CN105449211A - Storage battery electrode plate with carbon fiber membrane colloid laminated on surface layer and production and preparation method of storage battery electrode plate - Google Patents
Storage battery electrode plate with carbon fiber membrane colloid laminated on surface layer and production and preparation method of storage battery electrode plate Download PDFInfo
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- CN105449211A CN105449211A CN201510872089.5A CN201510872089A CN105449211A CN 105449211 A CN105449211 A CN 105449211A CN 201510872089 A CN201510872089 A CN 201510872089A CN 105449211 A CN105449211 A CN 105449211A
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- carbon
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- fiber film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a storage battery electrode plate with carbon fiber membrane colloid laminated on a surface layer and a preparation method. A positive electrode plate comprises a substrate and the surface layer, wherein the surface layer is formed in a laminating manner and mainly comprises the following components in percentage by mass: 95%-98% of lead (Pb), 0.06%-0.15% of calcium (CA), 0.03%-0.1% of stannum (Sn) and 1%-5% of a carbon fiber; and a carbon fiber membrane is prepared from the following components by mass fraction: 52%-67% of carbon (C), 12%-22% of graphene, 8%-21% of a PTFE binder and the balance being inevitable impurities. The electrode plate disclosed by the invention has relatively high heavy current discharge performance and relatively high hydrogen-evolution and oxygen-evolution over-potential, so that a storage battery electrolyte is relatively stable and free of maintenance.
Description
Technical field
The invention belongs to Lead-acid Battery Technology field, particularly relate to lead carbon battery technology.
Background technology
Lead-acid battery is as the power resources of new energy electric motor vehicle, the charge-discharge performance excellent because of it and long-life are subject to increasing application, at present, in lead-acid battery electrode plate, introduce activated carbon composition thus the characteristic of formation super capacitor, the performance of lead carbon battery can be improved greatly.At present, the skewness of traditional plumbous carbon battery material with carbon element, will facilitate negative pole state of cure (vulcanization) uneven, and shortcoming is that Ohmic resistance is large, gassing rate is high, and battery percentage of water loss increases.During ring, the corrosion rate of grid is larger, and along with the later stage of circulating battery, battery capacity can obviously decline.
Summary of the invention
Goal of the invention: for above-mentioned existing Problems existing and deficiency, the object of this invention is to provide a kind of top layer and roll carbon-fiber film colloid storage battery pole plate and preparation method thereof, the pole plate prepared by the method has excellent corrosion resistance and large current discharging capability, and liberation of hydrogen overpotential for oxygen evolution when discharge and recharge is higher, improve the deep-circulating performance of grid, make battery liquid more stable, avoid safeguarding.
Technical scheme: for achieving the above object, the present invention is by the following technical solutions: carbon-fiber film colloid storage battery pole plate is rolled on a kind of top layer, described pole plate comprises matrix and top layer, described top layer is shaping at matrix surface by the mode rolling adhesion, the component of described top layer mainly containing following mass percent:
Plumbous Pb:95 ~ 98%
Calcium Ca:0.06 ~ 0.15%;
Tin Sn:0.03 ~ 0.1%;
Carbon-fiber film: 1 ~ 5%;
Wherein carbon-fiber film contains the component of following mass fraction: carbon C:52 ~ 67%, Graphene: 12 ~ 22%, PTFE adhesive 8 ~ 21%; And the inevitable impurity of surplus.
As preferably, described matrix is the grid after plumbous, lead alloy or coating lead plaster.
As preferably, the thickness on described top layer is 0.01 ~ 0.035mm.
As preferably, described method for preparation of active carbon is as follows: add in strong acid solution in the mixed liquor that alcohols and organo-bismuth complex obtain, be then immersed in mixed liquor by active carbon, and react more than 2h at the temperature of 90 ~ 120 DEG C, eventually pass filtration drying.
Present invention also offers the preparation method rolling carbon-fiber film colloid storage battery pole plate in a kind of top layer to comprise the following steps:
(1) potassium sulfate of the tetrafluoroethene of the preparation of adhesive: in deionized water, add: 30 ~ 80g/L, the poly-propane of 8 ~ 20g/L, 5 ~ 40g/L, 1 ~ 5g/L silicon dioxide, and stirring and dissolving mixes;
(2) with metallic lead or lead alloy for grid matrix, and coating is containing the lead plaster of active material, is then cured under high humidity high temperature, adopts fine balance hydraulic press to make surperficial Formation Depth be the roughness of 0.02 ~ 0.04mm in solidification process;
(3) carbon-fiber film preparation: 100 parts of active carbons, 4 ~ 20 parts of Graphenes, the magnesium oxide of 15 ~ 30 parts mixs and grinds even;
(4) adhesive that the matrix obtained in step (2) is obtained by spray gun even application step (1), then the carbon-fiber film that step (3) obtains is coated in adhesive top layer, and then by equilibrium liquid press roller-compaction, finally dry more than 24h at the temperature of 60 ± 5 DEG C.
Further improvement, the concentration also adding 5 ~ 15 parts in step (3) is the sulfuric acid of 45%, simultaneously in step (4), carbon-fiber film is coated in adhesive top layer and after roller-compaction, need be also 98 ~ 99% in humidity, temperature be solidify under the condition of 75 ± 5 DEG C.
Beneficial effect: compared with prior art, the present invention rolls carbon fiber rete by top layer, has excellent corrosion resistance and large current discharging capability, and liberation of hydrogen overpotential for oxygen evolution when discharge and recharge is higher, improves the deep-circulating performance of grid; And active carbon carries out modification improves the hydrophily of active carbon and load to suppress the organo-bismuth of evolving hydrogen reaction, improve compactness and the charging performance of the active lead plaster of lead carbon battery, reduce the impedance of lead plaster, avoid coming off of active carbon in charge and discharge process, substantially increase the cycle life of lead carbon battery.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
First carry out activated carbon modified: first in the lactic acid aqueous solution of 50g/L, add the inorganic bismuth salt of the bismuth nitrate of the strong affinity of 15g/L, and to be obtained the solution of organo-bismuth complex by de-Bronsted acid alkali reaction with Carboxylic acid ligand.Then be the methyl alcohol adding 30KG in the 40KG nitric acid of 35.5% in concentration, and the complex of the organo-bismuth of 15KG stir and obtain modified solution, control temperature is at 90 ~ 120 DEG C, the active carbon dropping into modified solution weight 100KG soaks reaction more than 2h, then carries out vacuum filtration, drying obtains modified activated carbon.Through detecting, the specific area of modified active carbon is 3852m
2/ g, pore capacities is 1.512cm
3/ g, particle diameter D50 are 15.3 μm, and conductance is 0.37S/cm.And active carbon specific area is before modified 1400m2/g, pore capacities is 0.7cm3/g, and particle diameter D50 is 15.2 μm.By the active carbon that strong acid is modified, there is more excellent hydrophily, when the part as lead plaster and other active material can more combine closely, avoid the carbon dust after heavy-current discharge to peel off and dry linting phenomenon, the impedance reducing pole plate improves the utilance of active material.
Embodiment 1
The present embodiment, to apply the lead alloy of lead plaster for matrix, after application, its surface fine balance hydraulic press being pressed into the uneven shape of 0.03mm, sprays one deck PTFE adhesive with spray gun.
Concrete PTFE adhesive parameter is as follows: the potassium sulfate of the tetrafluoroethene of 40g/L, the poly-propane of 12g/L, 13g/L, the mixed dissolution of 1.8g/L silicon dioxide completely after, under well-beaten condition, distance pole plate 10MM place, sprays 3 ~ 10 microns.
Carbon-fiber film parameter is modified activated carbon 50g, Graphene: 2g. magnesium oxide 12g is mixed, grinding evenly, be coated on PTFE adhesive pole plate, after fine balance hydraulic press rolls, 60 degree of oven dry, this top layer main component is plumbous, and containing about 12% metal carbon, the fiber of 0.8% and the organic substance of trace.
Embodiment 2
The present embodiment, to apply the lead alloy of lead plaster for matrix, after application, its surface fine balance hydraulic press being pressed into the uneven shape of 0.04mm, sprays one deck PTFE adhesive with spray gun.
Concrete PTFE adhesive parameter is as follows: the potassium sulfate of the tetrafluoroethene of 40g/L, the poly-propane of 12g/L, 13g/L, the mixed dissolution of 1.8g/L silicon dioxide completely after, under well-beaten condition, distance pole plate 10MM place, sprays 3 ~ 10 microns.
Carbon-fiber film parameter is modified activated carbon 50g, Graphene: 6g. magnesium oxide 10g is mixed, grinding evenly, be coated on PTFE adhesive pole plate, after fine balance hydraulic press rolls, 60 degree of oven dry, this top layer main component is plumbous, and containing about 11% metal carbon, the fiber of 0.8% and the organic substance of trace.
Claims (6)
1. a carbon-fiber film colloid storage battery pole plate is rolled on top layer, it is characterized in that: described pole plate comprises matrix and top layer, and described top layer is shaping at matrix surface by the mode rolling adhesion, the component of described top layer mainly containing following mass percent:
Plumbous Pb:95 ~ 98%
Calcium Ca:0.06 ~ 0.15%;
Tin Sn:0.03 ~ 0.1%;
Carbon-fiber film: 1 ~ 5%;
Wherein carbon-fiber film contains the component of following mass fraction: carbon C:52 ~ 67%, Graphene: 12 ~ 22%, PTFE adhesive 8 ~ 21%; And the inevitable impurity of surplus.
2. carbon-fiber film colloid storage battery pole plate is rolled on top layer according to claim 1, it is characterized in that: described matrix is the grid after lead, lead alloy or coating lead plaster.
3. carbon-fiber film colloid storage battery pole plate is rolled on top layer according to claim 1, it is characterized in that: the thickness on described top layer is 0.01 ~ 0.035mm.
4. carbon-fiber film colloid storage battery pole plate is rolled on top layer according to claim 1, it is characterized in that: described method for preparation of active carbon is as follows: add in the mixed liquor that alcohols and organo-bismuth complex obtain in strong acid solution, then active carbon is immersed in mixed liquor, and more than 2h is reacted at the temperature of 90 ~ 120 DEG C, eventually pass filtration drying.
5. a preparation method for carbon-fiber film colloid storage battery pole plate is rolled on the arbitrary described top layer of Claims 1 to 4, it is characterized in that comprising the following steps:
(1) potassium sulfate of the tetrafluoroethene of the preparation of adhesive: in deionized water, add: 30 ~ 80g/L, the poly-propane of 8 ~ 20g/L, 5 ~ 40g/L, 1 ~ 5g/L silicon dioxide, and stirring and dissolving mixes;
(2) with metallic lead or lead alloy for grid matrix, and coating is containing the lead plaster of active material, is then cured under high humidity high temperature, adopts fine balance hydraulic press to make surperficial Formation Depth be the roughness of 0.02 ~ 0.04mm in solidification process;
(3) carbon-fiber film preparation: 100 parts of active carbons, 4 ~ 20 parts of Graphenes, the magnesium oxide of 15 ~ 30 parts mixs and grinds even;
(4) adhesive that the matrix obtained in step (2) is obtained by spray gun even application step (1), then the carbon-fiber film that step (3) obtains is coated in adhesive top layer, and then by equilibrium liquid press roller-compaction, finally dry more than 24h at the temperature of 60 ± 5 DEG C.
6. the preparation method of carbon-fiber film colloid storage battery pole plate is rolled on top layer according to claim 5, it is characterized in that: the concentration also adding 5 ~ 15 parts in step (3) is the sulfuric acid of 45%, simultaneously in step (4), carbon-fiber film is coated in adhesive top layer and after roller-compaction, need be also 98 ~ 99% in humidity, temperature be solidify under the condition of 75 ± 5 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872089.5A CN105449211B (en) | 2015-12-03 | 2015-12-03 | Carbon-fiber film colloid storage battery pole plate and its preparation method are rolled in a kind of surface layer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872089.5A CN105449211B (en) | 2015-12-03 | 2015-12-03 | Carbon-fiber film colloid storage battery pole plate and its preparation method are rolled in a kind of surface layer |
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| CN105449211A true CN105449211A (en) | 2016-03-30 |
| CN105449211B CN105449211B (en) | 2018-12-07 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008047452A (en) * | 2006-08-18 | 2008-02-28 | Shin Kobe Electric Mach Co Ltd | Paste type electrode plate and its manufacturing method |
| CN201732832U (en) * | 2009-11-04 | 2011-02-02 | 苏州大学 | Lead-acid storage battery positive plate with long service life |
| CN102484286A (en) * | 2009-10-26 | 2012-05-30 | 株式会社杰士汤浅国际 | Lead acid storage battery |
| CN102931379A (en) * | 2012-10-31 | 2013-02-13 | 苏州大学 | Enhanced positive plate of power lead-acid storage battery |
| CN103022427A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing positive pole plate for lead-acid storage battery |
| CN203456543U (en) * | 2013-07-15 | 2014-02-26 | 新乡学院 | Reinforced positive plate of power lead-acid storage battery |
-
2015
- 2015-12-03 CN CN201510872089.5A patent/CN105449211B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008047452A (en) * | 2006-08-18 | 2008-02-28 | Shin Kobe Electric Mach Co Ltd | Paste type electrode plate and its manufacturing method |
| CN102484286A (en) * | 2009-10-26 | 2012-05-30 | 株式会社杰士汤浅国际 | Lead acid storage battery |
| CN201732832U (en) * | 2009-11-04 | 2011-02-02 | 苏州大学 | Lead-acid storage battery positive plate with long service life |
| CN102931379A (en) * | 2012-10-31 | 2013-02-13 | 苏州大学 | Enhanced positive plate of power lead-acid storage battery |
| CN103022427A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing positive pole plate for lead-acid storage battery |
| CN203456543U (en) * | 2013-07-15 | 2014-02-26 | 新乡学院 | Reinforced positive plate of power lead-acid storage battery |
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| CN105449211B (en) | 2018-12-07 |
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