JPH06163071A - Sealed type nickel-hydrogen battery and its manufacture - Google Patents
Sealed type nickel-hydrogen battery and its manufactureInfo
- Publication number
- JPH06163071A JPH06163071A JP4336655A JP33665592A JPH06163071A JP H06163071 A JPH06163071 A JP H06163071A JP 4336655 A JP4336655 A JP 4336655A JP 33665592 A JP33665592 A JP 33665592A JP H06163071 A JPH06163071 A JP H06163071A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- nickel
- negative electrode
- positive electrode
- sealed
- 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
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 4
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 3
- 239000004677 Nylon Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 238000005096 rolling process Methods 0.000 abstract 2
- 238000004898 kneading Methods 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 210000003719 b-lymphocyte Anatomy 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、密閉型ニッケル・水素
電池並びにその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed nickel-hydrogen battery and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来の密閉型ニッケル・水素電池は、電
池容器内に、水素吸蔵合金負極とニッケル正極とをセパ
レータを介して積層して成る極板群を挿入し、更にアル
カリ電解液を注入した後、施蓋封口して製造したものが
一般である。2. Description of the Related Art In a conventional sealed nickel-hydrogen battery, an electrode plate group in which a hydrogen storage alloy negative electrode and a nickel positive electrode are laminated via a separator is inserted into a battery container, and an alkaline electrolyte is further injected. After that, it is generally manufactured by sealing the lid.
【０００３】[0003]
【発明が解決しようとする課題】上記従来の密閉型ニッ
ケル・水素電池は、充放電の繰り返しで、該負極は、水
素の吸蔵放出を繰り返し、合金の微粉化による充電効率
の低下が起こり、正極は、アルカリ電解液中でニッケル
の酸化還元を繰り返し、体積変化による膨脹を生じ、活
物質の利用率の低下を起こし、電池、容量及び寿命に悪
影響を与える。In the above-mentioned conventional sealed nickel-hydrogen battery, the negative electrode is repeatedly charged and discharged with repeated charging and discharging, and the charging efficiency is lowered due to atomization of the alloy. Repeats redox of nickel in an alkaline electrolyte, causes expansion due to volume change, causes a decrease in utilization rate of the active material, and adversely affects the battery, capacity and life.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記従来の密
閉型ニッケル・水素電池の課題を解決し、充放電の繰り
返しによる正、負極の劣化を防止し、電池特性の向上し
た密閉型ニッケル・水素電池を提供するもので、水素吸
蔵合金負極とニッケル正極とをセパレータを介して積層
して成る極板群を挿入し且つアルカリ電解液を注入して
成る密閉型ニッケル・水素電池において、内部に不活性
ガスが封入されていることを特徴とする。更に本発明
は、上記の密閉型ニッケル・水素電池の製造法に係り、
ニッケル正極と水素吸蔵合金負極とをセパレータを介し
て組み立てた極板群を挿入し、且つアルカリ電解液を注
入した後、該電池容器内に不活性ガスを注入し、次で、
施蓋封口することを特徴とする。DISCLOSURE OF THE INVENTION The present invention solves the problems of the above-mentioned conventional sealed nickel-hydrogen battery, prevents the positive and negative electrodes from deteriorating due to repeated charging and discharging, and has improved battery characteristics. -A hydrogen battery is provided, in which a sealed nickel-hydrogen battery is formed by inserting an electrode plate group in which a hydrogen storage alloy negative electrode and a nickel positive electrode are laminated via a separator and injecting an alkaline electrolyte. It is characterized in that an inert gas is sealed in. Further, the present invention relates to a method for manufacturing the above sealed nickel-hydrogen battery,
Insert the electrode plate group assembled with the nickel positive electrode and the hydrogen storage alloy negative electrode via the separator, and after injecting the alkaline electrolyte, injecting an inert gas into the battery container, then,
The feature is that the lid is sealed.
【０００５】[0005]
【作用】一般に、この種電池では、その充放電の繰り返
しにより、ニッケル正極板ではその酸化還元及び電解液
の滲み込み、これに伴い、該極板の膨潤が起きる一方、
水素吸蔵合金負極では、合金の微粉化が起きるが、本発
明の密閉電池は、予め不活性ガスが封入されているの
で、そのガス圧により、正極の膨潤を抑制し集電体と活
物質との密着性を良好に保つと同時に、水素吸蔵合金負
極の微細化を抑制し集電体、導電材との密着性を良好に
保つことができ、これにより、正負極の利用率の低下、
充放電効率の低下を防止し、電池容量の低下や内圧の上
昇、短命化等が防止される。In general, in this type of battery, repeated charging / discharging thereof causes oxidation / reduction of the nickel positive electrode plate and permeation of the electrolytic solution, which causes swelling of the electrode plate.
In the hydrogen storage alloy negative electrode, the alloy is pulverized, but the sealed battery of the present invention is filled with an inert gas in advance, so that the gas pressure suppresses the swelling of the positive electrode and the collector and the active material. While maintaining good adhesion, the hydrogen storage alloy negative electrode can be prevented from becoming finer, and good adhesion with the current collector and the conductive material can be maintained, which reduces the utilization rate of the positive and negative electrodes.
A decrease in charge / discharge efficiency is prevented, a decrease in battery capacity, an increase in internal pressure, and a shortened life are prevented.
【０００６】[0006]
【実施例】次に本発明の実施例を説明する。水素吸蔵合
金負極は、例えば、次のように製造したものを使用す
る。所望の水素吸蔵合金、例えばMmNi3.5 Co1.0 Al0.5
から成る組成のものを機械的に粉砕し、その合金粉末
に、結着剤として例えばポリフッ化ビニリデン（ＰＶｄ
Ｆ）粉末とカーボニルニッケルから成るNi粉末と増粘剤
として例えばＣＭＣ（カルボキシメチルセルロース）の
１wt.%水溶液とを混ぜ、均一に混練してスラリー状物と
する。次に、このスラリー状物をニッケル多孔シートの
両面に塗布、乾燥、圧延を行い、次でこれを真空雰囲気
下で 170℃、２時間加熱して水素吸蔵合金から成る負極
を製造する。EXAMPLES Examples of the present invention will be described below. As the hydrogen storage alloy negative electrode, for example, one manufactured as follows is used. The desired hydrogen storage alloy, for example MmNi 3.5 Co 1.0 Al 0.5
Mechanically crushed into a powder of the alloy, and used as a binder, for example, polyvinylidene fluoride (PVd).
F) Powder and Ni powder consisting of carbonyl nickel and a 1 wt.% Aqueous solution of CMC (carboxymethyl cellulose) as a thickener are mixed and uniformly kneaded to form a slurry. Next, the slurry-like material is applied to both surfaces of a nickel porous sheet, dried and rolled, and then heated in a vacuum atmosphere at 170 ° C. for 2 hours to produce a negative electrode made of a hydrogen storage alloy.
【０００７】ニッケル正極は、例えば次のように製造し
たものを使用する。即ち、水酸化ニッケル粉末とカーボ
ニルニッケルから成るNi粉末とを混合し、更に、ＣＭＣ
の１wt.%水溶液を加えて混練してペースト状物とし、こ
れを多孔金属性基板、例えば発泡ニッケル基板に充填
し、乾燥、圧延を行うことにより製造する。As the nickel positive electrode, for example, one manufactured as follows is used. That is, nickel hydroxide powder and Ni powder consisting of carbonyl nickel are mixed, and further, CMC is added.
1 wt.% Aqueous solution is added and kneaded to form a paste, which is filled in a porous metal substrate, for example, a foamed nickel substrate, and dried and rolled to manufacture.
【０００８】このように製造した負極板と正極板とを、
これらの間に厚さ0.18mmのナイロンセパレータを介在さ
せて積層、捲回して極板群を作製し、これを、電池容
器、例えば、鉄にニッケルメッキした円筒缶に挿入し、
次で所定量のＫＯＨなどのアルカリ電解液を注入する。
本発明によれば、次で該電池容器を、例えば不活性ガス
を充満させた密閉処理室内に導入し、不活性ガス、例え
ば、窒素ガスを該電池容器内に注入し、窒素ガス圧３Kg
f/cm2 まで注入した後、施蓋し、封口結着することによ
り、定格AA-1000mAhの本発明の不活性ガス封入の密閉型
ニッケル・水素電池を製造した。以下この本発明電池を
Ａ電池と称する。The negative electrode plate and the positive electrode plate thus manufactured are
A 0.18 mm-thick nylon separator is interposed between them to form an electrode plate group by laminating and winding, and this is inserted into a battery container, for example, a cylindrical can of nickel plated with iron,
Next, a predetermined amount of alkaline electrolyte such as KOH is injected.
According to the present invention, next, the battery container is introduced into a closed processing chamber filled with, for example, an inert gas, an inert gas, for example, nitrogen gas is injected into the battery container, and the nitrogen gas pressure is 3 Kg.
After injecting up to f / cm 2 , the lid was closed and the lid was sealed to manufacture a sealed nickel-metal hydride battery of the present invention with a rated AA-1000 mAh filled with an inert gas. Hereinafter, the battery of the present invention will be referred to as battery A.
【０００９】比較のため、これとは別個に、前記の電解
液を注入した金属缶を、従来法に倣い、直ちに施蓋、封
口結着することにより、従来の製造法により定格AA-100
0mAhの密閉型ニッケル・水素電池を製造した。以下この
従来電池をＢ電池と称する。For comparison, separately from the above, a metal can infused with the above-mentioned electrolytic solution was imitated by a conventional method, and a lid and a closure were immediately bonded to give a rating AA-100 by the conventional manufacturing method.
A sealed mA-hydrogen battery of 0 mAh was manufactured. Hereinafter, this conventional battery is referred to as a B battery.
【００１０】これらのＡ電池及びＢ電池につき、充放電
サイクル試験を行った。充放電サイクル試験は、充電を
１Ａで75分、終止電圧を１Ｖとして１Ａで放電すること
を繰り返した。その結果は、図１に示す通りであった。
同図のＡ電池及びＢ電池の充放電サイクルに対する容量
維持率を示す夫々の特性曲線から明らかなように、Ｂ電
池は、充放電サイクルの進行に伴う容量の低下が見られ
るが、Ａ電池は、当初の容量を維持している。このこと
は、Ａ電池は、封入されている不活性ガス圧により、正
極の膨脹を抑制し、また負極の合金の膨脹、微細化を抑
制し、夫々の活物質の利用率の低下を防止しているから
であると考えられる。A charging / discharging cycle test was conducted on these A battery and B battery. In the charge / discharge cycle test, charging was repeated at 1 A for 75 minutes and the final voltage was set at 1 V, and discharging was repeated at 1 A. The result was as shown in FIG.
As is clear from the respective characteristic curves showing the capacity retention ratios of the A battery and the B battery in the same figure, the capacity of the B battery decreases as the charging / discharging cycle progresses. , Maintaining the original capacity. This means that the battery A suppresses expansion of the positive electrode and expansion and refinement of the alloy of the negative electrode by the enclosed inert gas pressure, and prevents a decrease in utilization rate of each active material. It is thought to be because it is.
【００１１】また、Ａ電池とＢ電池につき、内圧試験を
行った。内圧試験は、充電を１Ａで4.5HR行い、終止電
圧を１Ｖとして、 0.2Ａで放電した。温度は20℃とし
た。その結果、50サイクル目の夫々の電池の内圧を測定
した所、Ｂ電池は12Kgf/cm2 であったに対し、Ａ電池は
４Kgf/cm2 と不活性ガスを封入したときの当初のガス圧
３Kgf/cm2 と殆ど変らない４Kgf/cm2 にすぎず、Ｂ電池
の内圧の３分の１の内圧に抑制することができた。この
ことは、Ｂ電池では、負極表面で正極から発生する酸素
を吸収し、その時の反応熱で負極の充電効率が低下し、
水素ガスを発生することにより、内圧が12Kgf/cm2 と上
昇したに対し、Ａ電池では、封入した不活性ガス圧によ
り、その水素ガスの発生が抑えられ、充電効率の低下が
少なくなるからであると考えられる。尚、不活性ガスの
注入方法は、上記の実施例に限定されるものではない。
例えば、電池容器を、トンネル状通路内に順次導入し、
その通路内で不活性ガスの注入と施蓋を自動的に行うよ
うにしてもよい。An internal pressure test was carried out on the batteries A and B. In the internal pressure test, charging was performed at 1 A for 4.5 HR, the final voltage was set to 1 V, and discharging was performed at 0.2 A. The temperature was 20 ° C. As a result, 50 where the internal pressure of the cycle of each of the batteries was measured, B cells whereas was 12 kgf / cm 2, A cell initial gas pressure when filled with an inert gas and 4 kgf / cm 2 The internal pressure was 4 Kgf / cm 2, which was almost unchanged from 3 Kgf / cm 2 , and could be suppressed to one third of the internal pressure of the B battery. This means that in the B battery, oxygen generated from the positive electrode is absorbed on the surface of the negative electrode, and the reaction heat at that time reduces the charging efficiency of the negative electrode.
By generating hydrogen gas, the internal pressure rose to 12 Kgf / cm 2 , whereas in the battery A, the hydrogen gas generation was suppressed by the enclosed inert gas pressure, and the decrease in charging efficiency was reduced. It is believed that there is. The method of injecting the inert gas is not limited to the above embodiment.
For example, battery containers are sequentially introduced into the tunnel-shaped passage,
You may make it inject the inert gas and cover automatically in the passage.
【００１２】[0012]
【発明の効果】このように本発明によるときは、不活性
ガスが封入された密閉型ニッケル・水素電池としたの
で、その不活性ガス圧により、電池充電時の正極の膨潤
を抑制すると共に、負極の充電効率の低下を抑制するこ
とができ、その結果、電池特性を安定良好に維持し、従
来のものに比し、電池特性の向上をもたらす。As described above, according to the present invention, since the sealed nickel-hydrogen battery is filled with an inert gas, the inert gas pressure suppresses the swelling of the positive electrode during battery charging, and The decrease in charging efficiency of the negative electrode can be suppressed, and as a result, the battery characteristics can be maintained stably and satisfactorily, and the battery characteristics can be improved as compared with the conventional one.
【図１】本発明の電池と従来の電池との充放電サイクル
試験の比較グラフを示す。FIG. 1 shows a comparative graph of a charge / discharge cycle test of a battery of the present invention and a conventional battery.
Claims (2)
パレータを介して積層して成る極板群を挿入し且つアル
カリ電解液を注入して成る密閉型ニッケル・水素電池に
おいて、内部に不活性ガスが封入されていることを特徴
とする密閉型ニッケル・水素電池。1. A sealed nickel-metal hydride battery comprising a negative electrode and a positive electrode, wherein a hydrogen storage alloy negative electrode and a nickel positive electrode are laminated via a separator, and an alkaline electrolyte is injected into the sealed nickel-hydrogen battery. A sealed nickel-metal hydride battery characterized in that
パレータを介して組み立てた極板群を挿入し、且つアル
カリ電解液を注入した後、該電池容器内に不活性ガスを
注入し、次で、施蓋封口することを特徴とする密閉型ニ
ッケル・水素電池の製造法。2. An electrode group in which a nickel positive electrode and a hydrogen storage alloy negative electrode are assembled via a separator is inserted, an alkaline electrolyte is injected, and then an inert gas is injected into the battery container. A method for manufacturing a sealed nickel-hydrogen battery, which is characterized in that a lid is sealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4336655A JPH06163071A (en) | 1992-11-24 | 1992-11-24 | Sealed type nickel-hydrogen battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4336655A JPH06163071A (en) | 1992-11-24 | 1992-11-24 | Sealed type nickel-hydrogen battery and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06163071A true JPH06163071A (en) | 1994-06-10 |
Family
ID=18301420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4336655A Pending JPH06163071A (en) | 1992-11-24 | 1992-11-24 | Sealed type nickel-hydrogen battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06163071A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015225826A (en) * | 2014-05-30 | 2015-12-14 | エクセルギー・パワー・システムズ株式会社 | Nickel metal hydride battery charge amount display device and charge amount display method |
| CN111740171A (en) * | 2020-05-20 | 2020-10-02 | 湖南科霸汽车动力电池有限责任公司 | Nickel-hydrogen battery and preparation method thereof |
-
1992
- 1992-11-24 JP JP4336655A patent/JPH06163071A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015225826A (en) * | 2014-05-30 | 2015-12-14 | エクセルギー・パワー・システムズ株式会社 | Nickel metal hydride battery charge amount display device and charge amount display method |
| CN111740171A (en) * | 2020-05-20 | 2020-10-02 | 湖南科霸汽车动力电池有限责任公司 | Nickel-hydrogen battery and preparation method thereof |
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