CN111816845A - Lead-carbon battery pole plate based on porous activated carbon material and preparation method thereof - Google Patents
Lead-carbon battery pole plate based on porous activated carbon material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 9
- 241001474374 Blennius Species 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000428 dust Substances 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000011133 lead Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000004021 humic acid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011505 plaster Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000001648 tannin Substances 0.000 claims description 6
- 235000018553 tannin Nutrition 0.000 claims description 6
- 229920001864 tannin Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 241001122767 Theaceae Species 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000035622 drinking Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000010926 waste battery Substances 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
- H01M4/14—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lead-carbon battery plate based on a porous activated carbon material, which comprises a grid and an active material coated on the grid, wherein the active material consists of the following components in percentage by weight: water: 5% -15%; sulfuric acid: 1% -20%; porous activated carbon: 1% -10%; additive: 0.1 to 5 percent; lead: and the balance, wherein the porous activated carbon material is prepared by taking seaweed leaves as a raw material, performing dust removal and drying, then performing carbonization treatment, then performing carbonate treatment, drying by distillation, washing, filtering and drying, and finally mixing the carbonized seaweed leaves with an activating agent and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere. The lead-carbon battery pole plate based on the porous activated carbon material in the embodiment of the invention adopts the seaweed leaves as the raw material to prepare the porous activated carbon, the surface area is large, the pores are developed, the distribution is uniform, and the lead-carbon battery pole plate is used as an electrode material and has high specific capacitance and excellent cycling stability.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a lead-carbon battery pole plate based on a porous activated carbon material and a preparation method thereof.
Background
At present, the electrodes of lead-acid batteries are mainly made of lead and its oxides, and the electrolyte is a sulfuric acid solution. Since 1859 the lead-acid battery invented by frant of french americans, the lead-acid battery has undergone more than 150 years of development process, the lead-acid battery has low cost, long service life and good safety performance, and the recovery utilization rate of the waste battery is as high as more than 95%, so the lead-acid battery is always the most widely used product in the battery field. However, the traditional lead-acid battery has the disadvantages of small specific power, low specific energy, short cycle life and service life, and the like.
With the rapid development of electric automobiles and electric bicycles. The novel storage battery based on the lead-carbon technology, namely the lead-carbon battery, is a novel super battery, integrates a lead-acid battery and a super capacitor, not only exerts the instant high-capacity charging advantage of the super capacitor, but also exerts the specific energy advantage of the lead-acid battery, has very good charging and discharging performance, prevents the negative sulfation phenomenon due to the addition of carbon, improves a factor of battery failure in the past, and prolongs the service life of the battery.
The current mainstream lead-carbon battery research and development scheme mainly uses active carbon, conductive graphite or acetylene black carbon material and lead to be mixed as an active substance of a negative electrode, introduces the characteristic of a super capacitor in the lead-acid battery to enhance the specific power of the lead-acid battery, and utilizes the carbon material to construct a conductive network in an electrode to relieve the sulfation problem of the negative electrode. However, the addition of the carbon material brings the following problems to the negative electrode: firstly, the difference of tap densities of the lead powder and the carbon material is large, so that the lead powder and the carbon material are difficult to uniformly mix, the stability of the negative electrode paste is influenced, the strength of a polar plate is reduced, and the circulation stability of the battery is reduced; secondly, the surface hydrogen evolution potential of the carbon material is lower than that of lead, the addition of the carbon material can increase the hydrogen evolution of the negative electrode of the battery, and excessive hydrogen evolution can cause water loss failure of the battery and influence the service life of the battery.
The activated carbon has a microporous structure with a large specific surface area, a high electric double layer capacity, but low conductivity, and is not easy to modify, so that micropores of the activated carbon are easily blocked by functional modification.
Graphite has the highest conductivity, but has a very small specific surface area, and cannot increase the electric double layer capacitance characteristics.
The acetylene black carbon has good conductivity, can increase the porosity of the polar plate, but has the defects of low specific surface area, difficult modification and the like.
Therefore, the traditional carbon materials can not effectively solve the problem of sulfation of the traditional lead-acid battery due to the characteristics of structure and property, and can not fully exert the advantages of the lead-carbon battery super battery.
Because of being limited by conditions, the built-in grid of the lead-carbon storage battery sold in the market still continues to be used for manufacturing the components of the grid of the lead-acid battery, wherein the negative grid is an important component of the lead-acid battery, and the main function of the negative grid has two functions:
1. current collection framework: the negative grid is a current collecting framework of the electrode, conducts and collects current, enables the current to be uniformly distributed and improves the utilization rate of the negative active material;
2. support carrier for negative electrode active material: the negative plate grid plays a role in supporting the negative active material through the frame and the ribs.
At present, the performance of a lead-acid battery can be greatly improved by introducing an active carbon component into a lead-acid battery pole plate to form the characteristic of a super capacitor, but the performance of the existing active carbon is not greatly improved when the active carbon is directly added into the pole plate, the active carbon needs to be modified, the modification of the active carbon is usually accompanied with the mixing and stirring of active carbon powder and a liquid modification raw material, and because the light-weight ultrafine powder with a large specific surface area of the active carbon is easy to float on the surface of the raw material liquid and easy to agglomerate in the mixing process, dust can be formed and fly, and the influence on the environment is brought.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a lead-carbon battery plate based on a porous activated carbon material and a method for preparing the same, wherein the lead-carbon battery plate has the advantages of improving the specific energy of the battery, reducing the impedance of lead paste, and avoiding the falling of activated carbon during the charging and discharging processes.
To this end, according to one aspect of the present invention, the present invention provides a lead-carbon battery plate based on a porous activated carbon material, and according to an embodiment of the present invention, the following technical solution is adopted:
a lead-carbon battery plate based on a porous activated carbon material comprises a grid and an active material coated on the grid, wherein the active material comprises the following components in percentage by weight:
water: 5% -15%;
sulfuric acid: 1% -20%;
porous activated carbon: 1% -10%;
additive: 0.1 to 5 percent;
lead: and (4) the balance.
The porous activated carbon material is prepared by taking seaweed leaves as a raw material, performing dust removal and drying, performing carbonization treatment, performing carbonate treatment, drying by distillation, washing, filtering, drying, mixing the carbonized seaweed leaves with an activating agent, and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere.
Therefore, the lead-carbon battery plate based on the porous activated carbon material in the embodiment of the invention adopts the porous activated carbon prepared from the seaweed leaves as the raw material, has large surface area, developed pores and uniform distribution, and has high specific capacitance and excellent cycle stability when being used as the electrode material.
In addition, the lead-carbon battery plate based on the porous activated carbon material, which is practical according to the invention, can also have the following additional technical characteristics:
in some embodiments of the invention, when the plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate.
In some embodiments of the invention, the specific surface area of the porous activated carbon is 4000-4500 square meters per gram, and the pore volume is 1.520-1.852 cm3(ii)/g, particle diameter of 14.5 + -0.2 μm, and conductivity of 0.39-0.41S/cm.
According to a second aspect of the present invention, the present invention also provides a method for preparing an electrode plate by using the above-mentioned lead-carbon battery electrode plate component based on a porous activated carbon material of the previous embodiment, and according to an embodiment of the present invention, the method further comprises:
(1) preparing porous activated carbon: based on seaweed leaves as raw materials, performing dust removal and drying, then performing carbonization treatment, then performing carbonate treatment, drying by distillation, washing, filtering and drying, and finally mixing the carbonized seaweed leaves with an activating agent and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere to prepare the seaweed tea;
(2) preparing lead plaster: grinding lead into lead powder, sequentially adding water and sulfuric acid with the mass concentration of 33.5% into the lead powder, and uniformly stirring; adding the additive and the porous active carbon again, and preparing mud-shaped lead plaster; when the polar plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate;
(3) coating lead plaster on a grid, and drying at the temperature of 150 ℃;
(4) curing and drying at 75 ℃.
In some embodiments of the present invention, the porous activated carbon in step (1) is prepared as follows:
(1) pretreatment: washing the seaweed leaves, removing dust, drying and crushing to obtain a seaweed leaf powder raw material;
(2) carbonizing treatment: preparing alkali metal carbonate or bicarbonate into a solution with the concentration of 0.5-5 mol/L, heating the seaweed leaf powder raw material to a calcination temperature, carrying out heat preservation calcination, cooling to room temperature to obtain a calcined product, mixing the calcined product and the alkali metal carbonate/bicarbonate according to the mass ratio of 1-5 at room temperature, stirring for 1-15 h, and evaporating water to obtain a seaweed leaf carbonized product;
(3) high-temperature activation: mixing the seaweed leaf carbonized product with an activating agent, carrying out high-temperature activation treatment for 0.5-10 h at the constant temperature of 200-1500 ℃, cooling, washing and filtering by using 0.01-2 mol/L hydrochloric acid and distilled water samples to be neutral, and finally drying in a vacuum drying oven at the temperature of 50-150 ℃ to constant weight to obtain the porous activated carbon.
In some embodiments of the invention, the pre-treatment comprises the steps of:
(1) treating seaweed leaves with 0.02-5 mol/L acid, stirring for 1-10 h at the temperature of 20-60 ℃, washing with deionized water, removing dust, performing suction filtration to neutrality, and drying the treated sample in a vacuum drying oven at the temperature of 60-150 ℃ to constant weight;
(2) and drying the dried sample at 80-150 ℃ for 5-10 h again, and crushing the sample by using a drinking powder grinding machine to obtain the seaweed leaf powder raw material.
In some embodiments of the present invention, the activating agent in the porous activated carbon preparation process in the step (1) is one or more of potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and phosphoric acid.
The lead-carbon battery plate prepared by the method based on the porous activated carbon material.
Has the advantages that: compared with the prior art, the porous activated carbon raw material of the invention belongs to green renewable resources, has rich sources and low cost, and the preparation process is environment-friendly;
the electrode plate constructed by the invention has the advantages of strong cycle stability, good charge and discharge performance and long service life.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The following examples are illustrative and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
A lead-carbon battery plate based on a porous activated carbon material comprises a grid and an active material coated on the grid, wherein the active material comprises the following components in percentage by weight:
water: 5% -15%;
sulfuric acid: 1% -20%;
porous activated carbon: 1% -10%;
additive: 0.1 to 5 percent;
lead: and (4) the balance.
The porous activated carbon material is prepared by taking seaweed leaves as a raw material, performing dust removal and drying, performing carbonization treatment, performing carbonate treatment, drying by distillation, washing, filtering, drying, mixing the carbonized seaweed leaves with an activating agent, and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere.
When the polar plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate.
The specific surface area of the porous activated carbon is 4000-4500 square meters per gram, and the pore volume is 1.520-1.852 cm3(ii)/g, particle diameter of 14.5 + -0.2 μm, and conductivity of 0.39-0.41S/cm.
Specific distribution of the lead-carbon battery plate components of examples 1 to 3 is shown in table 1:
table 1 example component ratio table
| Components | Example 1 (%) | Example 2 (%) | Example 3 (%) |
| Water (W) | 5 | 5 | 5 |
| Sulfuric acid | 10 | 10 | 10 |
| Porous activated carbon | 5 | 1 | 10 |
| Additive agent | 2 | 0.13 | 3.6 |
| Lead (II) | 78 | 83.87 | 71.4 |
According to the proportions listed in the three embodiments, the lead-carbon battery pole plate based on the porous activated carbon material is respectively prepared, the weight of each example of the ingredients is 100Kg, and the specific preparation process is as follows:
(1) preparing porous activated carbon: based on seaweed leaves as raw materials, performing dust removal and drying, then performing carbonization treatment, then performing carbonate treatment, drying by distillation, washing, filtering and drying, and finally mixing the carbonized seaweed leaves with an activating agent and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere to prepare the seaweed tea;
(2) preparing lead plaster: grinding lead into lead powder, sequentially adding water and sulfuric acid with the mass concentration of 33.5% into the lead powder, and uniformly stirring; adding the additive and the porous active carbon again, and preparing mud-shaped lead plaster; when the polar plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate;
(3) coating lead plaster on a grid, and drying at the temperature of 150 ℃;
(4) curing and drying at 75 ℃.
Wherein, the preparation steps of the porous activated carbon in the step (1) are as follows:
(1) pretreatment: washing the seaweed leaves, removing dust, drying and crushing to obtain a seaweed leaf powder raw material;
(2) carbonizing treatment: preparing alkali metal carbonate or bicarbonate into a solution with the concentration of 0.5-5 mol/L, heating the seaweed leaf powder raw material to a calcination temperature, carrying out heat preservation calcination, cooling to room temperature to obtain a calcined product, mixing the calcined product and the alkali metal carbonate/bicarbonate according to the mass ratio of 1-5 at room temperature, stirring for 1-15 h, and evaporating water to obtain a seaweed leaf carbonized product;
(3) high-temperature activation: mixing the seaweed leaf carbonized product with an activating agent, carrying out high-temperature activation treatment for 0.5-10 h at the constant temperature of 200-1500 ℃, cooling, washing and filtering by using 0.01-2 mol/L hydrochloric acid and distilled water samples to be neutral, and finally drying in a vacuum drying oven at the temperature of 50-150 ℃ to constant weight to obtain the porous activated carbon.
The pretreatment comprises the following steps:
(1) treating seaweed leaves with 0.02-5 mol/L acid, stirring for 1-10 h at the temperature of 20-60 ℃, washing with deionized water, removing dust, performing suction filtration to neutrality, and drying the treated sample in a vacuum drying oven at the temperature of 60-150 ℃ to constant weight;
(2) and drying the dried sample at 80-150 ℃ for 5-10 h again, and crushing the sample by using a drinking powder grinding machine to obtain the seaweed leaf powder raw material.
Wherein, the activating agent in the preparation of the porous activated carbon in the step (1) is one or more of potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and phosphoric acid.
The polar plates of the three examples are respectively charged together with the products in the prior art in the target lead-carbon battery to be used as a charging acceptance test, the test method executes GB22473-2008 'energy storage lead-acid storage battery', and the comparison table of the average charging acceptance of the three examples and the products in the prior art is shown as follows:
| name (R) | I0/A | I1/A | I1/I0 |
| Products of the prior art | 1.71 | 2.31 | 1.35 |
| Examples of the invention | 2.86 | 12.82 | 4.48 |
From the data recorded in the table, the maximum cycle charge acceptance of the embodiment of the invention is greatly improved compared with the prior art product.
Additional test results are given in the following table:
| energy density | Number of cycles | |
| Example 1 | 375Wh/kg | 27 ten thousand times |
| Example 2 | 355Wh/kg | 23.1 ten thousand times |
| Example 3 | 312Wh/kg | 19 ten thousand times |
From the above table, the battery plate based on the porous activated carbon provided by the invention effectively improves the energy density of the battery, and the service life is greatly prolonged.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. The lead-carbon battery plate based on the porous activated carbon material comprises a grid and an active material coated on the grid, and is characterized in that the active material consists of the following components in percentage by weight:
water: 5% -15%;
sulfuric acid: 1% -20%;
porous activated carbon: 1% -10%;
additive: 0.1 to 5 percent;
lead: and (4) the balance.
The porous activated carbon material is prepared by taking seaweed leaves as a raw material, performing dust removal and drying, performing carbonization treatment, performing carbonate treatment, drying by distillation, washing, filtering, drying, mixing the carbonized seaweed leaves with an activating agent, and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere.
2. The porous activated carbon material-based lead-carbon battery plate according to claim 1, wherein when the plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate.
3. The lead-carbon battery plate based on the porous activated carbon material as claimed in claim 1 or 2, wherein the specific surface area of the porous activated carbon is 4000-4500 square meters per gram, and the pore volume is 1.520-1.852 cm3(ii)/g, particle diameter of 14.5 + -0.2 μm, and conductivity of 0.39-0.41S/cm.
4. The preparation method of the lead-carbon battery pole plate based on the porous activated carbon material is characterized by comprising the following steps:
(1) preparing porous activated carbon: based on seaweed leaves as raw materials, performing dust removal and drying, then performing carbonization treatment, then performing carbonate treatment, drying by distillation, washing, filtering and drying, and finally mixing the carbonized seaweed leaves with an activating agent and performing high-temperature activation treatment in a vacuum constant-temperature atmosphere to prepare the seaweed tea;
(2) preparing lead plaster: grinding lead into lead powder, sequentially adding water and sulfuric acid with the mass concentration of 33.5% into the lead powder, and uniformly stirring; adding the additive and the porous active carbon again, and preparing mud-shaped lead plaster; when the polar plate is a positive electrode, the additive is a mixture of red lead, graphite and humic acid; when the polar plate is a negative electrode, the additive is a mixture of chopped carbon fibers, humic acid, tannin extract and barium sulfate;
(3) coating lead plaster on a grid, and drying at the temperature of 150 ℃;
(4) curing and drying at 75 ℃.
5. The method for preparing the lead-carbon battery plate based on the porous activated carbon material as claimed in claim 4, wherein the porous activated carbon in the step (1) is prepared by the following steps:
(1) pretreatment: washing the seaweed leaves, removing dust, drying and crushing to obtain a seaweed leaf powder raw material;
(2) carbonizing treatment: preparing alkali metal carbonate or bicarbonate into a solution with the concentration of 0.5-5 mol/L, heating the seaweed leaf powder raw material to a calcination temperature, carrying out heat preservation calcination, cooling to room temperature to obtain a calcined product, mixing the calcined product and the alkali metal carbonate/bicarbonate according to the mass ratio of 1-5 at room temperature, stirring for 1-15 h, and evaporating water to obtain a seaweed leaf carbonized product;
(3) high-temperature activation: mixing the seaweed leaf carbonized product with an activating agent, carrying out high-temperature activation treatment for 0.5-10 h at the constant temperature of 200-1500 ℃, cooling, washing and filtering by using 0.01-2 mol/L hydrochloric acid and distilled water samples to be neutral, and finally drying in a vacuum drying oven at the temperature of 50-150 ℃ to constant weight to obtain the porous activated carbon.
6. The method for preparing the lead-carbon battery plate based on the porous activated carbon material as claimed in claim 5, is characterized in that: the pretreatment comprises the following steps:
(1) treating seaweed leaves with 0.02-5 mol/L acid, stirring for 1-10 h at the temperature of 20-60 ℃, washing with deionized water, removing dust, performing suction filtration to neutrality, and drying the treated sample in a vacuum drying oven at the temperature of 60-150 ℃ to constant weight;
(2) and drying the dried sample at 80-150 ℃ for 5-10 h again, and crushing the sample by using a drinking powder grinding machine to obtain the seaweed leaf powder raw material.
7. The method for preparing the lead-carbon battery plate based on the porous activated carbon material as claimed in claim 4, is characterized in that: the activating agent in the step (1) is one or more of potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and phosphoric acid.
8. A lead-carbon battery plate based on a porous activated carbon material prepared according to the method of any one of claims 4 to 7.
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