JPS60208053A - Zinc electrode for alkaline storage battery - Google Patents
Zinc electrode for alkaline storage batteryInfo
- Publication number
- JPS60208053A JPS60208053A JP59064493A JP6449384A JPS60208053A JP S60208053 A JPS60208053 A JP S60208053A JP 59064493 A JP59064493 A JP 59064493A JP 6449384 A JP6449384 A JP 6449384A JP S60208053 A JPS60208053 A JP S60208053A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- electrode
- inorganic compound
- alkaline storage
- storage battery
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
亜鉛極を負極として用いるアルカリ蓄電池は冒エネルギ
ー密度、高出力密度を有するが、その反面寿命が短いと
いう欠点がある。この原因は亜鉛極の充放電に際し溶解
放出を繰返すことにより電極の形状が変化すること及び
電極面積が小さくなること等によシ亜鉛極の実効容量が
減少することに基〈ものである。DETAILED DESCRIPTION OF THE INVENTION Alkaline storage batteries using a zinc electrode as a negative electrode have a high energy density and a high output density, but have the disadvantage of a short life. The reason for this is that the shape of the electrode changes due to repeated dissolution and release during charging and discharging of the zinc electrode, and the effective capacity of the zinc electrode decreases due to a decrease in the electrode area.
従来この亜鉛極の変形を抑制するためにコンダクタ−全
バインダーと共に電極内部に固定することか試みられて
いる。然しなからこのような亜鉛極を充放電した場合、
次第に活物質亜鉛が表面に集りコンダクタ−やバインダ
ーを含む層と亜鉛層とに分離するおそれがある。このた
め有効に作用する電極表面積が減少し容量が低下するも
のであった。In order to suppress this deformation of the zinc electrode, attempts have been made to fix the conductor together with the entire binder inside the electrode. However, when such a zinc electrode is charged and discharged,
There is a possibility that the active material zinc gradually collects on the surface and separates into a layer containing a conductor and binder and a zinc layer. As a result, the effective electrode surface area is reduced, resulting in a decrease in capacity.
このバインダ一層と亜鉛層とが分離する原因として唸充
放電によって亜鉛が溶解して生成する空孔内に亜鉛の再
放出が困蛯となるためと考えられ、その理由は亜鉛の放
出のための電解液がバインダ一層中に十分に保持されて
いないこと並に放出すべき空間が極板によって押しつぶ
されて空間が保持されていないことによるものと考えら
れる。The reason for this separation of the binder layer and the zinc layer is thought to be that it becomes difficult to re-release the zinc into the pores that are created when the zinc dissolves due to charging and discharging. This is thought to be due to the fact that the electrolytic solution is not sufficiently retained in the binder layer, and also because the space to be discharged is crushed by the electrode plate and the space is not retained.
なおニッケル亜鉛電池においては極板ｇ＋が緊縛された
状態となっ、ているため常に極板に出力が加わっている
ものである。従って上ｂｃの如く充放電によシ亜鉛が溶
解して空孔部が生成８れるか該゛空孔部は上記の如き理
由によって維持する必要がある。In the case of a nickel-zinc battery, the electrode plate g+ is in a tightly bound state, so that an output is always applied to the electrode plate. Therefore, as shown in bc above, zinc is dissolved during charging and discharging to form pores, or these pores must be maintained for the reasons described above.
本発明はかかる現状に鑑み鋭意研究を行った結果、バイ
ンダ一層と亜鉛層との分離を防いで長期間充放電サイク
ルを繰返すも安定した電極表面を維持しうる亜鉛極を見
出したものである。The present invention has been made in view of the current situation, and as a result of extensive research, we have discovered a zinc electrode that can prevent separation of the binder layer and the zinc layer and maintain a stable electrode surface even after repeated charging and discharging cycles for a long period of time.
即ち本発明は弗素樹脂及びポリビニルアルコールを含有
せる亜鉛活物質中に１水酸化カルシウム、水酸化バリウ
ム、酸化チタン、酸化ジルコニウム、酸化マグネシウム
の内から選ばれた少くとも１種の無機化合物を添加した
ことを特徴とするものである。That is, in the present invention, at least one inorganic compound selected from monocalcium hydroxide, barium hydroxide, titanium oxide, zirconium oxide, and magnesium oxide is added to a zinc active material containing a fluororesin and polyvinyl alcohol. It is characterized by this.
本発明において上記の無機化合物を選定した理由は亜鉛
極の充放電にかかわらずアルカリ電解波中で安定して存
在し且つ水になじみ易い物を梵によるためである。The reason why the above-mentioned inorganic compound was selected in the present invention is that it exists stably in alkaline electrolytic waves regardless of charging and discharging of the zinc electrode and is easily compatible with water.
これらの無機化合物を亜鉛活物質即ち活物質亜鉛上弗素
樹脂としてポリテトラフルオロエチレン（ＰＴＦＥ）の
繊維状バインダー及びポリビニルアルコール（ＰＶＡ）
のゲル化剤との混合物中に添加することにより、ＰＴＦ
Ｅの表面をＰＶＡが覆い、この中に電解液や水が十分に
保持されると共に無機化合物例えば水酸化カルシウム（
ｃａ（ｏＨ）２）がＰＴＦＥ Ｋ固定されて亜鉛溶解後
の空孔を外部からの圧力をうけるもこれに対抗して孔部
な保持しうるものである。又Ｃａ（ＯＨ）２がＰＶＡの
流動性とおさえてＰＶＡを電極内に均一に分散し維持す
るため形状変化をおさえることができ長期に亘シ亜鉛極
の容量を減少せしめることがない。These inorganic compounds are used as a zinc active material, that is, a fluororesin on zinc as an active material, a fibrous binder of polytetrafluoroethylene (PTFE) and polyvinyl alcohol (PVA).
PTF by adding it into a mixture with a gelling agent of
The surface of E is covered with PVA, in which electrolyte and water are sufficiently retained, and inorganic compounds such as calcium hydroxide (
ca(oH)2) is fixed in PTFE K, and even if the pores are subjected to external pressure after zinc is dissolved, the pores can be maintained against this pressure. Furthermore, since Ca(OH)2 suppresses the fluidity of PVA and maintains the PVA uniformly dispersed within the electrode, changes in shape can be suppressed and the capacity of the zinc electrode will not decrease over a long period of time.
又本発明において弗素樹脂としては上記ＰＴＦＥの＃１
か三フッ化塩化エチレン樹脂、四フッ化エチレンー六フ
ッ化グロピレン共重合樹脂等が使用できる。In addition, in the present invention, the fluororesin is #1 of the above PTFE.
or trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropylene copolymer resin, etc. can be used.
本発明において弗素樹脂、ポリビニルアルコール及び前
記の無機化合物の配合層については特に限定するもので
はないが望ましくは下記の如き配合量が好ましく該配合
量において特に顕著な効果を示す。なお−配合量（％）
は亜鉛活物貴の全量を１００％としての含有菫でろる。In the present invention, the layer containing the fluororesin, polyvinyl alcohol, and the above-mentioned inorganic compound is not particularly limited, but it is preferable to use the following blending amounts, which exhibit particularly remarkable effects. In addition - blending amount (%)
The total amount of zinc active material is 100%.
Ａ 弗素樹脂 ３〜Ｉ Ｏｗｔ％
Ｂｆ！リビニルアルコール ０．３〜１５ ｗｔ ％Ｃ
無機化合物 ５〜２０ ｗｔ％
上記において弗素樹脂及びポリビニルアルコールの配合
量については従来の亜鉛極において添加される範囲のも
のである。A Fluororesin 3~I Owt% Bf! Rivinyl alcohol 0.3-15 wt%C
Inorganic compound 5 to 20 wt% In the above, the amounts of the fluororesin and polyvinyl alcohol are within the range that is added in conventional zinc electrodes.
又活性物中に酸化鉛（ｐｂｏ）等の導電性物質を添加し
てもよく、これＫよって亜鉛極の導電性をより向上せし
めることが出来る。Further, a conductive substance such as lead oxide (pbo) may be added to the active substance, and this K can further improve the conductivity of the zinc electrode.
次に本発明の実施例について説明する。Next, examples of the present invention will be described.
実施例（１）〜（４）及び比較例（１）〜（２）亜鉛（
Ｚｎ） Ｆ酸化亜鉛（ＺｎＯ） 、 ＰｂＯ、ＰＴＦＥ
。Examples (1) to (4) and Comparative Examples (1) to (2) Zinc (
Zn) F zinc oxide (ZnO), PbO, PTFE
.
ＰＶＡ ｒ Ｃａ（ＯＨ）２ ｒ酸化マグネシウム（Ｍ
ｇＯ）、酸化チタン（’ｒｔｏ２）、酸化ノルコニウム
（Ｚｒ０２）を第１辰に示す如き割合にて各々配合し、
混合して集電体に圧着しこれを化成してＺｎＯを活性化
せしめて本発明亜鉛極及び比較例亜鉛極を得た。PVA r Ca(OH)2 r Magnesium oxide (M
gO), titanium oxide ('rto2), and norconium oxide (Zr02) in the proportions shown in the first category,
The mixture was mixed and pressed onto a current collector, and the mixture was chemically converted to activate ZnO to obtain a zinc electrode of the present invention and a zinc electrode of a comparative example.
斯くして得た本発明亜鉛極及び比較例亜鉛極を使用して
容量１０ Ａｈのニッケル亜鉛電池を作製し、充電を充
電量１ｏ、ｓＡｈ、放電を１０Ａ１終止電圧１．２ Ｖ
／セルの条件でサイクル寿命を測定した。その結果は第
１図に示す通りである。A nickel-zinc battery with a capacity of 10 Ah was prepared using the zinc electrode of the present invention and the zinc electrode of the comparative example thus obtained, and the battery was charged at a charge amount of 10 sAh and discharged at a final voltage of 10 A1 and a final voltage of 1.2 V.
The cycle life was measured under the following cell conditions. The results are shown in FIG.
なお活物質の充てん量は電池全体でセル当９７０ｇであ
る。Note that the amount of active material filled in the entire battery was 970 g per cell.
図面よシ明らかの如′く本発明電極による電池は比較例
電池に比してサイクル初期においては低い容量を示すが
、長いサイクルに亘シ安定した容量を示すことが認めら
れ、寿命判断の基準となる１／２容量（５Ａｈ）になる
までのサイクル数が増大している。As is clear from the drawing, the battery using the electrode of the present invention exhibits a lower capacity at the beginning of the cycle than the comparative example battery, but it is recognized that it exhibits a stable capacity over a long cycle, which meets the criteria for life judgment. The number of cycles required to reach 1/2 capacity (5 Ah) is increasing.
以上詳述した如く本発明によれば長期間による充放電サ
イクルにわたり電極の形状を変化せしめることなく且つ
電極面積を減少せしめることなく安定した容量を保持し
うるためアルカリ蓄電池として極めて有用なものをうろ
ことが出来る。As detailed above, according to the present invention, a stable capacity can be maintained without changing the electrode shape or reducing the electrode area over a long period of charge/discharge cycles, making it extremely useful as an alkaline storage battery. I can do that.
【図面の簡単な説明】
図面は本発明アルカリ蓄電池用亜鉛極及び従来のアルカ
リ蓄電池用亜鉛極とのサイクル数と放電電気量との関係
曲線図である。
出願人代理人 弁理士 鈴 江 武 彦手続補正書
昭和 も９．９．２９日
特許庁長官 志 賀 学 殿
１、事件の表示
特願昭５９−６４４９３号
２、発明の名称
アルカリ蓄電池用亜鉛極
３、補正をする者
事件との関係 特許出願人
（５３８）古河亀池株式会社
４、代理人
７、補正の内容
（１） 明細書第１頁第１５行において「溶解放出」と
あるを「溶解析出」と訂正する。
伐） 同第２頁第９行において「再放出」とある′ｔ−
「再析出」と訂正する・
（８） 同第２頁第１０行において「放出」とある金「
析出」と訂正Ｔる。
（４）同第２頁第１２行において「放出」とある全「析
出」と訂正する。
（５） 同第２頁第１９行において「るか」とあるを「
るが」と訂正する。
（６）同第４頁第５衿において「とおさえて」とある全
「全おさえて」と訂正する。BRIEF DESCRIPTION OF THE DRAWINGS The drawing is a graph showing the relationship between the number of cycles and the amount of electricity discharged between the zinc electrode for an alkaline storage battery of the present invention and the conventional zinc electrode for an alkaline storage battery. Applicant's representative Patent attorney Takehiko Suzue Procedural amendment dated 9/9/29 Manabu Shiga, Commissioner of the Patent Office 1, Indication of the case Patent application No. 1983-64493 2, Name of the invention Zinc electrode for alkaline storage battery 3. Relationship with the case of the person making the amendment Patent applicant (538) Koga Kameike Co., Ltd. 4, Agent 7, Contents of the amendment (1) In line 15 of page 1 of the specification, the term “dissolution release” has been replaced with “dissolution release”. "Precipitation" is corrected. ) On page 2, line 9, it says ``re-release''.
(8) On page 2, line 10 of the same, the gold that is written as “release” is “re-precipitated.”
"Precipitation" is corrected. (4) On page 2, line 12, the word "release" is corrected to "precipitation." (5) On page 2, line 19, the word “ruka” is replaced with “
"Ruga," he corrected. (6) In the 5th collar of page 4 of the same page, the phrase ``tosabete'' is corrected to ``tosabete''.
Claims (1)
質中Ｋ、水酸化カルシウム、水酸化バリウム、酸化チタ
ン、酸化ジルコニウム、酸化マグネシウムの内から選ば
れた少くとも１種の無機化合物を添加したことを特徴と
するアルカリ蓄電池用亜鉛極。A zinc active material containing a fluororesin and polyvinyl alcohol is characterized by adding at least one inorganic compound selected from potassium, calcium hydroxide, barium hydroxide, titanium oxide, zirconium oxide, and magnesium oxide. Zinc electrodes for alkaline storage batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59064493A JPS60208053A (en) | 1984-03-31 | 1984-03-31 | Zinc electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59064493A JPS60208053A (en) | 1984-03-31 | 1984-03-31 | Zinc electrode for alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60208053A true JPS60208053A (en) | 1985-10-19 |
Family
ID=13259782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59064493A Pending JPS60208053A (en) | 1984-03-31 | 1984-03-31 | Zinc electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60208053A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529707A (en) * | 1994-11-17 | 1996-06-25 | Kejha; Joseph B. | Lightweight composite polymeric electrolytes for electrochemical devices |
| FR2788887A1 (en) * | 1999-01-27 | 2000-07-28 | Scps | ZINC ANODE ALKALINE SECONDARY ELECTROCHEMICAL GENERATORS |
| FR2843235A1 (en) * | 2002-07-30 | 2004-02-06 | Conseil Et De Prospective Scie | OXIDIZED PRE-TREATED CONDUCTIVE CERAMIC FOR ZINC ANODE OF ALKALINE SECONDARY ELECTROCHEMICAL GENERATORS |
| US7816035B2 (en) * | 2001-03-15 | 2010-10-19 | Powergenix Systems, Inc. | Methods for production of zinc oxide electrodes for alkaline batteries |
| WO2013027767A1 (en) | 2011-08-23 | 2013-02-28 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| JP2019021518A (en) * | 2017-07-18 | 2019-02-07 | 日本碍子株式会社 | Negative electrode for zinc secondary battery and zinc secondary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217628A (en) * | 1975-07-31 | 1977-02-09 | Tokyo Shibaura Electric Co | Zinc plate for alkaline battery |
| JPS5219231A (en) * | 1975-08-04 | 1977-02-14 | Tokyo Shibaura Electric Co | Lead plate for alkaline battery |
| JPS5372138A (en) * | 1976-12-08 | 1978-06-27 | Matsushita Electric Ind Co Ltd | Method of manufacturing zinc electrode for alkaline storage battery |
| JPS58163162A (en) * | 1982-03-19 | 1983-09-27 | Sanyo Electric Co Ltd | Alkaline zinc storage battery |
-
1984
- 1984-03-31 JP JP59064493A patent/JPS60208053A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217628A (en) * | 1975-07-31 | 1977-02-09 | Tokyo Shibaura Electric Co | Zinc plate for alkaline battery |
| JPS5219231A (en) * | 1975-08-04 | 1977-02-14 | Tokyo Shibaura Electric Co | Lead plate for alkaline battery |
| JPS5372138A (en) * | 1976-12-08 | 1978-06-27 | Matsushita Electric Ind Co Ltd | Method of manufacturing zinc electrode for alkaline storage battery |
| JPS58163162A (en) * | 1982-03-19 | 1983-09-27 | Sanyo Electric Co Ltd | Alkaline zinc storage battery |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529707A (en) * | 1994-11-17 | 1996-06-25 | Kejha; Joseph B. | Lightweight composite polymeric electrolytes for electrochemical devices |
| WO1997049106A1 (en) * | 1994-11-17 | 1997-12-24 | Lithium Technology Corporation | Lightweight composite polymeric electrolytes for electrochemical devices |
| FR2788887A1 (en) * | 1999-01-27 | 2000-07-28 | Scps | ZINC ANODE ALKALINE SECONDARY ELECTROCHEMICAL GENERATORS |
| JP2000228198A (en) * | 1999-01-27 | 2000-08-15 | Scps Soc De Conseil & De Prospective Scient Sa | Alkaline secondary electrochemical generator of zinc positive electrode |
| US6649305B1 (en) | 1999-01-27 | 2003-11-18 | S.C.P.S. Societe De Conseil Et De Prospective Scientifique S.A. | Secondary electrochemical generators of the zinc-anode alkaline type |
| US7816035B2 (en) * | 2001-03-15 | 2010-10-19 | Powergenix Systems, Inc. | Methods for production of zinc oxide electrodes for alkaline batteries |
| WO2004013064A2 (en) * | 2002-07-30 | 2004-02-12 | S.C.P.S. Société de Conseil et de Prospective Scientifique S.A. | Oxidation-pretreated ceramic conductor for a zinc anode of secondary alkaline electrochemical generators |
| WO2004013064A3 (en) * | 2002-07-30 | 2005-10-20 | Scps | Oxidation-pretreated ceramic conductor for a zinc anode of secondary alkaline electrochemical generators |
| JP2006504230A (en) * | 2002-07-30 | 2006-02-02 | エス．セー．ペー．エス ソシエテ ドゥ コンセイユ エ ドゥ プロスペクティヴ シアンティフィック エス．アー． | Conductive ceramic for zinc negative electrode pretreated oxidatively |
| FR2843235A1 (en) * | 2002-07-30 | 2004-02-06 | Conseil Et De Prospective Scie | OXIDIZED PRE-TREATED CONDUCTIVE CERAMIC FOR ZINC ANODE OF ALKALINE SECONDARY ELECTROCHEMICAL GENERATORS |
| US7858235B2 (en) | 2002-07-30 | 2010-12-28 | S.C.P.S. Societe De Conseil Et De Prospective Scientifique S.A. | Ceramic conductor pre-treated by oxidising for a zinc anode |
| WO2013027767A1 (en) | 2011-08-23 | 2013-02-28 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| JP2019021518A (en) * | 2017-07-18 | 2019-02-07 | 日本碍子株式会社 | Negative electrode for zinc secondary battery and zinc secondary battery |
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