonal or tetragonal with regular arrangement of N
A nickel-hydrogen storage battery having an aCl type structure.
は水酸化カリウムの単独水溶液か、あるいは混合水溶液
である請求項１から３のいずれかに記載のニッケル−水
素蓄電池。4. The nickel-hydrogen storage battery according to claim 1, wherein the alkaline electrolyte is a single aqueous solution of sodium hydroxide or potassium hydroxide or a mixed aqueous solution.
は水酸化カリウムの単独水溶液か、あるいは混合水溶液
に、水酸化ルビジウム、水酸化セシウムおよび水酸化リ
チウムのうちの少なくとも１種類を加えた混合水溶液で
ある請求項１から３のいずれかに記載のニッケル−水素
蓄電池。5. The alkaline electrolyte is a single aqueous solution of sodium hydroxide or potassium hydroxide, or a mixed aqueous solution obtained by adding at least one of rubidium hydroxide, cesium hydroxide and lithium hydroxide to a mixed aqueous solution. The nickel-hydrogen storage battery according to any one of claims 1 to 3.
と、水素吸蔵合金を主体とした負極と、水酸化ナトリウ
ムの８〜１２ｍｏｌ／ｌ水溶液からなるアルカリ電解液
と、セパレータとからなり、前記正極の主活物質である
水酸化ニッケルは、その金属ニッケルに対してＭｎを５
〜１０原子％，Ｃａを５〜１０原子％固溶していて、充
電状態のそれはＣｕＫαを線源としたＸ線回折における
回折角２θの１６〜１９度付近に（００ｌ）面の回折ピ
ークをもつ六方晶系もしくは正方晶系で、規則配列がＮ
ａＣｌ型構造をもったものであるニッケル−水素蓄電
池。6. A positive electrode mainly composed of nickel hydroxide as an active material, a negative electrode mainly composed of a hydrogen storage alloy, an alkaline electrolyte comprising 8 to 12 mol / l aqueous solution of sodium hydroxide, and a separator, Nickel hydroxide, which is the main active material of the positive electrode, has an Mn of 5 with respect to the metallic nickel.
-10 at% and Ca at 5-10 at% solid solution, and in the charged state, the (00l) plane diffraction peak at around 16-19 degrees of diffraction angle 2θ in X-ray diffraction using CuKα as a source. Hexagonal or tetragonal with regular arrangement of N
A nickel-hydrogen storage battery having an aCl type structure.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9095482A JPH10289716A (en) | 1997-04-14 | 1997-04-14 | Nickel-hydrogen storage battery |
| US09/058,227 US6074785A (en) | 1997-04-14 | 1998-04-10 | Nickel/metal hydride storage battery |
| DE69837121T DE69837121T2 (en) | 1997-04-14 | 1998-04-14 | Nickel / metal hydride storage battery |
| EP98106730A EP0872904B1 (en) | 1997-04-14 | 1998-04-14 | Nickel/metal hydride storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9095482A JPH10289716A (en) | 1997-04-14 | 1997-04-14 | Nickel-hydrogen storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10289716A true JPH10289716A (en) | 1998-10-27 |
Family
ID=14138841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9095482A Pending JPH10289716A (en) | 1997-04-14 | 1997-04-14 | Nickel-hydrogen storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10289716A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001243973A (en) * | 2000-03-01 | 2001-09-07 | Sanyo Electric Co Ltd | Alkaline storage battery |
| JP2007265670A (en) * | 2006-03-27 | 2007-10-11 | Panasonic Ev Energy Co Ltd | Battery |
-
1997
- 1997-04-14 JP JP9095482A patent/JPH10289716A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001243973A (en) * | 2000-03-01 | 2001-09-07 | Sanyo Electric Co Ltd | Alkaline storage battery |
| JP2007265670A (en) * | 2006-03-27 | 2007-10-11 | Panasonic Ev Energy Co Ltd | Battery |
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