CN105355861A - Preparation method of surface mount lead carbon battery electrode - Google Patents
Preparation method of surface mount lead carbon battery electrode Download PDFInfo
- Publication number
- CN105355861A CN105355861A CN201510813509.2A CN201510813509A CN105355861A CN 105355861 A CN105355861 A CN 105355861A CN 201510813509 A CN201510813509 A CN 201510813509A CN 105355861 A CN105355861 A CN 105355861A
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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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
The invention discloses a preparation method of a surface mount lead carbon battery electrode. The preparation method comprises following steps: sulfuric acid is mixed with water firstly, a binder is added for uniform stirring so as to obtain a diluted solution of the binder, and an additive is added for uniform stirring; modified active carbon and lead powder are subjected to dry mixing so as to obtain lead paste; the lead paste is subjected to roller rolling forming for at least one time so as to obtain carbon cloth with a thickness ranging from 0.1 to 0.2mm, the surface of a plate electrode is coated with the carbon cloth via rolling, and the carbon cloth is subjected to high moisture high temperature curing, and is dried for more than 24h at a temperature ranging from 55 to 65 DEG C. According to the preparation method, active carbon is modified via following steps: an alcoholic compound and an organic bismuth complex are added into a strong acid solution so as to obtain a mixed solution; active carbon is immersed in the mixed solution, and reaction is carried out for more than 2h at a temperature ranging from 90 to 120 DEG C; and at last an obtained product is filtered and dried. The preparation method is simple; cost is low; and prepared lead carbon batteries possess excellent charging performance and high hydrogen evolution over-potential.
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.But it is little that existing active carbon directly joins performance boost in pole plate, needs to carry out modification to it.And the modification of active carbon is often along with active carbon powder and liquid modifying raw material mix and blend, the ultramicrofine powder with very bigger serface of lightweight due to active carbon, in mixed process, easily swim in material liquid surface, and easily reunite, and also can form dust from flying when feeding intake, bring harmful effect to operational environment.
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 preparation method of SMD lead carbon battery electrode, production process is simple, cost is low, and the lead carbon battery made has excellent charging performance and higher overpotential of hydrogen evolution.
Technical scheme: for achieving the above object, the present invention is by the following technical solutions: a kind of preparation method of SMD lead carbon battery electrode, described pole plate comprises Polar plate matrix and is covered in the active material layer on Polar plate matrix surface, and described active material layer is made up of the component of following weight fraction: 1000 parts, lead powder; 70 ~ 150 parts, water; 70 ~ 150 parts, sulfuric acid; Modified activated carbon 30 ~ 80 parts; Binding agent 20 ~ 100 parts; Additive 30 ~ 70 parts, wherein preparation method comprises the following steps:
(1) first sulfuric acid is mixed with water, then add binding agent and stir and obtain the dilution of binding agent, then add additive and stir;
(2) modified activated carbon and lead powder are carried out being dry mixed conjunction, and drop in the mixed solution of step (1), and continue to stir at the temperature of 80 ~ 90 DEG C to obtain lead plaster;
(3) then to the cylinder roller-compaction that lead plaster carries out at least one times, thus obtain the thick charcoal cloth of 0.1 ~ 0.2mm, and by the roll extrusion of charcoal cloth at polar board surface, be finally 98 ~ 99% in humidity, temperature is solidify under the condition of 75 ± 5 DEG C, finally dry more than 24h at the temperature of 60 ± 5 DEG C;
The method of modifying of described modified activated 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.
As preferably, in step (3), lead plaster is through three cylinder roller-compactions, and the thickness obtaining charcoal cloth is followed successively by 0.5 ~ 1.0mm, 0.5 ~ 0.2mm, 0.1 ~ 0.2mm.
As preferably, described binding agent is polymethacrylates, polytetrafluoroethylene or butadiene-styrene rubber.
As preferably, described organo-bismuth complex is the complex carrying out inorganic bismuth source to be obtained by reacting bismuth in lactic acid, tartaric acid or apple aqueous acid.
As preferably, described alcohols is methyl alcohol, ethanol, butynediols or glycerol.
As preferably, described strong acid is nitric acid, sulfuric acid or hydrochloric acid.
As preferably, the specific area of described active carbon is 3000 ~ 4200m2/g, and pore capacities is 1.452 ~ 1.720cm3/g, and particle diameter D50 is 15.3 ± 0.2 μm, and conductance is 0.37 ~ 0.40S/cm.
As preferably, when described pole plate is anode plate, described additive is the mixture of red lead, chopped carbon fiber, graphite and humic acid; When described pole plate is negative pole, described additive is the mixture of chopped carbon fiber, humic acid, tannin extract and barium sulfate.
Beneficial effect: compared with prior art, what the present invention innovated utilizes SMD lead plaster layer, and production cost is low; 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.
Embodiment 1
The preparation of modified activated carbon: first in the lactic acid aqueous solution of 50g/L, adds 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.
The preparation of lead plaster: the sulfuric acid adding the 14.2g/L of 10KG in 10L pure water, then drops into the polymethylacrylic acid of 5KG, forms dilution, if there is insoluble matter, can rising temperature for dissolving, and for subsequent use.Then after the lead powder of the chopped carbon fiber of the modified activated carbon of 5KG, 2KG, 1.0KG part humic acid, 2.0KG part tannin extract and 1.5KG part barium sulfate and 100KG being dry mixed, to drop in dilution and in paste mixing machine, and carry out at 80 ~ 90 DEG C of temperature and cream process, obtain lead plaster.
The lead plaster made is rolled through twin-roll three grades, obtain the charcoal cloth that thickness is 0.5 ~ 1.0mm, 0.5 ~ 0.2mm, 0.1 ~ 0.2mm successively, and through shearing, paste the outer surface of common pole plate or grid, then under the condition of high humidity high temperature, roll forming is carried out, finally dry more than 24h at the temperature of 60 ± 5 DEG C.As battery positive plate, preparation process is substantially identical, and the additive being active material of difference is different.
Embodiment 2
The preparation of modified activated carbon: first in the lactic acid aqueous solution of 50g/L, adds 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.
The preparation of lead plaster: the sulfuric acid adding the 14.2g/L of 10KG in 10L pure water, then drops into the polymethylacrylic acid (polytetrafluoroethylene also can be tried out as binding agent) of 5KG, forms dilution, if there is insoluble matter, can rising temperature for dissolving, and for subsequent use.Then after the lead powder of the chopped carbon fiber of the modified activated carbon of 5KG, 2KG, 1.5KG part humic acid, 1.5KG part tannin extract and 1KG part barium sulfate and 100KG being dry mixed, to drop in dilution and in paste mixing machine, and carry out at 80 ~ 90 DEG C of temperature and cream process, obtain lead plaster.
The lead plaster made is rolled through twin-roll three grades, obtain the charcoal cloth that thickness is 0.5 ~ 1.0mm, 0.5 ~ 0.2mm, 0.1 ~ 0.2mm successively, and through shearing, paste the outer surface of common pole plate or grid, then under the condition of high humidity high temperature, roll forming is carried out, finally dry more than 24h at the temperature of 60 ± 5 DEG C.
Innovative point of the present invention has the following aspects: (1) the present invention innovation will be rolled into rete containing the lead plaster of binding agent and roll extrusion on the surface of common pole plate or grid, the simple cost of preparation technology is low, utilize hydrophilic active carbon and lead plaster component to combine closely simultaneously, improve polar plate battery performance, (2) by alcohols and strong acid such as nitric acid, modification is carried out to activated carbon surface, its hydrophily is substantially increased at activated carbon surface bonded hydroxy, simultaneously organo-bismuth complex can provide hydroxyl and carboxyl carries out β-cyclodextrin to activated carbon surface simultaneously, hydroxyl and carboxyl all have stronger hydrophily and can form bridge chain between the two, further increase the affinity of active carbon between other components of lead plaster, thus make lead plaster inside tightr, stronger with the adhesion of grid, reduce coming off in active carbon charge and discharge process, more reduce the impedance of lead plaster, improve chemical property and the cycle life of electrode, rare earth bismuth metal itself can suppress evolving hydrogen reaction in addition, improves charge efficiency, (3) relative in prior art and cream temperature be generally less than 75 DEG C (preventing excessive water consumption), the present invention can carry out and cream and can keep appropriate water content at 80 ~ 90 DEG C, and promotion active carbon, in the hydroxyl bonding degree of lead plaster, makes lead plaster tightr, (4) modified activated carbon has high specific area and pore capacities, has effect and the electrochemical permeation performance of more forceful electric power container, finally improves the charging performance of battery, (5) active carbon is as conductive materials, improves the conductivity of electrode active material.
Claims (8)
1. a preparation method for SMD lead carbon battery electrode, is characterized in that, described pole plate comprises Polar plate matrix and is covered in the active material layer on Polar plate matrix surface, and described active material layer is made up of the component of following weight fraction: 1000 parts, lead powder; 70 ~ 150 parts, water; 70 ~ 150 parts, sulfuric acid; Modified activated carbon 30 ~ 80 parts; Binding agent 20 ~ 100 parts; Additive 30 ~ 70 parts, wherein preparation method comprises the following steps:
(1) first sulfuric acid is mixed with water, then add binding agent and stir and obtain the dilution of binding agent, then add additive and stir;
(2) modified activated carbon and lead powder are carried out being dry mixed conjunction, and drop in the mixed solution of step (1), and continue to stir at the temperature of 80 ~ 90 DEG C to obtain lead plaster;
(3) then to the cylinder roller-compaction that lead plaster carries out at least one times, thus obtain the thick charcoal cloth of 0.1 ~ 0.2mm, and by the roll extrusion of charcoal cloth at polar board surface, be finally 98 ~ 99% in humidity, temperature is solidify under the condition of 75 ± 5 DEG C, finally dry more than 24h at the temperature of 60 ± 5 DEG C;
The method of modifying of described modified activated 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.
2. the preparation method of SMD lead carbon battery electrode according to claim 1, is characterized in that: in step (3), lead plaster is through three cylinder roller-compactions, and the thickness obtaining charcoal cloth is followed successively by 0.5 ~ 1.0mm, 0.5 ~ 0.2mm, 0.1 ~ 0.2mm.
3. the preparation method of SMD lead carbon battery electrode according to claim 1, is characterized in that: described binding agent is polymethacrylates, polytetrafluoroethylene or butadiene-styrene rubber.
4. the preparation method of SMD lead carbon battery electrode according to claim 1, is characterized in that: described organo-bismuth complex is the complex carrying out inorganic bismuth source to be obtained by reacting bismuth in lactic acid, tartaric acid or apple aqueous acid.
5. the preparation method of SMD lead carbon battery electrode according to claim 1, is characterized in that: described alcohols is methyl alcohol, ethanol, butynediols or glycerol.
6. the preparation method of SMD lead carbon battery electrode according to claim 1, is characterized in that: described strong acid is nitric acid, sulfuric acid or hydrochloric acid.
7. the preparation method of SMD lead carbon battery electrode according to claim 1, it is characterized in that: the specific area of described active carbon is 3000 ~ 4200m2/g, pore capacities is 1.452 ~ 1.720cm3/g, and particle diameter D50 is 15.3 ± 0.2 μm, and conductance is 0.37 ~ 0.40S/cm.
8. the preparation method of SMD lead carbon battery electrode according to claim 1, it is characterized in that: when described pole plate is anode plate, described additive is the mixture of red lead, chopped carbon fiber, graphite and humic acid; When described pole plate is negative pole, described additive is the mixture of chopped carbon fiber, humic acid, tannin extract and barium sulfate.
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| CN201510813509.2A CN105355861B (en) | 2015-11-23 | 2015-11-23 | A kind of preparation method of patch type lead carbon battery electrode |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025388A (en) * | 2016-08-03 | 2016-10-12 | 湖北润阳新能源有限公司 | Lead-acid storage battery paste mixing formula and technology |
| CN106229468A (en) * | 2016-08-25 | 2016-12-14 | 四川荣联电子科技有限公司 | A kind of lead-acid accumulator negative pole lead paste additive |
| CN106252654A (en) * | 2016-08-25 | 2016-12-21 | 四川荣联电子科技有限公司 | The lead-acid accumulator negative pole lead paste of inhibited oxidation |
| CN106252656A (en) * | 2016-09-08 | 2016-12-21 | 双登集团股份有限公司 | Lead-acid battery negative pole active substance and cream method |
| CN107302118A (en) * | 2016-04-15 | 2017-10-27 | 北京化工大学 | A kind of lead oxide that reclaims is as the high-performance lead-acid accumulator of active material |
| CN109148844A (en) * | 2018-08-06 | 2019-01-04 | 骆驼集团蓄电池研究院有限公司 | Suitable for using lead-acid accumulator negative pole lead paste and preparation method under ultra-low temperature surroundings |
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| CN104577216A (en) * | 2014-09-28 | 2015-04-29 | 江苏欧力特能源科技有限公司 | Lead carbon energy storage battery and production method thereof |
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| JP2008047452A (en) * | 2006-08-18 | 2008-02-28 | Shin Kobe Electric Mach Co Ltd | Paste type electrode plate and its manufacturing method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107302118A (en) * | 2016-04-15 | 2017-10-27 | 北京化工大学 | A kind of lead oxide that reclaims is as the high-performance lead-acid accumulator of active material |
| CN107302118B (en) * | 2016-04-15 | 2020-03-20 | 北京化工大学 | High-performance lead-acid storage battery with recovered lead oxide as active substance |
| CN106025388A (en) * | 2016-08-03 | 2016-10-12 | 湖北润阳新能源有限公司 | Lead-acid storage battery paste mixing formula and technology |
| CN106229468A (en) * | 2016-08-25 | 2016-12-14 | 四川荣联电子科技有限公司 | A kind of lead-acid accumulator negative pole lead paste additive |
| CN106252654A (en) * | 2016-08-25 | 2016-12-21 | 四川荣联电子科技有限公司 | The lead-acid accumulator negative pole lead paste of inhibited oxidation |
| CN106229468B (en) * | 2016-08-25 | 2018-09-11 | 四川荣联电子科技有限公司 | A kind of lead-acid accumulator negative pole lead paste additive |
| CN106252654B (en) * | 2016-08-25 | 2018-09-11 | 四川荣联电子科技有限公司 | Inhibit the lead-acid accumulator negative pole lead paste of oxidation |
| CN106252656A (en) * | 2016-09-08 | 2016-12-21 | 双登集团股份有限公司 | Lead-acid battery negative pole active substance and cream method |
| CN109148844A (en) * | 2018-08-06 | 2019-01-04 | 骆驼集团蓄电池研究院有限公司 | Suitable for using lead-acid accumulator negative pole lead paste and preparation method under ultra-low temperature surroundings |
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Effective date of registration: 20211117 Address after: 225600 No.88 Bosideng Avenue, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Patentee after: JIANGSU OLITER ENERGY TECHNOLOGY Co.,Ltd. Address before: 225600 No. 8 Bosten Avenue, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Patentee before: JIANGSU HAIDESEN ENERGY Co.,Ltd. |