WO2014077420A1 - Solid electrolyte and formation of lead battery using it - Google Patents

Solid electrolyte and formation of lead battery using it Download PDF

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Publication number
WO2014077420A1
WO2014077420A1 PCT/KP2013/000030 KP2013000030W WO2014077420A1 WO 2014077420 A1 WO2014077420 A1 WO 2014077420A1 KP 2013000030 W KP2013000030 W KP 2013000030W WO 2014077420 A1 WO2014077420 A1 WO 2014077420A1
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WO
WIPO (PCT)
Prior art keywords
solid electrolyte
formation
battery
lead battery
lead
Prior art date
Application number
PCT/KP2013/000030
Other languages
French (fr)
Inventor
Su Bok RYU
Kyong Myong KO
Original Assignee
PYO, Gwang Sun
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PYO, Gwang Sun filed Critical PYO, Gwang Sun
Priority to EP13855232.8A priority Critical patent/EP2951878A4/en
Publication of WO2014077420A1 publication Critical patent/WO2014077420A1/en

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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
    • H01M10/10—Immobilising of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte and a formation charge of lead batteries for power, energy storage and starting up.
  • US patent No. 4,317,872 discloses a lead battery utilizing a gel electrolyte containing silica particles.
  • the present invention provides a solid electrolyte to be used for formation of lead battery and formation method of lead battery using it in order to solve above problem.
  • the invention is aimed at decreasing pollution phenomena and reducing formation time by introducing solid electrolyte into formation process of lead battery.
  • the present invention provides a novel solid electrolyte which can be used in both plate formation process and lead battery.
  • the present invention provides manufacturing method of solid electrolyte.
  • the invention makes it possible to save labor and time to be wasted for changing electrolyte or drying pole plates after finishing formation charge.
  • gas deflation to be generated during formation process is decreased, self-discharge becomes less and time for formation charge is reduced.
  • Solid electrolyte of the present invention contains 75 ⁇ 86wt% of calcium sulfate, 9 ⁇ 12wt% of sulfuric acid and 5 ⁇ 16wt% of stabilizer.
  • the stabilizer of solid electrolyte described in the present invention consists of more than two metals, metallic oxides and metallic salts.
  • the solid electrolyte of the present invention is used as not only in formation process, but also as it was after formation process.
  • Lead batteries using solid electrolyte of the present invention are not limited in respect of size and shape.
  • the formation method of battery plate that is mostly used in the prior art is step-by-step method.
  • both single formation and bundle formation of lead batteries using electrolyte of the present invention are possible. Formation process is done for 12 ⁇ 14hours with current intensity equal to 1/12-1/14 of the lead battery capacity and current intensity regulation is not necessary during formation charge ( Figure 1, Figure 2).
  • both 2V single formation and 12V bundle formation using solid electrolyte of the present invention generate gas much less than formation of normal lead acid battery since formation voltages (2.2-2.3 V, 13V) are lower than gas generating- voltages (2.6V, 13.5V) and formation times are short.
  • Electrolyte used for formation charge can be used as it was, and changed.
  • the formation charge process of the lead battery according to the present invention makes it possible to provide high productivity and save electricity, labor and time since unformed plates are used as they were after being dried and thus there is no need to take them out, wash, dry or save them after charge.
  • Solid electrolyte is produced according to the following steps;
  • Solid electrolyte is produced according to the following steps;
  • Solid electrolyte is produced according to the following steps;
  • Solid electrolyte is produced according to the following steps;
  • a cycle charge time of lead battery after completing formation process is 60 ⁇ 80min ( Figure 3).
  • 12V-lead battery using solid electrolyte of the invention is allowed to be discharged to low voltage of 4.5-5V. Though it is discharged to low voltage, the battery capacity is still capable of being regenerated.
  • Self-discharge rates per a month of lead batteries using above mentioned examples of solid electrolyte of the invention are 0.8-1% at 60°C of temperature and 80% of relative humidity (Table 1).
  • Table 1 Lead battery using solid electrolyte of the invention has advantages of high capacity, short charge time and allowance of complete discharge, etc. It is more advantageous that the lead battery using solid electrolyte of the invention can be sealed since complete charge voltage for the solid electrolyte of the invention is lower than gas deflation voltage of the same.

Abstract

The present invention relates to a novel solid electrolyte and a method using it in the formation process of lead battery. The solid electrolyte to be used in the formation process of lead battery consists of 75~86wt% of calcium sulfate, 9~12wt% of sulfuric acid, 5~16wt% of stabilizer. Battery is formation-charged with unsealed upper lid after introducing uniformly electrolyte between battery plates. Formation charge of lead battery using solid electrolyte of the present invention can reduce deflation amount of gas and acid fog causing pollution phenomena to 4-8% compared with formation charge of normal lead acid battery. Solid electrolyte used for formation charge can be used as it was, and changed.

Description

Solid Electrolyte and Formation of Lead Battery Using It
Description
Field of the Invention
The present invention relates to a solid electrolyte and a formation charge of lead batteries for power, energy storage and starting up.
Background of the Invention
The atmosphere pollution phenomena to be caused by deflation of gas and acid fog generating in manufacturing process of lead battery, especially formation process inflict serious damages to human bodies and natural environment.
There have been a lot of methods relating to reducing gas deflation generating during use of lead battery.
US patent No. 4,317,872 discloses a lead battery utilizing a gel electrolyte containing silica particles.
Another method of gelling electrolyte is disclosed in US patent No. 4,465,748 where liquid electrolyte is immobilized when it is absorbed and retained in a very absorbent glass fiber.
International Patent Publication WO 03/067684 provides a novel- method of gelling electrolyte by filtration action of absorbent separators.
These relate to methods using plates which passed formation process, but not formation methods.
It has become an important problem to improve formation process and formation method.
The present invention provides a solid electrolyte to be used for formation of lead battery and formation method of lead battery using it in order to solve above problem.
The invention is aimed at decreasing pollution phenomena and reducing formation time by introducing solid electrolyte into formation process of lead battery.
Summary of the Invention
The present invention provides a novel solid electrolyte which can be used in both plate formation process and lead battery.
The present invention provides manufacturing method of solid electrolyte.
The invention makes it possible to save labor and time to be wasted for changing electrolyte or drying pole plates after finishing formation charge.
According to the present invention, gas deflation to be generated during formation process is decreased, self-discharge becomes less and time for formation charge is reduced.
Solid electrolyte of the present invention contains 75~86wt% of calcium sulfate, 9~12wt% of sulfuric acid and 5~16wt% of stabilizer.
The stabilizer of solid electrolyte described in the present invention consists of more than two metals, metallic oxides and metallic salts.
The solid electrolyte of the present invention is used as not only in formation process, but also as it was after formation process.
Lead batteries using solid electrolyte of the present invention are not limited in respect of size and shape.
At present, the formation method of battery plate that is mostly used in the prior art is step-by-step method. According to the present invention, both single formation and bundle formation of lead batteries using electrolyte of the present invention are possible. Formation process is done for 12~14hours with current intensity equal to 1/12-1/14 of the lead battery capacity and current intensity regulation is not necessary during formation charge (Figure 1, Figure 2).
As it is distinct through the figures, both 2V single formation and 12V bundle formation using solid electrolyte of the present invention generate gas much less than formation of normal lead acid battery since formation voltages (2.2-2.3 V, 13V) are lower than gas generating- voltages (2.6V, 13.5V) and formation times are short.
Electrolyte used for formation charge can be used as it was, and changed. The formation charge process of the lead battery according to the present invention makes it possible to provide high productivity and save electricity, labor and time since unformed plates are used as they were after being dried and thus there is no need to take them out, wash, dry or save them after charge.
The invention will be described in more detail with reference to the following examples:
Example 1
CaSO4-2H2O 75 wt% AI2O3 5.2 wt%
Na2CO3 10.7 wt% Ge 0.02 wt%
H2SO4
Solid electrolyte is produced according to the following steps;
mixing aluminum oxide, calcium sulfate and germanium in order with sulfuric acid; heating the mixture at temperature of 70°C~80°C forl 5-20min; adding sodium carbonate in the mixture and heating it at temperature of 110oC~120°C for 10~20min; and cooling the mixture to temperature of 15°C~35°C
Example 2
CaSO4 · 2H2O 78 wt% MgSO4 6.7 wt%
SrSO4 3.5 wt% Na2SO4 « 10H2O 1.35 wt%
H2SO4
Solid electrolyte is produced according to the following steps;
mixing strontium sulfate, calcium sulfate and magnesium sulfate in order with sulfuric acid; heating the mixture at temperature of 70°C~75oC for 20~30min; adding sodium sulfate in the mixture and heating it at temperature of 90eC~115°C for 15~25min; and cooling the mixture to temperature of 15"C~350C Example 3
CaSO4 « 2H2O 82 wt% Ti2(SO4) 3 3.5 wt%
ZnSO4 1.2 wt% CoSO4 * 7H20 2.3 wt%
BeSO4 « 4H2O 1.4 wt% H2SO4
Solid electrolyte is produced according to the following steps;
mixing zinc sulfate, calcium sulfate, beryllium sulfate and titan sulfate in order with sulfuric acid; heating the mixture at temperature of 80°C~90°C for 20-25min; adding cobalt sulfate in the mixture and heating it at temperature of 120°C~125°C for 10-15min; and cooling the mixture to temperature of 15°C~35°C Example 4
CaSO4 · 2H2O 86 wt% Al2 (SO4)3 · H2O 2.4wt%
CdSO4 · 4H2O 0.4 wt% Na2SO4 · I OH2O 2.2 wt%
H2SO4
Solid electrolyte is produced according to the following steps;
mixing sodium sulfate, aluminum sulfate and calcium sulfate in order with sulfuric acid; heating the mixture at temperature of 80oC~110°C for 15~20min; adding cadmium sulfate in the mixture and heating it at temperature of 125oC~130eC for 10~15min; and cooling the mixture to temperature of 15°C~35°C
According to the invention, a cycle charge time of lead battery after completing formation process is 60~80min (Figure 3).
12V-lead battery using solid electrolyte of the invention is allowed to be discharged to low voltage of 4.5-5V. Though it is discharged to low voltage, the battery capacity is still capable of being regenerated.
Self-discharge rates per a month of lead batteries using above mentioned examples of solid electrolyte of the invention are 0.8-1% at 60°C of temperature and 80% of relative humidity (Table 1).
Figure imgf000006_0001
Table 1 Lead battery using solid electrolyte of the invention has advantages of high capacity, short charge time and allowance of complete discharge, etc. It is more advantageous that the lead battery using solid electrolyte of the invention can be sealed since complete charge voltage for the solid electrolyte of the invention is lower than gas deflation voltage of the same.
While the invention has been described with particular examples to certain embodiments of the invention, it will be understood that changes and modifications may be made by those skilled in the art within the scope and spirit of the present invention as defined in the following claims.

Claims

Claims:
1. Solid electrolyte consisting of calcium sulfate, sulfuric acid and stabilizer.
2. Solid electrolyte according to claim 1, wherein content of calcium sulfate is 75-86%.
3. Solid electrolyte according to claim 1, wherein content of sulfuric acid is 9-12 wt%.
4. Solid according to claim 1, wherein stabilizer consists of more than two metals, metallic oxides and metallic salts and its content is 5-16%.
5. Formation charge of lead battery using solid electrolyte according to claim 1.
6. Formation charge of lead battery according to claim 5, which is done with current intensity equal to 1/12-1/14 of battery capacity for 12-14hours.
PCT/KP2013/000030 2012-11-17 2013-01-14 Solid electrolyte and formation of lead battery using it WO2014077420A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13855232.8A EP2951878A4 (en) 2012-11-17 2013-01-14 Solid electrolyte and formation of lead battery using it

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KP201210003352 2012-11-17
KP335212 2012-11-17

Publications (1)

Publication Number Publication Date
WO2014077420A1 true WO2014077420A1 (en) 2014-05-22

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Country Status (2)

Country Link
EP (1) EP2951878A4 (en)
WO (1) WO2014077420A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111525126A (en) * 2020-03-31 2020-08-11 河南超威正效电源有限公司 Positive lead paste for high-binding-force screen punching plate grid and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB332660A (en) * 1926-11-06 1930-07-31 Moritz Kugel Method of producing and maintaining constant the necessary supply of phosphoric acidin the electrolyte of lead accumulators
US5664321A (en) * 1995-04-08 1997-09-09 Compagnie Europeenne D'accumulateurs Process for the production of a lead accumulator
JP2006172937A (en) * 2004-12-16 2006-06-29 Zaisei Tomoda Solid electrolyte for lead-acid battery, its manufacturing method and lead-acid battery
US20070202414A1 (en) * 2006-02-24 2007-08-30 Ngk Insulators, Ltd. All-solid-state battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5000799B2 (en) * 1999-12-24 2012-08-15 古河電池株式会社 Lead acid battery
JP3957965B2 (en) * 2000-10-30 2007-08-15 古河電池株式会社 Sealed lead acid battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB332660A (en) * 1926-11-06 1930-07-31 Moritz Kugel Method of producing and maintaining constant the necessary supply of phosphoric acidin the electrolyte of lead accumulators
US5664321A (en) * 1995-04-08 1997-09-09 Compagnie Europeenne D'accumulateurs Process for the production of a lead accumulator
JP2006172937A (en) * 2004-12-16 2006-06-29 Zaisei Tomoda Solid electrolyte for lead-acid battery, its manufacturing method and lead-acid battery
US20070202414A1 (en) * 2006-02-24 2007-08-30 Ngk Insulators, Ltd. All-solid-state battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2951878A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111525126A (en) * 2020-03-31 2020-08-11 河南超威正效电源有限公司 Positive lead paste for high-binding-force screen punching plate grid and preparation method and application thereof
CN111525126B (en) * 2020-03-31 2022-11-04 河南超威正效电源有限公司 Positive lead paste for high-binding-force screen punching plate grid and preparation method and application thereof

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EP2951878A4 (en) 2016-08-17

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