CN1170332C - High-energy low-consumption long-life environment-protecting type lead battery and its preparation method - Google Patents
High-energy low-consumption long-life environment-protecting type lead battery and its preparation method Download PDFInfo
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- CN1170332C CN1170332C CNB991022920A CN99102292A CN1170332C CN 1170332 C CN1170332 C CN 1170332C CN B991022920 A CNB991022920 A CN B991022920A CN 99102292 A CN99102292 A CN 99102292A CN 1170332 C CN1170332 C CN 1170332C
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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
- 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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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The present invention relates to a lead-acid accumulator and a preparation method thereof. In the accumulator, additives of 2-benzimidazole sulfur, niacinamide, etc. are added to lead plaster of negative plate, and additives of oxyammonia sulfate, etc. are added to lead plaster of a positive plate; battery jar formation is adopted, and formation liquid is added by stages, so that the concentration of the formation liquid is increased gradually; additives of 6-aminopurine, 8-hydroxyquinoline-5-sulfonic acid, etc. are added to the formation liquid; additives of acetyl-acetanilide, anthranilic acid, etc. are added to formation replenishing liquid; an electrolyte is composed of a component A and a component B, the component A is sulphuric acid solution to which additives of sulfanilamide, etc. are added, and the component B is SiO4<4-> ion silica sol solution to which additives of tannic acid, sodium benzoate, sodium dioxide, etc. are added. The accumulator has the characteristics of high specific energy, volumetric capacity free from temperature influence, little power consumption, long service life and little pollution, and is suitable for being used as a power supply for various kinds of starting up, traction, illumination, UPS and battery cars.
Description
Technical field
Lead accumulator is a kind of of chemical power source, is widely used in automobile, diesel locomotive, the boats and ships communication etc., as illumination, UPS, fixing, startup, traction power source.
Background technology
At present existing plumbic acid battery is to use positive electrode PbO
2, negative electrode Pb is with rare H
2SO
4Make electrolyte, the grid of current collection and support is with alloy compositions such as lead, antimony, cadmium, cobalt, calcium, strontium, copper, silver, platinum, ruthenium, osmium, arsenic, selenium, tellurium, sulphur.Its shortcoming concentration polarization, electrochemical polarization, ohmic polarization that to be electrolyte produce electrode cause the battery lead plate passivation, rot, capacity reduce fast, the life-span is short, self discharge is fast, retention of charge is low, internal resistance is big, the current potential height is satisfied in charging, discharge potential is low.The electrolyte intermediate ion moves transmission in water, the water temperature change of properties makes the capacity temperature influence, and the low temperature capacity is low.Two anodizing reduction reaction speed width of cloth differences are big, cause the power consumption energy big, the percentage of water loss height, and charging is slow, discharge capacity is low.Grid is many with precious metal alloys cost height, bad performance.Can not overcharge during use the time has pernicious gas to separate out with overdischarge, charging to cause environmental pollution, non-refractory, low temperature, and capacity reduces significantly during low temperature, is 100% ,-15 ℃ as 25 ℃ of 20h discharge rates and is 50% ,-40 ℃ to be 20% ,-50 ℃ be 10%.Have in order to improve service condition, at rare H
2SO
4Contain SiO middle the adding
2Ludox make electrolyte colloidization, but because SiO
2Influence such as take place that insulating properties is arranged after the hydration, caking property, strong dispersion force, adsorptivity, tack, water-insoluble, acid are insoluble causes battery capacity to reduce, and internal resistance increases, and self discharge is accelerated, the lost of life.These problems are perplexing the development of lead accumulator and the application under the special environment condition always.
The objective of the invention is in order to provide a kind of and existing storage battery different prescription and manufacture method, solve of the influence of electrolyte intermediate ion to battery lead plate concentration polarization, electrochemical polarization and ohmic polarization, solve the influence of low temperature to capacity, the solution colloidal electrolyte is to the harmful effect in battery capacity, internal resistance, self discharge, life-span, and the speed width of cloth that reduces two anodizing reduction reactions is poor.Prepare that a kind of specific energy height, internal corrosion are light, no purifying, self discharge is slow and few with suppress not put certainly, internal resistance is little, charging is fast, the power consumption little energy, percentage of water loss is low, discharge power is strong, capacity is temperature influence not, the low temperature capacity strengthens, overcharging resisting, overdischarge, and cost is low, safeguard and lack with non-maintaining the environment-friendly lead accumulator that the life-span is long.Use to adapt under high temperature, severe cold areas natural environment and the service condition harsh conditions.
Summary of the invention
In order to reach above purpose, the present invention forms positive and negative plate lead plaster, chemical synthesizing method and change into liquid and form, and several aspects such as the preparation method of electrolyte are improved, and adopt following technical scheme:
A kind of preparation method of lead acid accumulator comprises the preparation of grid, and the preparation of negative, positive plate lead plaster changes into the preparation of liquid, the changing into of positive and negative pole plate, and the preparation of electrolyte, battery case charging and packaging process is characterized in that:
1. positive and negative pole lead paste
A. cathode lead plaster is that benchmark adds n-dodecane ammonia 0.01～0.2% with lead powder weight, 2～benzimidazole sulphur 0.01-0.02%, 3-5 diaminourea benzoic acid 0.01-0.2%, nicotinic acid 0.01-0.2%, niacinamide 0.01-0.2%, oxine or its metal complex 0.01-0.2%, barium sulfate 0.5%, carbon black 0.3%, stone is deceived powder 0.8%, humic acid 0.6%, 1-hydroxyl-2-naphthoic acid 0.02%;
B. add oxyammonia sulfate 0.1-0.8%, oxine additive or its metal complex 0.02～0.4% additive in the anode diachylon;
2. electrolyte
Preparation method of electrolyte is made up of for two doses A, B:
A component: be at d
25Be benchmark with sulfuric acid solution weight in the sulfuric acid solution of=1.240-1.630, acetyl group aniline 0.01-0.03%, sulphaguanidine 0.01-0.3% have been added, 2 amino-phenols-4-sulfonamide 0.01-0.3%, oxine or its sulfate 0.01-0.3%, sulfanilamide (SN) 0.01-0.03% additive;
B component: be to contain SiO
4 4-10-30% colloid diameter 100-400A, the silica sol solution of viscosity 1.0-1.5Pas ion, with weight is that benchmark adds tannic acid 0.01-0.3%, benzoic acid and sodium benzoate 0.01-0.2%, benzenediol or quinone 0.01-0.2%, sodium pyrophosphate 0.01-0.3%, phenyl acetamide 0.01-0.1%, NaOH or potassium 0.01-0.2%, sodium peroxide or potassium 0.01-0.2%, oxine or its metal compound 0.01-0.02 additive;
Electrolyte gets final product A component, B component in use with 1: 0.3～1.2 volume ratio mixing;
3. change into liquid and change into additional liquid
Change into liquid: in concentration is d
25=1.19～1.27g/cm
3Sulfuric acid liquid in, be benchmark with this solution weight, add adenine 0.01～0.3%, acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3%, 8-hydroxyl-5-sulfonic acid 0.01～0.3% additive;
Change into additional liquid: in concentration is d
25=1.3～1.5g/cm
3Sulfuric acid solution in, be benchmark with the solution weight, add adenine 0.01～0.3%, acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3%;
4. chemical synthesizing method:
Change into directly and carry out in battery case, changing into a branch 3-4 stage carries out, with 1-2A/dm
2Current density, the 3.5-7 that changes into electric weight and be rated capacity doubly, the time of changing into is 18-96 hour, changes into liquid when lacking, and replenishes in good time and changes into additional liquid.
In detail improvements are described below:
1. the composition of lead plaster
1. negative plate lead plaster is to be primary raw material with the lead powder in the prior art, adds a spot of barium sulfate, carbon black, graphite powder, humic acid, 1-hydroxyl-additives such as 2-naphthoic acid again, and the present invention has added n again on the basis of above prescription
-Additives such as dodecane ammonia, 2～benzimidazole sulphur, 3-5 diaminourea benzoic acid, nicotinic acid, niacinamide, oxine or its metal ion complex.Its addition is that benchmark is respectively n with the weight along powder
-Dodecane ammonia 0.01～0.2%, 2～benzimidazole sulphur, 0.01～0.02%, 3～5 diaminourea benzoic acids 0.01～0.2%, nicotinic acid 0.01～0.2%, niacinamide 0.01～0.2%, oxine or its metal complex 0.01-0.2% additive.
2. positive plate lead plaster is to be primary raw material with the lead powder in the prior art, adds a spot of terylene short fiber peacekeeping graphite powder again, and the present invention has added hydrogen sulfate ammonia, oxine or its metal complex on the basis of above basic components.Its addition is that benchmark is respectively oxyammonia sulfate 0.1～0.8%, oxine or its metal complex 0.02～0.4% with the weight of lead powder.
Wherein oxine or its metal ion complex can be the complex compounds of potassium, sodium, calcium, lead ion.
2. chemical synthesizing method and change into liquid and form
Battery case changes in the prior art green plate and changes into and manyly change into electrolytic bath, also have directly to change in battery case, but it is constant all the time to change into liquid concentration in the formation process.The present invention has prepared the used liquid that changes into of a kind of and prior art and has formed the different liquid that changes into, and has also prepared to change into additional liquid.In formation process, replenish liquid and make and change into liquid concentration in the battery case and constantly increase, can impel β-PbO in the positive plate lead plaster like this by constantly adding to change into
2Content improve α-PbO
2Content reduce, increase battery starting stage and the capacity that uses early stage.
The compound method that wherein changes into liquid is: in the concentration for preparing is d
25=1/19～1.27g/cm
3Sulfuric acid solution in, be benchmark with the weight of this solution, add adenine 0.01～0.3%; acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3%, oxine-5-sulfonic acid 0.01～0.3%; stir, the liquid color that changes into of preparation shows faint yellow.
Changing into the compound method of replenishing liquid is: in the concentration for preparing is d
25=1.3～.1.5g/cm
3In the sulfuric acid solution, be that benchmark adds adenine 0.01～0.3%, acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3% with the weight of this solution.
Chemical synthesis technology:
Green plate that drying is good is formed the pole plate group, and positive/negative plate flock-mate fork is arranged, and inserts dividing plate between positive/negative plate, and the group puts into battery case with pole plate, and through-wall welding connects, and puts into cooling bath and carries out battery case and change into.
To change into liquid and add respectively in each battery case, lower the temperature 4～6 hours, battery case positive terminal and negative pole end are connected in series, and energising changes into, and change into three to five stages of branch to carry out.
With 1～2A/dm
2Current density changes into electric weight and is 3.5～7 times of rated capacity, and the time of changing into is 18～96 hours.
In the formation process, when electrolytic bath is internalized into the liquid dehydration, change into liquid when being lower than the requirement liquid level, in time replenish and change into additional liquid.When changing into molten density at d
25=1.21～1.350g/cm
3Continue to stablize in 3 hours constant, prove to change into, can finish to change into.To change into liquid and pour out, and adjust density, next time is usefulness again, uses repeatedly and outwell for 3～5 times.
3. electrolyte preparation and application
Electrolyte of the present invention adopts A, the configuration of B bi-component to form, and wherein the A component is for having added acetyl group aniline, sulphoamidine, 2 amino-phenols-4-sulfonamide, oxine or additives such as its sulfate, sulfanilamide (SN); The B component is to contain SiO
4 4-The silica sol solution of ion has wherein added tannic acid, benzoic acid and sodium benzoate, benzenediol or quinone, sodium pyrophosphate, phenyl acetamide, NaOH or potassium, sodium peroxide or potassium and oxine or its metal complex additive.
The preparation of A component: the GB requirement preparation density by the preparation storage battery is d
25=1.240～1.630g/cm
3Sulfuric acid solution; with this solution weight is benchmark; in this sulfuric acid solution, add acetyl group aniline 0.01～0.03%, sulphoamidine 0.01～0.3%, 2 amino-phenols-4-sulfonamide 0.01～0.3%, oxine or its sulfate 0.01-0.3%; sulfanilamide (SN) 0.01-0.3%, color is faint yellow.
The preparation of B component: be to contain SiO
2Silica sol or the sodium silicate solution produced of ion-exchange add in the reactor, add tannic acid, benzenediol or quinone, benzoic acid and sodium benzoate, sodium pyrophosphate, phenyl acetamide, sodium peroxide or potassium, NaOH or potassium, 8-hydroxyl silicon quinoline or its metal complex, stir equal.Temperature remains on 85～95 ℃, continues 12 hours, makes SiO
2Molecular reaction changes into SiO
4 4-Ion is measured SiO
4 4-Ion concentration accounts for Sio in the solution
2The percentage of total amount, colloid diameter, pH value is determined reaction end.Emit this solution, be cooled to 25～30 ℃, this colloidal sol outward appearance is black or milky.
Preferred approach is to contain SiO
210～30% silica sol adds in the reactor, heat up, and be that benchmark adds tannic acid 0.01～0.3%, benzoic acid and sodium benzoate 0.01～0.2%, benzenediol or quinone 0.01～0.2%, sodium pyrophosphate 0.01～0.3%, phenyl acetamide 0.01～0.1%, NaOH or potassium 0.01～0.2%, sodium peroxide or potassium 0.01～0.2%, oxine or its metal complex 0.01～0.02%, stirs with the weight of this solution, reaction temperature remains on 85～95 ℃, continue 12 hours, make SiO
2Molecule changes into SiO
4 4-Ion is measured SiO
4 4-Ion accounts for SiO in the solution
2More than 95% of total amount, colloid diameter 100～400A, viscosity 1.0～1.5Pa, S, PH is 7.5～8.5, after having reacted, emits this solution, is cooled to 25～30 ℃.Measure SiO in the solution
4 4-Ion concentration is 10～30%, density d
25=1.050-1.270g/cm
3This silica sol outward appearance is black or milky.
Wherein oxine or its metal ion complex can be the complex compounds of potassium, sodium, calcium, lead ion.
With A component and B component with 1: 0.3～1.2 volume ratio mixed preparing electrolyte.Earlier quantitative electrolyte A component is inserted in plastics or the enamelled vessel, more quantitative B component is slowly added in the container and mix and continuous the stirring lasting 1～3 minute with the A component, appearance color is converted into faint yellow.In 5～10 minutes, this mixed liquor is added battery case, exceed 1～4cm, SiO to dividing plate
4 4-Ion concentration is 4～10%.Placed 1～3 hour, electrolyte is the light yellow gel shape, and the battery case temperature is reduced to below 30 ℃.
The net reaction of storage battery of the present invention is:
Pole plate in the battery case also need replenish electricity after changing into, the monomer series-connected connection of battery case is replenished.With 1/20 current charges of battery rated capacity 1～6 hour, stop charging to there being micro-minute bubbles to emerge.Cell tension is at 2.35～2.4V, and capacity is in more than 120～150% of rated capacity.
Replenishing behind the electricity shop one layer thickness in the every single lattice of battery case is asbestos cloth or glass fibre or the sponge layer of 1～4cm, puts the plastics of a slice band micropore or the thin slice of celluloid at top layer, has red indigo plant, Huang, green sign on the thin slice respectively.Cell through lid is sealed weldering or uses the glue good seal, weld pile crown, fix nut, rubber blanket.Show redly, orange, blue, blue or green, yellow, purple, green in the every single lattice of battery, the additional liquid of notes makes the color disappearance.Promptly prove lack of water if color shows between the operating period, in time supplementing water disappears its color.The battery surface cleaning is clean, can pack and dispatch from the factory.
Beneficial effect of the present invention is as follows:
1. saved in conventional production process that electrolytic bath changes into, battery lead plate drenches Xian, the oxygen-inhibiting agent impregnation process, bake drying refills before the adapted operations such as liquid feeding charging again.
2. additive in the electrolyte and the positive and negative ion in the electrolyte produce electrical power, can the distribution of balanced ion in electrolyte, weaken the concentration polarization that ion and the electrical power of electrode are caused, electrochemical polarization, ohmic polarization has the specific energy height, internal resistance is little, discharge power is strong, corrosion is light, long service life, and self discharge is few, characteristics such as retention of charge height.
3. the additive in negative plate lead plaster and the positive plate lead plaster can promote anodal oxidation, suppresses the negative pole reduction; It is slow to change between charge period oxidation reaction, and reduction reaction is fast, and the redox reaction in the circulation is filled, put to balance, and it is stressed to improve charging, and percentage of water loss is low, safeguards fewly, pollutes light.
4. the SiO in the electrolyte of the present invention
4 -Ion, in the charge and discharge process with the combining or disengaging of hydrogen ion, water, the electrolyte intermediate ion be can improve and hydration, transmission relied on, capacity is subjected to Temperature Influence, improves the low temperature capacity, overcharging resisting and high-temperature charging, the activity that still can keep the battery lead plate active material during dehydration, the excessive response that suppresses discharge condition ion and active material, anti-overdischarge, no passivation.
In electrolyte, be added with organic compounds and SiO
4 4-Ion has been avoided SiO
2Shortcomings such as the battery capacity that causes reduces, internal resistance is big, self discharge is fast, the life-span is short.The existing battery of the battery performance of preparation is significantly increased.Now concrete data are compared.See Table 1
Table 1 battery of the present invention and the contrast of existing battery performance
| Performance index | Actuated type | Trailed model | Fixed | UPS uses | ||||||
| A | B | A | B | A | B | A | B | |||
| Volumetric specific energy wh/dm 3 | 65～ 80 | 78～96 | 26～32 | 39～48 | 15～23 | 23～35 | 65～80 | 85～96 | ||
| Specific energy wh/kg | 34～ 45 | 40～54 | 12～16 | 18～25 | 12～15 | 18～23 | 34～45 | 48～54 | ||
| Temperature is to the influence of capacity | C 30℃％ | 100 | 130 | 100 | 130 | 100 | 150 | 100 | 140 | |
| C -15℃％ | 50 | 115 | 50 | 115 | 50 | 135 | 60 | 120 | ||
| C -40℃％ | 20 | 95 | 20 | 95 | 20 | 115 | 30 | 110 | ||
| C -50℃％ | 10 | 85 | 10 | 85 | 10 | 105 | 15 | 100 | ||
| Internal resistance | Be full of the single lattice of current potential V/ | 2.5～ 2.7 | 2.33～ 2.35 | 2.5～ 2.7 | 2.33～ 2.35 | 2.5～ 2.7 | 2.33～ 2.35 | 2.5～ 2.7 | 2.32～ 2.40 | |
| The single lattice of initial discharge current potential V/ | 2.1～ 2.15 | 2.2～ 2.30 | 2.10～ 2.15 | 2.2～ 2.30 | 2.05～ 2.10 | 2.20～ 2.30 | 2.05～ 2.15 | 2.15～ 2.30 | ||
| The single lattice of discharge stability current potential V/ | 1.90 | 2.0～ 2.05 | 1.90 | 2.0～ 2.05 | 1.90 | 2.0～ 2.05 | 1.90 | 2.05～ 2.10 | ||
| Electricity stops the single lattice of current potential V/ | 1.75 | 1.85 ～1.90 | 1.75 | 1.85～ 1.90 | 1.75 | 1.85～ 1.90 | 1.75 | 1.85～ 1.90 | ||
| Self discharge is % round the clock whenever | 0.3～ 3 | 0.1 | 3 | 0.1 | 3 | 0.1 | 0.3 | 0.05 | ||
| Retention of charge S after January | 0.1～ 0.3 | 0.8～ 0.9 | 0.1～ 0.15 | 0.8～ 0.9 | 0.1～ 0.15 | 0.8～ 0.9 | 0.3～ 0.6 | 0.90～ 1.0 | ||
| Charging interval h | 12～ 14 | 8～ 10 | 12～14 | 8～9 | 12～14 | 8～10 | Do not stop floating charge | 8～9 | ||
| Charging cycle time several | 200 350 | 350～ 550 | 250～ 350 | 450～ 650 | 300 500 | 500～ 750 | 300～ 450 | 500 750 | ||
| Active material utilization % | 50～ 60 | 85～90 | 50～60 | 85～95 | 50～65 | 85～95 | 60～70 | 85～95 | ||
* indicate: A is existing storage battery, and B is a storage battery of the present invention.
Capacity C is meant that battery accounts for the percentage of rated capacity at actual capacity at each temperature
Embodiment
Embodiment 1 actuated type (12V 60Ah)
One, (alloy of Pb+2～4%Sb) is cast into the radial pattern screen, and the plate ear is located at the middle side part of plate with plumbous antimony.
Two, the preparation of the negative plate lead plaster electrolysis shot lead powder 454kg that in paste mixing machine, packs into, add blanc fixe 2.27kg, humic acid 2.71kg, 1-hydroxyl-2-naphthoic acid 1.13kg, carbon black 1.14kg, graphite powder 3.5kg, 3-5 diamino benzoic acid 0.227kg, nicotinic acid 0.227kg, niacinamide 0.227kg, n-dodecane ammonia 10g again, 2～benzimidazole sulphur 20g, oxine calcium 100g start fully and mix.
200g is dispersed in the water of 60L with acrylic (or terylene) short fiber, it is added in the paste mixing machine fast continuous stirring half a minute.
Slowly adding density in paste mixing machine is d
25=1.400g/cm
3Dilution heat of sulfuric acid 39L, start cooling system simultaneously, the limit edged stirs, sulfuric acid added within 10～15 minutes, continuous stirring 35～40 minutes.
Measure the lead plaster apparent density, add low amounts of water in case of necessity again and adjust lead plaster density, make the lead plaster apparent density reach 4.30 ± 0.10kg/L, go out cream, shut down.
Three, mix positive plate lead plaster
The electrolysis ball milling lead powder 454kg that packs in paste mixing machine adds oxyammonia sulfate 3.15kg, graphite powder 3.5kg again, and oxine potassium 0.4kg starts mixer and fully mixes.
Other steps are with to mix negative lead plaster identical
Four, be coated with cream:
Be coated with the cream method routinely and be coated with cream, the heavy 101kg of the dried lead plaster of the negative plate of control, the heavy 92kg of the dried lead plaster of positive plate.
Five, solidify
Through rolling plate, drenching acid, send into the dry tack free stove, temperature is controlled at 100～120 ℃, and dry 2～5 minutes, make the pole plate water content be controlled at 8.0～11.0%, go out drying oven, cover with wet cotton felt, enter curing room.
The curing room temperature remains on 50～70 ℃, relative humidity and is not less than 85%, solidifies more than 18 hours.Solidified to take off to get and covered felt, be lower than 1% until water content through delivering to hothouse again.
Six, battery case changes into
The green plate that drying is good is formed the pole plate group, form 600 groups of positive plate groups with 3000 positive plates, form 600 groups of negative plate groups with 3600 negative plates, make positive/negative plate flock-mate insert row row, between positive/negative plate, insert polyethylene separator, form 600 groups of positive and negative plate groups, 600 groups of pole plate groups are put into the polypropylene plastics battery case of 100 12V 60Ah, through-wall welding connects, and puts into cooling bath and carries out battery case and change into
Change into the liquid preparation: get 133kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 317kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.220g/cm
3Add adenine 59g, acetyl-acetanilide 50g, ortho-aminobenzoic acid 60g, oxine-5-sulfonic acid 50g stirs.The liquid color that changes into of preparation shows faint yellow.
Change into and replenish the liquid preparation: get 50kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 50kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.40g/cm
3Add adenine 10kg, acetyl-acetanilide 20g, ortho-aminobenzoic acid 20g stirs.Should replenish liquid and be replenishing of dehydration when being used for battery case and changing into.
Chemical synthesis technology: will change into liquid and add respectively in each battery case, lower the temperature 4～6 hours, battery case positive terminal and negative pole end are connected in series, and energising changes into, and changes into the branch four-stage and carries out.
Phase I: electric current 3.2A changed into 4 hours
Second stage: electric current 6.4A changed into 16 hours
Phase III: electric current 4.5A changed into 12 hours
The quadravalence section: electric current 3.2A changed into 20 hours
Always the time of changing into is 52 hours, and electrolytic bath is internalized into liquid when lacking, and replenishes in good time and changes into additional liquid, and is density stabilized at d when changing into liquid
25=1.29g/cm
3And continue 3 hours constant, prove to change into, can finish to change into.To change into liquid and pour out, and adjust density, next time is usefulness again, uses repeatedly and outwell for 3～5 times.
Seven, preparation electrolyte
The preparation of A component: with storage battery standard sulfuric acid 190kg, slowly add in the 210kg deionized water, be cooled to below 32 ℃, adjust density d
25=1.375g/cm
3, in this sulfuric acid solution, adding acetyl group aniline 90g, sulphoamidine 90g, the yellow acid amides 45g of sulfanilamide (SN) 60g, 2-amino-phenol-4-, oxine 60g, it is faint yellow that outward appearance is.
The preparation of B component: will contain 25% silica sol 120kg, deionized water 20kg adds in the reactor, intensification is also added tannic acid 30g, Sodium Benzoate 15g, catechol or quinone 15g, sodium pyrophosphate 20g, phenyl acetamide 10g, NaOH 15g, sodium peroxide 15g, potassium superoxide 15g, oxine sodium 20g, stirs.Reaction temperature remains on 85～95 ℃, continues 12 hours, makes SiO
2Molecule changes into SiO
4 4-Ion is measured SiO
4 4-Ion accounts for SiO
295% of total amount, colloid diameter 100～200_, viscosity 1.0～1.5Pa.s, PH are 7.5～8.5.After having reacted, emit this solution, be cooled to 25～30 ℃, measure SiO in the solution
4 4-Ion concentration is 25%, and outward appearance is black, and density is d
20=1.05～1.25g/cm
3Seal standby
Eight, battery case adds electrolyte
Get electrolyte A component 15L, insert in plastics or the enamelled vessel, getting B component 5L slowly adds in the container and continuous the stirring lasting 1～3 minute, appearance color is converted into faint yellow, in 5～10 minutes this mixed liquor is added battery case, adds to dividing plate and exceeds 3cm, placed 1～3 hour, electrolyte is the light yellow gel shape, and the battery case temperature is reduced to below 30 ℃, and the monomer series-connected connection of battery case is replenished.
Nine, replenish
With 3A current charges 2～3 hours, stop charging to there being micro-minute bubbles to emerge.Battery case is checked voltage at 13～13.5V, and capacity is more than 120%.
Ten, cell package
Shop one layer thickness is asbestos cloth or glass fibre or the sponge layer of 1.5cm in the every single lattice of battery case, puts a slice thin slice of the celluloid of fine and close aperture redly at top layer.Battery case top cleaning is clean, and the heat-sealing cell through lid welds firm pile.The battery surface cleaning is clean, can pack and dispatch from the factory.
This battery volumetric specific energy reaches 78～86Wh/dm3 specific energy and reaches 40～50Wh/kg; Temperature is to the C that influences of capacity
30=120%, C
-15=85～95%, C
-40=80～90%; It is the single lattice of 2.33～2.36V/ that voltage is satisfied in charging, and vehicle can be full of voluntarily, does not need car to charge outward; Initial discharge voltage is increased to the single lattice of 2.24V/.Tripping force is increased; Stop current potential and be increased to the single lattice of 1.85V/; More than the high S=0.85 of retention of charge; Charge and discharge circulation and reach 500 times, the life-span was in 3～5 years.Overcharging resisting electricity, overdischarge.
Embodiment 2 enclosed-type batteries (12V 65Ah)
One～five method is with embodiment 1
Six, battery case changes into
The green plate that drying is good is formed the pole plate group, form 600 groups of positive plate groups with 3600 positive plates, form 600 groups of negative plate groups with 4200 negative plates, positive/negative plate flock-mate fork is arranged, between positive/negative plate, insert polyethylene separator, form 600 groups of positive and negative plate groups, 600 groups of pole plate groups are put into the ABS plastic battery case of 100 12V65Ah, through-wall welding connects, and puts into cooling bath and carries out battery case and change into
Change into the liquid preparation: get 172kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 330kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.255g/cm
3Add adenine 55g, acetyl-acetanilide 55g, ortho-aminobenzoic acid 65g stirs.The liquid color that changes into of preparation shows faint yellow.
Change into and replenish the liquid preparation: get 60kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 60kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.40g/cm
3Add adenine 12g, acetyl-acetanilide 24g, ortho-aminobenzoic acid 24g stirs.
Change into: will change into liquid and add respectively in each battery case, after the cooling, battery case positive terminal and negative pole end are connected in series, and energising changes into, and change into the branch four-stage and carry out.
Phase I: electric current 3.4A changed into 4 hours
Second stage: electric current 6.8A changed into 16 hours
Second stage: electric current 4.8A changed into 12 hours
The quadravalence section: electric current 3.4A changed into 20 hours
Always the time of changing into is 52 hours, and electrolytic bath is internalized into liquid when lacking, and replenishes in good time and changes into additional liquid.Density stabilized when changing into liquid at d
25=1.29g/cm
3And continue 3 hours constant, prove to change into, can finish to change into.To change into liquid and pour out, and adjust density, next time is usefulness again, uses repeatedly and outwell for 3～5 times.
Seven, preparation electrolyte
The preparation of A component: with density is d
20=1.840g/cm
3Storage battery standard sulfuric acid 208g, slowly join in the 210kg deionized water, be cooled to below 32 ℃, adjust density d
25=1.420g/cm
3, in this sulfuric acid solution, add acetyl group aniline 100g, sulphoamidine 100g, sulfanilamide (SN) 60g, the yellow acid amides 50g of 2-aminobenzene sweet smell-4-, oxine-5 sulfonic acid 60g, stir, it is faint yellow that color is.
The preparation of B component: will contain SiO
225% silica sol 125kg, deionized water 20kg adds in the reactor, intensification is also added tannic acid 32g, benzoic acid 15g, Sodium Benzoate 20g, hydroquinones or quinone 15g, sodium pyrophosphate 25g, phenyl acetamide 12g, sodium peroxide 18g, NaOH 18g, oxine sodium 12g, stirs.Reaction temperature remains on 85～95 ℃, continues 12 hours, makes SiO
2Molecule changes into SiO
4 -Ion is measured SiO
4 4-Ion accounts for SiO
295% of total amount, colloid diameter 100～200_, viscosity 1.5Pa.s, PH are 8.After having reacted, emit this solution, be cooled to 25～30 ℃, measure SiO in the solution
4 4-Ion concentration is 25%, and density is d
20=1.05～1.25g/cm
3Seal standby
Other are with embodiment 1
This battery volumetric specific energy reaches 85～96Wh/dm
3, specific energy reaches 48～54Wh/kg; Temperature is to the C that influences of quality
30=100%, C
-15=85～95%, C
-40=80～90%; It is the single lattice of 2.33～2.36V/ that voltage is satisfied in charging, stops current potential and is increased to the single lattice of 1.85V/; The high S=0.85 of retention of charge～more than 0.9; Charge and discharge circulation and reach 750 times, the life-span was in 10～15 years.
Embodiment 3 GF-500 type storage batterys
One, with embodiment 1
Two, the preparation of negative plate lead plaster
The electrolytic lead ball milling lead powder 454kg that packs in paste mixing machine adds blanc fixe 2.77kg, humic acid 2.5kg, graphite powder 3.5kg, 3-5 diamino benzoic acid 0.25kg, nicotinic acid 0.25kg, niacinamide 0.25kg again, starts mixer and fully mix.Other are with embodiment 1.
Three, the preparation of the positive plate lead plaster of tubular type
To be enclosed within on the lead-antimony alloy skeleton with the impregnated fiberglass pipe of thermosetting phenolic resin, in the ball milling lead powder, add activated carbon 5%, oxine lead 4%, graphite powder 8%, mix and be filled in the fibre pipe, immerse in the deionized water to take out in 15～25 minutes and dry.With Pb-Sb alloy back cover, make tubular plate, 5 pipe pole plates are formed positive plate group, put into d then
25=1.15g/cm
3Dilution heat of sulfuric acid in soaked 6 hours.
Four, be coated with the cream method routinely and be coated with negative plate lead plaster, the heavy 338g of the dried lead plaster of the negative plate of control.
Five, with embodiment 1
Six, battery case changes into
The green plate that drying is good is formed the pole plate group, get 2200 negative plates and form 200 groups (11 every group) negative plate group, get 200 groups of positive plate groups of (10 every group) tubular type, positive/negative plate flock-mate misplug is good, between positive/negative plate, insert rubber separator, form 200 groups of positive and negative plate groups, the pole plate group is put into polymethyl methacrylate or the plastic battery groove of 200 500Ah, cover battery cover and screw bolt, put into cooling bath and carry out battery case and change into
Change into the liquid preparation: get 510kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 2100kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.150g/cm
3Add adenine 220g, acetyl-acetanilide 220g, ortho-aminobenzoic acid 200g stirs.The liquid color that changes into of preparation shows faint yellow.
Change into and replenish the liquid preparation: get 330kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 330kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.40g/cm
3Add adenine 20g, acetyl-acetanilide 40g, ortho-aminobenzoic acid 40g stirs.
Change into: will change into liquid and add respectively in each battery case, after the cooling, battery case positive terminal and negative pole end are connected in series, and energising changes into, and change into the branch three phases and carry out.
Phase I: electric current 22.5A changed into 20 hours
Second stage: electric current 34A changed into 30 hours
Phase III: electric current 22.5A changed into 25 hours
Always the time of changing into is 75 hours, and electrolytic bath is internalized into liquid when lacking, and replenishes in good time and changes into additional liquid.Density stabilized when changing into liquid at d
25=1.25g/cm
3And continue 3 hours constant, prove to change into, can finish to change into.To change into liquid and pour out, and adjust density, next time is usefulness again, uses repeatedly and outwell for 3～5 times.
Seven, preparation electrolyte
The preparation of A component: with density is d
20=1.840g/cm
3Storage battery standard sulfuric acid 720Kg, slowly join in the 590kg deionized water, be cooled to below 32 ℃, adjust density d
25=1.420g/cm
3, in this sulfuric acid solution, add acetyl group aniline 160g, sulphoamidine 160g, sulfanilamide (SN) 100g, the yellow acid amides 65g of 2-aminobenzene sweet smell-4-, oxine-5 sulfonic acid 80g, stir, it is faint yellow that color is.
The preparation of B component: will contain SiO
210% silica sol 125kg, deionized water 20kg add in the reactor, and intensification is also added tannic acid 80g, benzoic acid 30g, Sodium Benzoate 30g, sodium pyrophosphate 40g, phenyl acetamide 40g, sodium peroxide 30g, oxine sodium 30g, stirs.Reaction temperature remains on 95～100 ℃, continues 12 hours, makes SiO
2Molecule changes into SiO
4 -Ion is measured SiO
4 4-Ion accounts for SiO
295% of total amount, colloid diameter 100～200_, viscosity 0.8Pa.s, PH are 8.After having reacted, emit this solution, be cooled to 25～30 ℃, measure SiO in the solution
4 4-Ion concentration is 25%, and density is d
20=1.05g/cm
3Seal standby
Get A component, the B component of equal volume during use, press the method configuration electrolyte of embodiment 1, add battery case.
Other are with embodiment 1
This battery volumetric specific energy reaches 23～35Wh/dm
3, specific energy reaches 18～23Wh/kg; Temperature is to the C that influences of quality
30=150%, C
-15=135%, C
-40=110%; It is the single lattice of 2.33～2.36V/ that voltage is satisfied in charging, and the high S=0.85 of retention of charge～0.9 charges and discharge circulation and reaches 600 times, and the life-span was in 10～15 years.
Embodiment 4 DG-250 traction-type celies
One～five with embodiment 3
Six, battery case changes into
The green plate that drying is good is formed the pole plate group, get 1200 negative plates and form 200 groups (6 every group) negative plate group, get 200 groups of tubular type green plate groups (5 every group), positive and negative pole plate group staggering is inserted, between positive/negative plate, insert rubber separator, form 200 groups of positive and negative plate groups, put into plastics or the rubber battery case of 200 250Ah, cover battery cover, put into cooling bath and carry out battery case and change into
Change into the liquid preparation: get 640Kg battery standard sulfuric acid d
25=1.835g/cm
3Add in the 1560kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.220g/cm
3Add adenine 170g, acetyl-acetanilide 170g, ortho-aminobenzoic acid 210g stirs.The liquid color that changes into of preparation shows faint yellow.
Change into and replenish the liquid preparation: get 450kg storage battery standard sulfuric acid d
25=1.835g/cm
3Add in the 450kg deionized water, be cooled to temperature below 32 ℃, make sulfuric acid solution concentration be adjusted into d
25=1.40g/cm
3Add adenine 17g, acetyl-acetanilide 30g, ortho-aminobenzoic acid 30g stirs.
Change into: will change into liquid and add respectively in each battery case, after the cooling, battery case positive terminal and negative pole end are connected in series, and energising changes into, and change into the branch three phases and carry out.
Phase I: electric current 12.5A changed into 20 hours
Second stage: electric current 19A changed into 30 hours
Second stage: electric current 12.5A changed into 25 hours
The quadravalence section: electric current 3.4A changed into 20 hours
Always the time of changing into is 95 hours, changes into 4.5 times of electric weight.Electrolytic bath is internalized into liquid when lacking, and replenishes in good time and changes into additional liquid.Density stabilized when changing into liquid at d
25=1.22g/cm
3And continue 3 hours constant, prove to change into, can finish to change into.To change into liquid and pour out, and adjust density, next time is usefulness again, uses repeatedly and outwell for 3～4 times.
Seven, preparation electrolyte
The preparation of A component: with density is d
20=1.835g/cm
3Storage battery standard sulfuric acid 610Kg, slowly join in the 740kg deionized water, be cooled to below 32 ℃, adjust density d
25=1.360g/cm
3, in this sulfuric acid solution, adding ortho-aminobenzoic acid 130g, sulfanilamide (SN) 80g, Sulfaguanidine 130g, the yellow acid amides 65g of 2-aminobenzene sweet smell-4-, chinosol 80g stir, and it is faint yellow that color is.
The preparation of B component: will contain SiO
225% silica sol 450kg, deionized water 450kg add in the reactor, and intensification is also added tannic acid 50g, benzoic acid 30g, Sodium Benzoate 30g, sodium pyrophosphate 35g, phenyl acetamide 30g, sodium peroxide 25g, oxine sodium 30g, stirs.Reaction temperature remains on 85～95 ℃, continues 12 hours, makes SiO
2Molecule changes into SiO
4 -Ion is measured SiO
4 4-Ion accounts for SiO
295% of total amount, colloid diameter 10mu, viscosity 1.5Pa.s, PH are that 8.2 reactions finish, and emit this solution, are cooled to 25～30 ℃, measure SiO in the solution
4 4-Ion concentration is 25%, and density is d
20=1.05～1.25g/cm
3Seal standby.Color is black.
Claims (2)
1. the preparation method of a lead acid accumulator comprises the preparation of grid, and the preparation of negative, positive plate lead plaster changes into the preparation of liquid, the changing into of positive and negative pole plate, and the preparation of electrolyte, battery case charging and packaging process is characterized in that:
(1) positive and negative pole lead paste
A. cathode lead plaster is that benchmark adds n with lead powder weight
-Dodecane ammonia 0.01～0.2%, 2～benzimidazole sulphur 0.01-0.02%, 3-5 diaminourea benzoic acid 0.01-0.2%, nicotinic acid 0.01-0.2%, niacinamide 0.01-0.2%, oxine or its metal complex 0.01-0.2%, barium sulfate 0.5%, carbon black 0.3%, stone is deceived powder 0.8%, humic acid 0.6%, 1-hydroxyl-2-naphthoic acid 0.02%;
B. add oxyammonia sulfate 0.1-0.8%, oxine additive or its metal complex 0.02～0.4% additive in the anode diachylon;
(2) electrolyte
Preparation method of electrolyte is made up of for two doses A, B:
A component: be at d
25Be benchmark with sulfuric acid solution weight in the sulfuric acid solution of=1.240-1.630, acetyl group aniline 0.01-0.03%, sulphaguanidine 0.01-0.3% have been added, 2 amino-phenols-4-sulfonamide 0.01-0.3%, oxine or its sulfate 0.01-0.3%, sulfanilamide (SN) 0.01-0.03% additive;
B component: be to contain SiO
4 4-110-30% colloid diameter 100-400_, the silica sol solution of viscosity 1.0-1.5Pas ion, with weight is that benchmark adds tannic acid 0.01-0.3%, benzoic acid and sodium benzoate 0.01-0.2%, benzenediol or quinone 0.01-0.2%, sodium pyrophosphate 0.01-0.3%, phenyl acetamide 0.01-0.1%, NaOH or potassium 0.01-0.2%, sodium peroxide or potassium 0.01-0.2%, 8～oxyquinoline or its metal compound 0.01-0.02 additive;
Electrolyte gets final product A component, B component in use with 1: 0.3～1.2 volume ratio mixing;
(3) change into liquid and change into additional liquid
Change into liquid: in concentration is d
25=1.19～1.27g/cm
3Sulfuric acid liquid in, be benchmark with this solution weight, add adenine 0.01～0.3%, acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3%, 8-hydroxyl-5-sulfonic acid 0.01～0.3% additive;
Change into additional liquid: in concentration is d
25=1.3～1.5g/cm
3Sulfuric acid solution in, be benchmark with the solution weight, add adenine 0.01～0.3%, acetyl-acetanilide 0.03～0.3%, ortho-aminobenzoic acid 0.02～0.3%;
(4) chemical synthesizing method:
Change into directly and carry out in battery case, changing into a branch 3-4 stage carries out, with 1-2A/dm
2Current density, the 3.5-7 that changes into electric weight and be rated capacity doubly, the time of changing into is 18-96 hour, changes into liquid when lacking, and replenishes in good time and changes into additional liquid.
2, preparation method as claimed in claim 1, the metal complex of the 8-hydroxyl quinoline that adds in its positive and negative pole plate lead plaster and the electrolyte is potassium, sodium, calcium, lead metal complex compound; Phenol that adds in its electrolyte or quinone are catechol or quinone, hydroquinones or quinone.
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| CNB991022920A CN1170332C (en) | 1999-02-11 | 1999-02-11 | High-energy low-consumption long-life environment-protecting type lead battery and its preparation method |
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| CNB991022920A CN1170332C (en) | 1999-02-11 | 1999-02-11 | High-energy low-consumption long-life environment-protecting type lead battery and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100384006C (en) * | 2006-02-21 | 2008-04-23 | 张西琮 | Electrolyte for acid-free ion lithium salt storage cell |
| CN100384007C (en) * | 2006-02-21 | 2008-04-23 | 张西琮 | Electrolyte for acid-free ion sodium salt storage cell |
| CN101792873A (en) * | 2010-03-26 | 2010-08-04 | 如皋市天鹏冶金有限公司 | Low-stibium multicomponent lead alloy and production technology and applications thereof |
| KR101850764B1 (en) | 2011-03-30 | 2018-05-30 | 삼성전자주식회사 | Electrolyte solution for seconndary lithium battery and secondary lithium battery using the same |
| US20120258372A1 (en) * | 2011-04-08 | 2012-10-11 | Takekuni Haneda | Battery life extender |
| CN105280963B (en) * | 2015-09-17 | 2017-08-22 | 超威电源有限公司 | The method and its lead-acid accumulator of a kind of lead-acid accumulator anacidity tank formation |
| CN105336945B (en) * | 2015-09-29 | 2018-05-15 | 双登集团股份有限公司 | A kind of high specific energy lead-acid battery production method |
| CN106252654B (en) * | 2016-08-25 | 2018-09-11 | 四川荣联电子科技有限公司 | Inhibit the lead-acid accumulator negative pole lead paste of oxidation |
| CN106229468B (en) * | 2016-08-25 | 2018-09-11 | 四川荣联电子科技有限公司 | A kind of lead-acid accumulator negative pole lead paste additive |
| CN108336422B (en) * | 2018-03-15 | 2020-03-31 | 天能电池集团股份有限公司 | Low-temperature-resistant storage battery electrolyte and preparation method thereof |
| CN109652023B (en) * | 2018-12-29 | 2020-11-06 | 中国船舶重工集团公司第七一八研究所 | Solar heat-conducting medium and preparation method thereof |
| CN110911751B (en) * | 2019-12-04 | 2020-12-01 | 上海电力大学 | Alkaline aluminum-air battery electrolyte additive, electrolyte and application thereof |
| CN114256515A (en) * | 2021-11-02 | 2022-03-29 | 浙江长兴绿色电池科技有限公司 | Research method for dynamic charge acceptance of exhaust type start-stop lead-acid storage battery |
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