CN108598472B - Low-temperature-resistant lead storage battery negative electrode lead paste and preparation method thereof - Google Patents
Low-temperature-resistant lead storage battery negative electrode lead paste and preparation method thereof Download PDFInfo
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- 238000003860 storage Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 abstract description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 19
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 19
- 239000004021 humic acid Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 16
- 235000018553 tannin Nutrition 0.000 claims abstract description 16
- 229920001864 tannin Polymers 0.000 claims abstract description 16
- 239000001648 tannin Substances 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims abstract description 9
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000006072 paste Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000006071 cream Substances 0.000 claims description 13
- 239000004615 ingredient Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000010008 shearing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 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 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011505 plaster Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 description 16
- 238000001514 detection method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 230000001804 emulsifying effect Effects 0.000 description 7
- 239000003273 ketjen black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XNJIWLMIBGJADS-UHFFFAOYSA-N formaldehyde;2-hydroxynaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(O)=CC=C21 XNJIWLMIBGJADS-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002023 wood 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
- H01M4/36—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
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- 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
- H01M10/12—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses low-temperature-resistant lead storage battery negative electrode lead plaster and a preparation method thereof, and belongs to the technical field of storage battery preparation. The negative lead plaster consists of lead powder, a negative additive, water and diachylon acid, wherein the negative additive comprises the following components in parts by weight based on 100 parts of the lead powder: 0.5-1.0 part of strontium sulfate or barium sulfate, 0.1-0.15 part of sodium lignosulfonate, 0.4-0.8 part of humic acid, 0.3-0.6 part of oak cup tannin extract, 0.6-1.2 parts of synthetic kneading agent, 0.1-0.2 part of carbon nano tube, 0.05-0.1 part of nano Keqin black, 0.1-0.15 part of conductive carbon fiber and 0.1-0.5 part of sodium hydroxymethyl cellulose. When the cathode lead plaster is prepared, the additive is pretreated firstly, and the dispersion degree is high. The low-temperature discharge capacity of the storage battery produced by the negative lead plaster can be improved by 10-25%, and the service life of the storage battery in a low-temperature environment is improved by 20-30%.
Description
Technical Field
The invention relates to the technical field of storage battery preparation, in particular to low-temperature-resistant lead storage battery negative electrode lead paste and a preparation method thereof.
Background
Lead-acid storage batteries are increasingly applied in the fields of communication and energy storage, but in alpine regions, because the lowest air temperature in winter can be reduced to be below-20 ℃, when the ambient temperature is lower than-20 ℃, the capacity of a common lead-acid storage battery can be reduced to be below 60% at normal temperature, and the cycle life can be reduced to be below 40% at normal temperature. This is mainly due to the reduced charge acceptance of conventional lead-acid batteries at low temperatures, due to the PbSO during charging4The solubility and dissolution rate of (a) are reduced at low temperatures, so that the pre-process of charging is restricted. The battery can not be fully charged in a low-temperature environment, so that the capacity and the service life of the battery are reduced, and the low battery is influencedThe main factor of the warm charge acceptance performance is the negative lead paste formula.
Patent document with application publication number CN 103779557 a discloses a low-temperature resistant lead storage battery negative electrode lead paste for an electric power-assisted vehicle, which comprises the following components in parts by weight: 1000 parts of lead powder with the concentration of 1.3-1.4 g/cm375-81 parts of sulfuric acid, 105-120 parts of pure water, 0.6-0.8 part of short fibers, 6.0-7.0 parts of barium sulfate, 1.0-1.5 parts of Norway lignin, 4.0-5.0 parts of humic acid, 3.0-5.0 parts of acetylene black and 1.0-1.5 parts of semi-carbonized wood chips.
The lignin and the humic acid can improve the low-temperature performance of the battery, and avoid the formation of a lead sulfate passivation layer on a negative plate, so that the further reaction of a negative lead active substance is prevented to reduce the capacity, therefore, the two substances are usually added into a negative lead plaster formula, but the general formula of the lignin sodium sulfonate and the humic acid can only meet the common standard requirements of the storage battery and can hardly meet the storage battery standards with high low-temperature performance requirements, such as the standard of 40 ℃ below zero of a starting storage battery and the standard of capacity discharge of 20 ℃ below zero of an electric vehicle.
The conductive agent in the traditional formula is mainly carbon black, activated carbon, graphite and the like, and although the materials are low in cost, the problems of poor dispersity and weak conductive capability exist.
In addition, in the traditional lead plaster and the preparation process, the mixing and adding mode of the additive is simple and rough, and the additive is not scientifically pretreated, so that the function of the additive is not completely released, and the problem of uneven dispersion exists.
The problems lead to poor low-temperature capability, low utilization rate of active substances and poor charging receiving capability of the produced storage battery, thereby influencing the service life of the storage battery.
Therefore, a new additive formula, an additive pretreatment method and a paste mixing method need to be researched to replace the traditional process so as to meet the low-temperature use requirement of the storage battery.
Disclosure of Invention
The invention aims to provide a low-temperature-resistant lead storage battery negative electrode lead paste to meet the use requirement of a storage battery under a low-temperature condition.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-temperature-resistant lead storage battery negative electrode lead paste consists of lead powder, a negative electrode additive, water and paste mixing acid, wherein the negative electrode additive comprises the following components in parts by weight based on 100 parts of the lead powder: 0.5-1.0 part of strontium sulfate or barium sulfate, 0.1-0.15 part of sodium lignosulfonate, 0.4-0.8 part of humic acid, 0.3-0.6 part of oak cup tannin extract, 0.6-1.2 parts of synthetic kneading agent, 0.1-0.2 part of carbon nano tube, 0.05-0.1 part of nano Keqin black, 0.1-0.15 part of conductive carbon fiber and 0.1-0.5 part of sodium hydroxymethyl cellulose.
The mixed cream acid has a density of 1.30-1.40g/cm3Sulfuric acid solution of (1). In the formula, the addition amount of the diacidic acid is 5-10 parts by weight based on 100 parts by weight of the lead powder; the addition amount of water is 10-12 parts.
The invention adds the oak cup tannin extract and the synthetic tanning agent on the basis of adding the sodium lignosulphonate and the humic acid, and reasonably matches the mixture to improve the low-temperature discharge capacity of the storage battery so as to meet the discharge requirement of the storage battery at minus 40 ℃.
The synthetic tanning agent is KN type synthetic tanning agent (namely naphthol and BETA-hydroxynaphthalene sulfonic acid formaldehyde condensate, synthetic tanning agent No. 3), and can improve the low-temperature performance of a storage battery, particularly the low-temperature performance of forty ℃ below zero when the storage battery is used.
In addition, the invention adds various conductive substances into the negative lead plaster to improve the charge and discharge capacity of the storage battery. For example, carbon nanotubes are a new conductive agent in recent years, not only can charge a 'wire' in a conductive network, but also have an electric double layer effect, so that the high rate characteristic of the supercapacitor is exerted, the good heat conduction performance of the supercapacitor is also beneficial to heat dissipation during charging and discharging of the battery, the polarization of the battery is reduced, the high and low temperature performance of the battery is improved, and the service life of the battery is prolonged. Preferably, the carbon nanotubes have a diameter of 5nm and a length of 10 to 20 μm.
For example, nano ketjen black has a unique branched form compared with conductive carbon black, and has the advantages that the conductive contacts of the conductor are more, and the branched chains form more conductive paths, so that the extremely high conductivity can be achieved only by a small amount of addition (other carbon blacks are mostly spherical or flaky, so that the required electrical property can be achieved by a high amount of addition).
For example, the conductive carbon fiber is a high-conductivity chopped carbon fiber material, has the characteristics of extremely outstanding conductivity and permanent conductivity, and has the advantages of low density, high strength, light weight, corrosion resistance and the like. Preferably, the length of the conductive carbon fiber is less than or equal to 3 mm.
The invention has a new breakthrough in improving the charge acceptance of the storage battery by reasonably adding the conductive substance, and the charge acceptance of the manufactured storage battery is improved by 20-30%.
Preferably, the particle size of the strontium sulfate or barium sulfate is 50 to 150 μm. The superfine powder has good dispersity and is more uniformly mixed.
Preferably, the negative electrode additive comprises the following components in parts by weight based on 100 parts by weight of lead powder: 0.7-0.8 part of strontium sulfate or barium sulfate, 0.11-0.12 part of sodium lignosulfonate, 0.5-0.6 part of humic acid, 0.4-0.5 part of oak cup tannin extract, 0.8-1.0 part of synthetic kneading agent, 0.15-0.17 part of carbon nano tube, 0.06-0.08 part of nano Keqin black, 0.12-0.13 part of conductive carbon fiber and 0.3-0.4 part of sodium hydroxymethyl cellulose; the addition amount of the water is 11-12 parts; the mixed cream acid has a density of 1.30-1.40g/cm3The amount of the sulfuric acid solution (2) added is 6.5 to 7.8 parts.
More preferably, the negative electrode additive comprises the following components in parts by weight based on 100 parts by weight of lead powder: 0.7 part of strontium sulfate or barium sulfate, 0.12 part of sodium lignosulphonate, 0.6 part of humic acid, 0.5 part of oak cup tannin extract, 0.8 part of synthetic tanning agent, 0.15 part of carbon nano tube, 0.08 part of nano Keqin black, 0.12 part of conductive carbon fiber and 0.3 part of sodium hydroxymethyl cellulose; the addition amount of the water is 11.5 parts; the addition amount of the cream mixing acid is 7.8 parts.
The invention also provides a method for preparing the low-temperature-resistant lead storage battery negative electrode lead plaster, which comprises the following steps:
(1) weighing the raw materials according to the formula ratio, mixing sodium lignosulphonate, humic acid and acorn tannin extract, and grinding until the powder clearance is 0.01-0.05mm to prepare a mixture I;
(2) preparing synthetic mashup agent with density of 1.045 + -0.005g/cm3Heating the aqueous solution to 70-80 ℃, adding sodium carboxymethylcellulose, strontium sulfate or barium sulfate, keeping the temperature, uniformly stirring, and cooling to obtain a material II;
(3) mixing carbon nano tubes and nano Keqin black, adding 20-40% of co-paste acid in the amount of the co-paste acid formula, uniformly stirring, adding the ingredient I and the ingredient II, heating to 60-80 ℃, pressurizing, shearing and dispersing, reducing the shearing speed, and recovering to normal temperature and normal pressure to obtain an ingredient III;
(4) mixing conductive carbon fibers with the ingredient III, stirring, and then carrying out ultrasonic homogenization and emulsification to prepare the negative electrode additive;
(5) and mixing and pasting the negative electrode additive with lead powder, water and the rest of the paste acid to obtain the low-temperature-resistant lead storage battery negative electrode lead paste.
The invention pretreats each raw material of the cathode additive, ensures that each raw material is high in dispersion degree and strong in consistency after being mixed with the lead powder, and improves the charge acceptance of the storage battery.
In the step (2), the preparation method of the synthetic mashup aqueous solution comprises the following steps: putting the synthetic tanning agent into a stainless steel container, introducing 0.3-0.5 MPa water vapor, directly blowing the solid matter of the synthetic tanning agent by a steam nozzle until the synthetic tanning agent is blown into a liquid state, then adding 2 times of pure water, cooling the aqueous solution of the synthetic tanning agent to 20-30 ℃, and adjusting the density to 1.045 +/-0.005 g/cm by using the pure water3。
In the step (2), the stirring is carried out at 1500-.
In the step (3), after the sulfuric acid solution is added into the carbon nano tube and the nano Ketjen black, the mixture is stirred for 10-20min at the speed of 100-.
In the step (3), the conditions of pressure shearing dispersion are as follows: the pressure is 2-3MPa, the shearing speed is 2500-.
In the step (4), the conductive carbon fiber is mixed with the ingredient III and stirred for 5-10min at the speed of 30-50 r/min. Then put into an ultrasonic homogenizer for homogenizing and emulsifying at normal temperature and normal pressure.
Preferably, the ultrasonic homogenizing emulsification frequency is 15-60kHz, each emulsification time is 20-30min, and the emulsification is repeated for 3-5 times.
In the step (5), the temperature of the paste is less than or equal to 70 ℃. The invention comprehensively considers the proportion of 4BS and 3BS generated in the lead plaster, the hardness of the lead plaster and the characteristics of subsequent internal formation, selects the temperature of the lead plaster which is not higher than 70 ℃, such as overhigh paste mixing temperature, lead plaster sand mold, high hardness, inconvenient production of the next procedure and inconvenient charging formation of the storage battery.
The invention has the following beneficial effects:
(1) according to the invention, the oak cup tannin extract and the synthetic tanning agent are added into the negative lead paste, and the low-temperature additives are reasonably proportioned, so that the low-temperature discharge capacity of the storage battery is improved, the use requirement of minus 40 ℃ is met, and the storage battery can be used for power batteries, starting batteries and energy storage and standby storage batteries.
(2) The invention adds the high-conductivity substance carbon nano tube and the nano Keqin black, has a new breakthrough in improving the charge acceptance of the storage battery, and improves the charge acceptance of the storage battery manufactured by the negative lead plaster of the invention by 20-30%.
(3) When the negative electrode lead plaster is prepared, the additive is pretreated, so that the negative electrode lead plaster has the characteristics of high dispersity and strong consistency, the charge acceptance of the storage battery can be improved, and the capacity and the service life of the storage battery are further improved. The low-temperature discharge capacity of the storage battery produced by the negative lead plaster can be improved by 10-25%, and the service life of the storage battery in a low-temperature environment is improved by 20-30%.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Comparative example 1
1. The negative lead plaster formula comprises: 100kg of lead powder, 0.8kg of barium sulfate, 0.15kg of sodium lignosulfonate, 0.4kg of humic acid, 0.2kg of carbon black, 0.06kg of short fiber and dilute sulfuric acid (1.30-1.40 g/cm)3)7.8kg and 11.5kg of water.
2. And (3) paste mixing process: adding lead powder with a formula amount into a paste mixer, adding an additive, starting the mixer to stir for 1min, then opening a purified water valve to add formula water at a uniform flow rate for about 3min, opening an acid inlet valve, simultaneously opening a cooling device to cool, uniformly spraying formula acid into the paste mixer within 5-8 min, continuously stirring for 15-18 min, and obtaining the cathode lead paste, wherein the temperature in the paste mixing process is not more than 65 ℃.
Example 1
1. The negative lead plaster formula comprises: 100kg of lead powder, 0.7kg of superfine strontium sulfate or barium sulfate, 0.12kg of sodium lignosulfonate, 0.6kg of humic acid, 0.5kg of oak tannin extract and 3# synthetic kneading agent (1.045 g/cm)3Aqueous solution) 0.8kg, carbon nano-tube 0.15kg, nano Ketjen black 0.08kg, conductive carbon fiber (length 3mm)0.12kg, sodium carboxymethyl cellulose CMC 0.3kg, dilute sulfuric acid (1.30-1.40 g/cm)3)7.8kg and 11.5kg of water for production.
2. The negative lead paste was prepared according to the paste mixing process of comparative example 1.
Example 2
1. The negative lead plaster formula comprises:
100kg of lead powder;
and (3) a negative electrode additive: 0.7kg of superfine strontium sulfate or barium sulfate, 0.12kg of sodium lignosulfonate, 0.6kg of humic acid, 0.5kg of oak cup tannin extract and 3# synthetic kneading agent (1.045 g/cm)3Aqueous solution) 0.8kg, carbon nano-tube 0.15kg, nano ketjen black 0.08kg, conductive carbon fiber (length 3mm)0.12kg, sodium carboxymethyl cellulose CMC 0.3 kg;
11.5kg of production water;
cream acid (density 1.30-1.40 g/cm)3Sulfuric acid solution) 7.8 kg.
2. Preparation method
(1) Putting the synthetic tanning agent into a stainless steel container, introducing 0.3-0.5 MPa water vapor, directly blowing the solid matter of the synthetic tanning agent by a steam nozzle until the synthetic tanning agent is blown into a liquid state, then adding 2 times of pure water, cooling the aqueous solution of the synthetic tanning agent to 20-30 ℃, and adjusting the density to 1.045 +/-0.005 g/cm by using the pure water3；
(2) Mixing sodium lignosulfonate, humic acid and oak cup tannin extract according to the formula amount, and then putting the mixture into a grinder for high-speed grinding, wherein the grinding gap is 0.01-0.05mm, and the grinding time is not less than 3 hours;
(3) heating the synthetic tanning agent with the formula amount to 70 ℃, then adding the hydroxymethyl cellulose sodium, the superfine strontium sulfate or the barium sulfate with the formula amount into the synthetic tanning agent for stirring, keeping the temperature, shearing and stirring at a high speed of 2500r/min for 60min, and then cooling to the normal temperature for later use;
(4) mixing the carbon nano tube and the nano Keqin black according to the formula amount, adding the mixture into 2.8kg of cream acid, stirring for 20min at the speed of 100r/min, adding the substances prepared in the steps 2 and 3, heating to the temperature of 60 ℃, pressurizing to the pressure of 3MPa, dispersing and stirring for 2h at the speed of 2500r/min by using a high-pressure high-speed shearing emulsifying machine, and then slowly stirring the mixture at the speed of 100r/min to recover the state of normal temperature and normal pressure;
(5) mixing the conductive carbon fiber with the formula amount with the substance prepared in the step 4, stirring at the speed of 30r/min for 10min, then putting into an ultrasonic vacuum homogenizing and emulsifying machine, emulsifying at normal temperature and normal pressure by a mean value of 60KHz for 20min each time, repeating for 3-5 times, and standing at normal temperature for later use.
(6) The above ingredients are mixed with 100kg of lead powder when preparing lead plaster, 5kg of paste acid and 11.5kg of water are added, and the mixing process is carried out according to the paste mixing process, wherein the temperature of the lead plaster in the mixing process is not more than 70 ℃.
Example 3
1. The negative lead plaster formula comprises:
100kg of lead powder;
and (3) a negative electrode additive: 0.8kg of superfine strontium sulfate or barium sulfate, 0.11kg of sodium lignosulfonate, 0.5kg of humic acid, 0.4kg of oak cup tannin extract and 3# synthetic kneading agent (1.045 g/cm)3Aqueous solution) 1.0kg, carbon nano tube 0.17kg, nano ketjen black 0.06kg, conductive carbon fiber (length 3mm)0.13kg, sodium carboxymethyl cellulose CMC 0.4 kg;
11.5kg of production water;
cream acid (density 1.30-1.40 g/cm)3Sulfuric acid solution) 7.3 kg.
2. Preparation method
(1) Putting the synthetic tanning agent into a stainless steel container, introducing 0.3-0.5 MPa water vapor, directly blowing the solid matter of the synthetic tanning agent by a steam nozzle until the synthetic tanning agent is blown into a liquid state, then adding 2 times of pure water, cooling the aqueous solution of the synthetic tanning agent to 20-30 ℃, and adjusting the density to 1.045 +/-0.005 g/cm by using the pure water3；
(2) Mixing sodium lignosulfonate, humic acid and oak cup tannin extract according to the formula amount, and then putting the mixture into a grinder for high-speed grinding, wherein the grinding gap is 0.01-0.05mm, and the grinding time is not less than 3 hours;
(3) heating the synthetic tanning agent with the formula amount to 80 ℃, then adding the hydroxymethyl cellulose sodium, the superfine strontium sulfate or the barium sulfate with the formula amount into the synthetic tanning agent for stirring, keeping the temperature, shearing and stirring at a high speed of 1500r/min for 90min, and then cooling to the normal temperature for later use;
(4) mixing the carbon nano tube and the nano Keqin black according to the formula amount, adding the mixture into 2.8kg of cream acid, stirring for 10min at the speed of 200r/min, adding the substances prepared in the steps 2 and 3, heating to the temperature of 80 ℃, pressurizing to the pressure of 2MPa, dispersing and stirring for 2h at the speed of 3500r/min by using a high-pressure high-speed shearing emulsifying machine, and then slowly stirring the mixture at the speed of 200r/min to recover the state of normal temperature and normal pressure;
(5) mixing the conductive carbon fiber with the formula amount with the substance prepared in the step 4, stirring at the speed of 50r/min for 5min, then putting into an ultrasonic vacuum homogenizing and emulsifying machine, emulsifying at normal temperature and normal pressure by mean value of 15KHz for 30min each time, repeating for 3-5 times, and standing at normal temperature for later use.
(6) The above ingredients are mixed with 100kg of lead powder when preparing lead plaster, 4.5kg of cream acid and 11.5kg of water are added, and the cream mixing process is carried out according to the cream mixing process, wherein the temperature of the lead plaster in the cream mixing process is not more than 70 ℃.
Application example
The negative electrode diachylon prepared in the comparative example and the example is prepared into a maintenance-free storage battery (capacity: 60 Ah; low-temperature large-current discharge Icc 500A) with the model number of 6-QW-60 according to the conventional process, and the battery performance test is carried out according to the GB/T5008.1-2013 test standard.
1. Reserve capacity
The detection method comprises the following steps: discharging at 25 deg.C + -2 deg.C under 25A, stopping at voltage of 10.5 + -0.05 v, and recording time.
2. Low temperature detection at-18 deg.C
The detection method comprises the following steps: keeping the temperature at minus 18 +/-1 ℃ for not less than 24 h. The voltage was recorded at 500A for 30s, 10s and 30s, at rest for 20s, at 300A for 40s, at 40s, the voltage was recorded, the final voltage was 10.5 + -0.05 v, and the recording time was recorded.
3. Rated capacity of 20h
The detection method comprises the following steps: discharging at 25 + -2 deg.C with 3A, stopping at 10.5 + -0.05 v, and recording time.
4. Low temperature detection at-41 deg.C
The detection method comprises the following steps: keeping the temperature at minus 41 +/-1 ℃ for not less than 24 h. The voltage was recorded at 300A for 30s, 10s, 30s, rest for 20s, at 240A for 40s, end voltage 10.5 + -0.05 v, recording time.
5. Charge acceptance capability
The detection method comprises the following steps: after the storage battery is completely charged, the storage battery is kept at the ambient temperature of 25 +/-2 ℃, is discharged for 5h by I0(6.4A), is placed at the ambient temperature of 0 +/-1 ℃ for 20h, is taken out for 1min and is charged according to the voltage of 14.4 +/-0.10 v, and the charging current Ica is recorded after 10 min.
6. Cycle life
The detection method comprises the following steps: the test was carried out according to 5.9.2 cycle endurance I test in GB/T5008.1-2013.
Specific results are shown in table 1.
TABLE 1
As shown in the table, the storage battery manufactured by the negative lead plaster produced by the conventional negative formula and the process in the comparative example 1 has poor detection result at the low temperature of 18 ℃ below zero and unqualified detection at the low temperature of 41 ℃ below zero, and the storage battery manufactured by the negative lead plaster has excellent low-temperature discharge performance, strong charge acceptance and longer service life by 30 percent.
Claims (9)
1. The low-temperature-resistant lead storage battery negative electrode lead paste is composed of lead powder, a negative electrode additive, water and paste mixing acid, and is characterized in that the negative electrode additive comprises the following components in parts by weight of 100 parts of the lead powder: 0.5-1.0 part of strontium sulfate or barium sulfate, 0.1-0.15 part of sodium lignosulfonate, 0.4-0.8 part of humic acid, 0.3-0.6 part of oak cup tannin extract, 0.6-1.2 parts of synthetic kneading agent, 0.1-0.2 part of carbon nano tube, 0.05-0.1 part of nano Keqin black, 0.1-0.15 part of conductive carbon fiber and 0.1-0.5 part of sodium hydroxymethyl cellulose;
the preparation method of the low-temperature-resistant lead storage battery negative electrode lead paste comprises the following steps:
(1) weighing the raw materials according to the formula ratio, mixing sodium lignosulphonate, humic acid and acorn tannin extract, and grinding until the powder clearance is 0.01-0.05mm to prepare a mixture I;
(2) preparing synthetic mashup agent with density of 1.045 + -0.005 g/cm3Heating the aqueous solution to 70-80 ℃, adding sodium carboxymethylcellulose, strontium sulfate or barium sulfate, keeping the temperature, uniformly stirring, and cooling to obtain a material II;
(3) mixing carbon nano tubes and nano Keqin black, adding 30-40% of co-paste acid in the amount of the co-paste acid formula, uniformly stirring, adding the ingredient I and the ingredient II, heating to 60-80 ℃, pressurizing, shearing and dispersing, reducing the shearing speed, and recovering to normal temperature and normal pressure to obtain an ingredient III;
(4) mixing conductive carbon fibers with the ingredient III, stirring, and then carrying out ultrasonic homogenization and emulsification to prepare the negative electrode additive;
(5) and mixing and pasting the negative electrode additive with lead powder, water and the rest of the paste acid to obtain the low-temperature-resistant lead storage battery negative electrode lead paste.
2. The low-temperature-resistant lead storage battery negative electrode lead paste as claimed in claim 1, wherein the negative electrode additive comprises the following components in parts by weight based on 100 parts by weight of lead powder: 0.7-0.8 part of strontium sulfate or barium sulfate, 0.11-0.12 part of sodium lignosulfonate, 0.5-0.6 part of humic acid, 0.4-0.5 part of oak cup tannin extract, 0.8-1.0 part of synthetic kneading agent, 0.15-0.17 part of carbon nano tube, 0.06-0.08 part of nano Keqin black, 0.12-0.13 part of conductive carbon fiber and 0.3-0.4 part of sodium hydroxymethyl cellulose; the addition amount of the water is 11-12 parts; the mixed cream acid has a density of 1.30-1.40g/cm3The amount of the sulfuric acid solution (2) added is 6.5 to 7.8 parts.
3. The low temperature resistant lead-acid battery negative electrode lead paste of claim 2, wherein the composition of the negative electrode additive comprises: 0.7 part of strontium sulfate or barium sulfate, 0.12 part of sodium lignosulphonate, 0.6 part of humic acid, 0.5 part of oak cup tannin extract, 0.8 part of synthetic tanning agent, 0.15 part of carbon nano tube, 0.08 part of nano Keqin black, 0.12 part of conductive carbon fiber and 0.3 part of sodium hydroxymethyl cellulose; the addition amount of the water is 11.5 parts; the addition amount of the cream mixing acid is 7.8 parts.
4. The negative electrode lead paste for the low-temperature-resistant lead-acid battery as claimed in any one of claims 1 to 3, wherein the grain size of the strontium sulfate or barium sulfate is 50 to 150 μm.
5. The negative electrode lead paste for the low temperature-resistant lead-acid battery of any one of claims 1 to 3, wherein the carbon nanotubes have a diameter of 5nm and a length of 10 to 20 μm.
6. The negative electrode lead paste for the low temperature-resistant lead-acid battery as claimed in any one of claims 1 to 3, wherein the length of the conductive carbon fiber is less than or equal to 3 mm.
7. The negative electrode lead paste for low temperature resistant lead-acid battery as claimed in claim 1, wherein in the step (3), the conditions for pressure shear dispersion are as follows: the pressure is 2-3MPa, the shearing speed is 2500-.
8. The negative electrode lead paste for the low temperature-resistant lead-acid battery as claimed in claim 1, wherein in the step (4), the frequency of ultrasonic homogeneous emulsification is 15-60kHz, and the emulsification is repeated for 3-5 times for 20-30min each time.
9. The negative electrode lead paste for low temperature resistant lead-acid battery as claimed in claim 1, wherein the temperature of the paste in step (5) is 70 ℃ or less.
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| CN111106315A (en) * | 2019-12-05 | 2020-05-05 | 安徽理士电源技术有限公司 | Lead-acid storage battery with high charge acceptance by adopting carbon material |
| CN111403681B (en) * | 2020-03-10 | 2021-07-06 | 浙江埃登达新能源材料有限公司 | Negative electrode expanding agent for storage battery |
| CN111864201B (en) * | 2020-06-28 | 2021-08-03 | 天能电池集团股份有限公司 | Negative pole lead plaster of storage battery with super-strong charge acceptance and preparation method thereof |
| CN113437255A (en) * | 2021-05-26 | 2021-09-24 | 浙江南都电源动力股份有限公司 | Low-temperature negative pole piece and preparation method thereof |
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