JPH11185747A - Positive electrode material for alkaline storage battery - Google Patents
Positive electrode material for alkaline storage batteryInfo
- Publication number
- JPH11185747A JPH11185747A JP9349799A JP34979997A JPH11185747A JP H11185747 A JPH11185747 A JP H11185747A JP 9349799 A JP9349799 A JP 9349799A JP 34979997 A JP34979997 A JP 34979997A JP H11185747 A JPH11185747 A JP H11185747A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode material
- ray diffraction
- storage battery
- alkaline storage
- 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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Links
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルカリ蓄電池用
正極材及び該正極材を用いたアルカリ蓄電池に関するも
のである。The present invention relates to a cathode material for an alkaline storage battery and an alkaline storage battery using the cathode material.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】ニッケ
ル・カドミウム蓄電池やニッケル・金属水素化物蓄電池
等のアルカリ蓄電池に共通的に使用される水酸化ニッケ
ル正極は、電池の高エネルギー密度化の要望が高まる中
で、従来の焼結式に代えて、高容量密度化が可能なペー
スト式が主体となりつつある。このペースト式ニッケル
正極は、９５％程度の高い多孔度を有する発泡ニッケル
基板やニッケル繊維基板に、水酸化ニッケル粉末をコバ
ルト化合粉末等と共に、充填、加圧成形して得られてい
る。このような発泡ニッケル基板は、ウレタン等の発泡
プラスチックにニッケルをメッキした後に加熱し、発泡
プラスチックを熱分解して発泡金属を得るものである。2. Description of the Related Art A nickel hydroxide positive electrode commonly used in alkaline storage batteries such as nickel-cadmium storage batteries and nickel-metal hydride storage batteries is required to have a high energy density. In the course of the increase, the paste type capable of increasing the capacity density has been mainly used instead of the conventional sintered type. The paste-type nickel positive electrode is obtained by filling a nickel foam powder or a nickel fiber substrate having a high porosity of about 95% with a nickel compound powder and a cobalt compound powder and press-forming. Such a foamed nickel substrate is obtained by plating nickel on a foamed plastic such as urethane and then heating it to thermally decompose the foamed plastic to obtain a foamed metal.
【０００３】アルカリ蓄電池用正極材である水酸化ニッ
ケルの充放電中の反応は、一般的には、β−Ｎｉ（Ｏ
Ｈ)2とβ−ＮｉＯＯＨの間の反応を利用しており、これ
は一電子反応であるが、最も安定な反応であり、汎用さ
れている。The reaction during charging and discharging of nickel hydroxide, which is a positive electrode material for an alkaline storage battery, is generally carried out by β-Ni (O
It utilizes the reaction between H) 2 and β-NiOOH, which is a one-electron reaction, but the most stable and widely used.
【０００４】これをβ−Ｎｉ（ＯＨ)2とγ−ＮｉＯＯＨ
の間の反応を利用することにより多電子反応とすると、
容量が増加するという利点がある。しかし、β−Ｎｉ
（ＯＨ）2 とγ−ＮｉＯＯＨの格子定数差により充放電
時の体積変化が大きいという問題がある。[0004] This is called β-Ni (OH) 2 and γ-NiOOH.
If a multi-electron reaction is obtained by utilizing the reaction between
There is an advantage that capacity is increased. However, β-Ni
There is a problem that the volume change during charging and discharging is large due to the difference in lattice constant between (OH) 2 and γ-NiOOH.
【０００５】一方、α−Ｎｉ（ＯＨ)2とγ−ＮｉＯＯＨ
の間の反応を利用すると、これも多電子反応であるので
容量が増加するという利点があり、かつα−Ｎｉ（Ｏ
Ｈ）2とγ−ＮｉＯＯＨでは格子定数差が小さいので充
放電時の体積変化も小さく、好ましいものである。On the other hand, α-Ni (OH) 2 and γ-NiOOH
Is advantageous in that the capacity is increased because this is also a multi-electron reaction, and α-Ni (O
H) 2 and γ-NiOOH have a small difference in lattice constant, so that the change in volume during charging and discharging is small, which is preferable.
【０００６】しかし、α−Ｎｉ（ＯＨ)2はアルカリ液中
で不安定であり、容易にβ−Ｎｉ（ＯＨ)2に変化してし
まうという問題があり、実用化できない原因となってい
た。。図１に代表的なα−Ｎｉ（ＯＨ)2のＸ線回折図と
そのピークの面指数を示す。However, α-Ni (OH) 2 is unstable in an alkaline solution and easily changes to β-Ni (OH) 2 . . FIG. 1 shows an X-ray diffraction diagram of a typical α-Ni (OH) 2 and the surface index of the peak.
【０００７】このようなα−Ｎｉ（ＯＨ)2を安定化する
試みとして、Ａｌ、Ｆｅ、Ｃｒ等でＮｉの一部を置換し
た報告があり、その中でもＡｌについては、Ａｌ濃度と
電池特性（放電電位）の相関についての報告がなされて
いる（特開昭４９−１０９８４２号公報）。しかし、同
公報においても、同一Ａｌ濃度における水酸化ニッケル
の結晶性と電池特性との相関については何等の報告もな
されていない。As an attempt to stabilize such α-Ni (OH) 2 , there is a report that part of Ni is replaced with Al, Fe, Cr or the like. There is a report on the correlation of the discharge potential (JP-A-49-109842). However, even in this publication, there is no report on the correlation between the crystallinity of nickel hydroxide and the battery characteristics at the same Al concentration.
【０００８】従って、本発明の目的は、利用率を向上さ
せたアルカリ蓄電池用正極材及び該正極材を用いたアル
カリ蓄電池を提供することを目的とする。Accordingly, an object of the present invention is to provide a positive electrode material for an alkaline storage battery with an improved utilization factor and an alkaline storage battery using the positive electrode material.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、鋭意検討
の結果、アルカリ蓄電池用正極材として用いられるアル
ミニウムを含有した水酸化ニッケルとして、そのＸ線回
折図から判断される結晶性を制御することで、アルミニ
ウム濃度を変えずに最大限の利用率を引き出し得ること
を知見した。Means for Solving the Problems As a result of intensive studies, the present inventors have controlled the crystallinity determined from the X-ray diffraction diagram of aluminum-containing nickel hydroxide used as a cathode material for alkaline storage batteries. By doing so, it was found that the maximum utilization rate can be obtained without changing the aluminum concentration.
【００１０】本発明は、上記知見に基づいてなされたも
ので、下記組成式 （Ａｌx Ｎｉ1-x )(ＯＨ)2Ｙ （但し、０．１５＜ｘ＜０．３、Ｙは陰イオン）で表さ
れるα型のＡｌ置換Ｎｉ（ＯＨ)2であって、Ｘ線回折図
における（００３）のピークの半値全幅が１．５ｄｅｇ
未満であることを特徴とするアルカリ蓄電池用正極材を
提供するものである。The present invention has been made based on the above findings, and has the following composition formula (Al x Ni 1 -x ) (OH) 2 Y (where 0.15 <x <0.3, Y is an anion) ) represented by α-type Al-substituted Ni (OH) a 2, full width at half maximum of the peak of the X-ray diffraction diagram (003) is 1.5deg
A positive electrode material for an alkaline storage battery, wherein
【００１１】また、本発明は、上記正極材を用いたアル
カリ蓄電池を提供するものである。Further, the present invention provides an alkaline storage battery using the above-mentioned positive electrode material.
【００１２】[0012]
【作用】合成条件を適当に設定することで、同一Ａｌ濃
度であっても結晶性を向上させ、Ｘ線回折図における
（００３）のピークの半値全幅が１．５ｄｅｇ未満にな
るようにすると、 （１）ｃ面（００１）面の面間隔が狭まる； （２）各ｃ面層のａ軸方向が揃ってくる； といったことが起こることが実験的に判っている。容量
の増大はこれらの事象と次の様に関係づけて考えること
ができる。By appropriately setting the synthesis conditions, the crystallinity can be improved even at the same Al concentration so that the full width at half maximum of the (003) peak in the X-ray diffraction diagram is less than 1.5 deg. It has been experimentally found that (1) the spacing between the c-plane (001) planes is reduced; (2) the a-axis directions of the respective c-plane layers are aligned; The increase in capacity can be considered in relation to these events as follows.
【００１３】水酸化物中でＮｉが２価として存在するの
に対し、Ａｌは３価で取り込まれていると考えられるの
で、その電荷補償のために、ｃ面の層間にＮＯ3 - 、Ｃ
Ｏ3 2 - 等の陰イオンが取り込まれる。しかし現実には、
ＯＨ欠陥も多く存在するので、その分の電荷補償のため
にも同様に陰イオンが層間に取り込まれ、Ａｌの電荷補
償に必要な分よりも多量の陰イオンが存在すると考えら
れる。合成条件を変え結晶性が向上するとｃ面の面間隔
が狭まるのは、ＯＨ欠損が減少しこれを補償していた陰
イオンが減ってＡｌの電荷補償に必要な量に近づいた結
果と考えられる。層間の陰イオンは充放電中のＨ+ の出
入りの障害となりやすいので、これが減少すれば、電池
の利用率が向上すると考えられる。[0013] While the present as bivalent Ni is in a hydroxide, it is considered that Al is incorporated by trivalent, because of its charge compensation, NO 3 between the layers of c-plane -, C
O 3 2 - such anions are incorporated. But in reality,
Since there are many OH defects, anions are similarly taken in between layers for charge compensation by that amount, and it is considered that a larger amount of anions is present than necessary for charge compensation of Al. It is considered that the reason why the spacing between the c-planes is reduced when the crystallinity is improved by changing the synthesis conditions is that the OH deficiency is reduced and the anions that compensated for this are reduced and the amount required for Al charge compensation is approached. . Since the anions between the layers are likely to hinder the entry and exit of H + during charging and discharging, it is considered that if the number of ions decreases, the utilization rate of the battery increases.
【００１４】また、層間の陰イオンやＨ2 Ｏはｃ面層の
ＯＨ基と水素結合していると考えられるが、各層のａ軸
方向が揃ってくれば層間の水素結合の分布に規則性が生
じ、充放電中のＨ+ の移動を妨げにくくなる。The anions and H 2 O between the layers are considered to be hydrogen-bonded to the OH groups in the c-plane layer. However, if the a-axis direction of each layer becomes uniform, the distribution of hydrogen bonds between the layers becomes regular. Occur, making it difficult to prevent the movement of H + during charge and discharge.
【００１５】[0015]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明のアルカリ蓄電池用正極材として用いられる水酸
化ニッケルは、下記組成式 （Ａｌx Ｎｉ1-x )(ＯＨ)2Ｙ （但し、０．１５＜ｘ＜０．３、Ｙは陰イオン）で表さ
れるα型のＡｌ置換Ｎｉ（ＯＨ)2である。ここにおい
て、ｘが０．１５以下では水酸化ニッケルのα相が安定
でなく、０．３以上では充放電に直接関与するニッケル
が減少することによる容量低下が、アルミニウム添加に
よる容量増加を上回ってしまう。また、Ｙは陰イオンを
示し、硫酸イオン、硝酸イオン、炭酸イオン等である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The nickel hydroxide used as the positive electrode material for an alkaline storage battery of the present invention has the following composition formula (Al x Ni 1 -x ) (OH) 2 Y (0.15 <x <0.3, Y is an anion) Is an α-type Al-substituted Ni (OH) 2 represented by Here, when x is 0.15 or less, the α phase of nickel hydroxide is not stable. When x is 0.3 or more, the capacity decrease due to the decrease in nickel directly involved in charge / discharge exceeds the capacity increase due to the addition of aluminum. I will. Y represents an anion, such as a sulfate ion, a nitrate ion, and a carbonate ion.
【００１６】また、上記水酸化ニッケルのＸ線回折にお
ける（００３）のピークの半値全幅が１．５ｄｅｇ未満
であることが必要であり、好ましくは０．５ｄｅｇ未満
である。（００３）のピークの半値全幅が１．５ｄｅｇ
以上では十分な利用率が得られない。Further, the full width at half maximum of the (003) peak in the X-ray diffraction of the above nickel hydroxide needs to be less than 1.5 deg, and preferably less than 0.5 deg. The full width at half maximum of the peak of (003) is 1.5 deg.
With the above, a sufficient utilization rate cannot be obtained.
【００１７】更に、上記水酸化ニッケルのＸ線回折図に
おける（００３）のピークのｄ値は特に制限されず任意
であるが、８．２Å未満であることが好ましい。Further, the d value of the (003) peak in the X-ray diffraction pattern of the nickel hydroxide is not particularly limited, and is arbitrary, but preferably less than 8.2 °.
【００１８】上述したアルミニウム置換α−水酸化ニッ
ケルは、以下の方法によって製造される。先ず、水酸化
ニッケル製造原料としての金属塩水溶液及びアルカリ水
溶液は、硫酸アルミニウム、硝酸アルミニウム、硫酸ニ
ッケル、硝酸ニッケル、水酸化カリウム、水酸化ナトリ
ウム、水酸化リチウム等が通常使用されるが、その他、
塩化アルミニウム、塩化ニッケル、アンモニア等も使用
できる。その中でも、同一合成条件下では硝酸塩と水酸
化リチウムの組み合わせから得られるアルミニウム置換
α−水酸化ニッケルの結晶性が最も良好である。The above-mentioned aluminum-substituted α-nickel hydroxide is produced by the following method. First, an aqueous metal salt solution and an aqueous alkali solution as a raw material for producing nickel hydroxide include aluminum sulfate, aluminum nitrate, nickel sulfate, nickel nitrate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
Aluminum chloride, nickel chloride, ammonia and the like can also be used. Among them, the crystallinity of aluminum-substituted α-nickel hydroxide obtained from a combination of nitrate and lithium hydroxide is the best under the same synthesis conditions.
【００１９】これらアルミニウム／ニッケルを上記範囲
内で所定割合とした金属塩水溶液とアルカリ水溶液とを
混合する。混合時において、アルカリ／金属比を一定と
し均一に反応させるには、スタティックミキサーを使用
するとよい。その後、熟成、洗浄、濾過、乾燥してアル
ミニウム置換α−水酸化ニッケルを得る。An aqueous solution of a metal salt and an aqueous solution of an alkali having a predetermined ratio of aluminum / nickel within the above range are mixed. At the time of mixing, a static mixer may be used to keep the alkali / metal ratio constant and to make the reaction uniform. Thereafter, aging, washing, filtration and drying are performed to obtain aluminum-substituted α-nickel hydroxide.
【００２０】ここで、（１）アルカリ／金属比は大きい
ほど、得られるアルミニウム置換α−水酸化ニッケルの
結晶性は向上する。（２）熟成時の時間及び温度は、長
いほどまた高いほど、アルミニウム置換α−水酸化ニッ
ケルの結晶性は向上する。しかし、α相の結晶性の向上
過程は、α→β転移反応との競合反応でもあるので、β
転移させずに高結晶なα相を得るためには、上記（１）
及び（２）の範囲に制限があり、それはＡｌ濃度によっ
て異なる。Here, (1) As the alkali / metal ratio increases, the crystallinity of the obtained aluminum-substituted α-nickel hydroxide improves. (2) The longer and higher the aging time and temperature, the better the crystallinity of the aluminum-substituted α-nickel hydroxide. However, since the process of improving the crystallinity of the α phase is also a competitive reaction with the α → β transition reaction,
In order to obtain a highly crystalline α phase without causing a transition, the above (1)
And the range of (2) is limited, and it depends on the Al concentration.
【００２１】すなわち、Ａｌ濃度が高いと、アルカリ／
メタル≧２（当量以上）の条件下でも、α相が維持され
結晶化が進む。また、Ａｌ濃度が低いと、当量では室温
熟成でもβ化がおこるのでアルカリ／メタル＜２に設定
する必要がある。That is, when the Al concentration is high, the alkali /
Even under the condition of metal ≧ 2 (equivalent or more), the α phase is maintained and crystallization proceeds. Also, if the Al concentration is low, β-formation occurs even at room temperature aging at an equivalent amount, so it is necessary to set alkali / metal <2.
【００２２】[0022]
【実施例】以下、実施例等に基づいて本発明を具体的に
説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments and the like.
【００２３】〔試験例１〕α−Ｎｉ（ＯＨ）2 中に置換
するＡｌ濃度のみを変えて、放電電位を評価した。その
結果を図２に示す。また、利用率を評価した。その結果
を図３に示す。この図２〜３から明らかなように、Ａｌ
２５％までは濃度の増加に応じて放電中間電位も利用率
も増加することが判る。Test Example 1 The discharge potential was evaluated by changing only the concentration of Al substituted in α-Ni (OH) 2 . The result is shown in FIG. In addition, the utilization rate was evaluated. The result is shown in FIG. As is apparent from FIGS.
It can be seen that up to 25%, the discharge intermediate potential and the utilization rate increase as the concentration increases.
【００２４】ここで利用率は、正極材の単位重量あたり
の放電容量をその材料に含有されるＮｉが２価から３価
に完全に酸化される時に得られる単位重量あたりの放電
容量で割った値とした。また、放電中間電位とは、３サ
イクル目の容量の半分の時点の電位を示す。Here, the utilization factor is obtained by dividing the discharge capacity per unit weight of the positive electrode material by the discharge capacity per unit weight obtained when Ni contained in the material is completely oxidized from divalent to trivalent. Value. The discharge intermediate potential indicates a potential at a half point of the capacity in the third cycle.
【００２５】〔試験例２〕Ａｌ置換Ｎｉ（ＯＨ）2 の合
成において、熟成温度とアルカリ／金属比を変えた場合
に得られる相の分布を図４に示す。図４において、それ
ぞれ（ａ）はアルミニウム含有量２０モル％（ｘ＝０．
２）、（ｂ）はアルミニウム含有量１０モル％（ｘ＝
０．１）、（ｃ）はアルミニウム含有量５モル％（ｘ＝
０．０５）である。また、●はα相単相、○はβ相単相
あるいはα＋β混合相である。図４から、Ａｌ１０モル
％及び５モル％では、当量条件ですでにβ相が生成する
のでα相が不安定なことが判る。Test Example 2 FIG. 4 shows the distribution of phases obtained when the aging temperature and the alkali / metal ratio were changed in the synthesis of Al-substituted Ni (OH) 2 . In FIG. 4, (a) shows an aluminum content of 20 mol% (x = 0.
2) and (b) show an aluminum content of 10 mol% (x =
0.1) and (c) are aluminum content of 5 mol% (x =
0.05). In addition, ● represents an α-phase single phase, and ○ represents a β-phase single phase or an α + β mixed phase. From FIG. 4, it can be seen that, when Al is 10 mol% and 5 mol%, the β phase is already generated under the equivalent conditions, so that the α phase is unstable.
【００２６】〔実施例１〕濃度１．５ｍｏｌ／ｌのＮｉ
ＳＯ4 又はＮｉ（ＮＯ3)2 ＋Ａｌ2(ＳＯ4)3 又はＡｌ
（ＮＯ3)3 （但し、Ｎｉ：Ａｌ＝８：２）の混合溶液１
リットルを、ＮａＯＨ、ＬｉＯＨ又はＮＨ3 の溶液１リ
ットルとスタティックミキサーを用いて混合した。Example 1 Ni with a concentration of 1.5 mol / l
SO 4 or Ni (NO 3 ) 2 + Al 2 (SO 4 ) 3 or Al
(NO 3 ) 3 (however, Ni: Al = 8: 2) mixed solution 1
One liter was mixed with one liter of a solution of NaOH, LiOH or NH 3 using a static mixer.
【００２７】アルカリ／金属比は１〜３、熟成にはオー
トクレーブを使用し、温度は３０〜１５０℃の間でα相
が生成するよう適当に設定した。熟成時間は１６時間で
ある。得られた沈殿は純水で洗浄し、濾過し５０℃で大
気乾燥した。この粉末を適当な手段で粉砕し、Ｘ線回折
を測定した。代表的なサンプル４種のＸ線回折図を図５
（ａ）〜（ｂ）及び図６（ａ）〜（ｂ）に、その合成条
件を表１に示す。なお、図５（ａ）は表１（ａ）の化合
物、図５（ｂ）は表１（ｂ）の化合物、図６（ａ）は表
１（ｃ）の化合物及び図６（ｂ）は表１（ｄ）の化合物
のＸ線回折図である。The alkali / metal ratio was 1 to 3, the autoclave was used for aging, and the temperature was appropriately set so that the α phase was formed at a temperature of 30 to 150 ° C. The aging time is 16 hours. The obtained precipitate was washed with pure water, filtered, and air-dried at 50 ° C. This powder was pulverized by an appropriate means, and X-ray diffraction was measured. FIG. 5 shows X-ray diffraction patterns of four representative samples.
Table 1 shows the synthesis conditions for (a)-(b) and FIGS. 6 (a)-(b). 5 (a) is the compound of Table 1 (a), FIG. 5 (b) is the compound of Table 1 (b), FIG. 6 (a) is the compound of Table 1 (c), and FIG. FIG. 2 is an X-ray diffraction diagram of the compound of Table 1 (d).
【００２８】[0028]
【表１】 [Table 1]
【００２９】電池試験は、これらの水酸化ニッケルを正
極材（正極活物質）として用い、正極材料：Ｃｏ（Ｏ
Ｈ）2 ：Ｃｏ：ＰＴＦＥバインダー＝５：２：３：１の
重量比となるように混合した正極合剤を０．１ｇ秤取
し、発泡ニッケルとニッケルメッシュで挟み込んだ構造
とした。対極にはニッケルメッシュを使用した。電解液
は０．１ＮＬｉＯＨを含有した７ＮＫＯＨとした。充放
電共に０．２Ｃで行い、充電は７．５時間、放電のカッ
トオフ電位はＨｇ／ＨｇＯ参照電極に対して０．１Ｖと
した。In the battery test, these nickel hydroxides were used as a cathode material (cathode active material), and the cathode material: Co (O
H) A structure was prepared in which 0.1 g of a positive electrode mixture mixed so as to have a weight ratio of 2: 2: 3: 1 with a 2 : Co: PTFE binder was weighed and sandwiched between nickel foam and a nickel mesh. A nickel mesh was used for the counter electrode. The electrolyte was 7 NKOH containing 0.1 N LiOH. Both charging and discharging were performed at 0.2 C, charging was performed for 7.5 hours, and discharge cutoff potential was set at 0.1 V with respect to the Hg / HgO reference electrode.
【００３０】この結果、同一条件下で電池試験を行った
標準サンプル（ＣｏとＺｎを含有し、Ｎｉ分は５５．８
重量％）の利用率は１４０％であった。As a result, a standard sample (containing Co and Zn and having a Ni content of 55.8) subjected to a battery test under the same conditions was used.
%) Was 140%.
【００３１】図７にＸ線回折図における（００３）のピ
ークの半値全幅に対する利用率を、図８にＸ線回折図に
おける（００３）のピークのｄ値に対する放電中間電位
を示す。この実施例１から同一Ａｌ濃度でも、結晶性が
向上すれば、Ｎｉに対する利用率も上るので、十分にγ
化し多電子反応が起こっていることが判る。また、同一
Ａｌ濃度でも、ｃ面の面間隔が狭まれば放電電位が上が
ることが判る。単位重量あたりの放電容量も結晶性が向
上すると増大するが、最もよいものでは標準サンプルに
対し１１０％となった。FIG. 7 shows the utilization factor of the (003) peak in the X-ray diffraction diagram with respect to the full width at half maximum, and FIG. 8 shows the discharge intermediate potential with respect to the d value of the (003) peak in the X-ray diffraction diagram. From Example 1, even with the same Al concentration, if the crystallinity is improved, the utilization factor for Ni is also increased.
It turns out that a multi-electron reaction is occurring. It can also be seen that, even at the same Al concentration, the discharge potential increases when the c-plane spacing decreases. The discharge capacity per unit weight also increases as the crystallinity improves, but the best one is 110% of the standard sample.
【００３２】図９に表１（ｄ）に示したサンプルと標準
サンプルの充放電図を示す。表１（ｄ）のサンプルでは
Ｎｉの充電部分と酸素発生部が明確に分離されているこ
とが分かる。これにより、従来アルカリ蓄電池の正極に
必要不可欠とされていた過充電の必要がなくなり、充電
効率が向上することが期待できる。FIG. 9 shows a charge / discharge diagram of the sample and the standard sample shown in Table 1 (d). In the sample of Table 1 (d), it can be seen that the charged portion of Ni and the oxygen generating portion are clearly separated. This eliminates the necessity of overcharging, which is conventionally indispensable for the positive electrode of an alkaline storage battery, and can be expected to improve charging efficiency.
【００３３】〔比較例１〕濃度１．５ｍｏｌ／ｌのＮｉ
ＳＯ4 ＋Ａｌ2(ＳＯ4)3 の混合溶液（Ｎｉ／Ａｌ＝８／
２）１リットルを、アルカリ／メタル＝４．３６となる
ように調製したＮａＯＨ溶液１リットルとスタティック
ミキサーを用いて混合し、オートクレーブ中１００℃で
熟成した他は、実施例１と同様にして処理し、実施例１
と同様に電池試験を行った。このアルミニウム含有水酸
化ニッケルのＸ線回折図を図１０に示す。Comparative Example 1 Ni having a concentration of 1.5 mol / l
SO 4 + Al 2 (SO 4 ) 3 mixed solution (Ni / Al = 8 /
2) 1 liter was mixed with 1 liter of a NaOH solution prepared so that alkali / metal = 4.36 using a static mixer, and aged at 100 ° C. in an autoclave. Example 1
A battery test was performed in the same manner as described above. FIG. 10 shows an X-ray diffraction diagram of this aluminum-containing nickel hydroxide.
【００３４】図１０からこのサンプルはα相単相でな
く、β相が混入していることが判る。このサンプルのα
相のピークについて注目すると、図５（ｂ）のサンプル
より結晶性が良く、図６（ａ）に近いにも拘わらず、利
用率は１４１％と図５（ｂ）のサンプルより２１％も低
かった。また放電電位も図５（ｂ）のサンプルよりも低
い。このことは、結晶性の良いα相の方がβ相よりも放
電電位も利用率も大きいと考えると説明がつく。このよ
うに、β−（Ａｌ，Ｎｉ)(ＯＨ)2よりも、α−（Ａｌ，
Ｎｉ)(ＯＨ)2の方が放電電位も高く利用率も大きい。FIG. 10 shows that this sample is not a single α-phase but a β-phase. Α of this sample
Focusing on the phase peaks, the crystallinity is better than the sample of FIG. 5 (b), and although it is close to FIG. 6 (a), the utilization is 141%, which is 21% lower than the sample of FIG. 5 (b). Was. Also, the discharge potential is lower than that of the sample of FIG. This can be explained by considering that the α phase having better crystallinity has a higher discharge potential and a higher utilization factor than the β phase. Thus, α- (Al, Ni, (OH) 2
Ni) (OH) 2 has a higher discharge potential and a higher utilization factor.
【００３５】[0035]
【発明の効果】以上説明したように、本発明のアルカリ
蓄電池用正極材によって、利用率を向上させることがで
きる。As described above, the utilization factor can be improved by the positive electrode material for an alkaline storage battery of the present invention.
【図１】図１は、代表的なα−Ｎｉ（ＯＨ)2のＸ線回折
図。FIG. 1 is an X-ray diffraction diagram of a typical α-Ni (OH) 2 .
【図２】図２は、試験例１におけるＡｌ濃度と放電中間
電位との関係を示すグラフ。FIG. 2 is a graph showing a relationship between an Al concentration and a discharge intermediate potential in Test Example 1.
【図３】図３は、試験例１におけるＡｌ濃度と利用率と
の関係を示すグラフ。FIG. 3 is a graph showing the relationship between Al concentration and utilization in Test Example 1.
【図４】図４は、（Ａｌx Ｎｉ1-x )(ＯＨ)2の合成にお
いて、熟成温度とアルカリ／メタルを変えた場合に得ら
れる相を示すグラフ。FIG. 4 is a graph showing phases obtained when the aging temperature and the alkali / metal are changed in the synthesis of (Al x Ni 1-x ) (OH) 2 .
【図５】図５は、実施例１で得られたサンプルの代表例
のＸ線回折図。FIG. 5 is an X-ray diffraction diagram of a representative example of a sample obtained in Example 1.
【図６】図６は、実施例１で得られたサンプルの代表例
のＸ線回折図。FIG. 6 is an X-ray diffraction diagram of a representative example of a sample obtained in Example 1.
【図７】図７は、実施例１における（００３）のピーク
の半値全幅に対する利用率を示すグラフ。FIG. 7 is a graph showing a utilization rate with respect to a full width at half maximum of a peak of (003) in Example 1.
【図８】図８は、実施例１における（００３）のピーク
のｄ値に対する放電中間電位を示すグラフ。FIG. 8 is a graph showing the discharge intermediate potential with respect to the d value of the peak of (003) in Example 1.
【図９】図９は、表１に示したサンプル（ｄ）と標準サ
ンプルの充放電図。FIG. 9 is a charge / discharge diagram of a sample (d) and a standard sample shown in Table 1.
【図１０】図１０は、比較例１で得られたサンプルのＸ
線回折図。FIG. 10 is a graph showing X of the sample obtained in Comparative Example 1.
Line diffraction diagram.
Claims (5)
れるα型のＡｌ置換Ｎｉ（ＯＨ)2であって、Ｘ線回折図
における（００３）のピークの半値全幅が１．５ｄｅｇ
未満であることを特徴とするアルカリ蓄電池用正極材。An α-type Al-substituted Ni (α) represented by the following composition formula (Al x Ni 1-x ) (OH) 2 Y (where 0.15 <x <0.3, Y is an anion) OH) 2 and the full width at half maximum of the (003) peak in the X-ray diffraction pattern is 1.5 deg.
A positive electrode material for an alkaline storage battery, wherein
ークの半値全幅が０．５ｄｅｇ未満である請求項１に記
載のアルカリ蓄電池用正極材。2. The positive electrode material for an alkaline storage battery according to claim 1, wherein the full width at half maximum of the (003) peak in the X-ray diffraction pattern is less than 0.5 deg.
のｄ値が８．２Å未満である請求項１又は２に記載のア
ルカリ蓄電池用正極材。3. The positive electrode material for an alkaline storage battery according to claim 1, wherein the d value of the peak of (003) in the X-ray diffraction diagram is less than 8.2 °.
のｄ値が８．２Å以上である請求項１又は２に記載のア
ルカリ蓄電池用正極材。4. The positive electrode material for an alkaline storage battery according to claim 1, wherein the d value of the peak of (003) in the X-ray diffraction pattern is 8.2 ° or more.
ルカリ蓄電池。5. An alkaline storage battery using the positive electrode material according to claim 1.
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|---|---|---|---|
| JP9349799A JPH11185747A (en) | 1997-12-18 | 1997-12-18 | Positive electrode material for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9349799A JPH11185747A (en) | 1997-12-18 | 1997-12-18 | Positive electrode material for alkaline storage battery |
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| Publication Number | Publication Date |
|---|---|
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ID=18406201
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010033909A (en) * | 2008-07-29 | 2010-02-12 | Gs Yuasa Corporation | Alkaline storage battery, and manufacturing method for positive electrode active material of alkaline storage battery |
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1997
- 1997-12-18 JP JP9349799A patent/JPH11185747A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010033909A (en) * | 2008-07-29 | 2010-02-12 | Gs Yuasa Corporation | Alkaline storage battery, and manufacturing method for positive electrode active material of alkaline storage battery |
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