WO2005011042A1 - 鉛蓄電池電解液用添加剤および鉛蓄電池 - Google Patents
鉛蓄電池電解液用添加剤および鉛蓄電池 Download PDFInfo
- Publication number
- WO2005011042A1 WO2005011042A1 PCT/JP2003/009528 JP0309528W WO2005011042A1 WO 2005011042 A1 WO2005011042 A1 WO 2005011042A1 JP 0309528 W JP0309528 W JP 0309528W WO 2005011042 A1 WO2005011042 A1 WO 2005011042A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lead
- additive
- acid battery
- battery
- electrolyte
- Prior art date
Links
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
- H01M10/06—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
Definitions
- the present invention relates to a lead-acid battery in which a decrease in battery capacity is suppressed, an additive for a lead-acid battery for suppressing a decrease in battery capacity of the lead-acid battery and for recovering the battery capacity, and an improvement in battery characteristics using the same.
- a lead-acid battery in which a decrease in battery capacity is suppressed
- an additive for a lead-acid battery for suppressing a decrease in battery capacity of the lead-acid battery and for recovering the battery capacity
- Lead-acid batteries are highly reliable and economical rechargeable batteries, and lead-acid batteries, which are widely used mainly as power sources for automobiles and motorcycles, especially electric vehicles such as forklifts, can be used over a long period of time. There is a problem that the function as a secondary battery is lost because the internal resistance increases and the charge / discharge efficiency of the lead storage battery decreases.
- a metal foil made of a highly conductive titanium compound or the like and a metal foil made of lead-tin-tin-calcium alloy are integrated and rolled to produce an electrode current collector.
- a metal foil made of a highly conductive titanium compound or the like and a metal foil made of lead-tin-tin-calcium alloy are integrated and rolled to produce an electrode current collector.
- an object of the present invention is to provide an additive that improves the battery characteristics of a lead storage battery and improves the charge and discharge efficiency. It is a further object of the present invention to provide an additive which prevents sulfation and further improves the charge / discharge efficiency.
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and found that when a solution containing titanium oxide or titanate used for a base material of a capacitor or the like is added to an electrolytic solution, lead They found that battery characteristics such as storage battery capacity and internal resistance were improved, and that charging and discharging efficiency was improved. As a result of further research, the present invention was completed. That is, the present invention relates to an additive for a lead storage battery electrolyte containing a titanium oxide and / or a titanate.
- the present invention relates to the additive for a lead-acid battery electrolyte described above, wherein the titanium oxide is one or more selected from the group consisting of titanium monoxide, dititanium trioxide and titanium dioxide. .
- the present invention relates to the additive for a lead-acid battery electrolytic solution, wherein the titanate is one or more selected from the group consisting of barium titanate and strontium titanate.
- the present invention relates to the additive for a lead-acid battery electrolyte described above, further comprising a calcium compound and / or a magnesium compound.
- the present invention also relates to the above additive for a lead storage battery electrolyte, wherein the calcium compound is calcium sulfate.
- the present invention relates to the additive for a lead-acid battery electrolyte according to the above, wherein the magnesium compound is magnesium sulfate.
- the present invention also relates to an electrolyte for a lead-acid battery, comprising the additive for a lead-acid battery.
- the present invention relates to a lead storage battery including the above-mentioned electrolyte solution for a lead storage battery. Further, the present invention relates to a lead storage battery including a titanium oxide and / or a titanate in an electrode, and a calcium compound and a magnesium compound in an electrolyte.
- each component of the additive of the present invention in a lead-acid battery is not necessarily clear, but by using titanium oxide and / or titanate, the conductive titanium compound becomes It is considered that the charge / discharge efficiency was improved because the electrode surface was maintained by being absorbed by the electrode active material.
- the calcium compound suppresses the oxidizing action of oxygen generated at the anode
- the magnesium compound contributes to the decomposition of sulfur in lead-acid batteries, because it absorbs hydrogen generated at the cathode. It is considered that the battery characteristics are improved. Therefore, according to the present invention, an electrochemically stable titanium oxide and / or citrate is added to an electrolytic solution without adding electrochemically unstable carbon or an organic polymer compound. This makes it possible to maintain the conductivity of the electrode interface and improve battery characteristics.
- the additive for a lead-acid battery electrolyte of the present invention to the electrolyte of a new lead-acid battery, the internal resistance of the battery can be reduced, and the charge / discharge efficiency can be improved.
- the additive of the present invention is added to the electrolyte of a battery deteriorated by sulfation, the battery capacity can be recovered.
- the additive for a lead-acid battery electrolyte of the present invention is typically a powder, and can be added directly to the electrolyte of a lead-acid battery. It can also be used as a liquid preparation in which each of the components is dissolved or dispersed in advance. When used as a solution, distilled water, dilute sulfuric acid, etc. are used as the solvent, but dilute sulfuric acid having a specific gravity of 1.28 (20 ° C), which is usually used for the electrolytic solution, is preferred.
- titanium monoxide (T iO), trioxide titanium (T i 2 0 3) and titanium dioxide (T i0 2) is Ru mentioned.
- titanium dioxide (T i0 2) is Ru mentioned.
- titanate used in the present invention is not particularly limited as long as the metal salt of the titanate, barium titanate (BAT i0 3), titanium Sens strontium (S rT i0 3), potassium titanate (K 2 T i0 3), sodium titanate (Na 2 T i 3 0 7 ), calcium titanate (CaT i0 3), magnesium titanate (Mg 2 T i0 4), magnesium metatitanic acid (M g T i 0 3) and the like. From the viewpoint of improvement of efficient electrical properties of these, barium titanate (B a T i 0 3) and titanate Sutoronchi ⁇ beam (S r T i 0 3) is preferable.
- the particle diameter of the titanium oxide and titanate used in the present invention is preferably from 1.0 to 1.5111, particularly preferably from the viewpoint of dispersibility and fluidity in an electrolytic solution. Is 1.05 to: 1.1 m.
- Examples of the calcium compound used in the present invention include calcium hydroxide, calcium oxide, calcium carbonate, calcium sulfate, calcium nitrate, calcium acetate, calcium chloride, etc., from the viewpoint of mixing, dispersibility, fluidity, etc. Calcium sulfate is preferred.
- the purity of the calcium compound used in the present invention is preferably 90% or more from the viewpoints of dispersibility, fluidity, and mixing property in an electrolytic solution.
- magnesium compound used in the present invention examples include magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, and the like. From the viewpoint, magnesium oxide and magnesium sulfate are preferred. Particularly, magnesium sulfate is preferred.
- the purity of the magnesium compound used in the present invention is preferably 90% or more from the viewpoint of dispersibility, fluidity, reactivity and the like in the electrolytic solution.
- the method of improving the battery characteristics using the additive of the present invention is a method of regenerating a lead storage battery determined to be used by sulfuration or extending the discharge time of a new lead storage battery. Is a method for improving the battery characteristics such as the internal resistance of a lead-acid battery and improving the charge / discharge efficiency.
- the addition may be carried out by adding a powder in which each additive is mixed, or by adding a dispersion in which each additive is previously dispersed in a liquid.
- the batteries to which the additive for a lead-acid battery electrolyte of the present invention can be used are not particularly limited as long as they are lead-acid batteries, and are used for automobiles, motorcycles, electric vehicles (especially for forklifts), ships, and aircraft. Etc., and is not limited by the rated capacity of the battery. '
- the titanium oxide and / or titanate is added to the electrolyte at a concentration of 2 to 10%, preferably 2.5 to 3.0%. . If it is less than 2%, the adsorption to the electrode active material may be insufficient and sufficient effect may not be obtained.If it exceeds 10%, the adsorption to the electrode active material becomes saturated and the lower part of the lead-acid battery case becomes Will precipitate.
- the calcium compound is added so as to have a concentration of 0.5 to 5.0%, preferably 2.0 to 3.0% in the electrolytic solution.
- the magnesium compound is added so as to have a concentration of 0.1 to 2.0%, preferably 1 to 1.2% in the electrolytic solution.
- the relationship between the concentrations of titanium oxide and / or titanate and calcium compound is considered from the viewpoint of dispersibility, fluidity, and reactivity.
- the calcium compound is preferably added so as to have a concentration of 2.0 to 3.0%.
- the relationship between the concentrations of titanium oxide and / or titanate and magnesium compound is considered from the viewpoint of dispersibility, fluidity, and reactivity.
- the magnesium compound When added to a concentration of 3.0%, the magnesium compound is preferably added to a concentration of 1.0 to 1.2%.
- battery characteristics can be further improved by repeating charge and discharge after the addition of the above additive.
- the charging condition when the rated capacity is 28 AH, the charging condition may be about 20 hours at 1.4 A, but preferably, it is 8 hours at 3.5 A. When the rated capacity is 350 AH, it may be about 8 hours at 44 A, but preferably, it is about 20 hours at 18 A.
- Charge conditions can be modified. In charging, if the current is too large, the electrodes may be damaged, and if it is too small, a sufficient effect cannot be expected.
- the terminal voltage is set to 1.70 V to 1.75 V at a time rate current regardless of the rated capacity, and discharge is preferably performed until the terminal voltage becomes 1.75 V. If the discharge is not sufficient, the effect of improving the electrical characteristics may be reduced, and if a sudden discharge is performed, the electrodes may be damaged.
- the electrolytic solution for a lead storage battery of the present invention contains titanium oxide and Z or titanate, a calcium compound, and a magnesium compound.
- Each of the components that can be used in the electrolytic solution of the present invention includes an additive of the present invention. It may be the same as that used in the above, and the compounding amount thereof may be the same as the concentration added in the method for improving battery characteristics.
- the lead storage battery of the present invention instead of adding titanium oxide and titanium oxide or titanate, a calcium compound, and a magnesium compound to the electrolyte solution, the lead storage battery may be contained in the electrode.
- the magnesium compound is preferably added to the electrolytic solution.
- the above components may be the same as those used for the additive of the present invention.
- Example 1 the method for improving the battery characteristics of the lead storage battery of the present invention will be described, but the present invention is not limited to these examples.
- Example 1 the method for improving the battery characteristics of the lead storage battery of the present invention will be described, but the present invention is not limited to these examples.
- the electrolyte of a new lead-acid battery (YUAS A) with a battery capacity of 28 AH contains 3.0% barium titanate (particle size 1.86 m), 3.0% calcium sulfate (98% purity), and magnesium sulfate ( (Purity 98%) was added to a concentration of 1.2% (battery (A)).
- the discharge was performed until the terminal voltage reached 1.75 V, and the battery was discharged while measuring the discharge time in a discharger (250 W, 1 hour).
- New lead-acid battery (YUASA) with a battery capacity of 28 AH The discharge time was measured without the light additive (battery (B)).
- the electrolyte of a deteriorated lead-acid battery (manufactured by GS) with a battery capacity of 350 AH contains 3.0% of potassium titanate (particle diameter 1.086 jm%) and calcium sulfate (98% pure). 3.0% and magnesium sulfate (98% purity) were added to a concentration of 1.2%.
- Discharging was performed until the terminal voltage reached 1.75 V, and charging was performed at a current of 18 A for 20 hours. The charging / discharging was repeated while measuring the discharge time in a discharger (250 W / day).
- the additive for a lead-acid battery electrolyte solution of the present invention can easily improve the charge-discharge efficiency of the lead-acid battery and extend the cycle life by being added to the lead-acid battery (new or used). .
- the additive for a lead storage battery electrolyte, the lead storage battery electrolyte, the lead storage battery electrode, and the lead storage battery of the present invention are used for automobiles, motorcycles, electric vehicles (particularly, forklifts), ships, and aircraft. It can be used for any purpose such as battery use, and can be used without any particular limitation on the rated capacity of the battery.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2003/009528 WO2005011042A1 (ja) | 2003-07-28 | 2003-07-28 | 鉛蓄電池電解液用添加剤および鉛蓄電池 |
AU2003254777A AU2003254777A1 (en) | 2003-07-28 | 2003-07-28 | Additive for electrolyte solution of lead acid battery and lead acid battery |
JP2005504576A JPWO2005011042A1 (ja) | 2003-07-28 | 2003-07-28 | 鉛蓄電池電解液用添加剤および鉛蓄電池 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2003/009528 WO2005011042A1 (ja) | 2003-07-28 | 2003-07-28 | 鉛蓄電池電解液用添加剤および鉛蓄電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005011042A1 true WO2005011042A1 (ja) | 2005-02-03 |
Family
ID=34090556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/009528 WO2005011042A1 (ja) | 2003-07-28 | 2003-07-28 | 鉛蓄電池電解液用添加剤および鉛蓄電池 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2005011042A1 (ja) |
AU (1) | AU2003254777A1 (ja) |
WO (1) | WO2005011042A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007066558A (ja) * | 2005-08-29 | 2007-03-15 | Furukawa Battery Co Ltd:The | 鉛蓄電池 |
JP2008108510A (ja) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | 鉛蓄電池補助液 |
JP2008108511A (ja) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | 鉛蓄電池電解液 |
JP2008243487A (ja) * | 2007-03-26 | 2008-10-09 | Furukawa Battery Co Ltd:The | 鉛電池 |
CN102945981A (zh) * | 2012-10-30 | 2013-02-27 | 中南大学 | 一种超级铅酸电池用电解液 |
CN105449274A (zh) * | 2014-09-26 | 2016-03-30 | 宁德时代新能源科技有限公司 | 锂离子电池及其电解液 |
JP2016072105A (ja) * | 2014-09-30 | 2016-05-09 | パナソニックIpマネジメント株式会社 | 鉛蓄電池 |
WO2016121327A1 (ja) * | 2015-01-30 | 2016-08-04 | パナソニックIpマネジメント株式会社 | 鉛蓄電池 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0210665A (ja) * | 1988-06-29 | 1990-01-16 | Furukawa Battery Co Ltd:The | 密閉形鉛蓄電池 |
JPH0794206A (ja) * | 1993-09-28 | 1995-04-07 | Shin Kobe Electric Mach Co Ltd | 密閉形鉛蓄電池 |
JPH09237632A (ja) * | 1995-12-26 | 1997-09-09 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板及びその製造法 |
JP3216450B2 (ja) * | 1994-12-09 | 2001-10-09 | トヨタ自動車株式会社 | 鉛蓄電池用の電解液 |
JP2002110219A (ja) * | 2000-09-29 | 2002-04-12 | Furukawa Battery Co Ltd:The | 鉛蓄電池 |
-
2003
- 2003-07-28 WO PCT/JP2003/009528 patent/WO2005011042A1/ja active Application Filing
- 2003-07-28 JP JP2005504576A patent/JPWO2005011042A1/ja active Pending
- 2003-07-28 AU AU2003254777A patent/AU2003254777A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0210665A (ja) * | 1988-06-29 | 1990-01-16 | Furukawa Battery Co Ltd:The | 密閉形鉛蓄電池 |
JPH0794206A (ja) * | 1993-09-28 | 1995-04-07 | Shin Kobe Electric Mach Co Ltd | 密閉形鉛蓄電池 |
JP3216450B2 (ja) * | 1994-12-09 | 2001-10-09 | トヨタ自動車株式会社 | 鉛蓄電池用の電解液 |
JPH09237632A (ja) * | 1995-12-26 | 1997-09-09 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板及びその製造法 |
JP2002110219A (ja) * | 2000-09-29 | 2002-04-12 | Furukawa Battery Co Ltd:The | 鉛蓄電池 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007066558A (ja) * | 2005-08-29 | 2007-03-15 | Furukawa Battery Co Ltd:The | 鉛蓄電池 |
JP2008108510A (ja) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | 鉛蓄電池補助液 |
JP2008108511A (ja) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | 鉛蓄電池電解液 |
JP2008243487A (ja) * | 2007-03-26 | 2008-10-09 | Furukawa Battery Co Ltd:The | 鉛電池 |
CN102945981A (zh) * | 2012-10-30 | 2013-02-27 | 中南大学 | 一种超级铅酸电池用电解液 |
CN105449274A (zh) * | 2014-09-26 | 2016-03-30 | 宁德时代新能源科技有限公司 | 锂离子电池及其电解液 |
JP2016072105A (ja) * | 2014-09-30 | 2016-05-09 | パナソニックIpマネジメント株式会社 | 鉛蓄電池 |
WO2016121327A1 (ja) * | 2015-01-30 | 2016-08-04 | パナソニックIpマネジメント株式会社 | 鉛蓄電池 |
JPWO2016121327A1 (ja) * | 2015-01-30 | 2017-11-24 | 株式会社Gsユアサ | 鉛蓄電池 |
Also Published As
Publication number | Publication date |
---|---|
AU2003254777A1 (en) | 2005-02-14 |
JPWO2005011042A1 (ja) | 2006-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4785482B2 (ja) | 非水電解質二次電池 | |
JP6989970B2 (ja) | 二次電池及び二次電池を含む装置 | |
JP2008243487A (ja) | 鉛電池 | |
US11211635B2 (en) | Battery, battery pack, and uninterruptible power supply | |
JP4839573B2 (ja) | 電気化学デバイス及び電極 | |
JP6168138B2 (ja) | 液式鉛蓄電池 | |
JP2004513501A (ja) | アルカリ電解液を有する亜鉛含有セルのための正負相互作用電極調合物 | |
JP2000149981A (ja) | 鉛蓄電池および鉛蓄電池用添加剤 | |
WO2010058240A1 (en) | Low water loss battery | |
JP4222488B2 (ja) | アルカリ電池 | |
JP7219462B2 (ja) | 亜鉛二次電池 | |
WO2005011042A1 (ja) | 鉛蓄電池電解液用添加剤および鉛蓄電池 | |
JP2001313064A (ja) | 鉛蓄電池およびその添加剤 | |
JP2008053222A (ja) | 水酸化ニッケル粉末、オキシ水酸化ニッケル粉末、これらの製造方法およびアルカリ乾電池 | |
CN101051687A (zh) | 应用于蓄电池的活性添加剂、可被活化或再生的蓄电池及使该蓄电池活化或再生的方法 | |
CN111342148A (zh) | 一种基于电化学冶金原理的二氧化锰电池 | |
JP3386801B1 (ja) | 鉛蓄電池の電解液組成物 | |
JP2006221832A (ja) | 非水系二次電池用正極ペーストの製造方法 | |
JP7384346B2 (ja) | マグネシウム二次電池用の絶縁抑制電解液及び絶縁抑制方法 | |
JP2002100347A (ja) | 鉛蓄電池 | |
JP2015530722A (ja) | 電池の電荷移動機構 | |
JP2004047406A (ja) | 非水電解質二次電池 | |
JP2003151618A (ja) | 鉛蓄電池および鉛蓄電池用添加剤 | |
JP2007213896A (ja) | 鉛蓄電池 | |
JP2005063876A (ja) | 蓄電池再生剤およびこれを用いた劣化蓄電池の再生方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005504576 Country of ref document: JP |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 69(1) EPC (EPO FORM DATED 24.10.2006 ) |
|
122 | Ep: pct application non-entry in european phase |