CN114204025A - Conductive agent in active substance of composite carbon paste extrusion type positive plate and preparation method of positive plate - Google Patents
Conductive agent in active substance of composite carbon paste extrusion type positive plate and preparation method of positive plate Download PDFInfo
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- CN114204025A CN114204025A CN202111392567.4A CN202111392567A CN114204025A CN 114204025 A CN114204025 A CN 114204025A CN 202111392567 A CN202111392567 A CN 202111392567A CN 114204025 A CN114204025 A CN 114204025A
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- China
- Prior art keywords
- positive plate
- composite carbon
- carbon paste
- conductive agent
- paste
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 239000013543 active substance Substances 0.000 title claims abstract description 24
- 239000006258 conductive agent Substances 0.000 title claims abstract description 18
- 238000001125 extrusion Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000006230 acetylene black Substances 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 239000011505 plaster Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 21
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 10
- 230000010287 polarization Effects 0.000 description 7
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/20—Processes of manufacture of pasted electrodes
-
- 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
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a conductive agent in a composite carbon paste-extruding type positive plate active substance and a preparation method of a positive plate, belonging to the technical field of power lead-acid storage batteries. The conductive agent in the composite carbon paste extrusion type positive plate active substance comprises one or two of the following raw materials in parts by mass, 8-10 parts of acetylene black and 1-2 parts of graphite. The conductive agent in the active substance of the composite carbon paste extrusion type positive plate further comprises a sodium carboxymethylcellulose assistant with the content of 1-2 parts by mass. The conductive agent in the active substance of the composite carbon paste-extruded positive plate has excellent conductivity and improves the charge acceptance of the plate; meanwhile, the invention provides a simple and convenient preparation method of the positive electrode plate.
Description
Technical Field
The invention relates to a conductive agent in a composite carbon paste-extruding type positive plate active substance and a preparation method of a positive plate, belonging to the technical field of power lead-acid storage batteries.
Background
The power type lead-acid storage battery has many advantages and characteristics, including good stability, low cost, long service life of the battery, and the like. Compared with the early dry powder type production mode, the paste squeezing type pole plate can form a good net structure inside, and the service life of the battery is prolonged. However, because the paste-extruding type positive plate is produced by adopting a constant-pressure linkage paste-extruding mode, active substances in the tube are relatively compact after paste extrusion, and the polarization problem is easy to occur during formation of the positive plate, namely, because the porosity of the active substances of the positive plate is low and the relative porosity is small, the polarization reaction of the positive plate is obvious in the initial charging stage of the battery, a good conductive network structure cannot be formed, and the formation effect of the battery is obviously influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the conductive agent in the active substance of the composite carbon paste-extruded positive plate, which has excellent conductivity and improves the charge acceptance of the plate; meanwhile, the invention provides a simple and convenient preparation method of the positive electrode plate.
The conductive agent in the composite carbon paste extrusion type positive plate active substance comprises one or two of the following raw materials in parts by mass, 8-10 parts of acetylene black and 1-2 parts of graphite.
Preferably, the conductive agent in the composite carbon paste-extruded positive plate active substance further comprises a sodium carboxymethylcellulose assistant with the content of 1-2 parts by mass. The addition of sodium carboxymethylcellulose can improve the cohesiveness of the active substance and is more favorable for prolonging the service life of the battery.
Preferably, the specific volume of the acetylene black is 30mL/g to 50mL/g, and the specific surface area of the graphite is 100m2/g～1000m2/g。
Preferably, the pretreatment process of the acetylene black is as follows: soaking acetylene black and acid in a ratio of 1:2 for 1h, and drying at 65-70 ℃ after soaking. After drying, the active substance is added into the positive plate active substance, so that the porosity of the positive plate active substance can be improved.
A preparation method of a composite carbon paste extrusion type positive pole plate comprises the following steps:
(1) adding the dried acetylene black, graphite and CMC into lead powder, stirring for 3min while adding, then adding water and acid, wherein the temperature is not more than 60 ℃ in the stirring process, the stirring time is not more than 45min, and measuring the apparent density and the paste discharge state of the lead paste after stirring is finished, wherein the lead paste is proper in hardness;
(2) the lead plaster is extruded into a plaster extruding pipe under certain pressure, and the problem of empty pipe or pipe wrinkling is not easy to occur in the plaster extruding process;
(3) and curing and drying the positive electrode plate after paste extrusion, wherein the curing temperature is 40-50 ℃, and the humidity is 70-90%. The drying time is 45-55h, the drying temperature is 55-65 ℃, the humidity is 20-40%, and the drying time is 24-30 h.
Compared with carbon black, the acetylene black has the advantages of light weight, small specific gravity, strong adsorption and more ideal conductivity, and not only can enhance the conductivity of the polar plate, but also can improve the charge acceptance of the battery.
After the composite carbon is used for producing the paste-extruding type positive plate, the multi-dimensional conductivity of the positive plate can be improved, the conductive framework system of the active substance in the positive plate is more compact, the polar plate formation effect can be effectively improved due to the high porosity and conductivity in the positive plate, the conversion rate of the active substance is improved, the effective formation is realized, the capacity of the battery is improved, and the service life of the battery is prolonged.
Compared with the prior art, the invention has the following beneficial effects:
(1) the addition of the acetylene black and the graphite improves the conductivity of the active material of the polar plate, effectively avoids the polarization problem of the battery in the charging process and improves the charge acceptance of the polar plate;
(2) the addition of the composite carbon improves the charging effect of the battery and the conversion efficiency of the polar plate, and realizes complete formation within effective time;
(3) the addition of the composite carbon forms a good conductive framework in the positive plate, so that the internal porosity of the positive plate is improved, and the binding force between active substances is enhanced.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The parts mentioned in the examples are parts by mass.
Example 1
A conductive agent in the active substance of a composite carbon paste extrusion type positive plate is a composite carbon material and comprises the following raw materials, 10 parts of acetylene black, and the apparent specific volume of the acetylene black is 50 mL/g.
Soaking acetylene black and acid in the raw materials in a mass ratio of 1:2 for 1h, and drying at 65 ℃ after soaking.
Adding the dried acetylene black, graphite and CMC into 88 parts of lead powder, stirring for 3min while adding, then adding water and acid, stirring at 55 ℃ for 40min, measuring the apparent density and the paste discharge state of the lead paste after stirring, wherein the apparent density of the lead paste is 4.2g/cm3。
And then extruding the lead paste into a paste extruding pipe under the pressure of 60kg, and curing and drying the positive electrode plate after the paste extruding is finished, wherein the curing temperature is 45 +/-5 ℃, the humidity is 70%, the drying time is 50h, the drying temperature is 60 +/-5 ℃, the humidity is 20%, and the drying time is 24 h.
The battery prepared by the method has no obvious polarization problem in the formation process, the formation time is shortened to 39 hours from the original 44 hours, the formation time is improved by 11 percent, the physicochemical indexes after formation are analyzed, the lead dioxide content is improved by 5.8 percent, the lead sulfate content is reduced by 30 percent, and the ratio of the detection holes is improved by 2 percent.
Example 2
A conductive agent in the active substance of a composite carbon paste extrusion type positive electrode plate is a composite carbon material, and comprises the following raw materials, 8 parts of acetylene black, 2 parts of graphite and 2 parts of CMC (sodium carboxymethylcellulose) auxiliary agent; the specific volume of acetylene black is 32mL/g, the specific surface area of graphite is 150m2/g。
Soaking acetylene black and acid in the raw materials in a mass ratio of 1:2 for 1h, and drying at 65 ℃ after soaking.
Adding dried acetylene black into 90 parts of lead powder, stirring while adding, stirring for 3min, adding water and acid, stirring at 55 deg.C for 35min, measuring apparent density and paste discharge state of lead paste, wherein the apparent density of lead paste is 4.15g/cm3。
And then extruding the lead paste into a paste extruding pipe under the pressure of 63kg, and curing and drying the positive electrode plate after the paste extruding is finished, wherein the curing temperature is 45 +/-5 ℃, the humidity is 80%, the drying time is 50h, the drying temperature is 60 +/-5 ℃, the humidity is 30%, and the drying time is 26 h.
The battery prepared by the method has no obvious polarization phenomenon in the formation process, the formation time is shortened to 41 hours from the original 44 hours, the formation time is improved by 6 percent, the physicochemical indexes after the formation are analyzed, the lead dioxide content is improved by 6.4 percent, the lead sulfate content is reduced by 31 percent, and the ratio of the detection holes is improved by 1.7 percent.
Example 3
A conductive agent in the active substance of the composite carbon paste-extruding type positive plate is a composite carbon material and comprises the following raw materials, 8 parts of acetylene black and 1 part of graphite. 1 part of CMC (sodium carboxymethyl cellulose) auxiliary agent; the specific volume of acetylene black is 35mL/g, the specific surface area of graphite is 750m2/g。
Soaking acetylene black and acid in the raw materials in a mass ratio of 1:2 for 1h, and drying at 65 ℃ after soaking.
Adding dried acetylene black, graphite and CMC into 90 parts of lead powder, stirring while adding for 3min, adding water and acid, stirring at 45 deg.C for 25min, measuring apparent density and paste discharge state of lead paste, wherein the apparent density of lead paste is 4.10g/cm3。
And then extruding the lead paste into a paste extruding pipe under the pressure of 65kg, and curing and drying the positive electrode plate after the paste extruding is finished, wherein the curing temperature is 45 +/-5 ℃, the humidity is 90%, the time is 55h, the drying temperature is 60 +/-5 ℃, the humidity is 40%, and the drying time is 30 h.
The battery prepared by the method has no polarization phenomenon in the formation process, the formation time is shortened to 40 hours from the original 44 hours, the formation time is improved by 9 percent, the physicochemical indexes after the formation are analyzed, the lead dioxide content is improved by 5.2 percent, the lead sulfate content is reduced by 26 percent, and the ratio of the lead dioxide to the lead sulfate is improved by 1.5 percent through a detection hole.
Comparative example 1
A conductive agent in the active substance of a composite carbon paste extrusion type positive electrode plate is a composite carbon material, and comprises the following raw materials, 8 parts of acetylene black, 2 parts of graphite and 2 parts of CMC (sodium carboxymethylcellulose) auxiliary agent; the specific volume of acetylene black is 32mL/g, the specific surface area of graphite is 150m2/g。
Adding untreated acetylene black into 90 parts of lead powder, stirring while adding for 3min, adding water and acid, stirring at 55 deg.C for 35min, measuring apparent density and paste discharge state of lead paste, wherein the apparent density of lead paste is 4.15g/cm3。
And then extruding the lead paste into a paste extruding pipe under the pressure of 63kg, and curing and drying the positive electrode plate after the paste extruding is finished, wherein the curing temperature is 45 +/-5 ℃, the humidity is 80%, the drying time is 50h, the drying temperature is 60 +/-5 ℃, the humidity is 30%, and the drying time is 26 h.
The battery prepared by the method has the advantages that the slight polarization phenomenon is discovered in the formation process, the white flower phenomenon is discovered on the surface of the positive active material when the formation time is up to 40 hours, the phenomenon is eliminated when the formation time is up to 44 hours, the physicochemical indexes after the formation are analyzed, the lead dioxide content is improved by 2.4 percent, the lead sulfate content is reduced by 10 percent, and the ratio of the detection holes is improved by 1.5 percent.
After the composite carbon is added, the conductivity and porosity of the paste-extruding type positive plate active material are obviously improved, the battery capacity is obviously improved, and the service life of the battery is more favorably prolonged.
Claims (8)
1. The conductive agent in the active substance of the composite carbon paste extrusion type positive plate is characterized in that: the material comprises, by mass, 8-10 parts of acetylene black and 1-2 parts of graphite.
2. The conductive agent in the composite carbon paste positive plate active material according to claim 1, wherein: and the sodium carboxymethyl cellulose additive accounts for 1-2 parts by mass.
3. The conductive agent in the composite carbon paste positive plate active material according to claim 1, wherein: the specific volume of acetylene black is 30 mL/g-50 mL/g, the specific surface area of graphite is 100m2/g～1000m2/g。
4. The conductive agent in the composite carbon paste positive plate active material according to claim 1, wherein: acetylene black needs to be pretreated, and the process is as follows:
soaking acetylene black and acid in a mass ratio of 1:2 for 1h, and drying at 65-70 ℃ after soaking.
5. A method for preparing a composite carbon paste anode plate according to any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) adding the dried acetylene black, graphite and sodium carboxymethylcellulose into lead powder, stirring while adding, then adding water and acid, and measuring the apparent density and the paste discharge state of the lead paste after stirring;
(2) extruding the lead plaster into an extruding tube under certain pressure;
(3) and curing and drying the positive electrode plate after the paste is extruded.
6. The method for preparing the composite carbon paste positive plate according to claim 5, wherein the method comprises the following steps: when water and acid are added, the temperature is less than or equal to 60 ℃ in the stirring process, and the stirring time is less than or equal to 45 min.
7. The method for preparing the composite carbon paste positive plate according to claim 5, wherein the method comprises the following steps: in the step (3), the curing temperature is 40-50 ℃, the humidity is 70-90%, and the time is 45-55 h.
8. The method for preparing the composite carbon paste positive plate according to claim 5, wherein the method comprises the following steps: in the step (3), the drying temperature is 55-65 ℃, the humidity is 20-40%, and the drying time is 24-30 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111392567.4A CN114204025B (en) | 2021-11-23 | Conductive agent in composite carbon paste-extrusion type positive electrode plate active material and preparation method of positive electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111392567.4A CN114204025B (en) | 2021-11-23 | Conductive agent in composite carbon paste-extrusion type positive electrode plate active material and preparation method of positive electrode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114204025A true CN114204025A (en) | 2022-03-18 |
| CN114204025B CN114204025B (en) | 2024-05-31 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185151A (en) * | 1999-12-24 | 2001-07-06 | Shin Kobe Electric Mach Co Ltd | Sealed lead acid 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 |
| CN103904331A (en) * | 2012-12-31 | 2014-07-02 | 陈荣 | Formula of additive for improving low-temperature charge property of lead-acid storage battery |
| CN108987690A (en) * | 2018-07-01 | 2018-12-11 | 深圳市今星光电源科技有限公司 | A kind of lead-acid accumulator anode diachylon |
| CN109148846A (en) * | 2018-08-07 | 2019-01-04 | 超威电源有限公司 | A kind of tubular cells anode diachylon and preparation method thereof |
| CN112886018A (en) * | 2021-03-04 | 2021-06-01 | 福州伯瑞电源科技有限公司 | Preparation method of positive lead plaster formed in lead-acid storage battery |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185151A (en) * | 1999-12-24 | 2001-07-06 | Shin Kobe Electric Mach Co Ltd | Sealed lead acid 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 |
| CN103904331A (en) * | 2012-12-31 | 2014-07-02 | 陈荣 | Formula of additive for improving low-temperature charge property of lead-acid storage battery |
| CN108987690A (en) * | 2018-07-01 | 2018-12-11 | 深圳市今星光电源科技有限公司 | A kind of lead-acid accumulator anode diachylon |
| CN109148846A (en) * | 2018-08-07 | 2019-01-04 | 超威电源有限公司 | A kind of tubular cells anode diachylon and preparation method thereof |
| CN112886018A (en) * | 2021-03-04 | 2021-06-01 | 福州伯瑞电源科技有限公司 | Preparation method of positive lead plaster formed in lead-acid storage battery |
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