JPH0268857A - Manufacture of lead acid battery - Google Patents
Manufacture of lead acid batteryInfo
- Publication number
- JPH0268857A JPH0268857A JP63220921A JP22092188A JPH0268857A JP H0268857 A JPH0268857 A JP H0268857A JP 63220921 A JP63220921 A JP 63220921A JP 22092188 A JP22092188 A JP 22092188A JP H0268857 A JPH0268857 A JP H0268857A
- Authority
- JP
- Japan
- Prior art keywords
- zrp
- positive electrode
- phosphate
- active material
- electrode active
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 11
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000011973 solid acid Substances 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 4
- 239000010452 phosphate Substances 0.000 abstract 4
- GYMNNGUBGFVLDI-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Zr+4].[Zr+4] Chemical compound P(=O)([O-])([O-])[O-].[Zr+4].[Zr+4] GYMNNGUBGFVLDI-UHFFFAOYSA-K 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 239000002003 electrode paste Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 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
- 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
- H01M4/627—Expanders for lead-acid accumulators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
【発明の詳細な説明】
産業上の利用分野
本発明は鉛蓄電池の製造法の改良に関するもので、放電
容量の大きい長寿命の鉛蓄電池を提供することを目的と
している。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improvement in the manufacturing method of a lead-acid battery, and an object thereof is to provide a lead-acid battery with a large discharge capacity and a long life.
従来の技術
鉛蓄電池は、他の蓄電池系に比較し、性能とコストのバ
ランスが良くとれた電池であるため、電子機器の電源や
電動車輌の電源として広く用いられている。BACKGROUND OF THE INVENTION Lead-acid batteries have a better balance between performance and cost than other storage battery systems, and are therefore widely used as power sources for electronic devices and electric vehicles.
これらの電源に要求される重点性能は、高容量化と長寿
命化の２点であるが、この２性能は相反する関係にある
ことが、一般的に知られており、この２性能の最適点で
電池設計がなされている。The two key performances required of these power supplies are high capacity and long life, but it is generally known that these two performances are in a contradictory relationship, and the optimum performance of these two performances is generally known. The battery design has been made in several points.
長寿命化に重点を置いた設計では、正極活物質の充填密
度を高くした電池が用いられているが、これは、ｍＩ述
のように、容量性能を犠牲にした設計である。容量低下
の原因は、活物質が高密度化されているため多孔度が低
下し、電解液中の硫酸イオンの拡散が阻害されるためで
あると考えられる。Batteries with a high packing density of positive electrode active material are used in designs that emphasize longevity, but as mentioned above, this is a design that sacrifices capacity performance. The reason for the decrease in capacity is considered to be that the porosity of the active material decreases due to its high density, which inhibits the diffusion of sulfate ions in the electrolyte.
これまで、このような課題を解決するために、異方性黒
鉛を正極ペースト中に添加することが、開示されている
（例えば特開昭６０−８９０７１号公報）。In order to solve these problems, it has been disclosed to add anisotropic graphite to a positive electrode paste (for example, Japanese Patent Laid-Open No. 60-89071).
これは、層状構造を有する正極ペースト中の異方性黒鉛
が硫酸中で陽極酸化され、黒鉛層間化合物が生成して膨
張し正極活物質中の空孔体積を増大させるため、硫酸イ
オンの拡散性が向上し、容量低下が防止できる。This is because the anisotropic graphite in the positive electrode paste, which has a layered structure, is anodized in sulfuric acid and graphite intercalation compounds are generated and expand, increasing the pore volume in the positive electrode active material. capacity is improved, and a decrease in capacity can be prevented.
しかしながら異方性黒鉛は放置中、あるいは充室中に酸
化される。これに伴ない電解液中の水と反応し、二酸化
炭素が発生し、電解液の減少が促進される。特に電解液
量の少ない密閉型鉛蓄電池においては、電解液量れの原
因となっていた。However, anisotropic graphite is oxidized during storage or during filling. Accompanying this, it reacts with water in the electrolyte, generates carbon dioxide, and accelerates the reduction of the electrolyte. Particularly in sealed lead-acid batteries where the amount of electrolyte is small, this causes the amount of electrolyte to run out.
発明が解決しようとする課題
長寿命化に重点を置いた高密度正極活物質の容量低下を
防止するために添加された異方性黒鉛は、放置あるいは
充電中に酸化され、電解液中の水と反応し減液の原因と
なっていた。また、電解液量の少ない密閉型鉛蓄電池で
は、電解液が個れ、電池性能の早期劣化をひき起こして
いた。Problems to be Solved by the Invention Anisotropic graphite, which is added to prevent capacity reduction in high-density cathode active materials with an emphasis on extending their lifespan, oxidizes during storage or charging, causing water in the electrolyte to oxidize. This caused a reaction and caused fluid loss. In addition, in sealed lead-acid batteries with a small amount of electrolyte, the electrolyte occupies, causing early deterioration of battery performance.
本発明は、この電解液減少を防止することを目的とする
ものである。The present invention aims to prevent this decrease in electrolyte solution.
課題を解決するための手段
上記の課題を解決するだめに、本発明では、異方性黒鉛
の代わりに層状結晶構造を有するリン酸ジルコニウムを
添加した鉛粉を用いて鉛蓄電池用（Ｒ：有機誘導体）で
示されるリン酸誘導体を含む希硫酸中で化成した後に、
さらにリン酸中に浸漬することによって、正極活物質中
の空孔体積を増大させたものである。Means for Solving the Problems In order to solve the above problems, in the present invention, lead powder for lead-acid batteries (R: organic After chemical conversion in dilute sulfuric acid containing the phosphoric acid derivative shown in
Furthermore, the pore volume in the positive electrode active material was increased by immersing it in phosphoric acid.
作用
リン酸ジルコニウムはＺｒ（ＨＰＯ４）２ ・２Ｈ２０
（以下、ＺｒＰと略す。） の組成式で示されるところ
の層状構造を有する固体酸であシ、耐酸性に優れた絶縁
物質である。その結晶構造はＺｒＯ２八面体より成る面
の上下に、リン酸基四面体（Ｏ５ＰＯＨ）が頂点の酸素
原子を共有して結合した構造を有して導体）で示される
リン酸誘導体の水溶液中で４６°Ｃに加熱すると、層間
リン酸基と溶液中のリン酸基が次式の反応に示すように
、交換反応を起こす。Action Zirconium phosphate is Zr(HPO4)2 2H20
(hereinafter abbreviated as ZrP) is a solid acid having a layered structure as shown by the composition formula, and is an insulating material with excellent acid resistance. Its crystal structure has a structure in which phosphate group tetrahedrons (O5POH) are bonded above and below a plane consisting of ZrO2 octahedrons by covalently bonding the oxygen atom at the apex. When heated to 46°C, an exchange reaction occurs between the interlayer phosphoric acid groups and the phosphoric acid groups in the solution as shown in the following reaction.
Ｚｒ（ＨＰＯ４）（ＲＰＪ）・ｘＨ２Ｏ＋ＨｓＰＯｉ＋
（２ｘ）Ｈ２Ｏ・・・・・・・・・・・・（１）
有機誘導体Ｈの大きさによシ、層間距離は可逆的に拡大
する。このＺｒＰ有機誘導体のモデル図を第２図に示し
た。なお、Ｒの種類と眉間距離の一例を次表に示した。Zr(HPO4)(RPJ)・xH2O+HsPOi+
(2x) H2O (1) Depending on the size of the organic derivative H, the interlayer distance reversibly increases. A model diagram of this ZrP organic derivative is shown in FIG. An example of the type of R and the distance between the eyebrows is shown in the following table.
ＺｒＰ を添加しだ鉛粉を用いて゛鉛蓄電池用ペスト
を調整し、リン酸誘導体（Ｒ−ＰＯ３Ｈ２）を含む希硫
酸中で化成すると、ペーストの化成反応と同時に上記（
１）式によるＺｒＰの層間反応が右に進行するため、正
極活物質内部でＺｒＰは、Ｒの大きさに応じた膨張状態
となる。次にリン酸液中に正極板を浸漬、加熱すると膨
張状態のＺｒＰ有機誘導体は、反応１が左に進行するた
め元のＺｒＰにもどり、層間距離が１２．３人まで収縮
する。このＺｒＰ 結晶粒子の膨張、収縮によって正極
活物質の空孔体積は増大し、前述した理由によって正極
活物質の高密度化による容量低下が防止できることとな
る。When a paste for lead-acid batteries is prepared using lead powder to which ZrP is added and chemically formed in dilute sulfuric acid containing a phosphoric acid derivative (R-PO3H2), the chemical formation reaction of the paste and the above (
Since the interlayer reaction of ZrP according to the formula 1) proceeds to the right, ZrP enters an expanded state according to the size of R inside the positive electrode active material. Next, when the positive electrode plate is immersed in a phosphoric acid solution and heated, the expanded ZrP organic derivative returns to the original ZrP because reaction 1 proceeds to the left, and the interlayer distance shrinks to 12.3. This expansion and contraction of the ZrP crystal particles increases the pore volume of the positive electrode active material, and for the reasons described above, it is possible to prevent a decrease in capacity due to increased density of the positive electrode active material.
また、ＺｒＰは酸に対して優れた安定性を示すため放置
または充電中に分解することはない。従って電解液の減
少が促進されることはなく、異方性黒鉛添加の場合に生
じた課題は解消される。Furthermore, since ZrP exhibits excellent stability against acids, it does not decompose during storage or charging. Therefore, the reduction of the electrolyte is not accelerated, and the problem that occurred when adding anisotropic graphite is solved.
実施例 本発明による一実施例について説明する。Example An embodiment according to the present invention will be described.
ｐｂｏ約７６％、残部ｐｂからなる通常の鉛粉を用いて
常法によシ調整した高密度正極ペーストの練合末期時に
、ＺｒＰを所定量添加した。用いたＺｒＰは、層間距離
１２．３人を有する結晶粉末である。またＺｒＰ結晶粒
子は板状形状をしておシ、本実施例に用いたものは、結
晶層方向に約４μｍの厚さを有した結晶であシ、約５０
μｍ径のふるいを通過したものである。このペーストを
厚さ３．６絹の鉛合金格子に充填し、所定の熟成、乾燥
工程によシ、未化成正極板とした。これをガラスマント
より成るセパレータを介して、負極板と組み合わせ、約
２０ｋｇ／ｄ−の圧力をかけた。次に３゜多硫酸の中に
フェニルホスホンａ （Ｃ６Ｈｓ−ＰＯｓＨ２）を５・
チ添加した電解液中に極板群を浸漬し、４５°Ｃで化成
を行なった。化成終了後、極板群を６チリン酸中に４５
°Ｃ１５時間浸漬した、その後４０％硫酸で十分洗浄し
た後、電槽内に極板群を移した。このようにして、正極
容量規制で１０Ａｈ容量（ＺｒＰ無添加時）の密閉型鉛
蓄電池を試作し、ＺｒＰの添加量と容量の変化を第３図
に示した。図中、縦軸はＺｒＰ 無添加の場合の容量に
対する容量割合、横軸は鉛粉Ｉ Ｋｇ当りに添加したＺ
ｒＰ の添加割合である。このように容量は添加量とと
もに増大し、０．５ｗｔ％ 添加でほぼ最大２０チの容
量アップが認められ、それ以上の添加しても横ばい状態
であった。A predetermined amount of ZrP was added at the final stage of kneading a high-density positive electrode paste prepared by a conventional method using ordinary lead powder consisting of about 76% PBO and the balance PB. The ZrP used is a crystalline powder with an interlayer distance of 12.3. The ZrP crystal particles have a plate-like shape, and the ones used in this example are crystals with a thickness of about 4 μm in the direction of the crystal layer, and about 50 μm.
It passed through a sieve with a diameter of μm. This paste was filled into a lead alloy grid having a thickness of 3.6 silk, and subjected to a predetermined aging and drying process to form an unformed positive electrode plate. This was combined with a negative electrode plate through a separator made of a glass mantle, and a pressure of about 20 kg/d- was applied. Next, add 5.
The electrode plate group was immersed in an electrolytic solution to which H was added, and chemical formation was performed at 45°C. After completion of chemical formation, the electrode plate group was placed in 6-thiphosphoric acid for 45 minutes.
After being immersed at °C for 15 hours and thoroughly washed with 40% sulfuric acid, the electrode plate group was transferred into a battery container. In this way, a sealed lead-acid battery with a capacity of 10 Ah (without ZrP) was fabricated as a prototype with positive electrode capacity regulations, and the changes in capacity versus the amount of ZrP added are shown in FIG. In the figure, the vertical axis is the capacity ratio to the capacity when no ZrP is added, and the horizontal axis is the Z added per kg of lead powder.
This is the addition ratio of rP. As described above, the capacity increased with the amount added, and when 0.5 wt% was added, the capacity increased by approximately 20 inches at the maximum, and remained unchanged even when more than that amount was added.
この密閉型鉛蓄電池を１００サイクル充放電をくり返し
た後に正極中に残存するＺｒＰ を定量すると、はぼ１
００％のＺｒＰが残存していた。また、減液量に関して
は無添加のものと同等であった。After 100 cycles of charging and discharging this sealed lead-acid battery, the amount of ZrP remaining in the positive electrode was quantified.
00% ZrP remained. Moreover, the amount of liquid reduction was equivalent to that without additives.
第４図は、密閉型鉛蓄電池のサイクル寿命を示したもの
である。図中、縦軸は容量チ、横軸はサイクル数である
。無添加の電池の初期容量を１ｏ。FIG. 4 shows the cycle life of a sealed lead acid battery. In the figure, the vertical axis is the capacity, and the horizontal axis is the number of cycles. The initial capacity of a battery without additives is 1o.
％とじて、０．２０の定電流で８０％の放電と、０．２
０で１００％の充電をくり返し６８〜毎に０．２Ｃの定
電流で容量測定（終止電圧１．７０ Ｖ／ｃｅｌｌ ）
したものである。ＺｒＰをｏ、５ｗｔ％添加したものと
無添加のものを比較すると、ＺｒＰをｏ、ａ ｗｔ％添
加することにより、寿命が延びていることがわかる。%, 80% discharge at constant current of 0.20 and 0.2
Repeat 100% charging at 0 and measure the capacity with a constant current of 0.2C every 68 minutes (final voltage 1.70 V/cell)
This is what I did. Comparing the product with and without the addition of ZrP at o.5wt%, it can be seen that the life is extended by adding o.a wt% of ZrP.
発明の効果
以上のように本発明によれば、高密度正極活物質中にＺ
ｒＰを添加することによって、高密度に起因する容量低
下を防止することができ、また、密閉化鉛蓄電池に適用
した場合、電解液間れによる早期容量低下をなくすこと
ができるという効果かえられる。Effects of the Invention As described above, according to the present invention, Z is present in the high-density positive electrode active material.
By adding rP, it is possible to prevent a capacity decrease due to high density, and when applied to a sealed lead-acid battery, it has the effect of eliminating an early capacity decrease due to electrolyte gaps.
第１図はＺｒＰ の層状構造を示すモデル図、第２図
はＺｒＰ有機誘導体のモデル図、第３図はＺｒＰの添加
量と容量の増加率の関係を示した図、第４図はＺｒＰ
ｏ、ｓ Ｗｔチ添加と無添加の密閉型鉛蓄電池のサイク
ル寿命を示す図である。
１図
第２図
ｈジθ Ｈ２Ｏ
ｈグθ
２３Ａ
Ｈ２Ｏ１−１２０Figure 1 is a model diagram showing the layered structure of ZrP, Figure 2 is a model diagram of ZrP organic derivatives, Figure 3 is a diagram showing the relationship between the amount of ZrP added and the rate of increase in capacity, and Figure 4 is a diagram of ZrP.
1 is a diagram showing the cycle life of sealed lead-acid batteries with and without addition of o, s Wt. 1 Figure 2 hji θ H2O hg θ 23A H2O1-120
Claims (1)
粉を用いて調整した鉛蓄電池用ペーストを、一般式▲数
式、化学式、表等があります▼（但しＲは有機誘導体） で示されるリン酸誘導体を含む希硫酸中で化成後、リン
酸中に浸漬した正極を用いることを特徴とする鉛蓄電池
の製造法。[Claims] A paste for lead-acid batteries prepared using lead powder added with zirconium phosphate having a layered crystal structure is prepared by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where R is an organic derivative). 1. A method for producing a lead-acid battery, comprising using a positive electrode immersed in phosphoric acid after chemical conversion in dilute sulfuric acid containing the shown phosphoric acid derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63220921A JPH0268857A (en) | 1988-09-02 | 1988-09-02 | Manufacture of lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63220921A JPH0268857A (en) | 1988-09-02 | 1988-09-02 | Manufacture of lead acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0268857A true JPH0268857A (en) | 1990-03-08 |
Family
ID=16758633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63220921A Pending JPH0268857A (en) | 1988-09-02 | 1988-09-02 | Manufacture of lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0268857A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002141066A (en) * | 2000-10-31 | 2002-05-17 | Shin Kobe Electric Mach Co Ltd | Control valve type lead acid battery |
-
1988
- 1988-09-02 JP JP63220921A patent/JPH0268857A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002141066A (en) * | 2000-10-31 | 2002-05-17 | Shin Kobe Electric Mach Co Ltd | Control valve type lead acid battery |
| JP4635325B2 (en) * | 2000-10-31 | 2011-02-23 | 新神戸電機株式会社 | Control valve type lead acid battery |
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