JPH09283147A - Sealed lead-acid battery and manufacture thereof - Google Patents
Sealed lead-acid battery and manufacture thereofInfo
- Publication number
- JPH09283147A JPH09283147A JP8097225A JP9722596A JPH09283147A JP H09283147 A JPH09283147 A JP H09283147A JP 8097225 A JP8097225 A JP 8097225A JP 9722596 A JP9722596 A JP 9722596A JP H09283147 A JPH09283147 A JP H09283147A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- carbon powder
- active material
- added
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は密閉形鉛蓄電池とそ
の製造方法の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed lead acid battery and an improvement in its manufacturing method.
【０００２】[0002]
【従来の技術】近年、密閉形鉛蓄電池は電気自動車及び
内燃機関とモーターを併用したハイブリッド形電気自動
車へ用途が拡大している。このような用途では、車全体
のエネルギー効率を向上させるため、制動時や降坂時の
エネルギーを回生エネルギーとして再び電池に蓄える技
術、すなわち回生充電の効率向上が重要である。回生充
電は、通常走行時においては数秒から数十秒という短時
間で行われるため、この間に蓄えるエネルギーを大きく
するためには充電電流をできるだけ大きくする必要があ
る。しかしながら、鉛蓄電池は一般に他の電池系に比べ
大電流での充電効率が低いため、実際には回生電流を制
限して回生充電を行っている。2. Description of the Related Art In recent years, applications of sealed lead-acid batteries have expanded to electric vehicles and hybrid electric vehicles that use both an internal combustion engine and a motor. In such applications, in order to improve the energy efficiency of the vehicle as a whole, it is important to improve the efficiency of regenerative charging, that is, the technology of storing energy during braking or downhill as regenerative energy in the battery again. Since regenerative charging is performed in a short time of several seconds to several tens of seconds during normal traveling, it is necessary to maximize the charging current in order to increase the energy stored during this period. However, lead-acid batteries generally have a lower charging efficiency at large currents than other battery systems, and therefore regenerative charging is actually performed by limiting the regenerative current.
【０００３】また、これらの用途では、始動用鉛蓄電池
のように常に充電状態で使用されることはほとんどな
く、通常、一部分が放電した充電不足の状態で使用され
る。鉛蓄電池はこのような充電不足下での使用では寿命
が著しく減少する問題点を有する。たとえば、負極上に
生成した放電後の活物質である硫酸鉛が充電不足により
長期間還元されずにいると、非常に不活性な硫酸鉛とな
り負極中に蓄積していく。硫酸鉛は導電性を持たないの
で、これにより負極板の充放電特性は劣化する。Also, in these applications, unlike a lead-acid battery for starting, it is rarely used in a charged state at all times, and is usually used in a state of insufficient charge in which a part is discharged. The lead acid battery has a problem that its life is significantly reduced when it is used under such insufficient charging. For example, if lead sulfate, which is the active material after discharge, generated on the negative electrode is not reduced for a long time due to insufficient charging, it becomes very inactive lead sulfate and accumulates in the negative electrode. Since lead sulfate does not have conductivity, this deteriorates the charge / discharge characteristics of the negative electrode plate.
【０００４】一方、電気自動車などの用途に限らずこれ
らの問題点は数多くの検討がなされてきた。前述のよう
に負極がこれらの問題点の要因となっているため、特に
負極の改善が図られてきた。その一つに負極への導電性
添加剤の適用がある。負極活物質は金属鉛であるため充
電末期には高い導電性を有しているが、放電深度が深く
なったり、前述のように硫酸鉛が活物質中に蓄積してい
くと単純に導電性が低下するばかりでなく、極板中に未
充電部分が残存しているにもかかわらず、すでに充電さ
れた部分において副反応である水の電気分解に電気量が
使われ、充電効率の低下を引き起こす。これによりさら
に硫酸鉛の蓄積速度が増大し、加速的に劣化が進行す
る。On the other hand, many studies have been made on these problems, not limited to applications such as electric vehicles. As described above, the negative electrode is one of the causes of these problems, and therefore the negative electrode has been particularly improved. One of them is the application of a conductive additive to the negative electrode. Since the negative electrode active material is metallic lead, it has high conductivity at the end of charging, but when the depth of discharge becomes deep and lead sulfate accumulates in the active material as described above, it simply becomes conductive. In addition to the decrease in battery charge, the amount of electricity used for electrolysis of water, which is a side reaction in the already charged part, decreases the charging efficiency even though there is an uncharged part in the electrode plate. cause. As a result, the lead sulfate accumulation rate further increases, and the deterioration progresses at an accelerated rate.
【０００５】そこで、導電性添加剤、一般的にはカーボ
ンを負極活物質中に添加することが行われている。カー
ボン粉末の導電性向上は一般的には粒子の細かい比表面
積の高いカーボンが適しているとされ、これに適合する
要件を備えたカーボン添加剤が種々提案されている。Therefore, a conductive additive, generally carbon, is added to the negative electrode active material. It is generally said that carbon having fine particles and a high specific surface area is suitable for improving the conductivity of carbon powder, and various carbon additives having requirements compatible with this have been proposed.
【０００６】しかしながら、これらのカーボンはその高
い比表面積のため活性度が高く、水素過電圧が低下して
定電圧充電時に副反応が起こりやすく、電池として電解
液の減少が促進され電解液枯渇による電池劣化を引き起
こしやすい。また、活性度が高いために負極活物質中に
添加したリグニンスルホン酸に代表される防縮剤を吸着
し、金属鉛の凝集を抑制する作用を消失させてしまい、
金属鉛の表面積を低下させる。このため、特に低温での
高率放電特性が低下したり、実質的な電流密度が増大
し、副反応比率の増大による充電効率の低下や、活物質
粒子間の結合が集中するなどして電池劣化が進行する。
このため、通常のカーボン添加剤はその添加量が実質的
には活物質に対し０．０１〜０．５ｗｔ％程度にしか上
げることができず、とくに、電気自動車などの用途に対
しては十分な回生充電特性を示すことができなかった。
また寿命特性も十分な値が得られるものではなかった。[0006] However, these carbons have high activity due to their high specific surface area, hydrogen overvoltage decreases, side reactions are likely to occur during constant voltage charging, and the decrease of the electrolyte solution is promoted as a battery, and the battery is exhausted due to electrolyte depletion. It is easy to cause deterioration. Further, because of its high activity, it absorbs a shrink preventive agent typified by lignin sulfonic acid added to the negative electrode active material, and loses the effect of suppressing the aggregation of metallic lead.
Reduces the surface area of metallic lead. For this reason, the high rate discharge characteristics are deteriorated especially at low temperature, the substantial current density is increased, the charging efficiency is decreased due to the increase of the side reaction ratio, and the bonds between the active material particles are concentrated. Deterioration progresses.
For this reason, the amount of the conventional carbon additive can be substantially increased to about 0.01 to 0.5 wt% with respect to the active material, and is particularly sufficient for applications such as electric vehicles. The regenerative charging characteristics could not be shown.
Further, the life characteristics were not sufficient.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記問題点に
鑑みてなされたもので、回生充電などの大電流充電効率
や、電気自動車用途などのアンダーチャージ下での寿命
向上を図ろうとするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is intended to improve the efficiency of high-current charging such as regenerative charging, and to improve the life of the electric vehicle when it is undercharged. Is.
【０００８】[0008]
【課題を解決するための手段】上記問題点を解決するた
めに本発明は、カーボン繊維または／およびカーボンウ
ィスカーを負極活物質に対し０．０１〜１ｗｔ％、カー
ボン粉末を負極活物質に対し０．０１〜１０ｗｔ％添加
した負極板を用いて構成したことを特徴とする密閉形鉛
蓄電池であり、また、該カーボン粉末に防縮剤を担持さ
せていることを特徴とする密閉形鉛蓄電池である。 前
記カーボン繊維またはカーボンウィスカーは、アスペク
ト比（長さを直径で除したもの）１０以上、長さ１μｍ
以上、比表面積３００ｍ2 ／ｇ以下であることが好まし
く、また、前記カーボン粉末は、直径１μｍ以下、比表
面積３００ｍ2 ／ｇ以上、多孔度が４０％以上であるこ
とが好ましい。In order to solve the above problems, the present invention provides 0.01 to 1 wt% of carbon fibers or / and carbon whiskers to the negative electrode active material, and 0 carbon powder to the negative electrode active material. A sealed lead acid battery characterized by comprising a negative electrode plate added with 0.01 to 10 wt%, and a sealed lead acid battery characterized in that a shrink proof agent is carried on the carbon powder. . The carbon fiber or carbon whisker has an aspect ratio (length divided by diameter) of 10 or more and a length of 1 μm.
As described above, the specific surface area is preferably 300 m 2 / g or less, and the carbon powder preferably has a diameter of 1 μm or less, a specific surface area of 300 m 2 / g or more, and a porosity of 40% or more.
【０００９】本発明の製造方法は、カーボン粉末に防縮
剤合物を担持させ、次いで、該カーボン粉末と、カーボ
ン繊維または／およびカーボンウィスカーとを負極活物
質中に添加したことを特徴とする。また、該カーボン粉
末の吸着性を抑制する前処理を行ってから該カーボン粉
末と、カーボン繊維または／およびカーボンウィスカー
とを負極活物質中に添加することを特徴とする。The method of the present invention is characterized in that the carbon powder is caused to carry a shrinkproofing agent compound, and then the carbon powder and carbon fibers and / or carbon whiskers are added to the negative electrode active material. Further, it is characterized in that the carbon powder and the carbon fibers and / or the carbon whiskers are added to the negative electrode active material after a pretreatment for suppressing the adsorptivity of the carbon powder.
【００１０】[0010]
【作用】カーボンウィスカーやカーボン繊維はその形状
から活物質粒子間を導電性ネットワーク状に接続する作
用を有するとして提案されてきたものであるが、実際は
粉末状のカーボンに比べ導電性が低く、十分な導電性ネ
ットワークを形成するほどの量を添加すると活物質粒子
間の抵抗はむしろ増大し、大電流放電特性、出力密度特
性が低下する。逆にカーボン粉末を多量に添加すると前
述のように水素過電圧が低下するため充電効率の低下を
引き起こす。[Function] Carbon whiskers and carbon fibers have been proposed as having a function of connecting between active material particles in a conductive network form due to their shape, but in reality, they have lower conductivity than powdered carbon, If the amount of such a conductive network is added, the resistance between the active material particles rather increases, and the large current discharge characteristics and the power density characteristics deteriorate. On the contrary, when a large amount of carbon powder is added, the hydrogen overvoltage is lowered as described above, and thus the charging efficiency is lowered.
【００１１】これに対し、本発明ではカーボンウィスカ
ーやカーボン繊維を導電性の高いカーボン粉末と同時に
添加することで、それぞれのカーボンの問題点である活
物質粒子間抵抗の増大および水素過電圧の低下を解決す
ることができる。また、これらの形状の異なるカーボン
を添加することで、カーボン粉末の二次、三次粒子間を
カーボンウィスカーが接続し、単独では得られないカー
ボン粒子ネットワークが形成されているものと推定され
る。これらの作用により、通常の添加量より少ない領域
から、単独添加では悪影響が発現する添加量まで幅広い
領域の添加量を選択することができる。また、カーボン
粉末に前処理を施すことで、これらの作用はさらに長期
間有効となるので、電気自動車用途に対しきわめて高性
能な負極板を提供することが可能になる。On the other hand, in the present invention, by adding carbon whiskers and carbon fibers at the same time as the carbon powder having high conductivity, it is possible to increase the resistance between active material particles and decrease the hydrogen overvoltage, which are problems of each carbon. Can be resolved. It is also presumed that the carbon whiskers are connected between the secondary and tertiary particles of the carbon powder by adding these carbons having different shapes, and a carbon particle network that cannot be obtained by itself is formed. Due to these effects, it is possible to select the addition amount in a wide range from the addition amount smaller than the usual addition amount to the addition amount where the adverse effect is caused by the single addition. Further, by pre-treating the carbon powder, these effects are effective for a longer period of time, and thus it is possible to provide an extremely high-performance negative electrode plate for electric vehicle applications.
【００１２】[0012]
【発明の実施の形態】以下、本発明を実施形態に基づき
詳細に説明する。 （実施形態１）アスペクト比６５、長さ３μｍ、比表面
積５８ｍ2 ／ｇのカーボンウィスカー、比表面積９８０
ｍ2 ／ｇ、多孔度６３％、一次粒子径約０．０２μｍの
カーボン粉末を用意し、種々の添加比率で負極活物質中
にリグニン、硫酸バリウム等公知の添加剤と共に添加
し、公知の方法で負極板を作製した。これを公知の方法
で作製した正極板と組み合わせ容量３Ａｈの密閉形単セ
ル電池を組み立てた。これらの電池を１Ａｈ放電した
後、２．５Ｖの定電圧充電を行い、その８秒目電流から
求めた回生充電密度と、満充電から６Ａの充放電を５秒
ずつ繰り返す寿命試験を２５℃中で実施した結果を図１
および図２に示す。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on embodiments. (Embodiment 1) Carbon whiskers having aspect ratio of 65, length of 3 μm and specific surface area of 58 m 2 / g, specific surface area of 980
m 2 / g, porosity 63%, primary particle diameter of about 0.02 μm carbon powder was prepared and added to the negative electrode active material at various addition ratios together with known additives such as lignin and barium sulfate, and a known method. Then, a negative electrode plate was produced. This was combined with a positive electrode plate manufactured by a known method to assemble a sealed single cell battery having a capacity of 3 Ah. After discharging these batteries for 1 Ah, constant voltage charging of 2.5 V was performed, and a regenerative charging density obtained from the current at the 8th second and a life test in which charging / discharging of 6 A from full charge was repeated for 5 seconds each at 25 ° C. Figure 1 shows the result
And FIG.
【００１３】これらの結果から明らかなように、カーボ
ンウィスカー添加量０．０１〜１ｗｔ％の範囲でカーボ
ン粉末添加量０．０１〜１０ｗｔ％と組み合わせた場
合、回生充電効率及び繰り返し寿命の大幅な向上を認め
ることができる。カーボンウィスカーの添加により寿命
向上を図る提案はこれまでにもなされていたが、本発明
のように、カーボンウィスカーとカーボン粉末を同時に
添加することで単独のカーボン添加では得られなかった
大幅な寿命向上が可能になる。As is clear from these results, when combined with the carbon powder addition amount of 0.01 to 10 wt% within the carbon whisker addition amount of 0.01 to 1 wt%, the regenerative charging efficiency and the repeated life are greatly improved. Can be admitted. Proposals to improve the life by adding carbon whiskers have been made so far, but by adding carbon whiskers and carbon powder at the same time as in the present invention, a significant improvement in life that could not be obtained by adding carbon alone Will be possible.
【００１４】ここで、実施形態１では本発明電池のカー
ボンウィスカーを、アスペクト比６５、長さ３μｍ、比
表面積５８ｍ2 ／ｇとしたが、アスペクト比が１０以
上、長さ１μｍ以上、比表面積３００ｍ2 ／ｇ以下、添
加量が０．０１〜１ｗｔ％であれば同等の効果を得るこ
とができる。アスペクト比および長さが前記要件以下に
なると活物質粒子および同時に添加するカーボン粉末と
の接続が不足し、カーボンによる導電性ネットワークを
構成するためには１ｗｔ％を越えて多量に添加しなけれ
ばならない。多量に添加するとカーボンよりも導電性の
高い金属鉛によるネットワークを破壊するので、図１、
２で示したように特性は低下し、コストも上昇するので
好ましくない。また、比表面積３００ｍ2 ／ｇを越える
と実質的にカーボン粉末と同様の性質を示すので、複合
添加の効果が発現しない。より顕著に複合添加の効果が
得られるのは比表面積１００ｍ2 ／ｇ以下の場合であ
る。Here, in Embodiment 1, the carbon whiskers of the battery of the present invention have an aspect ratio of 65, a length of 3 μm and a specific surface area of 58 m 2 / g, but the aspect ratio is 10 or more, the length is 1 μm or more, and the specific surface area is 300 m. If the amount is 2 / g or less and the addition amount is 0.01 to 1 wt%, the same effect can be obtained. If the aspect ratio and length are less than the above requirements, the connection between the active material particles and the carbon powder to be added at the same time will be insufficient, and in order to form a conductive network of carbon, a large amount of more than 1 wt% must be added. . If added in a large amount, the network of metallic lead, which is more conductive than carbon, will be destroyed, so
As shown in 2, the characteristics are deteriorated and the cost is increased, which is not preferable. Further, if the specific surface area exceeds 300 m 2 / g, it exhibits substantially the same properties as the carbon powder, so that the effect of composite addition does not appear. The more remarkable effect of composite addition is obtained when the specific surface area is 100 m 2 / g or less.
【００１５】また、実施形態１では本発明電池のカーボ
ン粉末を一次粒子径約０．０２μｍ、比表面積９８０ｍ
2 ／ｇ、多孔度６３％としたが、直径１μｍ以下、比表
面積３００ｍ2 ／ｇ以上、多孔度が４０％以上であるカ
ーボン粉末を０．０１〜１０ｗｔ％添加すれば同様の効
果を得ることができる。添加量がこれより大きいと図
１、２で示したように特性が低下するほか、体積的には
負極活物質量よりも多くなるので工業的な生産には実質
的に不適当である。また、直径がこれより大きくなると
活物質粒子間及び同時に添加するカーボンウィスカーま
たはカーボン繊維間にカーボン粉末が配置されることが
できにくくなり、導電性ネットワークの形成が困難にな
る。このため複合添加の効果が得られない。多孔度が４
０％よりも小さくなる場合も同様の理由で好ましくな
い。比表面積においては、前記要件より小さくなるとカ
ーボン粉末間の導電性が低下するので好ましくない。ま
た、カーボン粉末としての複合添加の発現がなくなる。
このため、比表面積は５００ｍ2 ／ｇ以上あることがよ
り好ましいが、実質的に得られるカーボン粉末では２０
００ｍ2 ／ｇ程度が上限である。In the first embodiment, the carbon powder of the battery of the present invention has a primary particle diameter of about 0.02 μm and a specific surface area of 980 m.
2 / g and a porosity of 63% were used, but the same effect can be obtained by adding 0.01 to 10 wt% of carbon powder having a diameter of 1 μm or less, a specific surface area of 300 m 2 / g or more, and a porosity of 40% or more. You can If the added amount is larger than this, the characteristics deteriorate as shown in FIGS. 1 and 2, and the volume becomes larger than the amount of the negative electrode active material, so that it is substantially unsuitable for industrial production. Further, if the diameter is larger than this, it becomes difficult to arrange the carbon powder between the active material particles and between the carbon whiskers or the carbon fibers added at the same time, which makes it difficult to form the conductive network. Therefore, the effect of composite addition cannot be obtained. Porosity is 4
When it is smaller than 0%, it is not preferable for the same reason. When the specific surface area is smaller than the above requirements, the conductivity between carbon powders is lowered, which is not preferable. In addition, the compound addition as carbon powder does not occur.
Therefore, it is more preferable that the specific surface area is 500 m 2 / g or more, but it is substantially 20 in the obtained carbon powder.
The upper limit is about 00 m 2 / g.
【００１６】（実施形態２）実施形態１で用いたカーボ
ン粉末を、リグニンスルホン酸の水溶液中で懸濁させ、
２４時間攪拌してカーボン粉末にリグニンを吸着担持さ
せた。このカーボン粉末を乾燥後、実施形態１で用いた
カーボンウィスカーと複合してリグニン、硫酸バリウム
等の添加剤と共に添加し、実施形態１と同様にして作製
した負極板を得た。この負極板を用いて構成した電池を
本発明電池Ａとする。実施形態１で用いたカーボン粉末
を、チャンバー中に置き、一酸化炭素（ＣＯ）ガスを通
気しカーボン粉末の活性度を低下させる前処理を行っ
た。このカーボン粉末を用いて本発明電池Ａと同様にし
て作製した電池を本発明電池Ｂとする。一方、なにも処
理しないカーボン粉末を用いて本発明電池Ａと同様にし
て作製した電池を本発明電池Ｃ、なにも処理しないカー
ボン粉末のみを添加して作製した負極板を用いた電池を
比較電池Ｄとした。カーボン粉末の添加量はいずれの電
池も処理前の重量として負極活物質の０．５ｗｔ％、カ
ーボンウィスカー添加量は負極活物質の０．１５ｗｔ％
とした。(Embodiment 2) The carbon powder used in Embodiment 1 is suspended in an aqueous solution of ligninsulfonic acid,
Lignin was adsorbed and supported on carbon powder by stirring for 24 hours. After this carbon powder was dried, it was combined with the carbon whiskers used in Embodiment 1 and added together with additives such as lignin and barium sulfate to obtain a negative electrode plate manufactured in the same manner as in Embodiment 1. A battery constituted by using this negative electrode plate is referred to as Battery A of the present invention. The carbon powder used in Embodiment 1 was placed in a chamber, and carbon monoxide (CO) gas was aerated to perform a pretreatment for reducing the activity of the carbon powder. A battery manufactured by using this carbon powder in the same manner as the battery A of the present invention is referred to as a battery B of the present invention. On the other hand, a battery manufactured in the same manner as the battery A of the present invention by using the carbon powder that was not treated was the battery C of the present invention, and a battery using the negative electrode plate prepared by adding only the carbon powder that was not treated. This is Comparative Battery D. The amount of carbon powder added was 0.5 wt% of the negative electrode active material as the weight before treatment in each battery, and the amount of carbon whiskers added was 0.15 wt% of the negative electrode active material.
And
【００１７】これらの電池を１／３Ｃで放電深度１００
％まで放電し、１／５Ｃで放電量の８０％充電する充放
電を繰り返し、５０サイクル毎に２Ｃ放電容量を確認す
る寿命試験を実施した。図３に寿命試験中の２Ｃ放電容
量の推移を示す。図から明らかなように本発明電池Ａ，
Ｂは容量低下が小さい。これに対し比較電池Ｄは容量低
下が大きい。これは、通常より多量に添加したカーボン
粉末によりリグニンが吸着され、活物質粒子が大きく成
長し、高率放電特性が低下したものと考えられ、本発明
電池Ａではリグニンを担持させたカーボン粉末により、
本発明電池Ｂではカーボン粉末の活性度を低下させたこ
とにより、リグニンの吸着が抑制され、高率放電特性が
維持できたものである。本発明電池Ｃは、カーボンウィ
スカーとカーボン粉末を混合添加した事による作用で、
単独添加である比較電池Ｄよりも容量低下は小さいもの
の、カーボン粉末へのリグニン吸着量が大きいため本発
明電池Ａ，Ｂよりも容量低下が大きい結果となった。以
上のように、本発明による前処理により多量にカーボン
を混合添加することが可能になる。These batteries were discharged at a discharge depth of 100 at 1 / 3C.
%, And 80% of the discharge amount at 1/5 C was repeatedly charged and discharged, and a life test was conducted to confirm the 2 C discharge capacity every 50 cycles. FIG. 3 shows the transition of the 2C discharge capacity during the life test. As is clear from the figure, the present invention battery A,
B has a small capacity decrease. On the other hand, the comparative battery D has a large decrease in capacity. It is considered that this is because the lignin was adsorbed by the carbon powder added in a larger amount than usual, the active material particles grew large, and the high rate discharge characteristics were deteriorated. In the battery A of the present invention, the carbon powder supporting lignin was used. ,
In the battery B of the present invention, the activity of the carbon powder was lowered, so that the adsorption of lignin was suppressed and the high rate discharge characteristics could be maintained. The battery C of the present invention operates by mixing and adding carbon whiskers and carbon powder,
Although the decrease in capacity was smaller than that of Comparative Battery D, which was added alone, the amount of lignin adsorbed on the carbon powder was large, resulting in a larger decrease in capacity than Batteries A and B of the present invention. As described above, the pretreatment according to the present invention makes it possible to mix and add a large amount of carbon.
【００１８】ここで、カーボン粉末へリグニンを前もっ
て担持させる方法を用いたが、負極中へのリグニン添加
量を増加させても寿命向上作用を得ることができる。し
かし、負極中へのリグニンの多量添加はカーボンに前も
って担持させる方法と異なり、吸着できず遊離したリグ
ニンが多量に存在するので、遊離したリグニンの正極で
の酸化により自己放電速度の増大や充電効率の低下など
悪影響が大きく、寿命向上の効果も本発明ほど顕著には
得られない。また、カーボン粉末の活性度を低下させる
処理として一酸化炭素処理を行ったが、これに限らず、
ＣＯ2 、メタンガスなどによって不活性化させてもよ
い。Here, the method of previously supporting lignin on the carbon powder was used, but the life improving effect can be obtained even if the amount of lignin added to the negative electrode is increased. However, the addition of a large amount of lignin to the negative electrode is different from the method of preliminarily supporting it on carbon, and there is a large amount of lignin that cannot be adsorbed and is released. The effect of improving the life is not so remarkable as that of the present invention. Further, although carbon monoxide treatment was performed as a treatment for reducing the activity of the carbon powder, the treatment is not limited to this.
CO 2, it may be inactivated by such methane.
【００１９】[0019]
【発明の効果】以上詳述したように、本発明は次の効果
を奏する。 （１）請求項１によれば、高率放電特性および寿命特性
が優れ、回生充電などの急速充電効率が飛躍的に向上す
る密閉形鉛蓄電池を提供できる。 （２）請求項２によれば、高率放電特性の低下を抑制で
きる。 （３）請求項３および４によれば、請求項１の効果を顕
著にできる。 （４）請求項５によれば、前もって防縮剤をカーボン粉
末とカーボン繊維などに担持させず添加する場合に比
べ、多量のカーボンを添加でき、寿命性能が向上でき
る。 （５）請求項６によれば、カーボン粉末が芳香族化合物
を吸着しなくなるので、高率放電特性の低下を抑制でき
る。また、カーボン粉末と一体化した活物質粒子が大き
く成長することがないので、容量の低下を防ぐことがで
きる。As described in detail above, the present invention has the following effects. (1) According to the first aspect, it is possible to provide a sealed lead-acid battery which has excellent high rate discharge characteristics and life characteristics and dramatically improves rapid charging efficiency such as regenerative charging. (2) According to claim 2, it is possible to suppress deterioration of the high rate discharge characteristics. (3) According to claims 3 and 4, the effect of claim 1 can be made remarkable. (4) According to claim 5, a large amount of carbon can be added, and the life performance can be improved, as compared with the case where the shrink-proofing agent is added without previously supporting it on the carbon powder and the carbon fiber. (5) According to claim 6, since the carbon powder does not adsorb the aromatic compound, it is possible to suppress deterioration of the high rate discharge characteristics. Moreover, since the active material particles integrated with the carbon powder do not grow significantly, it is possible to prevent the capacity from decreasing.
【図１】カーボンウィスカーとカーボン粉末の添加量に
対する回生充電密度を示すグラフである。FIG. 1 is a graph showing regenerative charge density with respect to the addition amounts of carbon whiskers and carbon powder.
【図２】カーボンウィスカーとカーボン粉末の添加量に
対する寿命サイクル数を示すグラフである。FIG. 2 is a graph showing the number of life cycles with respect to the amounts of carbon whiskers and carbon powder added.
【図３】本発明電池Ａ〜Ｃと比較電池Ｄの寿命特性を示
すグラフである。FIG. 3 is a graph showing life characteristics of batteries A to C of the present invention and comparative battery D.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中山 恭秀 大阪府高槻市城西町６番６号 株式会社ユ アサコーポレーション内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhide Nakayama 6-6 Josaimachi, Takatsuki City, Osaka Prefecture Yuasa Corporation
Claims (6)
ィスカーを負極活物質に対し０．０１〜１ｗｔ％、カー
ボン粉末を負極活物質に対し０．０１〜１０ｗｔ％添加
していることを特徴とする密閉形鉛蓄電池。1. A closed type in which 0.01 to 1 wt% of carbon fibers and / or carbon whiskers are added to the negative electrode active material and 0.01 to 10 wt% of carbon powder is added to the negative electrode active material. Lead acid battery.
いることを特徴とする請求項１の密閉形鉛蓄電池。2. The sealed lead acid battery according to claim 1, wherein the carbon powder carries a shrinkproofing agent.
カーがアスペクト比１０以上、長さ１μｍ以上、比表面
積３００ｍ2 ／ｇ以下であることを特徴とする請求項１
または２記載の密閉形鉛蓄電池3. The carbon fibers or carbon whiskers have an aspect ratio of 10 or more, a length of 1 μm or more, and a specific surface area of 300 m 2 / g or less.
Or the sealed lead-acid battery described in 2.
表面積３００ｍ2 ／ｇ以上、多孔度が４０％以上である
ことを特徴とする請求項１または２記載の密閉形鉛蓄電
池4. The sealed lead-acid battery according to claim 1, wherein the carbon powder has a diameter of 1 μm or less, a specific surface area of 300 m 2 / g or more, and a porosity of 40% or more.
で、該カーボン粉末と、カーボン繊維または／およびカ
ーボンウィスカーとを負極活物質中に添加することを特
徴とする密閉形鉛蓄電池の製造方法。5. A method for producing a sealed lead-acid battery, which comprises supporting a shrink preventive agent on carbon powder, and then adding the carbon powder and carbon fibers and / or carbon whiskers to a negative electrode active material.
を行い、次いで、該カーボン粉末と、カーボン繊維また
は／およびカーボンウィスカーとを負極活物質中に添加
することを特徴とする密閉形鉛蓄電池の製造方法。6. A sealed lead-acid battery characterized in that a pretreatment for suppressing adsorption of carbon powder is carried out, and then the carbon powder and carbon fibers and / or carbon whiskers are added to a negative electrode active material. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8097225A JPH09283147A (en) | 1996-04-19 | 1996-04-19 | Sealed lead-acid battery and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8097225A JPH09283147A (en) | 1996-04-19 | 1996-04-19 | Sealed lead-acid battery and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09283147A true JPH09283147A (en) | 1997-10-31 |
Family
ID=14186698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8097225A Pending JPH09283147A (en) | 1996-04-19 | 1996-04-19 | Sealed lead-acid battery and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09283147A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004327157A (en) * | 2003-04-23 | 2004-11-18 | Japan Storage Battery Co Ltd | Storage battery |
| JP2006049025A (en) * | 2004-08-03 | 2006-02-16 | Furukawa Battery Co Ltd:The | Control valve type lead-acid storage battery |
| WO2011090113A1 (en) * | 2010-01-21 | 2011-07-28 | 株式会社Ｇｓユアサ | Negative electrode plate for lead storage battery, process for producing same, and lead storage battery |
| CN102484286A (en) * | 2009-10-26 | 2012-05-30 | 株式会社杰士汤浅国际 | Lead acid storage battery |
| JP2015005528A (en) * | 2014-09-05 | 2015-01-08 | 株式会社Ｇｓユアサ | Lead storage battery |
| JP2016504743A (en) * | 2013-01-25 | 2016-02-12 | アルケマ フランス | Electrode paste manufacturing method |
| JP2016532638A (en) * | 2013-06-14 | 2016-10-20 | ユニヴァーシティー オブ サウス ウェールズ コマーシャル サービシズ リミテッド | Synthesis and hydrogen storage properties of manganese hydrides |
| US10465852B2 (en) | 2014-06-13 | 2019-11-05 | USW Commercial Services Ltd. | Synthesis and hydrogen storage properties of novel metal hydrides |
| US10974961B2 (en) | 2011-12-15 | 2021-04-13 | USW Commercial Services, Ltd. | Metal hydrides and their use in hydrogen storage applications |
-
1996
- 1996-04-19 JP JP8097225A patent/JPH09283147A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004327157A (en) * | 2003-04-23 | 2004-11-18 | Japan Storage Battery Co Ltd | Storage battery |
| JP2006049025A (en) * | 2004-08-03 | 2006-02-16 | Furukawa Battery Co Ltd:The | Control valve type lead-acid storage battery |
| CN102484286A (en) * | 2009-10-26 | 2012-05-30 | 株式会社杰士汤浅国际 | Lead acid storage battery |
| WO2011090113A1 (en) * | 2010-01-21 | 2011-07-28 | 株式会社Ｇｓユアサ | Negative electrode plate for lead storage battery, process for producing same, and lead storage battery |
| CN102725891A (en) * | 2010-01-21 | 2012-10-10 | 株式会社杰士汤浅国际 | Negative electrode plate for lead storage battery, process for producing same, and lead storage battery |
| JPWO2011090113A1 (en) * | 2010-01-21 | 2013-05-23 | 株式会社Ｇｓユアサ | Negative electrode plate for lead acid battery, method for producing the same, and lead acid battery |
| US10974961B2 (en) | 2011-12-15 | 2021-04-13 | USW Commercial Services, Ltd. | Metal hydrides and their use in hydrogen storage applications |
| US11851327B2 (en) | 2011-12-15 | 2023-12-26 | USW Commercial Services Ltd. | Metal hydrides and their use in hydrogen storage applications |
| JP2016504743A (en) * | 2013-01-25 | 2016-02-12 | アルケマ フランス | Electrode paste manufacturing method |
| JP2016532638A (en) * | 2013-06-14 | 2016-10-20 | ユニヴァーシティー オブ サウス ウェールズ コマーシャル サービシズ リミテッド | Synthesis and hydrogen storage properties of manganese hydrides |
| US10622655B2 (en) | 2013-06-14 | 2020-04-14 | Usw Commercial Services Ltd | Synthesis and hydrogen storage properties of novel manganese hydrides |
| US10465852B2 (en) | 2014-06-13 | 2019-11-05 | USW Commercial Services Ltd. | Synthesis and hydrogen storage properties of novel metal hydrides |
| JP2015005528A (en) * | 2014-09-05 | 2015-01-08 | 株式会社Ｇｓユアサ | Lead storage battery |
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