CN102244300B - Lead acid battery taking graphene as additive - Google Patents

Lead acid battery taking graphene as additive Download PDF

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Publication number
CN102244300B
CN102244300B CN201110150131.4A CN201110150131A CN102244300B CN 102244300 B CN102244300 B CN 102244300B CN 201110150131 A CN201110150131 A CN 201110150131A CN 102244300 B CN102244300 B CN 102244300B
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graphene
lead
additive
acid battery
battery
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CN102244300A (en
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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 lead-acid battery technology, be specifically related to a kind of Graphene of using as the lead-acid battery of additive.
Background technology
Lead-acid battery has had the history of 130 years, has dependable performance, and mature production technology, compared with Ni-MH battery and lithium battery low cost and other advantages.The current electric bicycle overwhelming majority adopts sealing-type lead-acid battery.Sealing-type lead-acid battery is that positive and negative pole plate interfolded is arranged in battery case, between positive and negative pole plate, with insulating barrier, isolates, and in electrolyte is filled with battery case, the lead on electrolyte and positive and negative pole plate carries out chemical reaction.When battery charges, the lead becoming on the positive and negative two-plate of lead sulfate is discharged into the sulfuric acid composition being fixed therein in electrolyte, becomes respectively lead and lead oxide, and the sulfuric acid concentration in electrolyte is constantly increased, and voltage rises, savings energy; During electric discharge, lead oxide in positive plate and the lead on negative plate and the sulfuric acid in electrolyte react and become lead sulfate, sulfuric acid concentration in electrolyte is constantly reduced, voltage drop, energy is reduced, battery is externally exported energy, therefore the cycle charge-discharge of battery is the process that electric energy and chemical energy are constantly changed, finally realizes storage and the release of energy.For improving the capacitance of storage of lead-acid battery, it is coarse and with the surface of grid that all make on two surfaces of common positive and negative pole plate, makes pole plate in minimum volume, store more lead.But lead-acid battery, after repeatedly discharging and recharging, inevitably makes part lead powder be adsorbed on the insulating barrier between positive and negative pole plate, its energy storage is reduced, battery is short, and lead-acid battery to discharge and recharge the time slow.
Summary of the invention
The present invention needs technical solution problem to be 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 be filled with the electrolyte in housing, it is characterized in that: on described anode plate grid, apply anode diachylon, by solidifying, be dried, changing into, make; On described negative electrode grid, apply cathode lead plaster, by solidifying, be dried, changing into, make; Described anode diachylon or cathode lead plaster or both all use Graphene as additive.
The content of Graphene in described positive and negative pole lead paste, calculates according to percentage by weight, and the quality of the Graphene adding in anode diachylon is active material 0.02~3%, and the quality of the Graphene adding in cathode lead plaster is active material 0.02~2%.
Described electrolyte consists of sulphur aqueous acid.
Described dividing plate consists of ultra-fine fibre glass.
Described Graphene consists of the former molecular nanoscale twins of monolayer carbon, its thickness in 0.34 nanometer between 10 nanometers.
The nanoscale twins that described Graphene is comprised of multilayer carbon atom forms, its thickness in 0.34 nanometer between 10 nanometers.
Beneficial effect of the present invention: the present invention adds after grapheme material in pole plate, due to the excellent conduction of grapheme material, heat conductivility and two-dimension plane structure, in addition, just can in positive/negative plate, set up effective conductive network seldom time, greatly improve the especially electron conduction of active material in grid lattice of active material in Polar plate matrix, thereby improved charging rate and the velocity of discharge of lead-acid battery; Due to the raising of active material electronic conductivity in grid lattice, the electrochemical polarization that has reduced the contact resistance between active material particle and brought, has improved the utilance of active material, so the capacity of lead-acid battery is greatly improved.Simultaneously due to Graphene self structure intensity and network connection thereof, the intensity of battery pole plates is greatly improved, avoided the softening and shedding of lead-acid battery plate active material 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 object 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 be filled with the electrolyte in housing, on anode plate grid, apply anode diachylon, by solidifying, be dried, changing into, make; On negative electrode grid, apply cathode lead plaster, by solidifying, be dried, changing into, make; Anode diachylon and cathode lead plaster are used Graphene as additive.
The content of Graphene in positive and negative pole lead paste, according to percentage by weight, calculate, the quality of the Graphene adding in anode diachylon is 1% of active material, the quality of the Graphene adding in cathode lead plaster is 0.8% of active material, electrolyte consists of sulphur aqueous acid, and dividing plate consists of ultra-fine fibre glass; Graphene consists of the former molecular nanoscale twins of monolayer carbon, and its thickness is in 0.6 nanometer.
As, 12Ah lead acid accumulator plate railings of anode and cathode adds Graphene additive and do not add pole plate that Graphene additive makes under other process conditions do not become situation in lead plaster, be assembled into 12V-12Ah storage battery and carry out contrast test:
The test of 12V-12Ah battery capacity:
Volume test after lead accumulator full charge, is that 6.0A constant-current discharge to cell voltage till 10.5V with 2 hour rates with national standard.
The battery discharge time that does not add Graphene additive emits 13.2Ah capacitance for 132 minutes;
The battery discharge time that adds Graphene additive emits 15.5Ah capacitance for 155 minutes.
Both improve 21% at more relative capacitance.
The test of 12V-12Ah accumulator cell charging and discharging cycle life:
It is that 6.0A is discharged to 10.5V as a circulation to take 2 hour rates after 14.8V that storage battery adopts current limliting constant voltage charge;
The accumulator cell charging and discharging cycle life that does not add Graphene additive is 276 times;
The accumulator cell charging and discharging cycle life that adds 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 in above-described embodiment and specification, describes 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 (2)

1. a Graphene is as the lead-acid battery of additive, comprise battery container, be positioned at the plate railings of anode and cathode of battery container, dividing plate between plate railings of anode and cathode and be filled with the electrolyte in housing, on described anode plate grid, apply anode diachylon, by solidifying, dry, change into and make, on described negative electrode grid, apply cathode lead plaster, by solidifying, dry, change into and make, it is characterized in that: described anode diachylon is used Graphene as additive, the content of Graphene in described anode diachylon, according to percentage by weight, calculate, the quality of the Graphene adding in anode diachylon is 0.02~3% of active material.
2. Graphene according to claim 1 is as the lead-acid battery of additive, it is characterized in that: described anode diachylon and cathode lead plaster are used Graphene as additive, the content of Graphene in described positive and negative pole lead paste, according to percentage by weight, calculate, the quality of the Graphene adding in anode diachylon is 0.02~3% of active material, and the quality of the Graphene adding in cathode lead plaster is active material 0.02~2%.
CN201110150131.4A 2011-06-03 2011-06-03 Lead acid battery taking graphene as additive Active CN102244300B (en)

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CN104183852A (en) * 2014-08-14 2014-12-03 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
TWI583043B (en) * 2014-03-31 2017-05-11 長興材料工業股份有限公司 Electrolyte composition
WO2017151842A1 (en) * 2016-03-04 2017-09-08 Hiroyuki Fukushima Graphene-based coating on lead grid for lead-acid batteries

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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
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
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
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
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
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
CN109461975B (en) * 2018-09-27 2020-12-22 泉州市凯鹰电源电器有限公司 Graphene lead-carbon power battery and manufacturing method thereof
US20200266498A1 (en) * 2019-02-19 2020-08-20 Neweem Ltd. Co. Lead-acid battery restoration agents containing graphene materials
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
CN111146419B (en) * 2019-12-26 2023-03-17 上海大学 Method for manufacturing long-life lead-acid battery cathode by using trace graphene oxide sheet
CN112510182B (en) * 2020-12-08 2022-03-11 广东奥克莱集团有限公司 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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TWI583043B (en) * 2014-03-31 2017-05-11 長興材料工業股份有限公司 Electrolyte composition
CN104183852A (en) * 2014-08-14 2014-12-03 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
WO2017151842A1 (en) * 2016-03-04 2017-09-08 Hiroyuki Fukushima Graphene-based coating on lead grid for lead-acid batteries

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