CN102800898A - Manufacturing method for lead-carbon battery used for mild hybrid vehicle - Google Patents
Manufacturing method for lead-carbon battery used for mild hybrid vehicle Download PDFInfo
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- CN102800898A CN102800898A CN2012102673948A CN201210267394A CN102800898A CN 102800898 A CN102800898 A CN 102800898A CN 2012102673948 A CN2012102673948 A CN 2012102673948A CN 201210267394 A CN201210267394 A CN 201210267394A CN 102800898 A CN102800898 A CN 102800898A
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- 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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- 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
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Abstract
The invention relates to a manufacturing method for lead-carbon batteries used for mild hybrid vehicles, comprising the following steps: step 1) oil removing, coarsening, neutralizing, pre-soaking, activating, chemical silvering and electroplating lead at last to polyurethane sponge in sequence, and obtaining a lead foam material; step 2) cutting to shape the lead foam material, coating negative active substance, wherein carbon black is used as additive to the active substance; step 3) solidifying and drying to obtain negative plates which are assembled to be finished batteries with positive plates manufactured by using common gravity casting method. The method can greatly improve the lead-carbon battery performance.
Description
Technical field
Patent of the present invention relates to the manufacture method of a kind of micro-hybrid automobile with lead-carbon battery.
Technical background
Chinese industrial and information portion pointed out that the micro-hybrid automobile will be realized industrialization 2015 in " energy-conservation and new-energy automobile industrial development planning (draft) ".Micro-hybrid system with automatic start-stop function becomes the passenger car standard configuration.The micro-hybrid automobile is a kind of in that automobile is intermittent when stopping, and lets the engine auto extinguishing, reduces the oil consumption of engine when idling and the novel energy-saving environment-friendly type automobile product of discharging.It is on Traditional engine, has installed the starting-generating integrated electric machine of belt drives additional, when automobile start, provides energy to start-up a car by storage battery.
Advantages such as traditional lead acid accumulator price is lower with respect to lithium battery, Ni-MH battery etc., and security performance is good, and starting current is big, and working temperature is wide are still the first-selection of micro-hybrid automotive battery.In little hybrid vehicle dynamical system, the frequent starting of automobile, parking, the number of times that needs storage battery to pilot engine obviously increases.And along with the raising of user to vehicle safety and comfortableness requirement; The quantity of vehicle mounted electrical equipment and electric power also obviously increase; When engine stop working; The electric energy of vehicle mounted electrical equipment all relies on storage battery to provide, and undoubtedly performance index such as the deep discharge performance of lead acid accumulator and usage frequency is had higher requirement.Traditional lead acid batteries problems such as the too early swelling set of pole plate, rib burn into active material soften, come off occur easily in frequent use, cause the battery life termination.To the deficiency of traditional lead acid batteries at battery deep discharge aspect of performance; We have invented a kind of micro-hybrid automobile that is suitable for lead-carbon storage battery; It is on the basis of traditional lead acid accumulator; Change its conventional negative grid structure, add novel active material additive-carbon black, increased substantially the performance of lead-acid battery.
Summary of the invention
The technical problem that the present invention solved is: a kind of manufacture method that can increase substantially the micro-hybrid automobile of lead-acid battery performance with lead-carbon battery is provided.
For solving technical problem proposed by the invention, the technical scheme that the present invention adopts is: a kind of micro-hybrid automobile is characterized in that may further comprise the steps with the manufacture method of lead-carbon battery:
Step 1), polyurethane sponge is carried out oil removing, alligatoring, neutralization, preimpregnation, activation, chemical silvering successively pass through lead plating at last, obtain the foam lead material;
Step 2), with above-mentioned foam lead material excision forming, apply negative electrode active material, add carbon black in its active material as additive;
Step 3), negative plate through solidify, after the drying and the positive plate made of traditional gravity casting be assembled into the finished product battery.
In the such scheme, described oil removing is: polyurethane sponge was soaked in the alkaline solution 1~10 minute, and said alkaline solution is NaOH 3~5g/L; Sodium carbonate 10~30g/L, tertiary sodium phosphate 5~10g/L, OP-10 emulsifying agent 0.5~5g/L; Temperature is a room temperature, through oil removal treatment, can remove sponge in processed and transportation; Be adsorbed on the greasy dirt and the dust on sponge silk surface, reach the purpose on cleaning sponge surface.
In the such scheme; Described alligatoring is: the polyurethane sponge after the oil removing was soaked in the strongly acidic solution etch 1~15 minute, described strongly acidic solution be two kinds of mixed liquor or chromic anhydride 10~100g/L and potassium bichromate 5~50 g/L of two kinds of sulfuric acid 100~500 ml/L and potassium bichromate 5~50 g/L three kinds of mixed liquor or sulfuric acid 100~500 ml/L, chromic anhydride 10~100g/L and potassium bichromate 5~50 g/L mixed liquor.Can make the surface microscopic of polyurethane sponge coarse through roughening treatment, surface area increases, thereby is easy to the adsorption activity material.
In the such scheme, described neutralization is: the polyurethane sponge after the alligatoring was soaked 1~10 minute in 50~100 g/L sodium hydroxide solutions.Its role is to neutralization materials remained on surface acid solution, avoid hexavalent chromium to be brought in the preimpregnation solution, shorten the useful life of preimpregnation solution.
In the such scheme, described preimpregnation is: the polyurethane sponge after will neutralizing, and place preimpregnation solution to soak 15~30 minutes, described presoak is the mixed liquor of stannous chloride 10~100 g/L and hydrochloric acid 20~200ml/L.
In the such scheme, described activation is: the polyurethane sponge after the preimpregnation is soaked in carried out activation processing in the activating solution 1~30 minute, described activating solution is the mixed liquor of silver nitrate 2~10g/L, ammoniacal liquor (25%) 5~25 ml/L.
In the such scheme, described chemical silvering is: with the polyurethane sponge after the activation, be soaked in the chemical silvering solution 3~10 minutes; Described chemical silvering solution is: silver nitrate 2~10g/L, ammoniacal liquor (25%) 5~25 ml/L, potassium hydroxide 1~5g/L; Glucose 5~15g/L, tartaric acid 1~3g/L, ethanol 50~100ml/L; Potassiumiodate 0.01~0.05g/L, asccharin 0.01~0.05g/L.
In the such scheme; The technology of said lead plating is: sponge that will be behind chemical silvering is as negative electrode, and as anode, electrolyte prescription is with pure stereotype: lead oxide 280~320g/L; Boric acid 200~240g/L hydrofluoric acid (50%) 240~280 ml/L; Peptone 3~5g/L, room temperature, current density are 1~5A/dm
2, electroplating time 60~150 minutes.
Through the foam lead material that said method obtains, have certain mechanical strength, in light weight, specific area is big, through-hole rate is high, be easy to welding, tin coating purity is high, impurity is few, the coating soft texture, porosity is low.After processing battery, after the corrosion of foam lead material, can not dissolve other harmful metal ion owing to its matrix, influence the chemical property of battery.
With the foam lead that makes in the such scheme, size excision forming as requested.Apply negative electrode active material by amount of calculation.Negative electrode active substance formulation is: lead powder 1000g, distilled water 130~150g, sulfuric acid (d=1.4) 20~30g, short fiber 1~2g, carbon black 10~30g.Through 72 hours, 45 ℃ of curing, drying obtained micro-hybrid electric vehicle accumulator negative plate behind the coated plate.Last and common anode plate combo, be assembled into micro-hybrid electric vehicle storage battery.
Beneficial effect of the present invention: (1) adopts the method for electronation behind oil removing, alligatoring, neutralization, preimpregnation, activation, chemical silvering; In the lead plating of polyurethane sponge surface electrical, obtain the foam lead material again, this kind method processing step is simple; Easy operating, solution are easy to maintenance; Production efficiency is high, and is with low cost, is suitable for large-scale production; (2) the foam lead material of employing three-dimensional structure replaces the stereotype grid of traditional gravity-assist pouring.This foam lead with three-dimensional structure have certain mechanical strength, in light weight, specific area is big, through-hole rate is high, be easy to the welding.Lead layer has the purity height.Impurity is few, coating soft texture, characteristics such as porosity is low.Owing to added carbon powder material in the negative electrode active material, reduced the bond degree of active material, the foam lead material of this three-dimensional structure can effectively be wrapped in active material in the foam lead, can not cause cream, takes off the generation of problems such as cream; (3) in cathode additive agent, add a certain proportion of carbon black constitute, the adding of carbon black material can reduce battery greatly in frequent use; The sulfation degree of negative plates; Be beneficial to the heavy-current discharge of battery, improve the utilance and the capacity of negative electrode active material, improve the charge acceptance of battery; Particularly effectively improve battery negative electrode sulfation in frequent large current density process, effectively prolonged the useful life of battery.
Description of drawings
Fig. 1 be among the embodiment 1 the micro-hybrid automobile with lead-carbon storage battery manufacture craft flow chart;
Fig. 2 prepares the micro-hybrid automobile with lead-carbon accumulator negative plate outside drawing for embodiment 1;
Fig. 3 prepares the micro-hybrid automobile with lead-carbon accumulator negative plate cut-away view for embodiment 1.
Embodiment
Embodiment 1: as shown in Figure 1, a kind of micro-hybrid automobile that is used for uses the making step of lead-carbon battery to be:
(1), oil removing: 200 * 200 * 2.5 millimeters polyurethane sponges be immersed in contain NaOH 3g/L, sodium carbonate 10g/L, tertiary sodium phosphate 5g/L, OP-10 emulsifying agent 0.5g/L, mixed solution in, temperature is a room temperature, soak time 2 minutes;
(2), alligatoring: the polyurethane sponge after the oil removing is immersed in the mixed solution of sulfuric acid 500ml/L and potassium bichromate 10g/L and corroded 5 minutes;
(3), neutralization: the polyurethane sponge after the alligatoring was soaked 1 minute in the sodium hydroxide solution of 80 g/L;
(4), preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 30 minutes, described presoak is stannous chloride 10g/L and hydrochloric acid 40ml/L;
(5), activation: the polyurethane sponge after the preimpregnation is soaked in the activating solution, carried out activation processing 5 minutes, activating solution is the mixed liquor of silver nitrate 2g/L, ammoniacal liquor (25%) 6ml/L;
(6), chemical silvering:, be soaked in the chemical silvering solution room temperature with the polyurethane sponge after the activation; 5 minutes, described chemical silvering solution was: silver nitrate 4g/L, ammoniacal liquor (25%) 10 ml/L; Potassium hydroxide 2g/L, glucose 8g/L, tartaric acid 1g/L; Ethanol 50ml/L, Potassiumiodate 0.01g/L, asccharin 0.01g/L;
(7), lead plating: as anode, the polyurethane sponge behind chemical silvering is as negative electrode with pure stereotype, and electrolyte prescription is: lead oxide 300g/L, boric acid 220g/L hydrofluoric acid (50%) 280 ml/L, peptone 3g/L, room temperature, current density are 5A/dm
2, electroplating time 60 minutes;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step;
(8), excision forming: the foam lead material that will obtain after will electroplating cuts into 150 * 180 * 2.5 millimeters square;
(9), apply negative electrode active material: negative electrode active substance formulation is: 1000 parts in lead powder, 138 parts of distilled water, 21 parts in sulfuric acid (d=1.4), 1.1 parts on short fiber, 10 parts of carbon blacks;
(10), be coated with that pole plate behind the cream solidified through 72 hours, drying, temperature is 45 ℃, obtains micro-hybrid electric vehicle accumulator negative plate;
The anode plate combo of (11), at last dried negative plates and common process being made, be assembled into micro-hybrid electric vehicle storage battery.
Present embodiment 1 resulting micro-hybrid electric vehicle storage battery, its negative plate photo as shown in Figures 2 and 3.Can find out from Fig. 2 negative plates outward appearance, the pole plate of this instance made, the outward appearance uniformity consistency is good, does not have and takes off cream, the generation of phenomenons such as be full of cracks.Can see that from the negative plates internal structure of Fig. 3 foam lead material and negative electrode active material combine closely, not have obvious hole and exist.
Press the resulting battery of manufacture method of embodiment 1; Its positive plate is the pole plate that common grid is processed; Negative plates is with the common made pole plate of grid material of the plumbous replacement of foam; In the active material of negative plate, added 1% carbon black as additive, be used for improving the cycle life of battery and delay the sulfation trend of negative plate.Through test, the heavy-current discharge performance of battery has significantly improved 13%, and the negative electrode active material utilance obviously increases by 22%, and prolonged 18% the useful life of battery.
Embodiment 2:
A kind of micro-hybrid automobile that is used for is with lead-carbon battery, making step be:
(1), oil removing: 200 * 200 * 2 millimeters polyurethane sponges be immersed in contain NaOH 5g/L, sodium carbonate 30g/L, tertiary sodium phosphate 10g/L, OP-10 emulsifying agent 3g/L, mixed solution in, temperature is a room temperature, soak time 10 minutes;
(2), alligatoring: the polyurethane sponge after the oil removing is immersed in the mixed solution of sulfuric acid 200ml/L and chromic anhydride 30g/L and corroded 10 minutes;
(3), neutralization: the polyurethane sponge after the alligatoring was soaked 5 minutes in the sodium hydroxide solution of 100 g/L;
(4), preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 15 minutes, described presoak is stannous chloride 10g/L and hydrochloric acid 40ml/L;
(5), activation: the polyurethane sponge after the preimpregnation is soaked in the activating solution, carried out activation processing 30 minutes, activating solution is the mixed liquor of silver nitrate 8g/L, ammoniacal liquor (25%) 24ml/L;
(6), chemical silvering:, be soaked in the chemical silvering solution room temperature with the polyurethane sponge after the activation; 10 minutes, described chemical silvering solution was: silver nitrate 8g/L, ammoniacal liquor (25%) 24ml/L; Potassium hydroxide 4g/L, glucose 15g/L, tartaric acid 3g/L; Ethanol 100ml/L, Potassiumiodate 0.05g/L, asccharin 0.05g/L;
(7), lead plating: as anode, the polyurethane sponge behind chemical silvering is as negative electrode with pure stereotype, and electrolyte prescription is: lead oxide 320g/L, boric acid 240g/L hydrofluoric acid (50%) 240 ml/L, peptone 5g/L, room temperature, current density are 2A/dm
2, electroplating time 150 minutes;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step;
(8), excision forming: the foam lead material that will obtain after will electroplating cuts into 120 * 150 * 2 millimeters square;
(9), apply negative electrode active material: negative electrode active substance formulation is: 1000 parts in lead powder, 150 parts of distilled water, 28 parts in sulfuric acid (d=1.4), 1.5 parts on short fiber, 30 parts of carbon blacks;
(10), be coated with that pole plate behind the cream solidified through 72 hours, drying, temperature is 45 ℃, obtains micro-hybrid electric vehicle accumulator negative plate;
The anode plate combo of (11), at last dried negative plates and common process being made, be assembled into micro-hybrid electric vehicle storage battery.
Press the resulting battery of manufacture method of embodiment 2; Its positive plate is the pole plate that common grid is processed; Negative plates is with the common made pole plate of grid material of the plumbous replacement of foam; In the active material of negative plate, added 3% carbon black as additive, be used for improving the cycle life of battery and delay the sulfation trend of negative plate.Through test, the heavy-current discharge performance of battery has significantly improved 15%, and the negative electrode active material utilance obviously increases by 23%, and prolonged 21% the useful life of battery.
Embodiment 3:
A kind of micro-hybrid automobile that is used for uses the making step of lead-carbon battery to be:
(1), oil removing: 200 * 200 * 2 millimeters polyurethane sponges are immersed in the mixed solution that contains NaOH 4g/L, sodium carbonate 20g/L, tertiary sodium phosphate 7g/L, OP-10 emulsifying agent 5g/L, and temperature is a room temperature, soak time 8 minutes;
(2), alligatoring: the polyurethane sponge after the oil removing is immersed in the mixed solution of sulfuric acid 400ml/L and chromic anhydride 90g/L and corroded 10 minutes;
(3), neutralization: the polyurethane sponge after the alligatoring was soaked 10 minutes in the sodium hydroxide solution of 70 g/L;
(4), preimpregnation: the polyurethane sponge after will neutralizing, be soaked in the presoak and soaked 22 minutes, described presoak is stannous chloride 60g/L and hydrochloric acid 200ml/L;
(5), activation: the polyurethane sponge after the preimpregnation is soaked in the activating solution, carried out activation processing 25 minutes, activating solution is the mixed liquor of silver nitrate 10g/L, ammoniacal liquor (25%) 12ml/L;
(6), chemical silvering: with the polyurethane sponge after the activation, soaking at room temperature in chemical silvering solution 6 minutes, described chemical silvering solution is: silver nitrate 10g/L; Ammoniacal liquor (25%) 7ml/L, potassium hydroxide 5g/L, glucose 7g/L; Tartaric acid 2g/L; Ethanol 80ml/L, Potassiumiodate 0.03g/L, asccharin 0.02g/L;
(7), lead plating: as anode, the polyurethane sponge behind chemical silvering is as negative electrode with pure stereotype, and electrolyte prescription is: lead oxide 300g/L, boric acid 223g/L, hydrofluoric acid (50%) 270ml/L, peptone 4g/L, room temperature, current density are 5A/dm
2, electroplating time 100 minutes;
Adopt the secondary reverse-flow rinsing process to clean between above-mentioned each step;
(8), excision forming: the foam lead material that will obtain after will electroplating cuts into 120 * 150 * 2 millimeters square;
(9), apply negative electrode active material: negative electrode active substance formulation is by weight: 1000 parts in lead powder, 150 parts of distilled water, 28 parts in sulfuric acid (d=1.4), 1.5 parts on short fiber, 30 parts of carbon blacks;
(10), be coated with that pole plate behind the cream solidified through 72 hours, drying, temperature is 45 ℃, obtains micro-hybrid electric vehicle accumulator negative plate;
The anode plate combo of (11), at last dried negative plates and common process being made, be assembled into micro-hybrid electric vehicle storage battery.
Press the resulting battery of manufacture method of embodiment 3; Its positive plate is the pole plate that common grid is processed; Negative plates is with the common made pole plate of grid material of the plumbous replacement of foam; In the active material of negative plate, added 3% carbon black as additive, be used for improving the cycle life of battery and delay the sulfation trend of negative plate.Through test, the heavy-current discharge performance of battery has significantly improved 14.1%, and the negative electrode active material utilance obviously increases by 23%, and prolonged 19% the useful life of battery.
Claims (9)
1. a micro-hybrid automobile is with the manufacture method of lead-carbon battery, and it is characterized in that: its method may further comprise the steps:
Step 1), polyurethane sponge is carried out oil removing, alligatoring, neutralization, preimpregnation, activation, chemical silvering successively pass through lead plating at last, obtain the foam lead material;
Step 2), with above-mentioned foam lead material excision forming, apply negative electrode active material, add carbon black in its active material as additive;
Step 3), negative plate through solidify, after the drying and the positive plate made of traditional gravity casting be assembled into the finished product battery.
2. micro-hybrid automobile as claimed in claim 1 is characterized in that with the manufacture method of lead-carbon battery: described deoiling step is: polyurethane sponge was soaked in the alkaline solution 1~10 minute, and said alkaline solution is NaOH 3~5g/L; Sodium carbonate 10~30g/L; Tertiary sodium phosphate 5~10g/L, OP-10 emulsifying agent 0.5~5g/L, temperature is a room temperature; Through oil removal treatment; Can remove sponge in processed and transportation, be adsorbed on the greasy dirt and the dust on sponge silk surface, reach the purpose on cleaning sponge surface.
3. micro-hybrid automobile as claimed in claim 1 is with the manufacture method of lead-carbon battery; It is characterized in that: described alligatoring step is: the polyurethane sponge after the oil removing was soaked in the strongly acidic solution etch 1~15 minute, described strongly acidic solution be two kinds of mixed liquor or chromic anhydride 10~100g/L and potassium bichromate 5~50 g/L of two kinds of sulfuric acid 100~500 ml/L and potassium bichromate 5~50 g/L three kinds of mixed liquor or sulfuric acid 100~500 ml/L, chromic anhydride 10~100g/L and potassium bichromate 5~50 g/L mixed liquor.
4. micro-hybrid automobile as claimed in claim 1 is characterized in that with the manufacture method of lead-carbon battery: described neutralization procedure is: the polyurethane sponge after the alligatoring was soaked 1~10 minute in 50~100 g/L sodium hydroxide solutions.
5. micro-hybrid automobile as claimed in claim 1 is with the manufacture method of lead-carbon battery; It is characterized in that: described preimpregnation step is: the polyurethane sponge after will neutralizing; Place preimpregnation solution to soak 15~30 minutes, described presoak is the mixed liquor of stannous chloride 10~100 g/L and hydrochloric acid 20~200ml/L.
6. micro-hybrid automobile as claimed in claim 1 is with the manufacture method of lead-carbon battery; It is characterized in that: described preimpregnation step is: described activation is: the polyurethane sponge after the preimpregnation is soaked in carried out activation processing in the activating solution 1~30 minute, described activating solution is the mixed liquor of silver nitrate 2~10g/L, ammoniacal liquor (25%) 5~25 ml/L.
7. micro-hybrid automobile as claimed in claim 1 is characterized in that with the manufacture method of lead-carbon battery: described preimpregnation is: described chemical silvering step is: with the polyurethane sponge after the activation, be soaked in the chemical silvering solution 3~10 minutes; Described chemical silvering solution is: silver nitrate 2~10g/L; Ammoniacal liquor (25%) 5~25 ml/L, potassium hydroxide 1~5g/L, glucose 5~15g/L; Tartaric acid 1~3g/L; Ethanol 50~100ml/L, Potassiumiodate 0.01~0.05g/L, asccharin 0.01~0.05g/L.
8. micro-hybrid automobile as claimed in claim 1 is with the manufacture method of lead-carbon battery; It is characterized in that: described preimpregnation step is: the technology of said lead plating is: sponge that will be behind chemical silvering is as negative electrode, and as anode, electrolyte prescription is with pure stereotype: lead oxide 280~320g/L; Boric acid 200~240g/L hydrofluoric acid (50%) 240~280 ml/L; Peptone 3~5g/L, room temperature, current density are 1~5A/dm
2, electroplating time 60~150 minutes.
9. micro-hybrid automobile as claimed in claim 1 is with the manufacture method of lead-carbon battery; It is characterized in that: described preimpregnation is: said negative electrode active substance formulation is: 1000 parts in lead powder; 130~150 parts of distilled water; 20~30 parts in sulfuric acid (d=1.4), 1~2 part on short fiber, 10~30 parts of carbon blacks.
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Cited By (1)
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CN115869967A (en) * | 2022-11-21 | 2023-03-31 | 昆明理工大学 | Foam copper catalyst with cross-scale pore-size structure and preparation method thereof |
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CN1159081A (en) * | 1996-12-31 | 1997-09-10 | 湘潭大学 | Production process of plate slab lattice of lead accumulator |
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CN115869967A (en) * | 2022-11-21 | 2023-03-31 | 昆明理工大学 | Foam copper catalyst with cross-scale pore-size structure and preparation method thereof |
CN115869967B (en) * | 2022-11-21 | 2023-09-08 | 昆明理工大学 | Foam copper catalyst with trans-scale pore diameter structure and preparation method thereof |
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