JPH01281683A - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JPH01281683A JPH01281683A JP62217163A JP21716387A JPH01281683A JP H01281683 A JPH01281683 A JP H01281683A JP 62217163 A JP62217163 A JP 62217163A JP 21716387 A JP21716387 A JP 21716387A JP H01281683 A JPH01281683 A JP H01281683A
- Authority
- JP
- Japan
- Prior art keywords
- metal ions
- storage battery
- lead storage
- overdischarging
- electrolyte
- 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
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000011149 active material Substances 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- H01M10/06—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は過放電放置後の充電性を改善した鉛蓄電池に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a lead-acid battery with improved chargeability after being left over-discharged.
従来の技術
一般に、鉛蓄電池は長期間放置されたり、また過放電の
状態で放置されると、充電不可能な状態となり使用不能
となることが多い。従来、この欠点を改善するために、
鉛蓄電池の電解液中にアルカリ金属イオンを存在させて
、過放電後の充電性を向上させる方法がある。また、格
子中のＳｎ濃度を増す方法がおｐｌその他に、電解液中
にリン酸を添加する方法も提案されている０
発明が解決しようとする問題点
過放電放置後の正極板には格子−活物質界面に絶縁性の
ｐｂｓｏ４皮膜が形成するため勾格子−活物質問に充電
電流が流れにくくなシ、そのために充電不可能となる欠
点がらる。この欠点を解決するために格子合金中にＳｎ
を含有させる方法が提案されているが、Ｓｎを含有させ
ることは多量のＳｎを必要とし、コスト高となる欠点が
ある。2. Description of the Related Art In general, if a lead-acid battery is left unused for a long period of time or left in an over-discharged state, it often becomes unchargeable and becomes unusable. Conventionally, to improve this shortcoming,
There is a method of making alkali metal ions exist in the electrolyte of a lead-acid battery to improve charging performance after overdischarge. In addition, there is a method of increasing the Sn concentration in the lattice.In addition, a method of adding phosphoric acid to the electrolyte has also been proposed.Problems to be solved by the invention - Since an insulating PBSO4 film is formed on the interface of the active material, it is difficult for charging current to flow through the gradient lattice-active material interlayer, which has the disadvantage of making charging impossible. In order to solve this drawback, Sn is added in the lattice alloy.
A method of incorporating Sn has been proposed, but incorporating Sn requires a large amount of Sn, which has the drawback of increasing costs.
一方、電解液の添加剤に関してはリン酸やアルカリ金属
イオンの添加が行なわれているが、リン酸の添加は寿命
初期における放電容量が低下し、自己放電も大きくなる
等の問題があシ、またアルカリ金属イオンの添加は過放
電時の電解液の伝導度が上がり確かに効果があるが、そ
れ単独ではあｔｒ大きな効果を期待できない。On the other hand, phosphoric acid and alkali metal ions have been added to the electrolyte as additives, but the addition of phosphoric acid has problems such as a decrease in discharge capacity at the beginning of life and an increase in self-discharge. Furthermore, although the addition of alkali metal ions increases the conductivity of the electrolytic solution during overdischarge and is certainly effective, a large effect cannot be expected by adding alkali metal ions alone.
問題点を解決するだめの手段
本発明は、上記の問題点を解決するために、ｓ ｏ ｏ
ｐｐｍ以上のアルカリ金属イオンを含む電解液にアル
カリ土類金属イオンを添加するものである。Means for Solving the Problems The present invention solves the above problems by
Alkaline earth metal ions are added to an electrolytic solution containing ppm or more of alkali metal ions.
作用
一般に鉛蓄電池は深い放電後放置されると充電不可能な
状態になることが多い。これは格子−活物質界面に非反
応性のｐｂｓｏ４皮膜が生成し、電池内部抵抗が高くな
るためである。特に正極板の内部抵抗の上昇が大きい。Function Generally, lead-acid batteries often become unrechargeable if they are left unattended after being deeply discharged. This is because a non-reactive pbso4 film is formed at the lattice-active material interface, increasing the internal resistance of the battery. In particular, the increase in internal resistance of the positive electrode plate is large.
これは格子−活物質界面で、Ｐｂ 、ＰｂＯ，、Ｈ，Ｓ
Ｏ２による局部電池反応が起こる結果ＰｂＳＯ４が界面
に形成されるからである。また、過放電放置された電池
の電解液比重は非常に下がっており、電解液抵抗が大き
くなる。これは、過放電放置後の充電性劣下の原因とな
る。また、過放電後の電解液比重は非常に下がっており
、水に近くなっている。そのため液抵抗が大きくなり充
電電流が流れにくくなる。This is the lattice-active material interface, Pb, PbO,, H, S
This is because PbSO4 is formed at the interface as a result of a local cell reaction caused by O2. In addition, the specific gravity of the electrolyte of a battery that has been left to over-discharge is extremely low, and the resistance of the electrolyte increases. This causes deterioration in charging performance after over-discharging. Furthermore, the specific gravity of the electrolyte after overdischarge has decreased significantly and is close to that of water. As a result, liquid resistance increases, making it difficult for charging current to flow.
従来、アルカリ金属イオンを添加することＫより、電解
液の伝導度を上昇させ充電電流を増加させる方法がとら
れている。Conventionally, a method has been used to increase the conductivity of the electrolytic solution and increase the charging current by adding alkali metal ions.
一方、硫酸マグネシウムを電解液に添加した場合、硫酸
鉛の溶解度が増加するため、格子界やすくなると考えら
れる。しかしながら、上記の２つの方法を単独で用いた
場合、その効果はおまり大きくなく、充電性能の回復は
１■良くないが、両者を併用することにより過放電放置
後の充電性を大きく改善できる。また、アルカリ金属イ
オンの濃度が５００ ｐｐｍ以下の場合、その効果はほ
とんどなく、効果を期待するためには少なくともｓｏｏ
ｐｐｍ以上必要である。On the other hand, when magnesium sulfate is added to the electrolytic solution, the solubility of lead sulfate increases, which is thought to facilitate lattice boundaries. However, when the above two methods are used alone, the effect is not so great and recovery of charging performance is not as good as 1 inch, but by using both methods in combination, charging performance after overdischarge can be greatly improved. In addition, if the concentration of alkali metal ions is 500 ppm or less, there is almost no effect, and in order to expect an effect, at least soo
ppm or more is required.
実施例
本発明の一実施例を説明する。以上の効果を確認するた
めに、１．２Ａｈ−２Ｖの電池を作製し Ｎａ＋、塊２
＋を全体で０２モルになるように、それぞれの濃度を変
えた電解液（比重１．３２０のＨβ０．）を調製し、こ
れらの溶液を規定量電池に注液し九。EXAMPLE An example of the present invention will be described. In order to confirm the above effects, a 1.2Ah-2V battery was fabricated with Na+, lump 2
Prepare electrolytic solutions (Hβ0. with a specific gravity of 1.320) with different concentrations so that the total amount of + is 0.2 mol, and pour a specified amount of these solutions into the battery.9.
これらの電池を初充電、初期容量試験後、２４時間定抵
抗で放電し、その後、開路状態とし、２５℃で１力月放
置した。放置後、これらの電池を２．４５Ｖで定電圧充
電を行ない、そのときの、１０秒目、３０秒目、６０秒
目の充電電流を測定した。After the initial charge and the initial capacity test, these batteries were discharged at constant resistance for 24 hours, and then left in an open circuit state for one month at 25°C. After standing, these batteries were charged at a constant voltage of 2.45 V, and the charging currents at 10 seconds, 30 seconds, and 60 seconds were measured.
それらの結果を第１表に示す。電流値は、陽３の１０秒
１電流を１００としたものである。Ｎａ＋とＭｇ２＋量
は、添加剤総量を０．２モルとしたときのそれぞれのイ
オンのモルチを示した。The results are shown in Table 1. The current value is determined by setting the positive 3 current per 10 seconds as 100. The amounts of Na+ and Mg2+ indicate the molarity of each ion when the total amount of additives is 0.2 mol.
以上の結果は無水のマグネシウムのものであるが、結晶
水を持つものについても同様な結果が得られた。The above results are for anhydrous magnesium, but similar results were obtained for magnesium with crystallization water.
第１表
Ｎａ＋とＭｇ２＋を混合したもの（宛２〜宛６）は単独
で用いたもの（ｆ％１ 、ｆ’ｈ７ ）と比較してよく
充電電流が流れており、 Ｎａ＋とＭｇ２＋添加の相関
性が我われでいる。特に、Ｎａ＋に関して０．０４モル
（約４００ｐｐｍ ）以下の領域では効果は小さく、特
に、Ｎａ＋を添加しない場合、効果がほとんどないこと
が分る。以上のようにＮａ＋及びＭｇ２＋添加について
相関性が認められ、過放電放置性能に対して大きな効果
のあることが解る。Table 1: The mixture of Na+ and Mg2+ (2 to 6) has a better charging current than the mixture of Na+ and Mg2+ (f%1, f'h7), and the correlation between the addition of Na+ and Mg2+ Gender is who we are. In particular, the effect is small in the region of 0.04 mol (approximately 400 ppm) or less of Na+, and in particular, it is found that there is almost no effect when Na+ is not added. As described above, a correlation is observed between the additions of Na+ and Mg2+, and it can be seen that they have a great effect on the overdischarge performance.
発明の効果
以上のように、本発明は過放電放置後の鉛蓄電池の充電
性能改善に大きな効果があ夛、その工業的価値は非常に
大きいと考えられる。Effects of the Invention As described above, the present invention has a great effect on improving the charging performance of lead-acid batteries after being left over-discharged, and its industrial value is considered to be very large.
Claims (1)
存在し、且つ同時に無水のアルカリ土類金属イオンまた
は結晶水をもつアルカリ土類金属イオンのいずれか一方
もしくは両方が存在することを特徴とする鉛蓄電池。1. A lead-acid battery characterized in that 500 ppm or more of alkali metal ions are present in an electrolytic solution, and at the same time, either or both of anhydrous alkaline earth metal ions and alkaline earth metal ions having crystal water are present.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62217163A JPH01281683A (en) | 1987-08-31 | 1987-08-31 | Lead storage battery |
| CA000575874A CA1323397C (en) | 1987-08-31 | 1988-08-26 | Lead accumulators |
| GB8820351A GB2209241B (en) | 1987-08-31 | 1988-08-26 | Lead accumulators |
| DE3829258A DE3829258A1 (en) | 1987-08-31 | 1988-08-29 | lead-acid battery |
| KR1019880011016A KR950004457B1 (en) | 1987-08-31 | 1988-08-29 | Lead battery |
| IT8821783A IT1226421B (en) | 1987-08-31 | 1988-08-31 | LEAD ACCUMULATORS. |
| FR8811610A FR2619961B1 (en) | 1987-08-31 | 1988-08-31 | LEAD ACCUMULATORS |
| GB9026551A GB2238159B (en) | 1987-08-31 | 1990-12-06 | Lead accumulators |
| GB9026552A GB2238160B (en) | 1987-08-31 | 1990-12-06 | Lead accumulators |
| GB9120453A GB2247344B (en) | 1987-08-31 | 1991-09-26 | Lead accumulators |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62217163A JPH01281683A (en) | 1987-08-31 | 1987-08-31 | Lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01281683A true JPH01281683A (en) | 1989-11-13 |
Family
ID=16699843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62217163A Pending JPH01281683A (en) | 1987-08-31 | 1987-08-31 | Lead storage battery |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH01281683A (en) |
| IT (1) | IT1226421B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008243487A (en) * | 2007-03-26 | 2008-10-09 | Furukawa Battery Co Ltd:The | Lead acid battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5272428A (en) * | 1975-12-13 | 1977-06-16 | Shigeyuki Yasuda | Electrolyte for lead battery |
| JPS547134A (en) * | 1977-06-18 | 1979-01-19 | Shigeyuki Yasuda | Electrolyte for lead storage battery |
-
1987
- 1987-08-31 JP JP62217163A patent/JPH01281683A/en active Pending
-
1988
- 1988-08-31 IT IT8821783A patent/IT1226421B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5272428A (en) * | 1975-12-13 | 1977-06-16 | Shigeyuki Yasuda | Electrolyte for lead battery |
| JPS547134A (en) * | 1977-06-18 | 1979-01-19 | Shigeyuki Yasuda | Electrolyte for lead storage battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008243487A (en) * | 2007-03-26 | 2008-10-09 | Furukawa Battery Co Ltd:The | Lead acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8821783A0 (en) | 1988-08-31 |
| IT1226421B (en) | 1991-01-15 |
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