CN102244300A - Lead acid battery taking graphene as additive - Google Patents

Lead acid battery taking graphene as additive Download PDF

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Publication number
CN102244300A
CN102244300A CN2011101501314A CN201110150131A CN102244300A CN 102244300 A CN102244300 A CN 102244300A CN 2011101501314 A CN2011101501314 A CN 2011101501314A CN 201110150131 A CN201110150131 A CN 201110150131A CN 102244300 A CN102244300 A CN 102244300A
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China
Prior art keywords
graphene
lead
additive
acid battery
battery
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CN2011101501314A
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CN102244300B (en
Inventor
黄建平
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Huayu New Energy Technology Co Ltd
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JIESHOU HUAYU POWER SUPPLY CO Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a lead acid battery taking graphene as an additive, and relates to a lead acid battery technology. The lead acid battery comprises a battery shell, a positive plate grid, a negative plate grid, a partition board and electrolyte, wherein the positive and negative plate grids are positioned in the battery shell; the partition board is positioned between the positive and negative plate grids; and the electrolyte is filled into the shell. The lead acid battery is characterized in that: the positive plate grid is manufactured by coating cathode lead paste and performing curing, drying and formation; the negative plate grid is manufactured by coating anode lead paste and performing the curing, the drying and the formation; and the cathode lead paste or the anode lead paste or both take the graphene as the additive. The lead acid battery provided by the invention takes the graphene material as the additive, can be rapidly charged and discharged, and simultaneously has high capacity and relatively longer charging and discharging circulation service life.

Description

Graphene is as the lead-acid battery of additive
Technical field
The present invention relates to the lead-acid battery technology, be specifically related to a kind of with the lead-acid battery of Graphene as additive.
Background technology
Lead-acid battery has had the history in 130 years, has dependable performance, and mature production technology is than Ni-MH battery and lithium battery low cost and other advantages.The present electric bicycle overwhelming majority adopts the sealing-type lead-acid battery.The sealing-type lead-acid battery is that positive and negative pole plate interfolded is arranged in the battery case, isolates with insulating barrier between the positive and negative pole plate, and in electrolyte charged into battery case, the lead on electrolyte and the positive and negative pole plate carried out chemical reaction.When battery charge, the lead that becomes on the positive and negative two-plate of lead sulfate is discharged into the sulfuric acid composition that is fixed therein in the electrolyte, becomes lead and lead oxide respectively, and the sulfuric acid concentration in the electrolyte is constantly increased, and voltage rises, the savings energy; During discharge, lead oxide in the positive plate and the lead on the negative plate and the sulfuric acid in the electrolyte react and become lead sulfate, sulfuric acid concentration in the electrolyte is constantly reduced, voltage descends, make energy reduce, battery is externally exported energy, so the cycle charge-discharge of battery is the process that electric energy and chemical energy are constantly changed, finally realizes the storage and the release of energy.For improving the capacitance of storage of lead-acid battery, surface coarse and the band grid is all made on two surfaces of common positive and negative pole plate, makes pole plate store more lead in the volume of minimum.But lead-acid battery is after repeatedly discharging and recharging, and the part lead powder is adsorbed on the insulating barrier between the positive and negative pole plate, and its energy storage is reduced, and battery is short useful life, and the time that discharges and recharges of lead-acid battery is slow.
Summary of the invention
The present invention needs the technical solution problem to provide a kind ofly can carry out fast charging and discharging, have high power capacity, long-life Graphene is as the lead-acid battery of additive.
Graphene is as the lead-acid battery of additive, comprise battery container, the plate railings of anode and cathode in battery container, the dividing plate between plate railings of anode and cathode and charge into electrolyte in the housing, it is characterized in that: apply anode diachylon on the described anode plate grid, by solidify, dry, change into and make; Apply cathode lead plaster on the described negative electrode grid, by solidify, dry, change into and make; Described anode diachylon or cathode lead plaster or both all use Graphene as additive.
The content of Graphene in the described positive and negative pole lead paste calculates according to percentage by weight, and the quality of the Graphene that adds in the anode diachylon is 0.02~3% of an active material, and the quality of the Graphene that adds in the cathode lead plaster is 0.02~2% of an active material.
Described electrolyte is made of the aqueous solution of sulfuric acid.
Described dividing plate is made of ultra-fine fibre glass.
The nanometer lamella that described Graphene is made up of the monolayer carbon atom constitutes, its thickness in 0.34 nanometer between 10 nanometers.
The nanometer lamella that described Graphene is made up of the multilayer carbon atom constitutes, its thickness in 0.34 nanometer between 10 nanometers.
Beneficial effect of the present invention: the present invention adds grapheme material in pole plate after, because the excellent conduction of grapheme material, heat conductivility and two-dimension plane structure, just can in positive/negative plate, set up effective conductive network in addition seldom the time, greatly improve the active material electron conduction of active material in the grid lattice especially in the Polar plate matrix, thereby improved the charging lead-acid cells speed and the velocity of discharge; Because the raising of active material electronic conductivity in the grid lattice, the electrochemical polarization that has reduced the contact resistance between the active material particle and brought has improved the utilance of active material, so the capacity of lead-acid battery is greatly improved.Simultaneously because Graphene self structure intensity and network connection thereof, the intensity of battery pole plates is greatly improved, avoided lead-acid battery plate active material softening and coming off when long-time charge and discharge cycles, so greatly improved the useful life of lead-acid battery.
Embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Graphene is as the lead-acid battery of additive, comprise battery container, the plate railings of anode and cathode in battery container, the dividing plate between plate railings of anode and cathode and charge into electrolyte in the housing, apply anode diachylon on the anode plate grid, by solidify, dry, change into and make; Apply cathode lead plaster on the negative electrode grid, by solidify, dry, change into and make; Anode diachylon and cathode lead plaster use Graphene as additive.
The content of Graphene in the positive and negative pole lead paste, calculate according to percentage by weight, the quality of the Graphene that adds in the anode diachylon is 1% of an active material, the quality of the Graphene that adds in the cathode lead plaster is 0.8% of an active material, electrolyte is made of the aqueous solution of sulfuric acid, and dividing plate is made of ultra-fine fibre glass; The nanometer lamella that Graphene is made up of the monolayer carbon atom constitutes, and its thickness is in 0.6 nanometer.
Under other process conditions do not become situation, in lead plaster, add the Graphene additive and do not add pole plate that the Graphene additive makes as, 12Ah lead acid accumulator plate railings of anode and cathode and be assembled into the 12V-12Ah storage battery and compare test:
The test of 12V-12Ah battery capacity:
Volume test with national standard behind the lead accumulator full charge, with 2 hour rates be the 6.0A constant-current discharge to cell voltage to 10.5V till.
The battery discharge time that does not add the Graphene additive was promptly emitted the 13.2Ah capacitance in 132 minutes;
The battery discharge time that adds the Graphene additive was promptly emitted the 15.5Ah capacitance in 155 minutes.
Both are capacitance raising 21% relatively relatively.
The test of 12V-12Ah accumulator cell charging and discharging cycle life:
It is that to be discharged to 10.5V be a circulation to 6.0A with 2 hour rates to the 14.8V that storage battery adopts the current limliting constant voltage charge;
The accumulator cell charging and discharging cycle life that does not add the Graphene additive is 276 times;
The accumulator cell charging and discharging cycle life that adds the Graphene additive is 540 times;
Charge and discharge circulation life improves 96% relatively.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (6)

1. Graphene is as the lead-acid battery of additive, comprise battery container, the plate railings of anode and cathode in battery container, the dividing plate between plate railings of anode and cathode and charge into electrolyte in the housing, it is characterized in that: apply anode diachylon on the described anode plate grid, by solidify, dry, change into and make; Apply cathode lead plaster on the described negative electrode grid, by solidify, dry, change into and make; Described anode diachylon or cathode lead plaster or both all use Graphene as additive.
2. Graphene according to claim 1 is as the lead-acid battery of additive, it is characterized in that: the content of Graphene in the described positive and negative pole lead paste, calculate according to percentage by weight, the quality of the Graphene that adds in the anode diachylon is 0.02~3% of an active material, and the quality of the Graphene that adds in the cathode lead plaster is 0.02~2% of an active material.
3. Graphene according to claim 1 is characterized in that as the lead-acid battery of additive: described electrolyte is made of the aqueous solution of sulfuric acid.
4. Graphene according to claim 1 is characterized in that as the lead-acid battery of additive: described dividing plate is made of ultra-fine fibre glass.
5. Graphene according to claim 1 is characterized in that as the lead-acid battery of additive: the nanometer lamella that described Graphene is made up of the monolayer carbon atom constitutes, its thickness in 0.34 nanometer between 10 nanometers.
6. Graphene according to claim 1 is characterized in that as the lead-acid battery of additive: the nanometer lamella that described Graphene is made up of the multilayer carbon atom constitutes, its thickness in 0.34 nanometer between 10 nanometers.
CN201110150131.4A 2011-06-03 2011-06-03 Lead acid battery taking graphene as additive Active CN102244300B (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544452A (en) * 2012-03-02 2012-07-04 陈振富 Maintenance-free lead acid battery electrode group and I-shaped chip-packaging process
CN102709567A (en) * 2012-06-18 2012-10-03 奇瑞汽车股份有限公司 Lead-acid cell
CN102760868A (en) * 2012-07-25 2012-10-31 哈尔滨工业大学 Superbattery polar plate containing vacuum puffed grapheme, preparation method thereof and lead acid superbattery assembled thereby
CN102760867A (en) * 2012-07-25 2012-10-31 哈尔滨工业大学 Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby
CN103367753A (en) * 2013-07-25 2013-10-23 山东大学 Lead-acid cell cathode lead-paste modified by grapheme dispersion liquid, and preparation method thereof
CN103490106A (en) * 2013-09-28 2014-01-01 德清创诺尔新材料科技有限公司 Method capable of enhancing capacity of mobile power supply
CN103633331A (en) * 2013-11-28 2014-03-12 江苏科能电源有限公司 Positive active material for lead-acid power battery and preparation method of positive active material
CN103700893A (en) * 2013-10-15 2014-04-02 双登集团股份有限公司 High temperature resisting middle-sealing battery
CN105047880A (en) * 2015-08-28 2015-11-11 天能电池集团有限公司 Lead-graphene composite material and preparation method and application thereof
CN105990579A (en) * 2016-06-17 2016-10-05 超威电源有限公司 Graphene conducting polymer lead-acid cell and preparation method thereof
CN106207101A (en) * 2016-08-03 2016-12-07 湖北润阳新能源有限公司 Lead-acid accumulator and preparation method thereof
CN107611446A (en) * 2017-09-20 2018-01-19 厦门稀土材料研究所 A kind of liberation of hydrogen inhibitor, preparation method and applications
CN107634186A (en) * 2017-08-30 2018-01-26 北京工业大学 One kind doping In2O3Lead carbon battery anode preparation method
CN108199016A (en) * 2017-12-18 2018-06-22 河北超威电源有限公司 A kind of automobile-used graphene battery of electric road
CN109037691A (en) * 2018-07-25 2018-12-18 江苏永达电源股份有限公司 A kind of battery novel anode material additive
CN109461975A (en) * 2018-09-27 2019-03-12 泉州市凯鹰电源电器有限公司 A kind of graphene lead carbon power battery and its manufacturing method
CN109888409A (en) * 2019-04-03 2019-06-14 山东星火科学技术研究院 The high-capacity lead-acid battery and its synthesis technology of a kind of graphene as additive
US10388964B2 (en) 2016-03-04 2019-08-20 Xg Sciences, Inc. Graphene-based coating on lead grid for lead-acid batteries
CN110190204A (en) * 2019-05-15 2019-08-30 佛山赛能新能源有限公司 A kind of production method of hot-resistant valve control lead-acid battery and its positive plate
CN110265663A (en) * 2019-06-25 2019-09-20 深圳中天烯源科技有限公司 Electri forklift carbene valve-regulated sealed lead-acid batteries and production technology
US10511016B2 (en) * 2016-11-30 2019-12-17 Global Graphene Group, Inc. Graphene-protected lead acid batteries
CN111509309A (en) * 2019-02-19 2020-08-07 广州纳为新材料科技有限公司 Graphene-containing lead-acid battery repairing agent and preparation method thereof
CN112510182A (en) * 2020-12-08 2021-03-16 英德奥克莱电源有限公司 Lead paste for lead-acid storage battery and lead-acid storage battery
CN112786884A (en) * 2021-01-05 2021-05-11 浙江南都电源动力股份有限公司 High-performance graphene storage battery for starting and stopping automobile
WO2021129793A1 (en) * 2019-12-26 2021-07-01 上海大学 Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes
US11225418B2 (en) 2017-10-02 2022-01-18 Cwze Power Inc. Method of preparing carbon-graphene-lead composite particles

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TWI583043B (en) * 2014-03-31 2017-05-11 長興材料工業股份有限公司 Electrolyte composition
CN104183852B (en) * 2014-08-14 2017-02-15 济南圣泉集团股份有限公司 Phenolic resin-graphite-graphene composite battery bipolar grid plate and preparation method thereof

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CN101383411A (en) * 2008-09-12 2009-03-11 浙江永达电力实业股份有限公司 Solidifying and drying process for lead-acid cell chemical polar board
CN101719563A (en) * 2009-12-11 2010-06-02 湖南大学 Novel lead carbon battery and manufacture method thereof

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CN2400909Y (en) * 1999-11-22 2000-10-11 诸殿淙 Lead-acid accumulator and series-parallel rapid converter
CN1426122A (en) * 2002-12-16 2003-06-25 武汉大学 Method for preparing lead-acid battery negative pole
CN101383411A (en) * 2008-09-12 2009-03-11 浙江永达电力实业股份有限公司 Solidifying and drying process for lead-acid cell chemical polar board
CN101719563A (en) * 2009-12-11 2010-06-02 湖南大学 Novel lead carbon battery and manufacture method thereof

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544452A (en) * 2012-03-02 2012-07-04 陈振富 Maintenance-free lead acid battery electrode group and I-shaped chip-packaging process
CN102709567A (en) * 2012-06-18 2012-10-03 奇瑞汽车股份有限公司 Lead-acid cell
CN102760867B (en) * 2012-07-25 2014-09-10 哈尔滨工业大学 Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby
CN102760868A (en) * 2012-07-25 2012-10-31 哈尔滨工业大学 Superbattery polar plate containing vacuum puffed grapheme, preparation method thereof and lead acid superbattery assembled thereby
CN102760867A (en) * 2012-07-25 2012-10-31 哈尔滨工业大学 Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby
CN103367753A (en) * 2013-07-25 2013-10-23 山东大学 Lead-acid cell cathode lead-paste modified by grapheme dispersion liquid, and preparation method thereof
CN103367753B (en) * 2013-07-25 2015-12-23 山东大学 Lead-acid battery cathode lead plaster of a kind of graphene dispersing solution modification and preparation method thereof
CN103490106A (en) * 2013-09-28 2014-01-01 德清创诺尔新材料科技有限公司 Method capable of enhancing capacity of mobile power supply
CN103490106B (en) * 2013-09-28 2015-11-18 德清创诺尔新材料科技有限公司 A kind of method strengthening portable power source capacity
CN103700893A (en) * 2013-10-15 2014-04-02 双登集团股份有限公司 High temperature resisting middle-sealing battery
CN103700893B (en) * 2013-10-15 2016-01-20 双登集团股份有限公司 High temperature resistant middle density battery
CN103633331A (en) * 2013-11-28 2014-03-12 江苏科能电源有限公司 Positive active material for lead-acid power battery and preparation method of positive active material
CN105047880A (en) * 2015-08-28 2015-11-11 天能电池集团有限公司 Lead-graphene composite material and preparation method and application thereof
US10388964B2 (en) 2016-03-04 2019-08-20 Xg Sciences, Inc. Graphene-based coating on lead grid for lead-acid batteries
CN105990579A (en) * 2016-06-17 2016-10-05 超威电源有限公司 Graphene conducting polymer lead-acid cell and preparation method thereof
CN105990579B (en) * 2016-06-17 2018-09-07 超威电源有限公司 A kind of graphene conductive polymer lead-acid battery and preparation method thereof
CN106207101A (en) * 2016-08-03 2016-12-07 湖北润阳新能源有限公司 Lead-acid accumulator and preparation method thereof
US10511016B2 (en) * 2016-11-30 2019-12-17 Global Graphene Group, Inc. Graphene-protected lead acid batteries
CN107634186A (en) * 2017-08-30 2018-01-26 北京工业大学 One kind doping In2O3Lead carbon battery anode preparation method
CN107611446A (en) * 2017-09-20 2018-01-19 厦门稀土材料研究所 A kind of liberation of hydrogen inhibitor, preparation method and applications
US11225418B2 (en) 2017-10-02 2022-01-18 Cwze Power Inc. Method of preparing carbon-graphene-lead composite particles
CN108199016A (en) * 2017-12-18 2018-06-22 河北超威电源有限公司 A kind of automobile-used graphene battery of electric road
CN109037691A (en) * 2018-07-25 2018-12-18 江苏永达电源股份有限公司 A kind of battery novel anode material additive
CN109461975A (en) * 2018-09-27 2019-03-12 泉州市凯鹰电源电器有限公司 A kind of graphene lead carbon power battery and its manufacturing method
CN111509309A (en) * 2019-02-19 2020-08-07 广州纳为新材料科技有限公司 Graphene-containing lead-acid battery repairing agent and preparation method thereof
CN111509309B (en) * 2019-02-19 2022-05-17 广州纳为新材料科技有限公司 Graphene-containing lead-acid battery repairing agent and preparation method thereof
CN109888409A (en) * 2019-04-03 2019-06-14 山东星火科学技术研究院 The high-capacity lead-acid battery and its synthesis technology of a kind of graphene as additive
CN110190204A (en) * 2019-05-15 2019-08-30 佛山赛能新能源有限公司 A kind of production method of hot-resistant valve control lead-acid battery and its positive plate
CN110265663A (en) * 2019-06-25 2019-09-20 深圳中天烯源科技有限公司 Electri forklift carbene valve-regulated sealed lead-acid batteries and production technology
WO2021129793A1 (en) * 2019-12-26 2021-07-01 上海大学 Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes
CN112510182A (en) * 2020-12-08 2021-03-16 英德奥克莱电源有限公司 Lead paste for lead-acid storage battery and lead-acid storage battery
CN112786884A (en) * 2021-01-05 2021-05-11 浙江南都电源动力股份有限公司 High-performance graphene storage battery for starting and stopping automobile

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