CN114243000A - Lead storage battery negative electrode lead paste and preparation method thereof - Google Patents
Lead storage battery negative electrode lead paste and preparation method thereof Download PDFInfo
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- CN114243000A CN114243000A CN202111611803.7A CN202111611803A CN114243000A CN 114243000 A CN114243000 A CN 114243000A CN 202111611803 A CN202111611803 A CN 202111611803A CN 114243000 A CN114243000 A CN 114243000A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 19
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000012141 vanillin Nutrition 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 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 12
- 239000004021 humic acid Substances 0.000 claims abstract description 12
- 229920005610 lignin Polymers 0.000 claims abstract description 12
- 239000011505 plaster Substances 0.000 claims abstract description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 20
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 19
- 239000006230 acetylene black Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 229920002197 Sodium polyaspartate Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- 239000013543 active substance Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 108010064470 polyaspartate Proteins 0.000 abstract description 6
- 229920000805 Polyaspartic acid Polymers 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 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 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000005187 foaming Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 230000019635 sulfation Effects 0.000 abstract description 2
- 238000005670 sulfation reaction Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 17
- 238000001514 detection method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 8
- 239000011149 active material Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- 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
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lead storage battery cathode lead plaster and a preparation method thereof. The additive of the negative pole lead plaster can be adsorbed on the surfaces of lead and lead sulfate by adding Polyaspartic Acid Sodium (PASP) and hydroxyl, carboxyl and methoxy groups in lignin and humic acid, and can inhibit the lead sulfate layer from being converted to a selective semipermeable membrane, thereby playing the roles of passivating and preventing or slowing sulfation. Meanwhile, the addition of indium trioxide and vanillin improves the hydrogen evolution overpotential of the negative electrode, inhibits hydrogen gas evolution and prolongs the service life of the battery. The carboxymethyl cellulose plays a role in bonding in the active substance, prevents the active substance from foaming and separating from a grid, enables the electrolyte to be more soluble and easily permeate into the active substance due to the excellent water absorption characteristic, and increases the utilization rate of the active substance and the high-current discharge performance.
Description
Technical Field
The invention relates to the technical field of lead storage batteries, in particular to a lead paste for a negative electrode of a lead storage battery and a preparation method thereof.
Background
With the increasing awareness of environmental protection and the increasing demand for clean and renewable energy, the lead-acid battery has been converted from low current and low power to high current and high power in various applications, which requires the lead-acid battery to have higher specific energy and longer service life. The negative electrode of the existing lead storage battery is easy to be sulfated in the use process, so that the porosity of the pole plate is reduced, the conductivity is reduced, and the charge and discharge capacity is reduced.
Acetylene black in a traditional negative electrode additive is used as a conductive material, for example, the invention application with the publication number of CN113394400A discloses a negative electrode lead paste of a lead storage battery, a negative plate and the lead storage battery, belonging to the technical field of the lead storage battery. The negative electrode lead plaster of the lead storage battery comprises lead powder and an additive, wherein the additive comprises, by mass of the total lead powder, 0.9-1 wt% of barium sulfate, 0.3-0.4 wt% of acetylene black, 0.05-0.08 wt% of lignin, 0.5-0.8 wt% of humic acid, 0.07-0.08 wt% of short fibers, 0.03-0.05 wt% of nano silica sol and 0.55-0.7 wt% of sulfamic acid.
For another example, the invention application with publication number CN104900876A discloses a novel negative electrode active material for a lead-acid battery, which uses graphene as an additive, and comprises the following components in percentage by weight: 0.5-1.2% of colloidal graphite, 0.5-0.8% of humic acid, 0.3-0.8% of lignin, 0.5-1.2% of barium sulfate, 0.07-0.2% of short fiber, 0.05-0.15% of polytetrafluoroethylene, 0.03-0.2% of polyvinyl alcohol, 0.1-0.2% of 1, 2-propylene glycol, 0.1-0.3% of graphene, 0.8-1.5% of acetylene black, 75-85% of lead powder, 7-10% of dilute sulfuric acid solution and the balance of deionized water.
The following disadvantages occur during practical use: 1. acetylene black can cause severe hydrogen evolution at the terminal stage of battery charging, particularly severe water loss after 100% DOD200 of the battery for the rest of times, and lead to early end of the service life of the battery; 2. the polytetrafluoroethylene is an insulator, and the polytetrafluoroethylene can be bonded with active substances in the formula, but can increase the internal resistance of the battery and reduce the low-temperature performance of the storage battery; 3. the low-temperature performance of the storage battery can be improved by using lignin and humic acid, but the low-temperature capacity is seriously attenuated in the circulation process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the lead storage battery cathode lead plaster and the preparation method thereof, and the indium trioxide and the vanillin are added in the formula to improve the hydrogen evolution overpotential of the cathode and inhibit the hydrogen evolution, so that the service life of the battery is prolonged; sodium polyaspartate is added in the formula to control the crystallization process of lead sulfate, the crystal form and the crystal size of the lead sulfate are improved, the utilization rate of a negative electrode active substance can be improved, the internal resistance of a negative electrode plate is reduced, and the attenuation of low-temperature capacity of the negative electrode in the circulation process can be prevented and slowed down; the carboxymethyl cellulose is added in the formula to prevent the negative plate from bubbling and the grid from separating and improve the large-current discharge performance of the storage battery.
The formula of the lead storage battery negative electrode lead plaster comprises lead powder, a negative electrode additive, deionized water and diachylon acid, wherein the negative electrode additive comprises the following components in parts by weight based on 100 parts by weight of the lead powder:
preferably, the negative electrode additive comprises the following components in parts by weight, based on 100 parts by weight of lead powder:
preferably, the addition ratio of the humic acid, the sodium polyaspartate and the lignin is as follows: 2-3: 1-1.5.
Preferably, the addition ratio of the graphene to the acetylene black is as follows: 1: 2 to 2.33.
Preferably, the weight part of the deionized water is 10.5-11 parts based on 100 parts of the lead powder.
Preferably, the weight portion of the lead powder is 100 portionsThe weight part of the cream acid is 7.6-8 parts. The density of the cream acid is 1.4 +/-0.001 g/cm3。
The preparation method of the lead storage battery negative electrode lead paste comprises the following steps:
(1) adding lead powder, lignin, barium sulfate, humic acid, sodium polyaspartate, acetylene black, carboxymethyl cellulose and indium oxide into a paste combining machine, and stirring uniformly;
(2) 2 parts of water is taken in the formula water, the formula amount of graphene, fiber and vanillin are added into the formula water, the mixture is stirred until the vanillin is dissolved, the graphene and the fiber are uniformly dispersed in the water, and the fiber is free from agglomeration.
(3) Adding deionized water into the paste mixer while stirring, and adding the suspension generated in the step (2) while stirring uniformly;
(3) adding paste mixing acid into a paste mixing machine while stirring, controlling the paste mixing temperature to be 40-55 ℃ at most, and uniformly stirring;
(4) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
The negative electrode of the storage battery has very abundant pores and a highly developed surface area, and in this state, the surface of the negative electrode has high surface energy and is in an unstable state, and the surface area of an active material is shrunk along with the increase of the cycle number of the battery, so that the capacity of the battery is attenuated, and the low-temperature performance of the battery is poor.
The negative pole lead plaster additive of the invention, sodium polyaspartate (PASP) and hydroxyl, carboxyl and methoxy groups in lignin and humic acid can be adsorbed on the surfaces of lead and lead sulfate, and can inhibit the lead sulfate layer from transforming to a selective semipermeable membrane, thereby playing the roles of passivating and preventing or slowing sulfation. The main functional groups of the polyaspartic acid are carboxyl, carbonyl, imino, amide and the like, the expansion effect of the polyaspartic acid is different due to the difference of the functional groups, and the addition of the polyaspartic acid can control the crystallization process of the lead sulfate, improve the crystal form and the crystal size of the lead sulfate, improve the utilization rate of a negative active substance, reduce the internal resistance of a negative plate and prevent and slow down the attenuation of low-temperature capacity of the negative plate in the circulation process.
Graphene and acetylene black have conductive characteristics, so that a high-conductivity network is rapidly formed by the negative active material in the formation process, and the formation efficiency is improved. In the mixing process of the lead paste, the graphene and the acetylene black are influenced by the particle size and the affinity characteristic to lead, the graphene is mainly gathered on the branches of the active material framework and the surface of the active material, the charge acceptance of the active material is improved, and the acetylene black is a framework component forming the active material and can also play a role of a super capacitor. However, in the later charging period, due to the fact that the voltage of the storage battery is too high, hydrogen evolution of graphene and acetylene black is serious, and particularly after the battery is deeply cycled for more than 200 times, water loss is serious, and the service life of the battery is stopped in advance. Therefore, the indium trioxide and vanillin are added in the formula, so that the hydrogen evolution overpotential of the negative electrode is improved, the hydrogen evolution is inhibited, and the service life of the battery is prolonged. The carboxymethyl cellulose plays a role in bonding in the active substance, prevents the active substance from foaming and separating from a grid, enables the electrolyte to be more soluble and easily permeate into the active substance due to the excellent water absorption characteristic, and increases the utilization rate of the active substance and the high-current discharge performance.
Drawings
FIG. 1 is a graph comparing the 2Hr capacity measured in GB/T22199.1-2017 for 20AH cells prepared from examples 1-3 and comparative examples 1-3 and pastes and 20AH cells prepared from conventional formulation of negative electrode lead paste for electric vehicles produced by the company.
FIG. 2 is a comparison graph of the-18 ℃ low-temperature capacity of 20AH batteries prepared by using the pastes of examples 1-3 and comparative examples 1-3 and a conventional electric vehicle cathode lead paste formula produced by the company according to GB/T22199.1-2017.
FIG. 3 is a comparison graph of capacity retention rates of 20AH batteries prepared by using the pastes of examples 1-3 and comparative examples 1-3 and a conventional electric vehicle negative electrode lead paste formula produced by a company according to GB/T22199.1-2017.
FIG. 4 is a comparison graph of the cycle life of 20AH batteries prepared by the pastes of examples 1-3 and comparative examples 1-3 and 20AH batteries prepared by the conventional formulation of the negative electrode lead paste for electric vehicles produced by the company according to GB/T22199.1-2017.
FIG. 5 is a comparison graph of the-18 ℃ low-temperature capacity measured at intervals of 50 times in the battery cycle life measurement process according to GB/T22199.1-2017 for 20AH batteries prepared by examples 1-3 and comparative examples 1-3 and pastes and 20AH batteries prepared by conventional electric vehicle negative lead paste formulations produced by the company.
Detailed Description
Example 1
The formula of the negative pole lead plaster of the lead storage battery comprises the following components:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
Wherein, polyester staple fiber, sodium lignosulphonate, barium sulfate, acetylene black and sodium polyaspartate are special additives for the storage battery provided by Guangzhou Edanda;
wherein, the graphene is Gc-powder 48 produced by Ningbo Moxic science and technology company;
wherein the indium trioxide and vanillin are analytically pure from Szelong scientific corporation.
The preparation method of the lead paste for the negative electrode of the lead storage battery comprises the following steps:
(1) adding lead powder, lignin, barium sulfate, humic acid, sodium polyaspartate, acetylene black, carboxymethyl cellulose and indium oxide into paste mixing machine, and stirring for 5 min;
(2) 2 parts of water is taken in the formula water, the formula amount of graphene, fiber and vanillin are added into the formula water, the mixture is stirred until the vanillin is dissolved, the graphene and the fiber are uniformly dispersed in the water, and the fiber is free from agglomeration.
(3) Adding the deionized water with the rest formula amount into the paste mixer in the step (1) while stirring, adding the suspension generated in the step (2) while finishing adding within 3min, and continuing wet stirring for 5 min;
(4) adding the formula with the weight density of 1.4 +/-0.001 g/cm into the paste mixer in the step (3) while stirring3The acid adding time of the sulfuric acid solution is controlled to be 17 minutes, a water cooling system is opened when the paste temperature reaches 40 ℃ in the acid adding process, and the paste temperature reaches 48 ℃ automaticallyOpening an air cooling system, controlling the maximum paste mixing temperature to be 55 ℃, and uniformly stirring;
(5) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
Example 2
The formula of the negative pole lead plaster of the lead storage battery comprises the following components:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
Wherein, polyester staple fiber, sodium lignosulphonate, barium sulfate, acetylene black and sodium polyaspartate are special additives for the storage battery provided by Guangzhou Edanda;
wherein, the graphene is Gc-powder 48 produced by Ningbo Moxic science and technology company;
wherein the indium trioxide and vanillin are analytically pure from Szelong scientific corporation.
The preparation method of the lead paste for the negative electrode of the lead storage battery comprises the following steps:
(1) adding lead powder, lignin, barium sulfate, humic acid, sodium polyaspartate, acetylene black, carboxymethyl cellulose and indium oxide into paste mixing machine, and stirring for 5 min;
(2) 2 parts of water is taken in the formula water, the formula amount of graphene, fiber and vanillin are added into the formula water, the mixture is stirred until the vanillin is dissolved, the graphene and the fiber are uniformly dispersed in the water, and the fiber is free from agglomeration.
(3) Adding the deionized water with the rest formula amount into the paste mixer in the step (1) while stirring, adding the suspension generated in the step (2) while finishing adding within 3min, and continuing wet stirring for 5 min;
(4) adding the formula with the weight density of 1.4 +/-0.001 g/cm into the paste mixer in the step (3) while stirring3The acid adding time of the sulfuric acid solution is controlled to be 17 minutes, a water cooling system is opened when the paste temperature reaches 40 ℃ in the acid adding process, an air cooling system is automatically opened when the paste temperature reaches 48 ℃, the paste mixing temperature is controlled to be 55 ℃ at most, and the sulfuric acid solution is uniformly stirred;
(5) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
Example 3
The formula of the negative pole lead plaster of the lead storage battery comprises the following components:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
Wherein, polyester staple fiber, sodium lignosulphonate, barium sulfate, acetylene black and sodium polyaspartate are special additives for the storage battery provided by Guangzhou Edanda;
wherein, the graphene is Gc-powder 48 produced by Ningbo Moxic science and technology company;
wherein the indium trioxide and vanillin are analytically pure from Szelong scientific corporation.
The preparation method of the lead paste for the negative electrode of the lead storage battery comprises the following steps:
(1) adding lead powder, lignin, barium sulfate, humic acid, sodium polyaspartate, acetylene black, carboxymethyl cellulose and indium oxide into paste mixing machine, and stirring for 5 min;
(2) 2 parts of water is taken in the formula water, the formula amount of graphene, fiber and vanillin are added into the formula water, the mixture is stirred until the vanillin is dissolved, the graphene and the fiber are uniformly dispersed in the water, and the fiber is free from agglomeration.
(3) Adding the deionized water with the rest formula amount into the paste mixer in the step (1) while stirring, adding the suspension generated in the step (2) while finishing adding within 3min, and continuing wet stirring for 5 min;
(4) adding the formula with the weight density of 1.4 +/-0.001 g/cm into the paste mixer in the step (3) while stirring3The acid adding time of the sulfuric acid solution is controlled to be 17 minutes, a water cooling system is opened when the paste temperature reaches 40 ℃ in the acid adding process, an air cooling system is automatically opened when the paste temperature reaches 48 ℃, the paste mixing temperature is controlled to be 55 ℃ at most, and the sulfuric acid solution is uniformly stirred;
(5) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
Comparative example 1
The negative pole lead paste formula without adding polyaspartic acid sodium comprises the following components:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
The corresponding material purchase source and lead paste preparation method in the lead paste additive are the same as those of example 1.
Comparative example 2
The formula of the negative pole lead paste without adding carboxymethyl cellulose comprises the following steps:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
The corresponding material purchase source and lead paste preparation method in the lead paste additive are the same as those of example 1.
Comparative example 3
The negative lead plaster formula without adding indium trioxide and vanillin is as follows:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
The corresponding material purchase source and lead paste preparation method in the lead paste additive are the same as those of example 1.
Detection example 1
The positive plate lead paste formula and the blending process are as follows:
wherein, the sulfuric acid solution: the density is 1.4 +/-0.001 g/cm3；
Wherein, the polyester short fiber, the graphene, the stannous sulfate, the antimony trioxide and the bismuth trioxide are special additives for the storage battery provided by Angstroma, Guangzhou;
the preparation method of the lead paste of the positive electrode of the lead storage battery comprises the following steps:
(1) adding lead powder, stannous sulfate, bismuth trioxide and antimony trioxide into a paste mixing machine, and stirring for 5 min;
(2) 2 parts of water is taken in the formula water, the graphene and the polyester short fibers with the formula amount are added into the formula water and stirred until the graphene and the fibers are uniformly dispersed in the water, and the fibers are free from agglomeration.
(3) Adding the deionized water with the rest formula amount into the paste mixer in the step (1) while stirring, adding the suspension generated in the step (2) while finishing adding within 3min, and continuing wet stirring for 5 min;
(4) adding the formula with the weight density of 1.4 +/-0.001 g/cm into the paste mixer in the step (3) while stirring3The acid adding time of the sulfuric acid solution is controlled to be 12 minutes, a water cooling system is opened when the paste temperature reaches 68 ℃ in the acid adding process, an air cooling system is automatically opened when the paste temperature reaches 72 ℃, the paste mixing temperature is controlled to be 80 ℃ at most, and the mixture is uniformly stirred;
(5) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
The lead pastes in the examples 1 to 3 and the comparative examples 1 to 2 are respectively prepared into negative plates, and the negative plates and the positive plates prepared according to the formula and the preparation process of the positive plate lead paste are combined to prepare 20AH batteries with the same model, and the battery performance is detected.
(1)2Hr Capacity detection
FIG. 1 is a graph showing a comparison of 2Hr capacities according to GB/T22199.1-2017 of 20AH batteries manufactured by examples 1-3 and comparative examples 1-3 and paste.
As can be seen from the detection results, all the examples and the comparative examples exceed the capacity detection standard of GB/T22199.1-2017 to be more than or equal to 20AH, wherein for the example 2 and the comparative example 2, the 2Hr capacity is relatively highest and exceeds the standard by 12.5%, and the process is seen to improve the battery capacity.
(2) Low temperature capacity test at-18 deg.C
FIG. 2 is a comparison of the-18 ℃ low temperature capacity of 20AH batteries made using examples 1-3 and comparative examples 1-3 and paste, measured according to GB/T22199.1-2017.
As can be seen from the detection results, all the examples and the comparative examples exceed the 18 ℃ low-temperature capacity detection standard of GB/T22199.1-2017 and are not less than 14AH, but the comparative example 2 is obviously lower in low-temperature capacity than the other examples and comparative examples, and the sodium polyaspartate has a good effect.
(3) Capacity preservation Rate detection
FIG. 3 is a graph showing a comparison of capacity retention rates according to GB/T22199.1-2017 of 20AH batteries manufactured by examples 1 to 3 and comparative examples 1 to 3 and paste.
As can be seen from the detection results, all the examples and the comparative examples except the comparative example 3 do not reach the capacity storage rate standard of GB/T22199.1-2017, the other examples exceed the standard and are not less than 90%, and the comparative example 3 is obviously lower than the other examples and the comparative examples, so that the indium trioxide and the vanillin play a role in preventing self-discharge.
(4) Battery life reliability detection
FIG. 4 is a comparison graph of the cycle life of 20AH batteries manufactured by examples 1 to 3 and comparative examples 1 to 3 and paste according to GB/T22199.1-2017.
From the detection results, all the cells of the examples and the comparative examples exceed the standard of GB/T22199.1-2017 that the service life reliability is more than or equal to 200 times, and the formula and the unique preparation process have the characteristic of prolonging the service life of the storage battery, but the service life of the comparative example 3 is shortest in the examples and the comparative examples, and the loss of late water is probably not inhibited by the indium trioxide and the vanillin.
(5) Low temperature capacity detection at-18 ℃ in cycle life detection process
FIG. 5 is a graph showing comparison between 20AH batteries manufactured according to examples 1 to 3 and comparative examples 1 to 3 and paste, which were charged at intervals of 49 times, maintained in a cryostat at-18 ℃ for 5 hours, and discharged at 10A to a low-temperature capacity of 10.5V/cell in a life reliability test according to GB/T22199.1-2017.
From the detection results, the low-temperature effects of the examples 1,2 and 3 in the low-temperature capacity detection at-18 ℃ in the cycle life detection process are better, and the storage battery of the comparative example 2 and 1 is obviously better than that of the storage battery of the comparative example 1.
Claims (8)
1. The formula of the lead storage battery negative electrode lead plaster comprises lead powder, a negative electrode additive, deionized water and diachylon acid, and is characterized in that the negative electrode additive comprises the following components in parts by weight, based on 100 parts by weight of the lead powder:
2. the lead storage battery negative electrode lead paste as defined 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:
3. the lead-acid battery negative electrode lead paste as defined in claim 1, wherein the addition ratio of humic acid, sodium polyaspartate and lignin is: 2-3: 1-1.5.
4. The lead storage battery negative electrode lead paste as claimed in claim 1, wherein the addition ratio of the graphene to the acetylene black is as follows: 1: 2 to 2.33.
5. The lead storage battery negative electrode lead paste as defined in claim 1, wherein the deionized water is 10.5 to 11 parts by weight based on 100 parts by weight of the lead powder.
6. The negative electrode lead paste for lead-acid batteries according to claim 1, wherein the amount of the complex paste acid is 7.6 to 8 parts by weight based on 100 parts by weight of the lead powder.
7. The lead-acid battery negative electrode lead paste of claim 6, wherein the density of the diacidic acid is 1.4 ± 0.001g/cm3。
8. The preparation method of the lead storage battery negative electrode lead paste as defined in claims 1 to 7, characterized by comprising the following steps:
(1) adding lead powder, lignin, barium sulfate, humic acid, sodium polyaspartate, acetylene black, carboxymethyl cellulose and indium oxide into a paste combining machine, and stirring uniformly;
(2) 2 parts of water is taken in the formula water, the formula amount of graphene, fiber and vanillin are added into the formula water, the mixture is stirred until the vanillin is dissolved, the graphene and the fiber are uniformly dispersed in the water, and the fiber is free from agglomeration.
(3) Adding deionized water into the paste mixer while stirring, and adding the suspension generated in the step (2) while stirring uniformly;
(3) adding paste mixing acid into a paste mixing machine while stirring, controlling the paste mixing temperature to be 40-55 ℃ at most, and uniformly stirring;
(4) and taking the lead paste out of the pot for coating when the temperature of the lead paste is lower than 45 ℃.
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| CN112786843A (en) * | 2021-02-02 | 2021-05-11 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
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