JPH0398261A - Manufacture of hydrogen storage electrode - Google Patents
Manufacture of hydrogen storage electrodeInfo
- Publication number
- JPH0398261A JPH0398261A JP1235145A JP23514589A JPH0398261A JP H0398261 A JPH0398261 A JP H0398261A JP 1235145 A JP1235145 A JP 1235145A JP 23514589 A JP23514589 A JP 23514589A JP H0398261 A JPH0398261 A JP H0398261A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- microcapsules
- hydrogen
- fep
- storage 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.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000003094 microcapsule Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000004898 kneading Methods 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 6
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 abstract description 2
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 abstract description 2
- ZSJFLDUTBDIFLJ-UHFFFAOYSA-N nickel zirconium Chemical compound [Ni].[Zr] ZSJFLDUTBDIFLJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、水素を負極活物質とするアルカリ二次電池の
負極として用いられる水素吸蔵電極の製造方法に関し、
詳しくは、大型電極の製造を容易化しかつその放電特性
の改善を図った水素吸蔵電極の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a hydrogen storage electrode used as a negative electrode of an alkaline secondary battery using hydrogen as a negative electrode active material.
Specifically, the present invention relates to a method for manufacturing a hydrogen storage electrode that facilitates the manufacture of large electrodes and improves the discharge characteristics thereof.
［従来技術］
従来、アルカリ二次電池の一つとして金属酸化物を正極
活物質とし水素を負極活物質とする金属酸化物／水素電
池があるが、この金属酸化物／水素電池の一つとして、
水素を可逆的に吸蔵・放出する水索吸蔵合金を含有する
水索吸蔵電極を負極としたものがある。[Prior art] Conventionally, as an alkaline secondary battery, there is a metal oxide/hydrogen battery that uses a metal oxide as a positive electrode active material and hydrogen as a negative electrode active material. ,
There is one in which a water cable storage electrode containing a water cable storage alloy that reversibly stores and releases hydrogen is used as a negative electrode.
この水素吸蔵電極は水素の吸蔵放出が良好で、かつ低抵
抗とする必要があり、一般に、水素吸蔵合金粉末を結着
材と混合して成型される。This hydrogen storage electrode must have good hydrogen storage and release properties and low resistance, and is generally formed by mixing hydrogen storage alloy powder with a binder.
上記結着材の使用例として、特開昭６１−１６４７０号
公報は、ポリテトラフルオロエチレン（ＰＴＦＥ）粉末
を開示し、特開昭６１−２１４３６０号公報は、ポリビ
ニルアルコール溶液を開小している。As an example of the use of the above-mentioned binder, JP-A-61-16470 discloses polytetrafluoroethylene (PTFE) powder, and JP-A-61-214360 discloses a polyvinyl alcohol solution. .
特開昭６１−１０１９５７号公報は、水素吸蔵合金粉末
の表面を銅で被覆してマイクロカプセル化し、このマイ
クロカプセルとフッ素樹脂粉末（結着材〉とを混練し、
集電体に圧接して水素吸蔵電極とすることを開示してい
る。また、この特開昭６１−１０１９５７公報は上記マ
イクロカプセルを集電体に圧着固定した後でこれをフッ
素樹脂の懸濁液に浸漬し引上げた後、不活性ガス又は水
素ガス雰囲気中で熱処理する方法も開示している。JP-A No. 61-101957 discloses that the surface of hydrogen-absorbing alloy powder is coated with copper to form microcapsules, and the microcapsules and fluororesin powder (binder) are kneaded,
It discloses that it is pressed into contact with a current collector to form a hydrogen storage electrode. Moreover, this Japanese Patent Application Laid-Open No. 61-101957 discloses that after the microcapsules are crimped and fixed to a current collector, they are immersed in a fluororesin suspension, pulled up, and then heat-treated in an inert gas or hydrogen gas atmosphere. The method is also disclosed.
［発明が解決しようとする課題］
上記した各先行技術にもかかわらず、従来の水素吸Ｍ電
極は、水素吸蔵合金粉末が充放電により変形するので形
状安定性に劣る点と、急速（高率〉放電時の容量低下が
大きい点とに問題があった。[Problems to be Solved by the Invention] Despite the above-mentioned prior art, conventional hydrogen-absorbing M electrodes have poor shape stability because the hydrogen-absorbing alloy powder deforms during charging and discharging, and rapid (high rate of deformation). >There was a problem in that the capacity decreased significantly during discharge.
これら問題は特に大型電極において顕著である。These problems are particularly noticeable in large electrodes.
すなわち体積変化率や変形率が同じでも、大型電極は小
型電極よりも絶対的な体積変化量や変形量が大となり、
その結果として、水素吸蔵電極よりの合金粉末の脱落な
どの障害が生じる。結着材の増量により強度向上を図る
ことは可能であるが、そうすると、合金粉末分量の減量
、水素流通の妨害、電気抵抗の増加が生じ高率放電時の
容量低下が顕著となる。In other words, even if the rate of volume change and deformation are the same, a large electrode will have a larger absolute amount of volume change and deformation than a small electrode.
As a result, problems such as falling of alloy powder from the hydrogen storage electrode occur. Although it is possible to improve the strength by increasing the amount of binder, this will reduce the amount of alloy powder, impede hydrogen flow, and increase electrical resistance, resulting in a noticeable decrease in capacity during high rate discharge.
また、水素吸蔵合金粉末を東電休に圧着してから、フッ
素樹脂の懸濁液に浸漬する方法では、電極表面部ではフ
ッ素樹脂の含有比率が高くなり過ぎてこの表面部の内部
抵抗か増加し、電極内部ではフッ素樹脂の含有比率が低
すぎて結合力が低下するという問題があった。In addition, in the method of compressing hydrogen-absorbing alloy powder onto a TEPCO suspension and then immersing it in a fluororesin suspension, the content ratio of fluororesin becomes too high on the surface of the electrode, increasing the internal resistance of this surface. However, there was a problem in that the content ratio of the fluororesin inside the electrode was too low, resulting in a decrease in bonding strength.
本発明は、上記問題に鑑みなされたものであり、優れた
放電特性及び形状保持性を有し大型電極に好適な水素吸
蔵電極の製造方法を提供することをその解決すべき課題
としている。The present invention has been made in view of the above problems, and an object to be solved is to provide a method for manufacturing a hydrogen storage electrode that has excellent discharge characteristics and shape retention and is suitable for large-sized electrodes.
［課題を解決するための手段］
本発明の水素吸蔵電極の製造方法は、水素吸蔵合金粉末
の表面を銅又はニッケルで水素流通可能に被覆してマイ
クロカプセル化し、該マイクロカプセルとＦＥＰ （四
フッ化エチレンと六フッ化プロピレンの共重合体）分敗
液とを固形分総量に対して分散質が５〜１０重量％とな
るように混練した後、集電体で支持して、２４０〜２６
０℃の加熱温度、２００〜４００ｋｇ／Ｃｍ２の成型圧
力により加熱加圧成型することを特徴としている。[Means for Solving the Problems] The method for producing a hydrogen storage electrode of the present invention involves coating the surface of a hydrogen storage alloy powder with copper or nickel to allow hydrogen to flow therein to form microcapsules, and then combining the microcapsules with FEP (four-fluoride A copolymer of ethylene and hexafluorinated propylene) was kneaded so that the amount of dispersoid was 5 to 10% by weight based on the total solid content, and then supported by a current collector to give a 240 to 26
It is characterized by heating and pressure molding at a heating temperature of 0°C and a molding pressure of 200 to 400 kg/Cm2.
水素吸蔵粉末としては、チタン一ニッケル合金、ランタ
ン一ニッケル合金、ジルコニウム一ニッケル合金などを
採用することができ、平均粒径は１０〜１００μｍ程度
が好適である。銅又はニッケルの被覆量はマイクロカプ
セルの５〜３０重量％とすることが好ましい。As the hydrogen storage powder, titanium-nickel alloy, lanthanum-nickel alloy, zirconium-nickel alloy, etc. can be used, and the average particle size is preferably about 10 to 100 μm. The amount of copper or nickel coated is preferably 5 to 30% by weight of the microcapsules.
ＦＥＰ分散液としては、例えば、ダイキン工業株式会社
製のＮＤ−１、ＮＤ−２、ＮＤ−４などを用いることが
できる。分敗質すなわちＦＥＰ含有量が上記混合物の５
重量％以下であると充分な結合力が得られず、１０重量
％を超えると水素吸蔵電極の導電性が低下して高率放電
時の容量が減少する。As the FEP dispersion, for example, ND-1, ND-2, ND-4 manufactured by Daikin Industries, Ltd. can be used. The fractionation substance or FEP content is 5% of the above mixture.
If it is less than 10% by weight, sufficient bonding strength cannot be obtained, and if it exceeds 10% by weight, the conductivity of the hydrogen storage electrode will decrease and the capacity during high rate discharge will decrease.
成型時の加圧力が２ ０ ０ ｋ ａ ／ ｃ ｍ ２
を下回ると電極の機械的強度が低下するため充分な結合
力が得られず、マイクロカプセルの脱落が生じやすくな
る。４００ｋｇ／ｃｍ２を超えるとマイクロカプセル間
が密になり過ぎて多孔構造が失われ、電気化学的な水素
の吸蔵放出が円滑に行なわれなり、また、内部抵抗が増
加して高率放電時の容量が低下する。Pressure force during molding is 200 ka/cm2
If it is less than this, the mechanical strength of the electrode decreases, so that sufficient bonding force cannot be obtained, and the microcapsules tend to fall off. If it exceeds 400 kg/cm2, the microcapsules become too dense, the porous structure is lost, electrochemical hydrogen storage and release becomes smooth, and the internal resistance increases and the capacity during high rate discharge decreases. decreases.
５
成型時の加熱温度は約２５０’Ｃ近傍が好ましく、２４
０’Ｃを下回るとＦＥＰが溶融せず結合力が低下し、２
６０℃を超えると気孔が減少して電極内部の反応速度が
低下する。5 The heating temperature during molding is preferably around 250'C, and 24
If the temperature drops below 0'C, FEP will not melt and the bonding strength will decrease.
When the temperature exceeds 60°C, pores decrease and the reaction rate inside the electrode decreases.
［実施例］
（第１実施例〉
合金組成ｌａＮｉ２．ＳＣＯ２．４ＡＩＯ．ｔを負極用
の水素吸蔵合金として用いた。この合金を機械的に１０
０メッシュ以下の粉末とし、市販のメッキ溶液を用いて
無電解銅メッキを行った。[Example] (First example) Alloy composition laNi2.SCO2.4AIO.t was used as a hydrogen storage alloy for the negative electrode.This alloy was mechanically
The powder was made into a powder of 0 mesh or less, and electroless copper plating was performed using a commercially available plating solution.
このときのメッキ量はマイクロカプセル、すなゎち銅メ
ッキした合金粉末に対して、２０重最％になるようにし
た。The amount of plating at this time was set to be a maximum of 20% by weight of the microcapsules, that is, the copper-plated alloy powder.
このマイクロ力プセノレ０．６ＣＩに、マイクロカプセ
ルと結着剤とを合わせた総量に対して分散質が５重量％
となるように市販のＦＥＰ分敗液（ダイキン工業株式会
社製のＮＤ−１）を加え、混練して予備成型した後、そ
の両側をニツケルメッシュ（すなわち、本発明でいう集
電体）で挟んで２５０’Ｃ，３００ｋｇ／ｃｍ２１７）
ＪＩ力で加熱加ＪＩ 戒６
型して水索吸蔵電極を製作した。なお、上記分敗液にお
けるＦＥＰ含有率は５０重量％である。なお比較例とし
て、マイクロカプセル０．６Ｃｌに対してＰＴＦＥ粉末
を、それらの総量に対して５重量％加えて混練し、加熱
温度が３００℃である他は前と同じ条件で製造した水索
吸蔵電極も用意した。各電極の大きさは直径１３ｍｍで
厚さは約１ｍｍのコイン型とした。次に、各水素吸蔵電
極を一ツケル極を対極として６Ｎか性カリ水溶液中に浸
漬して充放電を繰り返し、完全に活性化処理したものを
電池用の負極として供した。この水素吸蔵電極の初期容
量は約１００ｍＡｈであった。5% by weight of dispersoids is added to this microforcepsenole 0.6CI based on the total amount of microcapsules and binder.
A commercially available FEP separation solution (ND-1 manufactured by Daikin Industries, Ltd.) was added, kneaded, and preformed, and both sides of the mixture were sandwiched between nickel meshes (i.e., current collectors in the present invention). at 250'C, 300kg/cm217)
A water cable occlusion electrode was manufactured by heating and molding with JI force. Incidentally, the FEP content in the above-mentioned separation liquid was 50% by weight. As a comparative example, a water cable occlusion was produced under the same conditions as before except that 5% by weight of PTFE powder was added to 0.6 Cl of microcapsules and kneaded, and the heating temperature was 300°C. Electrodes were also prepared. Each electrode was coin-shaped with a diameter of 13 mm and a thickness of about 1 mm. Next, each hydrogen storage electrode was immersed in a 6N caustic potassium aqueous solution with the one-layer electrode as a counter electrode, and charged and discharged repeatedly, and the completely activated electrode was used as a negative electrode for a battery. The initial capacity of this hydrogen storage electrode was about 100 mAh.
次に、電解液として６Ｎか性カリ水溶液を用い、水素吸
蔵電極よりもはるかに容量の大きい焼結式酸化ニッケル
板を正極とし、水素吸蔵電極を負極として対置させ、酸
化水銀参照電極を使って負極のみの容量変化を調べ゛る
負極規制の電池（公称容量１００ｍＡｈ）を構威した。Next, a 6N caustic potassium aqueous solution was used as the electrolyte, a sintered nickel oxide plate with a much larger capacity than the hydrogen storage electrode was used as the positive electrode, the hydrogen storage electrode was placed opposite as the negative electrode, and a mercury oxide reference electrode was used. A negative electrode regulated battery (nominal capacity 100 mAh) was constructed to examine the change in capacity of only the negative electrode.
製造した電池を２０’Ｃ，０．５０ （５０ｍＡ＞の電
流で３時間充電し、０．５Ｃ、ＩＣ、２Ｃ、３Ｃ、４Ｃ
、５Ｃの各放電電流で放電終了電圧０．６■まで放電さ
せて電池容量の放電電流依存性を調べた。この結果を第
１図に示す。The manufactured battery was charged at 20'C, 0.50 (50mA) current for 3 hours, 0.5C, IC, 2C, 3C, 4C.
The dependence of the battery capacity on the discharge current was investigated by discharging the battery at discharge currents of , 5C, and 5C to a discharge end voltage of 0.6■. The results are shown in FIG.
この実験結果からわかるように、結着材としてＦＥＰ分
散液を用いた水索吸蔵電極は比較例のものに比べて高率
放電での容量低下が小ざいことが判明した。As can be seen from the results of this experiment, it was found that the water cord storage electrode using the FEP dispersion liquid as a binder had a smaller capacity drop during high rate discharge than the comparative example.
｛第２実施例｝
マイクロカプセルを６ｇとし、電極形状を縦４ｃｍｘ横
３ｃｍｘ厚さ約１ｍｍの平板状とし初期容量を約１００
０ｍＡｈとした以外は、実施例１と同一の水素吸蔵電極
を負極とした。{Second Example} The microcapsule was 6 g, the electrode shape was a flat plate measuring 4 cm long x 3 cm wide x about 1 mm thick, and the initial capacity was about 100.
The same hydrogen storage electrode as in Example 1 was used as the negative electrode, except that the voltage was 0 mAh.
次に、電解液として５Ｎか性カリ水一溶液に水酸化リチ
ウムを１ｍＯ＋／リットルの割合で溶解したものを用い
、正極として容量３ ５ ０ｍＡ ｈの焼結式酸化ニッ
ケル板を用い、セパレータとしてのナイロン不織布を挟
んで、正、負極を対置し、正極規制の電池（公称容量が
３ ５ ０ｍＡ ｈ ）を構或した。比較例としてＦＥ
Ｐ粉末を５重量％混合した水素吸蔵電極を有する同一条
件の電池、分散質が５重量％となるようにＰＴＦＥ分散
液を加えた水素吸蔵電極を有する電池及び上記ＰＴＦＥ
粉末使用の電池も試験した。Next, lithium hydroxide dissolved in a 5N caustic potassium aqueous solution at a rate of 1 mO+/liter was used as the electrolyte, a sintered nickel oxide plate with a capacity of 350 mAh was used as the positive electrode, and a separator was used as the separator. A positive electrode and a negative electrode were placed opposite each other with a nylon nonwoven fabric sandwiched between them to construct a positive electrode-regulated battery (nominal capacity: 350 mAh). FE as a comparative example
A battery under the same conditions that has a hydrogen storage electrode mixed with 5% by weight of P powder, a battery that has a hydrogen storage electrode with a PTFE dispersion added so that the dispersoid is 5% by weight, and the above PTFE.
Powder-based batteries were also tested.
製造した電池を２０゜Ｃ１’０．５Ｃ （１ ７５ｍＡ
＞の電流で３時間充電し、０．５Ｃ，ＩＣ、２Ｇ，３Ｃ
、４Ｃ、５Ｃの各放電電流で放電終了電圧０．８ｖまで
放電させて電池容量の放電電流依存性を調べた。この結
果を第２図に示す。The manufactured battery was heated to 20°C1'0.5C (1 75mA
>Charged for 3 hours with a current of 0.5C, IC, 2G, 3C
, 4C, and 5C to an end-of-discharge voltage of 0.8V, and the dependence of the battery capacity on the discharge current was investigated. The results are shown in FIG.
この実験結果からわかるように、結着材としてＦＥＰ分
敗液を用いた水素吸蔵電極は比較例のものに比べて高率
放電での容量低下が小さいことが判明した。As can be seen from the results of this experiment, it was found that the hydrogen storage electrode using the FEP decomposition liquid as a binder had a smaller capacity drop during high rate discharge than the comparative example.
（第３実施例〉
次に、結着剤として上記ＦＥＰ分敗液を用いたＦＥＰ含
有量と高率放電時の容量維持率との関係を第３図に示す
。なお、上記容量維持率は０． ５Ｃ放電に対する５Ｃ
放電時の放電容量の割合を示す。他の条件は第２実施例
と同じである。(Third Example) Next, Fig. 3 shows the relationship between the FEP content using the above FEP separation liquid as a binder and the capacity retention rate during high rate discharge. 5C for 0.5C discharge
Shows the percentage of discharge capacity during discharge. Other conditions are the same as in the second embodiment.
この結果から、ＦＥＰ含有量を５〜１０重量％とすると
、良好な容量維持率が得られることがわ９
かった。From this result, it was found that a good capacity retention rate can be obtained when the FEP content is 5 to 10% by weight.
（第４実施例〉
次に、結着剤としてＦＥＰ分散液を用いた水素吸蔵電極
の成型温度及び成型圧力と高率放電時の容量維持率との
関係を第４図、第５図に示す。「ＥＰ含有量は５重量％
とした。上記容量維持率も０．５０放電に対する５Ｃ放
電時の放電容量の割合を示し、他の条件は第２実施例と
同じである。(Fourth Example) Next, Figures 4 and 5 show the relationship between the molding temperature and molding pressure of a hydrogen storage electrode using FEP dispersion as a binder and the capacity retention rate during high rate discharge. ``The EP content is 5% by weight.
And so. The above capacity retention rate also shows the ratio of discharge capacity at 5C discharge to 0.50 discharge, and other conditions are the same as in the second example.
この結果から、戊型圧力は２００〜４． Ｏ Ｏ ｋ
ｇ／Ｃｍ２、或形温度は２５０’Ｃ近傍（例えば２４０
〜２６０℃とすると、良好な容量維持率か得られること
が判明した。From this result, the hollow pressure is 200~4. OOk
g/Cm2, or the temperature is around 250'C (e.g. 240'C)
It was found that a good capacity retention rate could be obtained when the temperature was set at ~260°C.
［発明の効果］
以上説明したように、本発明の水素吸Ｒ電極の製造方法
は、マイクロカプセルとＦＥＰ分敗液と集電体とを素材
として上記した製造条件で製造することにより、高率放
電時の容量維持性に優れた水素吸蔵電極を得ることがで
きる。[Effects of the Invention] As explained above, the method for manufacturing a hydrogen absorbing R electrode of the present invention can achieve high efficiency by manufacturing under the above-mentioned manufacturing conditions using microcapsules, FEP separation liquid, and current collector as raw materials. A hydrogen storage electrode with excellent capacity retention during discharge can be obtained.
結着材として、ＦＥＰ粉末よりもＦＥＰ分敗液が格段に
優れている理由について、理論的には不１０
明であるが分敗液とすることによって良好なマイクロカ
プセル保持性や形状安定性が得られるものと思われる。The reason why the FEP separation liquid is much better than FEP powder as a binder is theoretically unclear, but it is possible that the separation liquid provides good microcapsule retention and shape stability. It seems that you can get it.
マイクロカプセル保持性や形状安定性が改善されると、
内部抵抗の増加や水素流通性の劣化が抑止され、結果と
して、高率放電時の容量低下が抑制されるのではないか
と考えられる。When microcapsule retention and shape stability are improved,
It is thought that an increase in internal resistance and a deterioration in hydrogen flowability are suppressed, and as a result, a decrease in capacity during high rate discharge is suppressed.
水素吸蔵電極の形状安定性の向上は、大型電極用とにお
いて特に重要である。Improving the shape stability of hydrogen storage electrodes is particularly important for large electrodes.
また、ＦＥＰはＰＴＦＥなどに比較して融点付近での溶
融粘度が極端に低いので（ＦＥＰ：１０４〜１０５ｐＯ
ｉＳｅ，ＰＴＦＥ：１０１１〜１０’ ｉ ｐｏ ｉ
ｓｅ）、分敗性に優れており、その結果としてＰＴＦＥ
などに比較して一層、マイクロカプセル保持性や形状安
定性が良好になるのではないかと思われる。In addition, compared to PTFE, FEP has an extremely low melt viscosity near its melting point (FEP: 104 to 105 pO
iSe, PTFE: 1011~10' i po i
se), has excellent separability, and as a result, PTFE
It is thought that microcapsule retention and shape stability will be even better compared to other methods.
更に、本発明では水素吸蔵合金粉末はその表面が多孔性
被膜により被膜されて平滑化されているのでＦＥＰの微
小粒子がマイクロカプセル間に良好に分散することがで
きる利点もある。Furthermore, in the present invention, since the surface of the hydrogen storage alloy powder is smoothed by being coated with a porous film, there is an advantage that the fine particles of FEP can be well dispersed between the microcapsules.
【図面の簡単な説明】
１１
第１図及び第２図は、本発明の製造方法で製造された水
索吸蔵電極を用いた電池の放電容量と放電電流の関係を
示す特性図である。第３図はＦＥＰ含有量と容量維持率
との関係を示す特性図、第４図は成型温度と容量維持率
との関係を示ず特性図、第５図は成型圧力と容量維持率
との関係を示す特性図である。BRIEF DESCRIPTION OF THE DRAWINGS 11 FIGS. 1 and 2 are characteristic diagrams showing the relationship between discharge capacity and discharge current of a battery using a water cable storage electrode manufactured by the manufacturing method of the present invention. Figure 3 is a characteristic diagram showing the relationship between FEP content and capacity retention rate, Figure 4 is a characteristic diagram showing the relationship between molding temperature and capacity retention rate, and Figure 5 is a characteristic diagram showing the relationship between molding pressure and capacity retention rate. It is a characteristic diagram showing a relationship.
Claims (1)
流通可能に被覆してマイクロカプセル化し、該マイクロ
カプセルとＦＥＰ（四フッ化エチレンと六フッ化プロピ
レンの共重合体）分散液とを、固形分総量に対して分散
質が５〜１０重量％となるように混練した後、該混合物
を集電体で支持して、２４０〜２６０℃の加熱温度、２
００〜４００ｋｇ／ｃｍ＾２の成型圧力により加熱加圧
成型することを特徴とする水素吸蔵電極の製造方法。(1) The surface of a hydrogen-absorbing alloy powder is coated with copper or nickel to allow hydrogen to flow, and the microcapsules and FEP (a copolymer of tetrafluoroethylene and hexafluoropropylene) dispersion liquid are combined. After kneading so that the dispersoid amount is 5 to 10% by weight based on the total solid content, the mixture is supported by a current collector and heated at a heating temperature of 240 to 260 °C, 2
A method for producing a hydrogen storage electrode, characterized by carrying out heating and pressure molding at a molding pressure of 00 to 400 kg/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1235145A JPH0824040B2 (en) | 1989-09-11 | 1989-09-11 | Method for manufacturing hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1235145A JPH0824040B2 (en) | 1989-09-11 | 1989-09-11 | Method for manufacturing hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0398261A true JPH0398261A (en) | 1991-04-23 |
| JPH0824040B2 JPH0824040B2 (en) | 1996-03-06 |
Family
ID=16981721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1235145A Expired - Lifetime JPH0824040B2 (en) | 1989-09-11 | 1989-09-11 | Method for manufacturing hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824040B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02183964A (en) * | 1989-01-09 | 1990-07-18 | Agency Of Ind Science & Technol | Manufacture of hydrogen storage electrode |
-
1989
- 1989-09-11 JP JP1235145A patent/JPH0824040B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02183964A (en) * | 1989-01-09 | 1990-07-18 | Agency Of Ind Science & Technol | Manufacture of hydrogen storage electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0824040B2 (en) | 1996-03-06 |
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