JPH0480516B2 - - Google Patents
Info
- Publication number
- JPH0480516B2 JPH0480516B2 JP58132574A JP13257483A JPH0480516B2 JP H0480516 B2 JPH0480516 B2 JP H0480516B2 JP 58132574 A JP58132574 A JP 58132574A JP 13257483 A JP13257483 A JP 13257483A JP H0480516 B2 JPH0480516 B2 JP H0480516B2
- Authority
- JP
- Japan
- Prior art keywords
- electrodes
- lead
- electrode
- potential
- specific gravity
- 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.)
- Expired - Lifetime
Links
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 18
- 230000005484 gravity Effects 0.000 claims description 16
- 239000003990 capacitor Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 17
- 238000007599 discharging Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 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
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/484—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring electrolyte level, electrolyte density or electrolyte conductivity
-
- 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
Description
【発明の詳細な説明】
本発明は鉛蓄電池の電解液比重の検出法、特に
二酸化鉛と鉛からなる電極を用いたものの改良に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for detecting the specific gravity of an electrolyte in a lead-acid battery, particularly one using electrodes made of lead dioxide and lead.
鉛蓄電池の充電状態は周知のように電解液比重
に表われている。最近では負荷の大きさに対し
て、鉛蓄電池は小形化され、小容量のものが使用
されているが、充電器の出力は大きくなつて、放
電後速やかに充電できる。そこで電池の充電状態
を検出して充電器に信号を送る比重センサーのニ
ーズが高まつている。 As is well known, the state of charge of a lead-acid battery is expressed by the specific gravity of the electrolyte. Recently, lead-acid batteries have become smaller and have smaller capacities in response to the size of the load, but the output of chargers has increased, allowing them to be charged quickly after discharging. Therefore, there is a growing need for a specific gravity sensor that detects the state of charge of the battery and sends a signal to the charger.
上記比重センサーとしては、二酸化鉛（PbO2）
と鉛（Pb）からなる電極の電位差を計測する電
極式が種々試みられている。しかし、これらの電
極には次の欠点があつた。 The above specific gravity sensor uses lead dioxide (PbO 2 ).
Various electrode methods have been attempted to measure the potential difference between electrodes made of lead (Pb) and lead (Pb). However, these electrodes had the following drawbacks.
(1) PbO2電極やPb電極は希硫酸中で自己放電に
より硫酸鉛（PbSO4）になり、長期間経過する
と正常な電位を示さなくなる。(1) PbO 2 electrodes and Pb electrodes become lead sulfate (PbSO 4 ) due to self-discharge in dilute sulfuric acid, and do not show normal potential after a long period of time.
(2) PbO2電極やPb電極は電極によつて充電の過
電圧に差があり、充電中の電位を計測しても比
重センサーとして使い難い。(2) PbO 2 electrodes and Pb electrodes have different charging overvoltages depending on the electrode, so it is difficult to use them as specific gravity sensors even if they measure the potential during charging.
(3) PbO2電極やPb電極は充電後の開回路で、電
位が安定するまでには長時間を要する。従つて
常時は充電しておいて、計測時に開回路にして
も比重としての精度は低くなる。(3) PbO 2 electrodes and Pb electrodes are open circuits after charging, and it takes a long time for the potential to stabilize. Therefore, even if the battery is always charged and the circuit is opened during measurement, the accuracy of the specific gravity will be low.
本発明は従来のPbO2電極やPb電極の上記欠点
を解消し、長期間にわたつて精度の良い比重セン
サーを得ることを目的としたものであり、その要
旨は、常時は小電流で充電してあるPbO2とPbか
らなる電極の電位差（電圧）を計測時に開回路と
すると同時に両電極間にコンデンサを接続して閉
回路を形成し、コンデンサの中へ瞬時大電流かつ
定電気量放電を行い両電極間の電位差の安定をは
かり、閉回路の状態で両電極間の電位差を計測す
ることにある。 The purpose of the present invention is to eliminate the above-mentioned drawbacks of conventional PbO 2 electrodes and Pb electrodes, and to obtain a specific gravity sensor with high accuracy over a long period of time. When measuring the potential difference (voltage) between electrodes made of PbO 2 and Pb, an open circuit is created and at the same time a capacitor is connected between the two electrodes to form a closed circuit, and an instantaneous large current and constant electric charge is discharged into the capacitor. The purpose is to stabilize the potential difference between the two electrodes and measure the potential difference between the two electrodes in a closed circuit state.
PbO2電極とPb電極とについて硫酸第一水銀
（Hg SO4）電極に対する電位差を安定した状態
で測定した結果を第１図に示す。この第１図より
明らかなように、電解液比重0.010当りPbO2電極
は６ｍＶ、Pb電極は−３ｍＶそれぞれ変化し、
両方の電極の差は９ｍＶとなる。したがつて、こ
の電位差を計測することによつて、電解液比重を
検出できる。 FIG. 1 shows the results of stable measurement of the potential difference between the PbO 2 electrode and the Pb electrode with respect to the mercurous sulfate (Hg SO 4 ) electrode. As is clear from Fig. 1, the PbO 2 electrode changes by 6 mV and the Pb electrode changes by -3 mV per electrolyte specific gravity of 0.010.
The difference between both electrodes will be 9 mV. Therefore, by measuring this potential difference, the electrolyte specific gravity can be detected.
本願発明は、開回路状態でなければ精確な硫酸
濃度の測定はできない、ということを前提にして
いる。 The present invention is based on the premise that the sulfuric acid concentration cannot be accurately measured unless the circuit is open.
二酸化鉛／鉛電極対に充電電流を流すと、電流
を切つて開回路状態にしても長時間にわたつて両
電極の電位は平衡電位に到達しないため、精度よ
く硫酸濃度を検出することができない。 When a charging current is applied to a lead dioxide/lead electrode pair, the potential of both electrodes does not reach the equilibrium potential for a long time even if the current is cut off and the circuit is opened, making it impossible to accurately detect the sulfuric acid concentration. .
電位が長時間安定しない原因は二酸化鉛電極に
あり、電気化学的に作製した二酸化鉛は非化学量
論的な物質で鉛原子と酸素原子の比率が１：２に
はなつていない（PbO1.8〜1.9として表示される）。
組成は充電電流の大きさや、温度、硫酸濃度など
で決まり、酸素原子の多いもの、少ないものが混
在している。 The reason why the potential is not stable for a long time is due to the lead dioxide electrode. Lead dioxide produced electrochemically is a non-stoichiometric substance and the ratio of lead atoms to oxygen atoms is not 1:2 (PbO 1.8 ~1.9 ).
The composition is determined by the magnitude of the charging current, temperature, sulfuric acid concentration, etc., and there is a mixture of those with many oxygen atoms and those with few oxygen atoms.
長時間放置すると電位が安定することから、多
量の中心的組成のものが存在すると考えられる。
しかし、充電中止直後の開回路では、中心的組成
のものより不安定ではあるが酸素原子比が
PbO1.8〜1.9よりも多きな酸化物が含まれていて、
高い電位を示すが、これらが先行して崩壊してい
くため、時間の経過とともに平衡電位に漸近す
る。 Since the potential stabilizes when left for a long time, it is thought that a large amount of core composition exists.
However, in the open circuit immediately after charging is stopped, the oxygen atomic ratio is unstable, although it is less stable than that of the central composition.
Contains oxides greater than PbO 1.8-1.9 ,
Although it exhibits a high potential, as these decay in advance, the potential approaches an equilibrium potential over time.
二酸化鉛／鉛電極対硫酸比重センサは基本的に
鉛蓄電池と同じであり、センサ機能で分けると能
動素子であり、内臓したエネルギーを消費するこ
とで機能するものであり、自己放電もしている。 A lead dioxide/lead electrode vs. sulfuric acid specific gravity sensor is basically the same as a lead-acid battery, and when divided by sensor function, it is an active element that functions by consuming built-in energy and also self-discharges.
したがつて、消費したエネルギーを補給してや
らなければ作動しなくなつてしまう。そのため微
小電流でのフロート充電や通常電流での間欠的充
電など方法の違いはあつても充電は不可避であ
る。 Therefore, unless the consumed energy is replenished, it will stop working. Therefore, although there are different methods such as float charging with a minute current and intermittent charging with a normal current, charging is unavoidable.
硫酸濃度検出は開回路で行い、充電も行うとい
う互いに相反する条件の下で、検出時間を長くす
るためには充電時間を短くし、かつ充電電流を切
つて開回路にしたとき短時間で電位を安定させな
ければならない。本発明はこの問題の解決のため
に提案したものである。 Sulfuric acid concentration detection is performed in an open circuit, and charging is also performed, which are mutually contradictory conditions.In order to increase the detection time, the charging time should be shortened, and when the charging current is cut and the circuit is opened, the potential will increase in a short time. must be stabilized. The present invention has been proposed to solve this problem.
充電で生じた酸素原子比の大きな鉛酸化物を早
く消滅させるためには、充電打ち切り後直ちに大
電流で短時間放電させることが有効であることが
分かつた。大電流で放電させようとすると、大容
量の半導体素子やタイマーを必要としたり、装置
が大型化する問題があつた。 It has been found that in order to quickly eliminate lead oxide with a high oxygen atomic ratio generated during charging, it is effective to discharge the battery at a large current for a short period of time immediately after charging is terminated. When attempting to discharge with a large current, there were problems such as requiring a large-capacity semiconductor element and a timer, and increasing the size of the device.
本発明は、センサ電極の放電電気量を電気量に
対応する容量のコンデンサの中へ放電させること
で、タイマーや複雑な放電装置を使用せずに大電
流放電と定電気量放電を行うことを可能にし、か
つ放電装置を簡潔にしたことにある。 The present invention makes it possible to perform large current discharge and constant charge discharge without using a timer or complicated discharge device by discharging the amount of electricity discharged from the sensor electrode into a capacitor with a capacity corresponding to the amount of electricity. The purpose of this invention is to make it possible and to simplify the discharge device.
充電されたコンデンサの放電は、長時間の硫酸
濃度検出中に小さい抵抗を使用して徐々に行うこ
とで達成される。 Discharge of the charged capacitor is achieved gradually using a small resistance during long sulfuric acid concentration sensing.
PbO2電極とPb電極とを電極表面に対し、１ｍ
Ａ／cm2の電流密度で充電しておき、これを開回路
にしたときの電位変化を第２図に実線で示す。こ
の場合、数分間ではPbO2電極もPb電極も安定し
ないことが判る。また前記のように充電しておい
た電極を開回路にすると同時に10000μFのコンデ
ンサで短絡したときの電位変化を第２図に点線で
示す。この場合、PbO2電極およびPb電極の電位
の安定性は極めて良い。したがつて、この電位差
から精度良く比重を検出することができる。よつ
て本発明に基づき、常時は小電流で充電してある
PbO2電極とPb電極の電圧を計測時に開回路とす
ると同時に両電極間をコンデンサを介して短絡し
た状態にして両電極間の電位差を計測することに
より、精度良く比重を検出することができる。 Place the PbO 2 electrode and the Pb electrode at a distance of 1 m from the electrode surface.
The solid line in Figure 2 shows the change in potential when the battery is charged at a current density of A/cm 2 and the battery is opened. In this case, it can be seen that neither the PbO 2 electrode nor the Pb electrode is stable within several minutes. Furthermore, the dotted line in FIG. 2 shows the change in potential when the charged electrodes are opened as described above and simultaneously short-circuited with a 10,000 μF capacitor. In this case, the potential stability of the PbO 2 electrode and the Pb electrode is extremely good. Therefore, the specific gravity can be detected with high accuracy from this potential difference. Therefore, based on the present invention, the battery is always charged with a small current.
The specific gravity can be detected with high accuracy by setting the voltage between the PbO 2 electrode and the Pb electrode to an open circuit when measuring the voltage, and at the same time short-circuiting the two electrodes via a capacitor and measuring the potential difference between the two electrodes.
また電位差の計測回路のインピーダンスはでき
るだけ大きいことが望ましい。これは電極が放電
して、電位が変化することを防ぐためである。さ
らにPbO2電極やPb電極は鉛合金からなる導電体
にPbO2やPbの多孔体を密着させた構造が望まし
く、ペースト式、クラツド式またはチユードル式
の極板を小形にしたものを用いればよい。 Further, it is desirable that the impedance of the potential difference measurement circuit be as large as possible. This is to prevent the electrode from discharging and changing its potential. Furthermore, it is desirable for the PbO 2 electrode or Pb electrode to have a structure in which a porous body of PbO 2 or Pb is adhered to a conductor made of a lead alloy, and a paste-type, clad-type, or chudle-type electrode plate made of a smaller size may be used. .
本発明による電解液比重検出法は上記した如き
ものであるため、次のような特徴を有している。 Since the electrolyte specific gravity detection method according to the present invention is as described above, it has the following characteristics.
(1) 常時は充電されているので、希硫酸との反応
による劣化がない。(1) Since it is always charged, there is no deterioration due to reaction with dilute sulfuric acid.
(2) 部分的な放電にコンデンサを使用しているの
で、放電時間のコントロールなしに放電量を一
定に保つことができ、その状態で開路状態と同
じになり、放電による分極がなく、電極間のバ
ラツキが少ない。(2) Since a capacitor is used for partial discharge, the amount of discharge can be kept constant without controlling the discharge time, and in that state it is the same as an open circuit state, and there is no polarization due to discharge, and there is no polarization between the electrodes. There is little variation.
(3) 短時間の放電によつて充電時の分極が短時間
に解消しているので安定した電位を、すなわち
精度の良い計測ができる。(3) Polarization during charging is quickly eliminated by short-time discharging, so a stable potential can be measured with high accuracy.
以上述べたように本発明によれば、鉛蓄電池の
充電状態を検出して充電を制御する長寿命でかつ
精度の良い比重センサーを提供することができ、
その実用的価値は大である。 As described above, according to the present invention, it is possible to provide a long-life and highly accurate specific gravity sensor that detects the state of charge of a lead-acid battery and controls charging.
Its practical value is great.
第１図は種々な比重の希硫酸中における二酸化
鉛電極および鉛電極の硫酸第一水銀電極に対する
電位を示す特性図、第２図は希硫酸中における二
酸化鉛および鉛電極の充電後の開回路における電
位変化、充電後コンデンサにより短絡したときの
電位変化を示す特性図である。
Figure 1 is a characteristic diagram showing the potential of a lead dioxide electrode and a lead electrode with respect to a mercurous sulfate electrode in dilute sulfuric acid of various specific gravity, and Figure 2 is an open circuit diagram of lead dioxide and a lead electrode after charging in dilute sulfuric acid. FIG. 3 is a characteristic diagram showing a potential change when a capacitor is short-circuited after charging.
Claims (1)
らなるセンサ電極の電圧計測時に、両電極間を開
回路とすると同時に、両電極間にセンサ電極の電
位差安定に必要な放電電気量に対応する容量のコ
ンデンサを接続して閉回路を形成し、閉回路の状
態で両電極間の電位差を計測することを特徴とす
る鉛蓄電池の電解液比重検出法。1 When measuring the voltage of the sensor electrode made of lead dioxide and lead, which is normally charged with a small current, an open circuit is created between the two electrodes, and at the same time, the amount of electricity discharged between the two electrodes is required to stabilize the potential difference between the sensor electrodes. A method for detecting the specific gravity of an electrolyte in a lead-acid battery, which is characterized by forming a closed circuit by connecting a capacitor with a capacity of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58132574A JPS6023978A (en) | 1983-07-19 | 1983-07-19 | Measurement of specific gravity of electrolyte in lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58132574A JPS6023978A (en) | 1983-07-19 | 1983-07-19 | Measurement of specific gravity of electrolyte in lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6023978A JPS6023978A (en) | 1985-02-06 |
| JPH0480516B2 true JPH0480516B2 (en) | 1992-12-18 |
Family
ID=15084496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58132574A Granted JPS6023978A (en) | 1983-07-19 | 1983-07-19 | Measurement of specific gravity of electrolyte in lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6023978A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01167966A (en) * | 1987-12-23 | 1989-07-03 | Japan Storage Battery Co Ltd | Charging condition detecting method for lead cell |
-
1983
- 1983-07-19 JP JP58132574A patent/JPS6023978A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6023978A (en) | 1985-02-06 |
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