CN117712297A - Preparation method of negative plate of storage battery for parking air conditioner - Google Patents
Preparation method of negative plate of storage battery for parking air conditioner Download PDFInfo
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- CN117712297A CN117712297A CN202311455527.9A CN202311455527A CN117712297A CN 117712297 A CN117712297 A CN 117712297A CN 202311455527 A CN202311455527 A CN 202311455527A CN 117712297 A CN117712297 A CN 117712297A
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- storage battery
- air conditioner
- parking air
- negative plate
- plate
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- 238000003860 storage Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229920000767 polyaniline Polymers 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 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 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011505 plaster Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229960002903 benzyl benzoate Drugs 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 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 9
- 239000004021 humic acid Substances 0.000 claims description 9
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000013543 active substance Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 7
- 230000019635 sulfation Effects 0.000 abstract description 7
- 238000005670 sulfation reaction Methods 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 229910000337 indium(III) sulfate Inorganic materials 0.000 abstract description 4
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000011087 paperboard Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 238000004378 air conditioning Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 10
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 7
- 230000036961 partial effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 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 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a negative plate of a storage battery for a parking air conditioner, and belongs to the technical field of lead storage batteries. The hydrogen evolution inhibiting additive adopts the combination of indium hydroxide and polyaniline to inhibit the precipitation of hydrogen, the indium hydroxide is different from the prior indium oxide and indium sulfate, the indium sulfate is insoluble In water, and the indium hydroxide has more free In the reaction process of the indium hydroxide and the sulfuric acid 3+ Ions appear, so that the ions can be better adsorbed on the surface of the carbon material, the hydrogen evolution overpotential is improved, and the hydrogen evolution can be inhibited. The invention uses the conductive fiber composite coated paperboard to embed the conductive fiber into the surface of the polar plate, thus not only forming a conductive network on the surface of the polar plate, improving the conductivity of the surface of the polar plate and reducing the polar plateThe irreversible sulfation of the plate occurs and the binding force between the active substances is increased.
Description
Technical Field
The invention belongs to the technical field of lead storage batteries, and particularly relates to a preparation method of a negative plate of a storage battery for a parking air conditioner.
Background
1. Development background of parking air conditioner storage battery:
for a truck driver who works for long-term long-distance transportation, the truck driver is heavy in work and is guaranteed to fully rest and avoid fatigue driving, the truck driver basically rests in the truck when the truck driver parks to be loaded and stops halfway, the truck driver rarely opens a vehicle engine to operate a vehicle-mounted air conditioner when the truck driver rests due to the problems of high oil price and engine noise, and the vehicle-mounted parking storage battery is used for supplying power to ensure the normal operation of the vehicle-mounted air conditioner mostly, so that the vehicle-mounted air conditioner becomes a necessary spare part for each truck driver under the requirement. At present, parking air-conditioning storage batteries become standard in the trucking industry, and each vehicle is basically provided with more than two parking air-conditioning storage batteries.
2. Industry problems
When the parking air conditioner is used, the parking air conditioner battery is required to ensure that a driver can supply electricity to the air conditioner for more than 6 hours under the condition that no motive power is developed, and the vehicle is ensured to strike fire normally when the driver takes a departure after taking a rest, so that the parking air conditioner storage battery is required to have deep discharging capacity and normal-temperature high-current starting capacity after deep discharging.
The application and the using mode of the parking air conditioner storage battery are greatly different from those of the existing power storage battery, energy storage battery, starting storage battery and start-stop storage battery, the parking air conditioner storage battery has the deep discharging capability characteristic of the power storage battery and the energy storage battery, has the large current starting capability of the starting storage battery, and is different from the high-frequency shallow discharging mode of the start-stop storage battery, so the parking air conditioner storage battery is a novel storage battery which is newly developed and rapidly grows in the years.
The parking air conditioner storage battery encounters a plurality of problems in the development process of the parking air conditioner storage battery, because the battery is used in a vehicle-mounted charging and discharging mode, the battery is difficult to guarantee to be in a fully charged state when being reused due to different running time of a truck after the storage battery is deeply discharged, and in order to guarantee that the battery can be quickly fully charged, a vehicle-mounted generator of an air conditioner system is often provided with a quick charging mode, so that part of the storage battery can be in an overshoot state, and the failure mode of the existing parking air conditioner storage battery is often negative plate sulfation, negative plate active material shrinkage, positive plate active material falling and pole plate corrosion.
In order to solve the failure modes, various manufacturers develop deep researches on parking air-conditioning batteries, and sequentially push out lead-antimony alloy dry charge parking air-conditioning batteries, tubular parking air-conditioning batteries, rich liquid maintenance-free parking air-conditioning batteries, AGM valve control sealing parking air-conditioning batteries and lithium ion parking air-conditioning batteries in the years, and compared, the rich liquid maintenance-free parking air-conditioning batteries still have great advantages in terms of service life, performance and customer investment contrast, occupy 70% of markets, and other parking air-conditioning batteries have certain market space, but have obvious defects and are basically not the first choice of most customers.
3. Technical bottleneck
The storage battery supplied by various large-brand manufacturers in the market at present is mainly a rich maintenance-free storage battery, market practice is carried out, various large manufacturers carry out multiple technical improvement and optimization innovation on the rich maintenance-free storage battery, but from the aspect of using effect, the main problems are not solved, the service life of the storage battery of the parking air conditioner in the domestic market is difficult to break through two years, the problem of short service life of the storage battery of the parking air conditioner is not fundamentally solved, the irreversible sulfation of a negative plate, the shrinkage failure of a negative plate active substance and the falling of a positive plate active substance are still main problems of the service life failure of the storage battery of the parking air conditioner, wherein the irreversible sulfation of the negative plate accounts for more than 50% of the total failure amount, the shrinkage problem of the negative plate active substance accounts for more than 20% of the total failure amount, and therefore the problem of the negative plate is the main problem of influencing the service life of the storage battery of the parking air conditioner not to reach the standard.
Disclosure of Invention
According to the invention, a lead-carbon double-layer capacitance theory mode is mainly adopted, the formula optimization adjustment and partial process optimization are carried out on the negative plate, the process formula is adjusted by adding carbon materials and inhibiting hydrogen evolution additives, carbon is used for replacing partial negative electrode active substances, a negative electrode reaction mechanism is changed, and the lead-carbon battery double-layer capacitance mechanism is adopted, so that irreversible sulfation of the negative plate under a high-rate partial state of charge is inhibited, the cycle life of the high-rate partial state of charge of the lead-carbon negative electrode is prolonged, and the cycle life of the lead-acid storage battery for parking is prolonged.
After a large amount of carbon material with high specific area is added into the negative electrode, the effect of electric double layer storage charge of a carbon/solution interface is highlighted, a hybrid energy storage system of the electric double layer and chemical reaction is formed, two circuit systems appear on the negative electrode, 1, a capacitor system is formed by the electric double layer capable of being charged and discharged with high multiplying power, and the reversibility is good, but the specific capacity is low; 2. the lead electrochemical system formed by oxidizing lead discharge into lead sulfate and the lead electrochemical system formed by the lead discharge through the reverse process has slower charging, but has higher specific capacity, and the high-magnification part charge state cycle life of the lead carbon cathode can be improved because the high-magnification and small DOD charge-discharge highly reversible capacitance system can share current.
In the process of charge-discharge reaction of the storage battery, lead can be deposited and attached on the surface of large-particle carbon through the charge process, even the whole carbon particle is wrapped and fused with a lead frame into a whole to form a part of the lead frame, and as lead crystal nucleus is deposited and grows into new branches on the surface of the carbon, in the lead-carbon active material, the pores of the active carbon are filled with electrolyte to form an electric double layer capacitor,
during charging, charges are accumulated in the double electric layers, then the whole path resistance is very small in each part of the lead crystal branch, and the lead-carbon battery realizes the hybrid energy storage of the super capacitor and the battery reaction through the synergistic effect, so that the electrochemical active surface area of the negative electrode active material is increased, the charging process is easier, and the charging acceptance of the negative electrode is further improved.
The surface of the lead-carbon active substance promotes the large-scale generation of small-particle lead sulfate on the surface of the carbon particles during discharge, prevents the growth of lead sulfate grains, has high solubility, increases the electrochemical active surface area due to a large amount of small-particle substances, is easy to reduce into sponge lead during electrode charging, reduces the reaction overpotential of lead sulfate reduction into lead, and is favorable for providing charging efficiency and prolonging the cycle life under the high-rate partial charge state.
The invention provides a preparation method of a negative plate of a storage battery for a parking air conditioner, which comprises a grid and lead plaster coated on the grid,
the formula of the lead plaster comprises the following components in parts by weight: 100 parts of lead powder, 1.1 to 1.2 parts of barium sulfate, 0.8 to 0.9 part of humic acid, 0.4 to 0.5 part of acetylene black, 1.3 to 1.4 parts of expanded graphite, 1.3 to 1.5 parts of polyaniline, 0.1 to 0.11 part of indium hydroxide, 0.2 to 0.3 part of benzyl benzoate, 0.11 to 0.12 part of polyester staple fiber, 11 to 11.5 parts of water and 1.4g/cm density 3 10 to 10.5 parts of sulfuric acid solution;
the preparation method of the negative plate of the storage battery for the parking air conditioner comprises the following steps:
(1) Uniformly mixing barium sulfate, humic acid, acetylene black and expanded graphite to obtain a mixture;
(2) Adding polyaniline, indium hydroxide and benzyl benzoate into a first dose of water, stirring uniformly, adding polyester staple fibers, and dispersing uniformly to obtain a mixed solution;
(3) Adding a second dose of water into the mixture obtained in the step (1) to mix uniformly, adding the mixed solution obtained in the step (2), mixing uniformly, adding sulfuric acid solution, and mixing to obtain lead plaster;
(4) And (3) coating the lead plaster obtained in the step (3) on the grid to obtain a negative plate after coating, covering Tu Banzhi on the surface of the negative plate after coating, and drying to obtain the negative plate of the storage battery for the parking air conditioner.
1. Carbon content
When the carbon content is 1.5% -2%, the total internal resistance of the polar plate is also minimum, the lead sulfate amount is minimum, the aperture of the active substance is minimum, and the polar plate is a high-solubility small crystal, so that the charging conversion efficiency can be improved, the irreversible sulfation of the negative plate under the high-rate partial charge state can be inhibited, the acetylene black is controlled between 0.4% -0.5%, and the expanded graphite is controlled between 1.3% -1.4%.
2. Expanding agent
Because the active material shrinkage of the negative plate is found to occupy a great proportion in the use practice of the parking air conditioner, the invention does not adopt lignin products which are easy to dissolve in dilute sulfuric acid electrolyte, only adopts nano barium sulfate and humic acid products which are not decomposed at high temperature, and the content of the barium sulfate is 1.0-1.2%, and the content of the humic acid is 0.8-0.9%.
3. Hydrogen evolution inhibitor
Because the hydrogen evolution overpotential of the carbon material is lower than that of the lead surface, the hydrogen evolution is inevitably aggravated, the effect of inhibiting the hydrogen evolution of the indium element is better, the indium ions added into the negative lead plaster can react with sulfuric acid, and In the solution 3+ The catalyst is adsorbed on the surface of a carbon material, improves hydrogen evolution overpotential and can inhibit hydrogen evolution.
The polyaniline has the advantages of minimum hydrogen evolution current, good conductivity, high specific capacitance, small size of polyaniline agglomerated particles, porous surface transportation and irregular shape, is favorable for lead sulfate precipitation in the charge and discharge process, and avoids growing large-particle lead sulfate.
In order to inhibit the precipitation of hydrogen, reduce the water decomposition and counteract the negative effect caused by adding a large amount of carbon, the hydrogen inhibiting additive adopts the combination of indium hydroxide and polyaniline to inhibit the precipitation of hydrogen.
4. Sulfate growth inhibitor
By reduction of PbSO 4 The recrystallization size and speed can prevent and delay the generation of negative plate sulfate under the high-rate partial charge state of the storage battery.
Benzyl benzoate is PbSO 4 Effective inhibitor for crystal growth, and PbSO generated in the process of charge-discharge reaction of negative plate after benzyl benzoate is added 4 Crystal ratio PbSO generated by polar plate without adding 4 The crystal is tiny and round, the occurrence of sulfation of the polar plate can be reduced, and the initial capacity and the cycle life of the storage battery are improved.
Specifically, in the step (2), first, a first dose of water is heated to 70 ℃, polyaniline, indium hydroxide and benzyl benzoate are added into the first dose of water, and uniformly stirred for 10-15 min, and polyester staple fibers are added after the temperature is reduced to below 40 ℃ and uniformly dispersed, so that a mixed solution is obtained. At high temperatures, polyaniline, indium hydroxide, and benzyl benzoate dissolve faster.
The ratio of the first dose in step (2) to the second dose in step (3) is 1:2.
In the step (3), the sulfuric acid solution is added by spraying. The time for adding the sulfuric acid solution is not less than 10min, and the reaction temperature is not more than 60 ℃ when the sulfuric acid solution is added.
In the step (3), the density of the lead plaster is 4.1-4.3 g/cm 3 。
The invention also provides a storage battery negative plate for the parking air conditioner, which is prepared by the preparation method.
The invention also provides a storage battery for the parking air conditioner, which comprises a positive plate and a negative plate, wherein the negative plate is the negative plate of the storage battery for the parking air conditioner.
The invention has the beneficial effects that:
the hydrogen evolution inhibiting additive adopts the combination of indium hydroxide and polyaniline to inhibit the precipitation of hydrogen, the indium hydroxide is different from the prior indium oxide and indium sulfate, the indium sulfate is insoluble In water, and the indium hydroxide has more free In the reaction process of the indium hydroxide and the sulfuric acid 3+ Ions appear, so that the ions can be better adsorbed on the surface of the carbon material, the hydrogen evolution overpotential is improved, and the hydrogen evolution can be inhibited.
Detailed Description
Example 1
A preparation method of a negative plate of a storage battery for a parking air conditioner comprises the following steps:
s1: 1.2kg of barium sulfate, 0.8kg of humic acid, 0.4kg of acetylene black and 1.3kg of expanded graphite are uniformly premixed for standby;
s2: taking out 3kg of water, heating to 70 ℃, adding 1.5kg of polyaniline, 0.1kg of indium hydroxide and 0.2kg of benzyl benzoate into the water, uniformly stirring for 13min, adding 120g of short fibers when the temperature is reduced to below 40 ℃, stirring until the fibers are uniformly dispersed, and then standing by;
s3: when mixing paste, adding 100kg of lead powder into a paste mixing machine, putting the mixture prepared in the step S1, uniformly adding the rest 8kg of water in the stirring process, stirring for 5 minutes, adding the additive mixed solution prepared in the step S2, and continuously stirring for 5 minutes;
s4: pouring 10kg of dilute sulfuric acid (density 1.4 g/cm) 3 ) At the same time, the cooling measure is started, and the sulfuric acid is sprayed into the furnace for a long timeThe temperature is less than 10min, the instant temperature in the pouring process is not more than 60 ℃, the stirring is carried out for 5min after the sulfuric acid pouring is finished, and the density of the lead plaster is measured to be 4.1-4.3 g/cm 3 Between them;
s5: coating plate
Adjusting a plate coating machine before coating the plate, adjusting the direction of the coated plate paper, and adjusting the pressure of a plate coating shaping roller to enable the coated plate paper to be coated on the surface of the polar plate;
s6: the curing process adopts a conventional curing process to obtain a negative plate of the storage battery for the parking air conditioner;
the conventional curing process steps are shown in table 1.
TABLE 1
| Temperature/. Degree.C | Humidity/% | Time/h |
| 60 | 95 | 3 |
| 65 | 95 | 26 |
| 60 | 90 | 10 |
| 60 | 80 | 2 |
| 60 | 60 | 2 |
| 70 | 40 | 2 |
| 80 | 20 | 10 |
| 85 | 1 | 6 |
Example 2
A preparation method of a negative plate of a storage battery for a parking air conditioner comprises the following steps:
s1: 1.1kg of barium sulfate, 0.9kg of humic acid, 0.5kg of acetylene black and 1.4kg of expanded graphite are uniformly premixed for standby;
s2: taking out 3.5kg of water, heating to 70 ℃, adding 1.3kg of polyaniline, 0.11kg of indium hydroxide and 0.3kg of benzyl benzoate into the water, uniformly stirring for 15min, adding 110g of short fibers when the temperature is reduced to below 38 ℃, stirring until the fibers are uniformly dispersed, and then standing by;
s3: when mixing paste, adding 100kg of lead powder into a paste mixing machine, putting the mixture prepared in the step S1, uniformly adding the rest 8kg of water in the stirring process, stirring for 5 minutes, adding the additive mixed solution prepared in the step S2, and continuously stirring for 5 minutes;
s4: 10.5kg of dilute sulfuric acid (density 1.4 g/cm) 3 ) Simultaneously, the cooling measure is started, the sulfuric acid is sprayed in for not less than 10min, the instantaneous temperature in the spraying process is not more than 60 ℃, the sulfuric acid is stirred for 5min after being sprayed in, and the density of the lead plaster is measured to be 4.1-4.3 g/cm 3 Between them;
s5: coating plate
Adjusting a plate coating machine before coating the plate, adjusting the direction of the coated plate paper, and adjusting the pressure of a plate coating shaping roller to enable the coated plate paper to be coated on the surface of the polar plate;
s6: the curing process used a conventional curing process (table 1) to obtain a negative plate of a storage battery for a parking air conditioner.
Comparative example 1
A preparation method of a negative plate of a storage battery for a parking air conditioner comprises the following steps:
s1: 100kg of lead powder is added into a lead powder machine, and 0.7kg of barium sulfate, 0.6kg of humic acid, 0.2kg of sodium wood plastic sulfonate and 110g of fiber additive are added into the lead powder machine.
S2: after dry stirring for three minutes, water is added, the water adding amount is 11kg, the water adding time is 3-5 min,
s3: pouring 10kg of dilute sulfuric acid (density 1.4 g/cm) 3 ) Simultaneously, the cooling measure is started, the sulfuric acid spraying time is not less than 10min, the stirring is carried out for 5min after the sulfuric acid spraying is finished, and the density of the lead plaster is measured to be 4.1-4.3 g/cm 3 Between them;
s4: the curing process used a conventional curing process (table 1) to obtain a negative plate of a storage battery for a parking air conditioner.
Test example 1
The plate produced by the conventional process in comparative example 1 and the plate assembled with the rich solution produced by the embodiment 1 of the invention are used for maintenance-free parking air conditioner storage battery N220, and the capacity, low-temperature starting (-18 ℃) of 20h (520A), charging acceptance and vibration resistance test are carried out according to the national standard GB/T5008.1-2013 standard and the test method of the simulated working condition,
the 20h capacity testing method comprises the following steps: stopping discharging at 11A current to 10.5+/-0.05V in an environment of 25+/-2 ℃, recording the discharging time, and calculating the battery capacity through the time;
the test method for low-temperature start (-18 ℃) of (1200A) comprises the following steps: when the battery is cooled to the temperature of-18+/-1 ℃, discharging for 30s by using 1200A current, then discharging for 40s by using 720A current after standing for 20s, and recording terminal voltages at several stages in the process;
the test method for charging acceptance comprises the following steps: the accumulator is in the environment of 25 plus or minus 2 ℃ and is characterized by I 0 (A) Immediately discharging the current for 5h, immediately placing into a low-temperature box with the temperature of 0+/-1 ℃, charging for 10min according to the voltage of 14.40+/-0.1V after at least 20h, and recordingCharging current I ca (A)；
The test method for vibration resistance comprises the following steps: the storage battery is vertically vibrated for 2 (h) at the maximum acceleration of 3g at the frequency of 30+/-2 Hz in the environment of 25+/-2 ℃, and the storage battery is not charged in the environment of 25+/-2 ℃ within 4h after the vibration is finished, and the vibration is finished by the vibration of the storage battery, wherein the vibration is represented by the formula I cc (1200A) Current discharge 30s records terminal voltage;
the test method for the simulation working condition comprises the following steps:
the cells were placed in a water bath at 25 ℃ ± 2 ℃ during the experiment and tested according to the following steps:
(1) Constant current discharge is carried out for 6+/-0.1 h by 4+/-0.1A;
(2) Constant voltage 14+ -0.1V current limit 70+ -1A charge for 6+ -0.1 h;
(3) 27+ -0.1A constant current discharge for 3+ -0.1 h:
(4) Then charging for 6+/-0.1 h with a constant voltage of 14+/-0.1V current limit of 70+/-1A:
(5) Forming a complete test cycle according to the steps (1) - (4), wherein the end voltage of the cycle process is lower than the lowest protection voltage of the rich liquid parking air-conditioning battery, and judging that the test is terminated, and the lowest protection voltage of the liquid parking air-conditioning battery is 11V; after 50 more cycles, at 0.6I cc Performing low temperature test at-18deg.C+ -1deg.C, I cc The end voltage of the discharge 30s is not lower than the lowest starting voltage of the whole vehicle, the lowest starting voltage of the whole vehicle is 7.2V, otherwise, the test is judged to be ended: and the number of complete test cycles is more than or equal to 150, and is qualified. The test results are shown in Table 1.
TABLE 1
As can be seen from the test data in Table 1, although the batteries assembled by the two processes are qualified through standard tests, the battery test results obtained by the process of the invention are better than the batteries produced by the process in low-temperature starting, charging acceptance and simulated working condition life test.
Claims (9)
1. The preparation method of the storage battery negative plate for the parking air conditioner comprises a grid and lead plaster coated on the grid, and is characterized in that,
the formula of the lead plaster comprises the following components in parts by weight: 100 parts of lead powder, 1.1 to 1.2 parts of barium sulfate, 0.8 to 0.9 part of humic acid, 0.4 to 0.5 part of acetylene black, 1.3 to 1.4 parts of expanded graphite, 1.3 to 1.5 parts of polyaniline, 0.1 to 0.11 part of indium hydroxide, 0.2 to 0.3 part of benzyl benzoate, 0.11 to 0.12 part of polyester staple fiber, 11 to 11.5 parts of water and 1.4g/cm density 3 10 to 10.5 parts of sulfuric acid solution;
the preparation method of the negative plate of the storage battery for the parking air conditioner comprises the following steps:
(1) Uniformly mixing barium sulfate, humic acid, acetylene black and expanded graphite to obtain a mixture;
(2) Adding polyaniline, indium hydroxide and benzyl benzoate into a first dose of water, stirring uniformly, adding polyester staple fibers, and dispersing uniformly to obtain a mixed solution;
(3) Adding a second dose of water into the mixture obtained in the step (1) to mix uniformly, adding the mixed solution obtained in the step (2), mixing uniformly, adding sulfuric acid solution, and mixing to obtain lead plaster;
(4) And (3) coating the lead plaster obtained in the step (3) on the grid to obtain a negative plate after coating, covering Tu Banzhi on the surface of the negative plate after coating, and drying to obtain the negative plate of the storage battery for the parking air conditioner.
2. The method for preparing a negative plate of a storage battery for a parking air conditioner according to claim 1, wherein in the step (2), first, a first dose of water is heated to 70 ℃, polyaniline, indium hydroxide and benzyl benzoate are added into the first dose of water, and uniformly stirred for 10-15 min, and polyester staple fibers are added after the temperature is reduced to below 40 ℃ and uniformly dispersed, so that a mixed solution is obtained.
3. The method of manufacturing a negative electrode plate for a storage battery for a parking air conditioner according to claim 1, wherein a ratio of the first dose in step (2) to the second dose in step (3) is 1:2.
4. the method for producing a negative plate of a storage battery for a parking air conditioner according to claim 1, wherein in the step (3), the sulfuric acid solution is added by spraying.
5. The method for manufacturing a negative plate of a storage battery for a parking air conditioner according to claim 4, wherein the time for adding the sulfuric acid solution is not less than 10 minutes, and the reaction temperature is not more than 60 ℃ when the sulfuric acid solution is added.
6. The method for producing a negative plate of a storage battery for a parking air conditioner according to claim 1, wherein in the step (3), the density of the lead paste is 4.1 to 4.3g/cm 3 。
7. The method for manufacturing a negative plate of a storage battery for a parking air conditioner according to claim 1, wherein the oxidation degree of the lead powder is 74% -78%.
8. A negative electrode plate for a storage battery for a parking air conditioner, which is produced using the production method according to any one of claims 1 to 7.
9. A storage battery for a parking air conditioner, comprising a positive electrode plate and a negative electrode plate, wherein the negative electrode plate is the storage battery for a parking air conditioner according to claim 8.
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