JP4232385B2 - Control valve type lead acid battery - Google Patents
Control valve type lead acid battery Download PDFInfo
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- JP4232385B2 JP4232385B2 JP2002145827A JP2002145827A JP4232385B2 JP 4232385 B2 JP4232385 B2 JP 4232385B2 JP 2002145827 A JP2002145827 A JP 2002145827A JP 2002145827 A JP2002145827 A JP 2002145827A JP 4232385 B2 JP4232385 B2 JP 4232385B2
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- 239000002253 acid Substances 0.000 title claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 19
- 230000001172 regenerating effect Effects 0.000 claims description 15
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 17
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Electric Propulsion And Braking For Vehicles (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は電解液を含浸保持するマットセパレータを備え、電解液の殆どすべてが極板群に保持されていて、極板群から遊離した電解液を殆ど保有しない制御弁式鉛蓄電池に関するものである。
【０００２】
【従来の技術】
鉛蓄電池は安価であり、比較的広い温度領域でも信頼性が高いことから自動車用電池として広く用いられている。
【０００３】
通常、始動用の自動車用電池ではオルタネータにより発電された電力により電池が満充電状態になるようにレギュレータで充電電圧を規制しながら充電し、充電した電力を用いてエンジン始動やライト点灯を行う。
【０００４】
近年、自動車の燃費向上の目的に、電池の充電電圧を低下させることによって、オルタネータの回転数を低下させてエネルギーロスを削減したり、エンジンとモータとを組み合わせたハイブリッド車両が実用化されている。
【０００５】
このような車両に電池を用いる場合、車速の減速時のエネルギーを積極的に回生エネルギーとして蓄電する必要がある。この回生エネルギーは減速時に発生するため、発電量および発電時間は無作為であり、このエネルギーを蓄電池の充電に適した電圧、電流に変換する必要があり、また、このような回生エネルギーによる充電（以降、回生充電という）を効率よく受け入れるために蓄電池の充電状態（以降、ＳＯＣという）を適切に制御する必要があった。
【０００６】
この回生充電を効率良く受け入れるために、例えば特開平８−３０８０１８号公報に示されているように定格電圧１２Ｖの鉛蓄電池を１３Ｖで充電し、ＳＯＣを６０％〜９０％程度で制御することが記載されている。また、電解液の硫酸濃度を低下させることによって回生充電の充電受け入れ性を改善することが提案されている。
【０００７】
これらの電解液の硫酸濃度を低くした鉛蓄電池のＳＯＣを５０％〜９０％の中間状態で制御することにより回生充電時の受け入れ性は改善する反面、電解液の硫酸濃度が低い状態で蓄電池が使用される頻度が多くなる。硫酸濃度の低下によって電解液の凝固点が上昇することによって、電解液は凍結しやすくなり、電池特性を著しく低下させたり、凍結した電解液の体積変化によって、電槽が変形したり、場合によっては電槽が破損するという課題があった。
【０００８】
【発明が解決しようとする課題】
本発明は前記した課題、すなわち回生充電効率の向上を目的として電解液の硫酸濃度を低下させるとともに、ＳＯＣを中間状態で使用しても電解液の凍結を抑制し、また、電解液が凍結したとしても、電槽の変形、破損を抑制した制御弁式鉛蓄電池を提供することを目的とする。
【０００９】
【課題を解決するための手段】
前記した課題を解決するために、本発明の請求項１記載に係る発明はガラス繊維もしくは合成樹脂繊維からなるマットセパレータと正極板および負極板とにより構成される極板群が電槽に収納され、前記極板群に保持されていて極板群から遊離した電解液を実質的に保有せず、車速の減速時のエネルギーを回生エネルギーとして蓄電池の充電に適した電圧、電流に変換して受け入れ、かつ、蓄電池の充電状態を５０％〜９０％の中間状態で制御する制御弁式鉛蓄電池であって、前記極板群が前記電槽に収納された状態において、前記マットセパレータの空孔体積をＶとし、前記マットセパレータに含浸保持された電解液の体積をＶｅとした時に、比率（Ｖｅ／Ｖ）を０．９２以下に設定するとともに、前記電解液の硫酸濃度を２６．０質量％〜３７．０質量％としたことを特徴とする制御弁式鉛蓄電池を示すものである。
【００１０】
また、本発明の請求項２記載に係る発明は、請求項１記載における比率（Ｖｅ／Ｖ）の下限値を０．８０とした請求項１記載の制御弁式鉛蓄電池を示すものである。
【００１１】
【発明の実施の形態】
本発明の一実施の形態を以下に説明する。
【００１２】
鉛蓄電池用の正極板および負極板をマットセパレータを介して配置して極板群を構成する。マットセパレータは耐酸化性、耐酸性を有しているガラス繊維マット、ポリプロピレン樹脂繊維マットやこれらを混抄したものを用いる。この極板群を電槽に収納後、必要に応じて極板群間の接続を行う。その後、電槽開口部を蓋で封止するとともに、極板群から導出される入出力端子と蓋もしくは電槽間の封止を行う。その後、電解液を注入し、充電を行い、制御弁式鉛蓄電池を構成する。
【００１３】
本発明の制御弁式鉛蓄電池においては満充電状態における電解液の硫酸濃度を２６．０質量％乃至３７．０質量％の範囲にするとともに、極板群が電槽に収納された状態における、マットセパレータの空孔体積をＶとし、このマットセパレータの空孔に保持された電解液の体積をＶｅとした時の比率（Ｖｅ／Ｖ）を０．９２以下とする。
【００１４】
このような構成により、制御弁式鉛蓄電池の回生充電効率の向上と、ＳＯＣを中間状態で用いた場合における電解液の凍結とこれによる電槽の変形、破損を抑制することができる。
【００１５】
なお、比率（Ｖｅ／Ｖ）の下限値については回生充電における充電受け入れ性および放電容量が急激に低下することから、少なくともこの比率を０．８０以上に設定することが好ましい。
【００１６】
【実施例】
本発明の実施例による鉛蓄電池と比較例による鉛蓄電池とを対比することによって本発明の効果を明らかにした。
【００１７】
鉛−０．０７質量％カルシウム−１．２５質量％錫合金を鋳造して得たスラブを多段階に圧延して得た圧延鉛シートをエキスパンド加工して集電体を作製した。この集電体にそれぞれ正極活物質ペースト、負極活物質ペーストを充填し、熟成乾燥することにより、それぞれ鉛蓄電池用の正極板および負極板とした。これらの正極板と負極板とをガラス繊維で構成されたマットセパレータを介して積層し、同極性の極板耳部を集合溶接して極板群を作製した。
【００１８】
この極板群の６個を６個のセル室を有する電槽に収納後、極板群間を直列接続した後、電槽開口部を蓋で閉塞し、蓋に一体成形された鉛ブッシングに極柱を挿通させ、鉛ブッシングと極柱とを溶接して端子部を形成した。
【００１９】
その後、それぞれのセル室に対応して蓋に設けた注液口から電解液である希硫酸を注入し、注液口に電槽内圧に応じて開閉する制御弁を取りつけて化成充電を行うことにより公称電圧１２Ｖ、５時間率定格容量１０Ａｈの制御弁式鉛蓄電池を構成した。
【００２０】
本実施例においては注液する希硫酸の硫酸濃度と注液量を変化させることによって化成充電後、すなわち満充電状態における電解液中の硫酸濃度とセパレータの空孔体積Ｖとセパレータ空孔に含浸保持された電解液体積Ｖｅとの比率を種々に変化させて電池を構成した。なお、極板群圧は１９６００Ｎ／ｍ2に設定した。
【００２１】
これらの電池を５時間率電流で放電を行い、ＳＯＣを５０％の状態とした。これらの電池をそれぞれ満充電状態の電解液の硫酸濃度に対応した電解液の凝固点温度よりもさらに１０℃低い温度で２４時間放置した時の電槽の変形度合いを確認した。なお、電槽変形度合いの評価としては膨れ等の変形寸法が１ｍｍ以下であり、殆ど変形のないものを○、変形寸法は５ｍｍ以上で著しい変形のあるものを△、変形によって電槽に割れが発生したものを×とした。これらの結果を表１に示す。
【００２２】
【表１】
表１に示した結果から比率（Ｖｅ／Ｖ）が０．９２を超えて大きくした場合、電解液の硫酸濃度によっては電槽変形が発生し始めることがわかる。
【００２４】
電池の電槽変形度合いの評価後、電槽割れの発生した電池を除いた電池を２５℃雰囲気下に４８時間放置した後、１００Ａの定電流放電を行い、放電開始後２秒目の放電電圧Ｅを測定した。この結果を表２に示す。
【００２５】
【表２】
表２に示した結果から比率（Ｖｅ／Ｖ）が０．７５で放電電圧４．２Ｖと急激に出力電圧が低下することがわかる。また、硫酸濃度が２５．０質量％で他の硫酸濃度が２６．０質量％、３０．０質量％、３７．０質量％、３８．０質量％、４０．０質量％の場合に比較して、急激な出力電圧の低下が認められた。
【００２７】
次に電解液の硫酸濃度と回生充電時の充電受け入れ性を評価した。
【００２８】
ここでは各試験電池のＳＯＣを５０％とし、２５℃中で１７Ｖ定電圧充電した場合に、充電開始１秒目の充電電流を測定することによって充電受け入れ性を評価した。
【００２９】
これらの結果を図１に示す。
【００３０】
図１に示した結果から検討を行ったすべての（Ｖｅ／Ｖ）範囲において電解液の硫酸濃度を３７質量％を超えて増加させると充電電流が急激に低下することがわかる。これは硫酸濃度が高い領域では充電時に正極板および負極板表面近傍で発生した硫酸の拡散が抑制されて充電電流が制限されるものと推測できる。
【００３１】
これらの結果から、回生充電時の充電受け入れ性を低下させることなく、電池を低温放置した場合に発生する電解液の凍結による電槽変形、破損を抑制するためには比率（Ｖｅ／Ｖ）を０．９２以下にするとともに、前記電解液の硫酸濃度を２６．０質量％〜３７．０質量％としたことが必要である。また、出力特性の低下を抑制するためには少なくとも比率（Ｖｅ／Ｖ）を０．８０以上とすることが好ましい。
【００３２】
【発明の効果】
以上説明したように、本発明の構成によれば回生充電効率向上を目的として電解液の硫酸濃度を低下させた場合において、ＳＯＣを中間状態で使用しても電解液の凍結を抑制できる。また、電解液が凍結したとしても、電槽の変形、破損を抑制した制御弁式鉛蓄電池を提供することができることから、工業上極めて有用である。
【図面の簡単な説明】
【図１】電解液の硫酸濃度と充電電流との関係を示す図[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a control valve type lead storage battery that includes a mat separator that is impregnated and held with an electrolytic solution, almost all of the electrolytic solution is held in an electrode plate group, and has almost no electrolyte released from the electrode plate group. .
[0002]
[Prior art]
Lead storage batteries are inexpensive and widely used as automobile batteries because of their high reliability even in a relatively wide temperature range.
[0003]
Normally, a starting automobile battery is charged while regulating the charging voltage with a regulator so that the battery is fully charged by the electric power generated by the alternator, and the engine is started and lights are turned on using the charged electric power.
[0004]
In recent years, for the purpose of improving the fuel efficiency of automobiles, by reducing the charging voltage of the battery, the rotational speed of the alternator is reduced to reduce energy loss, or a hybrid vehicle combining an engine and a motor has been put into practical use. .
[0005]
When a battery is used in such a vehicle, it is necessary to positively store energy at the time of deceleration of the vehicle speed as regenerative energy. Since this regenerative energy is generated at the time of deceleration, the power generation amount and power generation time are random, it is necessary to convert this energy into a voltage and current suitable for charging the storage battery, and charging with such regenerative energy ( Hereinafter, in order to efficiently accept regenerative charging), it is necessary to appropriately control the state of charge of the storage battery (hereinafter referred to as SOC).
[0006]
In order to efficiently accept this regenerative charge, for example, as shown in JP-A-8-308018, a lead storage battery having a rated voltage of 12V is charged at 13V, and the SOC is controlled at about 60% to 90%. Are listed. Further, it has been proposed to improve the charge acceptability of regenerative charging by reducing the sulfuric acid concentration of the electrolytic solution.
[0007]
By controlling the SOC of the lead storage battery in which the sulfuric acid concentration of these electrolytes is low in an intermediate state of 50% to 90%, the acceptability at the time of regenerative charging is improved, while the storage battery is in a state where the sulfuric acid concentration of the electrolyte is low. Increased frequency of use. When the freezing point of the electrolyte rises due to a decrease in the sulfuric acid concentration, the electrolyte is more likely to freeze, and the battery characteristics are significantly reduced, the battery case is deformed due to the volume change of the frozen electrolyte, and in some cases There was a problem that the battery case was damaged.
[0008]
[Problems to be solved by the invention]
The present invention reduces the sulfuric acid concentration of the electrolytic solution for the purpose of improving the regenerative charging efficiency as described above, suppresses the freezing of the electrolytic solution even when the SOC is used in an intermediate state, and the electrolytic solution is frozen. However, it aims at providing the control valve type lead acid battery which suppressed the deformation | transformation and breakage of a battery case.
[0009]
[Means for Solving the Problems]
In order to solve the above-described problem, the invention according to
[0010]
The invention according to claim 2 of the present invention shows the control valve type lead storage battery according to
[0011]
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of the present invention will be described below.
[0012]
A positive electrode plate and a negative electrode plate for a lead storage battery are arranged via a mat separator to constitute an electrode plate group. As the mat separator, a glass fiber mat, a polypropylene resin fiber mat having oxidation resistance and acid resistance, or a mixture of these is used. After this electrode plate group is stored in the battery case, the electrode plate groups are connected as necessary. Thereafter, the battery case opening is sealed with a lid, and the input / output terminal derived from the electrode plate group and the lid or the battery case are sealed. Thereafter, an electrolytic solution is injected and charged to form a control valve type lead storage battery.
[0013]
In the control valve type lead storage battery of the present invention, the sulfuric acid concentration of the electrolytic solution in a fully charged state is in the range of 26.0 mass% to 37.0 mass%, and the electrode plate group is housed in the battery case. The ratio (Ve / V) is 0.92 or less when the pore volume of the mat separator is V and the volume of the electrolyte solution retained in the pores of the mat separator is Ve.
[0014]
With such a configuration, it is possible to improve the regenerative charging efficiency of the control valve type lead storage battery, and to prevent the electrolytic solution from being frozen and the battery case to be deformed or damaged when the SOC is used in an intermediate state.
[0015]
In addition, about the lower limit of ratio (Ve / V), since charge acceptance in regenerative charge and discharge capacity fall rapidly, it is preferable to set this ratio to 0.80 or more at least.
[0016]
【Example】
The effect of the present invention was clarified by comparing the lead storage battery according to the embodiment of the present invention with the lead storage battery according to the comparative example.
[0017]
A rolled lead sheet obtained by rolling a slab obtained by casting lead-0.07 mass% calcium-1.25 mass% tin alloy in multiple stages was expanded to produce a current collector. The current collector was filled with a positive electrode active material paste and a negative electrode active material paste, respectively, and aged and dried to obtain a positive electrode plate and a negative electrode plate for a lead storage battery, respectively. The positive electrode plate and the negative electrode plate were laminated through a mat separator made of glass fiber, and electrode plate ears having the same polarity were collectively welded to produce an electrode plate group.
[0018]
After storing six of these electrode plate groups in a battery case having six cell chambers, the electrode plate groups were connected in series, and then the battery case opening was closed with a lid, and a lead bushing formed integrally with the lid. The terminal was formed by inserting the pole column and welding the lead bushing and the pole column.
[0019]
Then, dilute sulfuric acid, which is an electrolyte, is injected from the injection port provided on the lid corresponding to each cell chamber, and a control valve that opens and closes according to the internal pressure of the battery is attached to the injection port for chemical charging. Thus, a control valve type lead-acid battery having a nominal voltage of 12V and a rated capacity of 10Ah for 5 hours was constituted.
[0020]
In this embodiment, the sulfuric acid concentration of the dilute sulfuric acid to be injected and the amount of the injected liquid are changed, and after the chemical charging, that is, the sulfuric acid concentration in the electrolytic solution in the fully charged state, the separator volume V, and the separator holes are impregnated The battery was configured with various ratios to the retained electrolyte volume Ve. The electrode plate group pressure was set to 19600 N / m 2 .
[0021]
These batteries were discharged at a 5 hour rate current to bring the SOC to 50%. When these batteries were left for 24 hours at a
[0022]
[Table 1]
From the results shown in Table 1, it can be seen that when the ratio (Ve / V) is increased beyond 0.92, the battery case starts to deform depending on the sulfuric acid concentration of the electrolytic solution.
[0024]
After the evaluation of the degree of battery case deformation, the battery excluding the battery with the battery case cracked was left in an atmosphere at 25 ° C. for 48 hours, and then a constant current discharge of 100 A was performed. E was measured. The results are shown in Table 2.
[0025]
[Table 2]
From the results shown in Table 2, it can be seen that when the ratio (Ve / V) is 0.75, the output voltage is drastically reduced to 4.2V. Compared with the case where the sulfuric acid concentration is 25.0% by mass and the other sulfuric acid concentrations are 26.0% by mass, 30.0% by mass, 37.0% by mass, 38.0% by mass and 40.0% by mass. As a result, a sudden drop in output voltage was observed.
[0027]
Next, the sulfuric acid concentration of the electrolytic solution and the charge acceptability during regenerative charging were evaluated.
[0028]
Here, when the SOC of each test battery was set to 50% and charging was performed at a constant voltage of 17 V at 25 ° C., the charge acceptability was evaluated by measuring the charging current at the first second of charging.
[0029]
These results are shown in FIG.
[0030]
From the results shown in FIG. 1, it can be seen that when the sulfuric acid concentration of the electrolytic solution is increased beyond 37% by mass in all the (Ve / V) ranges examined, the charging current rapidly decreases. It can be presumed that in a region where the sulfuric acid concentration is high, diffusion of sulfuric acid generated near the surfaces of the positive electrode plate and the negative electrode plate during charging is suppressed, and the charging current is limited.
[0031]
From these results, the ratio (Ve / V) is used to suppress battery cell deformation and breakage due to freezing of the electrolyte that occurs when the battery is left at a low temperature without reducing the charge acceptance during regenerative charging. It is necessary to adjust the sulfuric acid concentration of the electrolytic solution to 26.0 mass% to 37.0 mass% while setting it to 0.92 or less. In order to suppress a decrease in output characteristics, at least the ratio (Ve / V) is preferably 0.80 or more.
[0032]
【The invention's effect】
As described above, according to the configuration of the present invention, when the sulfuric acid concentration of the electrolytic solution is lowered for the purpose of improving the regenerative charging efficiency, the freezing of the electrolytic solution can be suppressed even when the SOC is used in an intermediate state. In addition, even if the electrolyte is frozen, it is possible to provide a control valve type lead-acid battery that suppresses deformation and breakage of the battery case, which is extremely useful industrially.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the sulfuric acid concentration of an electrolyte and the charging current
Claims (2)
車速の減速時のエネルギーを回生エネルギーとして蓄電池の充電に適した電圧、電流に変換して受け入れ、かつ、蓄電池の充電状態を５０％〜９０％の中間状態で制御する制御弁式鉛蓄電池であって、
前記極板群が前記電槽に収納された状態において、前記マットセパレータの空孔体積をＶとし、前記マットセパレータに含浸保持された電解液の体積をＶｅとした時に、比率（Ｖｅ／Ｖ）を０．９２以下に設定するとともに、前記電解液の硫酸濃度を２６．０質量％〜３７．０質量％としたことを特徴とする制御弁式鉛蓄電池。An electrode plate group composed of a mat separator made of glass fiber or synthetic resin fiber, a positive electrode plate and a negative electrode plate is housed in a battery case, and the electrolyte solution held by the electrode plate group and released from the electrode plate group is substantially Do not own,
It is a control valve type lead-acid battery that converts the energy at the time of deceleration of the vehicle speed into regenerative energy and converts it into a voltage and current suitable for charging the storage battery, and controls the charged state of the storage battery in an intermediate state of 50% to 90%. And
In a state where the electrode plate group is housed in the battery case, a ratio (Ve / V) where V is the pore volume of the mat separator and Ve is the volume of the electrolyte solution impregnated and held in the mat separator. Is set to 0.92 or less, and the sulfuric acid concentration of the electrolytic solution is set to 26.0 mass% to 37.0 mass%.
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